Mixture of styrene block-copolymers and propylene-alpha-olefin copolymers
SUBSTANCE: composition contains from 30 wt % to less than 50 wt % propylene-alpha-olefin copolymer and from more than 50 wt % to 70 wt % styrene block-copolymer. The propylene-alpha-olefin copolymer has at least 70 wt % links formed from propylene, and from 10 to 25 wt % links formed from C2- or C4-C10-alpha-olefin and has heat of fusion less than 37 J/g and melt flow index from 0.1 to 100 g/10 min. The composition has modulus of elasticity in tension less than 20 MPa, ultimate tensile stress of at least 5 MPa and elongation at failure of at least 900% and low relative instantaneous shrinkage.
EFFECT: composition has good physical properties such as elasticity and flexibility, and can also be easily processed using traditional equipment for processing polyolefins.
21 cl, 8 dwg, 2 tbl
The technical field
The present invention relates to compositions of propylene-alpha-olefin copolymers and styrene block copolymers. More specifically, the present invention relates to elastomeric compositions containing niskonatalitetna propylene-alpha-olefin copolymers and styrene block copolymers.
The level of technology
Styrene block copolymers such as SEBS (polystyrene-/saturated polybutadiene-polystyrene), SBS (polystyrene-polybutadiene-polystyrene), SES (polystyrene/saturated polyisoprene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene) and SEPSEP known in this field. These block copolymers have excellent physical properties such as elasticity and flexibility. Often, however, they cannot easily processed on conventional equipment for processing of polyolefin in the absence of amplifiers fluidity and other process additives.
Propylene-alpha-olefin copolymers are easily processed using conventional equipment for the processing of polyolefins. However, the propylene-alpha-olefin copolymers generally are not as flexible and elastic as styrene block copolymers.
It would be desirable to have a thermoplastic elastomer composition which has excellent physical properties, such as elasticity and flexibility, and at the same time the Le is to be processed using conventional equipment for the processing of polyolefins.
The purpose of the present invention
The purpose of the present invention is to create a composition comprising a propylene-alpha-olefin copolymer (preferably an elastomer based on polypropylene) and also containing a styrene block copolymer. The composition should be flexible (usually 2% secant modulus, tensile of less than 20 MPa, preferably less than 15 MPa and more preferably less than 10 MPa, when measured in accordance with the geometry of the specimen ASTM D1708 with basic long sample 22,25 mm and at a speed of stretching 111,25 mm/min (strain-rate of 500%/min)), must have a high tensile strength (usually at least 5 MPa, preferably at least 10 MPa, when measured in accordance with the geometry of ASTM D1708 and strain rate described above)should be high tensile (normal elongation at break of at least 900%, when measured using the geometry of ASTM D1708 and initial basic long sample 22,25 mm, the corresponding strain rate described above), and should have relatively low immediate shrinkage in 2-cyclofem 500% hysteresis test. In addition, the composition should be easily processed on conventional equipment for processing of polyolefins. Amplifiers fluidity or other technology to the where it is refuelled are optional. Preferably the composition will have a melt flow index of 1 to 100 g/10 min, more preferably from 5 to 75 g/10 min, also more preferably from 10 to 60 g/10 min, and most preferably from 12 to 50 g/10 min (ASTM 1238, of 2.16 kg, 230°C).
The essence of the invention
In the first embodiment, the invention is a composition containing:
(a) a propylene-alpha-olefin copolymer having essentially the isotactic sequence of propylene, and at least seventy weight percent (70% wt.) links formed from propylene, and from ten to twenty-five weight percent (10-25% wt.) links formed from C2 - or C4-C10-alpha-olefin and propylene-alpha-olefin exhibits a heat of fusion by DSC analysis from 0 to 37 Joules/gram and a melt flow index from 0.1 to 50 g/10 minutes; and
(b) a styrene block copolymer, where the mass ratio of propylene-alpha-olefin copolymer to styrene block copolymer is from 3:7 to 7:3 and where the composition exhibits the following:
(1) 2% secant modulus, tensile, as measured using the sample geometry ASTM D1708 less than 20 MPa at a strain rate of 500%/min, preferably less than 18 MPa, more preferably less than 10 MPa, and in some preferred aspects less than 7 MPa, and most preferably less than 6 MPa;<> (2) elongation at rupture of at least 900%, preferably at least 950%, more preferably at least 1000% at a strain rate of 500%/minute;
(3) ultimate tensile strength of at least 5 MPa, preferably at least 7 MPa, more preferably at least 10 MPa, and in some particularly preferred aspects, at least 15 MPa (measured using the geometry of the specimens ASTM D1708 and strain rate of 500%/minute); and
(4) immediate relative shrinkage after the initial application 400% strain of less than 2X, where X is an immediate shrinkage shown as a single component (C) after application of 400% strain 2-cycle test.
In the second embodiment, the invention is a composition, the composition essentially contains:
(a) at least one propylene-alpha-olefin copolymer having essentially the isotactic sequence of propylene, and at least seventy weight percent (70% wt.) links formed from propylene, and from ten to twenty-five weight percent (10-25% wt.) links formed from C2 - or C4-C10-alpha-olefin and propylene-alpha-olefin exhibits a heat of fusion by DSC analysis from 2 to 30 Joules/gram and a melt flow index of 0.2 to 40 g/10 the minutes; and
(b) at least one styrene block copolymer, where the mass ratio of propylene-alpha-olefin copolymer to styrene block copolymer is from 3:7 to 7:3 and where the composition exhibits the following:
(1) 2% secant modulus, tensile, as measured using the sample geometry ASTM D1708, less than 18 MPa at a strain rate of 500%/minute, more preferably less than 10 MPa, and in some preferred aspects less than 7 MPa, and most preferably less than 6 MPa;
(2) elongation at rupture of at least 950%, more preferably at least 1000% at a strain rate of 500%/minute;
(3) ultimate tensile strength (measured using the sample geometry ASTM D1708 and strain rate of 500%/minute)of at least 10 MPa, and in some particularly preferred aspects, at least 15 MPa;
(4) immediate relative shrinkage after the initial application 400% strain of less than 2X, where X is an immediate shrinkage shown as a single component (C) after the initial application 400% strain 2-cycle test.
In the third embodiment, the invention is a composition containing:
(a) a propylene-alpha-olefin copolymer having essentially the isotactic sequence propylene, and, by at least seventy weight percent (70% wt.) links formed from propylene, and from ten to twenty-five weight percent (10-25% wt.) links formed from C2 - or C4-C10-alpha-olefin and propylene-alpha-olefin exhibits a heat of fusion by DSC analysis from 1 to 37 Joules/gram and a melt flow index from 0.1 to 40 g/10 minutes; and
(b) a styrene block copolymer, where the mass ratio of propylene-alpha-olefin copolymer to styrene block copolymer is from 3:7 to 7:3 and where the composition exhibits the following:
(1) 2% secant modulus, tensile, as measured using the sample geometry ASTM D1708 (at a strain rate of 500%/minute) less than 20 MPa, preferably less than 18 MPa, more preferably less than 10 MPa, and in some preferred aspects less than 7 MPa;
(2) elongation at rupture of at least 900%, preferably at least 950%, more preferably at least 1000% at a strain rate of 500%/minute;
(3) ultimate tensile strength of at least 5 MPa, preferably at least 7 MPa, more preferably at least 10 MPa, and in some particularly preferred aspects, at least 15 MPa (measured using the geometry of ASTM D1708 and strain rate of 500%/minute); and
(4) immediate shrinkage less than 120% Defoe is received after 2 cycles of test hysteresis 500%, preferably less than 100% strain, more preferably less than 89% strain, and most preferably less than 60%.
In the fourth embodiment, the invention is a product comprising the composition according to any from the first to the third embodiments of the invention. The preferred products are the loop diaper, the wings of the car (elastic laminates containing at least one woven and one elastic component, such as film, tape or thread), medical wipes, products for adults with incontinence, training pants, household products, packaging for food storage, soft shell over the formed products, such as the handles of tools, and others
The inventive compositions have an amazing ratio of elasticity, ultimate tensile strength, immediate shrinkage, relative elongation at break and resistance to solvent compared to conventional mixtures of styrene block copolymers and conventional polyolefins.
Figure 1 shows the range of13With NMR propylene-ethylene copolymer (obtained with activated demetallation catalyst with a Central metal and heteroaryl ligand, similar to catalyst A), which is similar to the propylene-ethylene the copolymers described in paragraph is imarah.
Figure 2 shows the range of13With the NMR of the same propylene-ethylene copolymer, as in figure 1. However, the spectrum is shown with the increase in scale of Y-axis from 1 to more clearly show the peaks Regio-error at about a 14.6 and 15.7 ppm
Figure 3 shows the range of13With NMR propylene-ethylene copolymer obtained using a metallocene catalyst. Figure 3 illustrates the absence of peaks Regio-error at about 15 ppm in the case of propylene-ethylene copolymer produced with a metallocene catalyst.
Detailed description of the invention
STYRENE BLOCK COPOLYMER:
Examples of the styrene block copolymers, it is acceptable for the present invention are described in the publications EP 0712892 B1, WO 204041538 A1, US 6582829 B1; US 2004/0087235 A1; US 2004/0122408 A1; US 2004/0122409 A1; US 4789699; US 5093422; US 5332613; which are incorporated by reference in their guidelines pertaining to the styrene block-copolymers.
In the General case, styrene block copolymers suitable for the present invention have at least two monoelectronic arenovich unit, preferably two polystyrene block, separated by a busy block of a conjugated diene, and containing less than 20% residual ethylene unsaturation, preferably a block of a saturated polybutadiene. The preferred styrene block copolymers have Anuy structure, although branched or radial polymers or functionalityand block copolymers are useful compounds.
Typically, polystyrene/saturated polybutadiene/-polystyrene (S-EB-S) block copolymer (S represents styrene, E represents ethylene and represents a butylene) and polystyrene/saturated isoprene/-polystyrene (S-EP-S) block copolymer (P represents a propylene) contain polystyrene end blocks having srednecenovogo molecular weight of from 5000 to 35000, and medium-sized blocks of saturated polybutadiene or saturated polyisoprene having srednecenovogo molecular weight of from 20,000 to 170000. Blocks of saturated polybutadiene preferably have from 35 to 55% of 1,2-configuration, and blocks of saturated polyisoprene preferably have more than 85% of the 1,4-configuration.
General Brednikova molecular weight styrene block copolymer is preferably from 30,000 to 250,000, if the copolymer has a linear structure. Such block copolymers generally have an average content of polystyrene from 10 to 35 wt.%.
The block copolymer of S-EB-S, used in a particularly preferred aspect of the present invention, is supplied by the company Kraton Polymers (Houston, TX) and has srednecenovogo molecular weight of 50,000 g / mol with polystyrene end blocks, each of which has among the non-numerical molecular weight of 7200 g / mol and a polystyrene content of 30% wt.
Styrene block copolymers can be obtained by methods known to experts in this field of technology. For example, styrene block copolymers can be obtained using free-radical, cationic and anionic initiators or polymerization catalysts. Such polymers can be obtained using the techniques of polymerization in bulk, in solution or in emulsion. In any case, the styrene block copolymer containing at least ethylene unsaturation, generally will be allocated in the form of solids such as grit, powder, pellets or so
Typically, when using the method of anionic polymerization in solution, paired diolefin polymers and copolymers of conjugated diolefins and alkenyl aromatic hydrocarbons are produced by entering into contact with the monomer or monomers to be polymerized simultaneously or sequentially with an organic compound of an alkali metal in a suitable solvent at a temperature in the range from -150 to 300°C, preferably at a temperature in the range from 0 to 100°C. Particularly effective initiators for anionic polymerization are organolithium compounds having the General formula:
RLinwhere R represents an aliphatic, cycloaliphatic, aromatic or alkylthio the military aromatic hydrocarbon radical, containing from 1 to 20 carbon atoms; and n represents an integer from 1 to 4.
In addition to consistent methods for obtaining triblocal, tetrabromo and repetitive structures of higher order, at least, anionic initiators can be used to obtain iblokov styrene-politian having reactive (live) the end of the chain on the diene block, which can be introduced into the reaction through an agent combinations, to create, for example, structure (S-I)xY or (S -)xY, where x takes integer values from 2 to 30, Y is an agent combinations, I is isoprene, b is a butadiene, and more than 65% iblokov S-I or S-B is chemically attached to the agent combinations. Y typically has a molecular weight which is small compared to the resulting polymers, and may consist of any number of materials known in the field, including halogenated organic compounds; halogenated alkylsilane; alkoxysilane; various esters such as alkyl - and University, difunctional aliphatic esters, such as dialkyldimethyl etc.; polyfunctional agents such as divinylbenzene (DVB, DVB) and low molecular weight polymers of DVB. Depending on the selected agent combination of the final polymer may be fully or cha is in part related linear triblock-polymer (x=2), that is SIYIS; or may be branched, radial or star-shaped configuration. Agent combinations, being of low molecular weight, in fact, does not affect the properties of the final polymer. Oligomer DVB usually used to create a star-shaped polymers, where the number of diene rays can be from 7 to 20 or even more.
In related polymers do not want all the links iblokov were identical. In fact, a variety of "live" links iblokov can be brought together in the reaction mix, giving a lot of asymmetrical structures, that is, the total length of the chain iblokov can be different as the length of the subsequent blocks of styrene and diene.
Preferably the block copolymers are gidrirovanie to improve the ability to transfer atmospheric conditions and increase resistance to oxidation. In General, hydrogenation or selective hydrogenation of the polymer can be performed using any of hydrogenation processes known in the art. For example, the hydrogenation can be carried out using methods such as presented in U.S. patent№№ 3494942, 3634594, 3670054, 3700633; and in the link 27145, which are included as references to guidelines pertaining to the hydrogenation of styrene block copolymers and polymers, which are formed in the result is the same. Methods known in the art for the hydrogenation of polymers containing ethylene unsaturation, and for hydrogenation or selective hydrogenation of polymers containing aromatic and ethylene unsaturation include the use of a suitable catalyst, particularly a catalyst or catalyst precursor containing a metal atom from the group of iron, in particular cobalt or Nickel, and a suitable reducing agent, such as alkylamine.
In General, the hydrogenation can be carried out in a suitable solvent at a temperature in the range from 20 to 100°C. and at a partial pressure of hydrogen in the range from 7 MPa (105PA) to 340 ATM (105PA), preferably from 7 MPa (105PA) to 70 MPa (105PA). As a rule, use the concentration of catalyst within the range from 10 to 500 wt. hours/million metal of the iron group based on the whole solution, and an introduction to contact in the conditions of hydrogenation lasts for a period of time in the range from 60 to 240 minutes After completion of the hydrogenation the hydrogenation catalyst and catalyst residues are usually separated from the polymer.
The mass ratio of propylene-alpha-olefin copolymer to styrene block copolymer is from 3:7 to 7:3, preferably from 3:7 to 65:35, before occhialino from 4:6 to 6:4, more preferably from 45:55 to 55:45. Propylene-alpha-olefin copolymer is usually from 30 to 70 wt.%. based on the whole composition of the polymer, preferably from 30 to 65 wt.%. based on the whole composition of the polymer, more preferably from 40 to 60 wt.%. based on the whole composition of the polymer and more preferably from 45 to 55 wt.%. based on the whole composition of the polymer. When the propylene-alpha-olefin copolymer has a heat of fusion of more than 22 j/g, a propylene-alpha-olefin copolymer is preferably 50% or less of thermoplastic polymers in the composition, more preferably less than 40% of thermoplastic polymers in the composition.
Propylene-alpha-olefin copolymer of the present invention is characterized as having essentially the isotactic sequence of propylene. "Essentially isotactic the sequence of propylene and similar definitions mean that the sequence has an isotactic triad (mm)measured13With NMR, approximately more than 0.85 are preferably approximately more than 0.90, more preferably approximately more than 0.92 and most preferably approximately more than 0,93. Isotactic triad known in this field and are described, for example, in the publications USP 5504172 and WO 00/01745 that relate to isotactic the WMD the sequence in terms of the process unit in the molecular chain of the copolymer, defined using spectrum13WITH NMR. The NMR spectra are given as described below.
Propylene-alpha-olefin copolymers of the present invention typically have a melt flow index (engineers, MFR)of at least 0.1 g/10 min, preferably at least 0.3 and more preferably at least 1.0 g/10 min, Preferably the inventive composition satisfies the following equation:
whereηSBCrepresents the viscosity of the styrene block copolymer,ηPBPErepresents the viscosity of the propylene-alpha-olefin copolymer,φSBCrepresents the volume of the styrene block copolymer,φPBPErepresents the volume of the styrene block copolymer in the recipe.
The above ratio of the viscosities determined in the following way.
Dynamic mechanical spectrometer TA Instruments Ares LS Model (New Castle, Delaware, USA)equipped with parallel plates with a diameter of 25 mm, is used to determine the dynamic rheological data. The scan frequency with five logarithmically separated by dots on a dozen passes from 0.1 to 100 rad/sec atTexptso, toTexptrepresented a temperature specific to the way of transformation and technological conditions. Deformation, as defined in point is adalah linear viscoelastic regime at the expense of the implementation of the sweep strain at 0.1 rad/sec and Texpt(C) by scanning for deformation from 2 to 30% step 2%to determine the minimum required deformation to obtain the torque within the technical characteristics of the Converter; another sweep deformation at 100 rad/sec andTexpt(C) is used to determine the maximum deformation before the onset of nonlinearity in accordance with the method described in the publication J.M. the dealy, K.F. Wissbrun “Melt Rheology and Its Role in Plastics Processing”, Van Nostrand, New York (1990). All testing is carried out by blowing with nitrogen to minimize the degradation due to oxidation. For similarity rheological behavior of the ratio of the viscosities obtained when the shear rate used in the application forms. If the speed of the shift when the application is above the interval of measurement, the ratio of the viscosity is determined at a shear rate of 100 rad / second (rad/sec).
At a speed of 100 rad/s ratio of viscosity and volume is:
More preferably, the ratio of viscosity and volume is:
Most preferably, the ratio of viscosity and volume is:
so, whatηAndis the viscosity of phase a;ηInis the viscosity of phase;φAndis the Wallpaper volumetric fraction of phase A; φInrepresents the volumetric fraction of phase C. Phase And preferably enriched in component styrene block copolymer (SBS). Phase preferably enriched component of the propylene-alpha-olefin copolymer (RWRE).
The volume ratio of the phases can be determined from the formulation by dividing the weight percent of each component on their respective densities. The volume ratio can be defined on existing formulations based on the analysis of cross-sections of the sample. Cross sections can be obtained, as a rule, in a variety of ways, including using microtome, which can include or not to include microtome in cryogenic conditions in order to minimize the deformation of the sample. Usually the way to prepare many slices. The analysis area is performed on the images obtained using the technology of microscopy, which is able to detect the differences of the individual phases. Microscopic methods include, but are not limited to, optical microscopy, optical microscopy using polarized light, scanning electron microscopy, transmission electron microscopy and atomic force microscopy. Such spectroscopic methods may require or not to require the use of additional methods of preparing the image is s, to show the contrast between the individual phases. Such methods of preparation of samples include, but are not limited to, methods of differential staining. For example, the ruthenium trioxide is usually used for staining thin sections for transmission electron microscopy. Typically, the analysis area then carried out using software for image analysis on the cut, such as Image Pro (Media Cybernetics Inc., Silver Springs GA). The analysis is usually repeated on a sufficient number of slices to obtain a statistically significant measurement of the ratio of the squares of the phases, which can then be translated in detachable relation phases.
Propylene-alpha-olefin copolymer of the present invention consists of units derived from propylene, and from links formed from alpha-olefins. Preferred comonomers used for the production of propylene-alpha-olefin copolymer, are C2 and C4-C10-alpha-olefins, preferably C2, C4, C6 and C8 alpha-olefins, most preferably ethylene.
Copolymer based on propylene of the present invention contains at least 70% wt. links formed from propylene, and exhibits a heat of fusion of from 0 to 37 Joules/gram, as measured by differential scanning calorimetry. Copolymer based on propylene of the present invention with the contains from 12 to 24 mol%. links formed from alpha-olefin co monomer, more preferably from 14 to 22 mol%. links formed from alpha-olefin co monomer. When the co monomer is ethylene, the copolymer based on propylene contains from 10 to 25 mol%. units formed from ethylene, preferably from 10 to 19 mol%. units formed from ethylene, more preferably from 11 to 17 mol%. units formed from ethylene, even more preferably from 12 to 16 mol%. units formed from ethylene, most preferably from 13 to 15 mol%. units formed from ethylene. The heat of fusion is preferably from 1 to 37 j/g, more preferably from 2 to 30 j/g, even more preferably from 4 to 25 j/g and most preferably from 4 to 19 j/g
Spectroscopy13With NMR is one of the many techniques known in the field, to measure the introduction of the co monomer in the polymer. An example of such a technique is described for determining the content of comonomers in the case of the ethylene/α-olefin copolymers in the publication Randll (Journal of Macromolecular Science, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3), 201-317 (1989)). Based method for determining the content of comonomers for the olefinic interpolymer includes obtaining spectrum13With NMR in conditions where the intensity of peaks corresponding to different carbon atoms in the sample, right PR is portionally total number of contributing nuclei in the sample. Methods of providing such proportionality, known in the art, and they include the provision of sufficient time for relaxation after a pulse, the methodology adjustable junction, agents, relaxation, etc. Relative intensity of the peak or group of peaks on practice of computer integration. After obtaining the spectrum and integrating peaks install those peaks that are associated with the co monomer. This distribution can be performed using correlation with known spectra or with literature data, or by synthesis and analysis of model compounds, or by using labeled with isotopes of co monomer. Mol % of co monomer can be determined by a ratio of integrals, corresponding to the number of moles of co monomer, the integrals corresponding to the number of moles of all monomers in interpolymer, as described, for example, in the publication Randll.
Data are collected using an NMR spectrometer Varian UNITI Plus 400 MHz, corresponding to a resonance frequency of nuclei13With To 100.4 MHz. Detection parameters are chosen so that to provide quantitative data on nuclei13With the presence of the agent relaxation. Data obtained using controlled junction on1N, 4000 short single pulses on the data file, the delay is overenia pulse 7 sec the spectral width 24200 Hz and file size of 32K data points, with the probe head heated to 130°C. the Sample is prepared by adding approximately 3 ml of a mixture of tetrachlorethane-d2/ortho-dichlorobenzene (50/50), that is, 0.025 M in chromium acetylacetonate (agent relaxation), to 0.4 g sample in a 10 mm NMR tube. The blank space of the tube is blown from oxygen by replaced by pure nitrogen. The sample is dissolved and homogenized by heating the tube and its contents to 150°C intermittent irrigation initiated using a heat gun.
After collecting the data, chemical shifts are internally referred to as the side chain mmmm when 21,90 ppm Isotacticity at the level of the triad (mm) is determined from methyl integrals representing the triad mm (from 22.5 to 21,28 ppm), the triad mr (21,28-20,40 ppm) and the triad rr (20,67 and 19.4 ppm). The percentage of tact (the regularity of the molecular structure) mm determined by dividing the intensity rants mm in the amount of triads mm, mr and rr. For propylene-ethylene copolymers made using catalytic systems, such as nepetalactone catalyst with a Central metal and heteroaryl ligands (described below), region mr is correct with regard to ethylene and Regio-errors by subtracting the contribution from PPQ and PPE. Such propylene-ethylene copolymers region rr adjusted taking into account ethylene and Regio-errors by Vici the project contribution from PQ and ORE. In the case of copolymers with other monomers that yield peaks in the areas of mm, mr and rr, the integrals for these areas similarly adjusted by subtracting the interfering peaks using standard NMR techniques after identifying peaks. This can be accomplished, for example, by analyzing a series of copolymers with different levels of introduction of comonomers, with distribution according to literature data, using isotopic labels or other means known in the art.
For copolymers made using demetallizing catalyst with a Central metal and heteroaryl ligands, for example the catalyst described in U.S. patent No. V (Stevens at al, issued November 1, 2005), the peaks in the spectrum of13With NMR, corresponding Regio-error at about a 14.6 and 15.7 ppm are considered to be the result of stereoselective errors 2,1-insertion parts of propylene in the growing polymer chain. In the General case, the content of co monomer higher levels of Regio-errors lead to a decrease of the melting temperature and the elastic modulus of the polymer, whereas lower levels lead to higher melting point and a higher modulus of elasticity of the polymer.
In the case of propylene-alpha-olefin copolymers comonomeric composition and distribution in order whic is ogene can be determined using methods well-known experts in this field. For example, such properties may be determined in accordance with the publication Koenig J.W. (Spectroscopy of Polymers, American Chemical Society, Washington, D.C., 1992).
In a preferred aspect, in the case of propylene-ethylene copolymers, the following technique can be used to determine comonomeric composition and distribution in order. From the spectrum13With NMR to determine the integral of the square and enter in the calculation of the matrix to determine the molar fraction of each process sequence. Then use the matrix distribution integrals to obtain the molar fraction of each triad. The calculation of the matrix represents the implementation of the linear least squares method of Randall (Randall,Journal of Macromolecular Chemistry and Physics, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3), 201-317 (1989)), modified to include additional peaks and sequences for unique 2,1 Regio-errors described above (if it is present in the polymer). Table a shows the integral of the area and the designation of the triads used in the distribution matrix. Numbers associated with each carbon atom, indicate in which region of the spectrum they will resonate.
Mathematically, the Method of the Matrix is a vector equation s=fM, where M is the distribution matrix, s submitted is a vector-line of the spectrum and f is a vector-the composition mole fraction. The successful implementation of the matrix method requires M, f and s were determined so that the resulting equation was defined or overridden (equal to or more independent equations than variables) and to the solution of the equation contained the molecular information needed to calculate the desired structural information. The first stage matrix method consists in the determination of elements in vector-the composition of f. The elements of this vector must be a molecular parameters are chosen so as to give structural information about the system under investigation. For copolymers with a reasonable set of parameters can be any odd n-ad distribution. Usually peaks from individual triads are sufficiently well resolved and easily installed, therefore, the distribution of triads is most often used in this vector-the composition of f. Triad for copolymer P/E represent EEE, EER, RAY, PEP, PPP, RRE, SWU and ORE. For polymer chains with high molecular weight (≥10000 g/mol) in experiments13With NMR cannot distinguish air from a YARD or re from SWU. Since all the P/E copolymers Markovian have a molar fraction of a YARD and SWU, are equal to each other, when implementing the method was also selected constraint equality. The same treatment is carried out for re and SWU. The above two limitations equality reduce eight triads what about the six independent variables. For clarity, the vector composition f is still available all eight triads. Restrictions equality implement internal constraints when solving the matrix. The second stage matrix method consists of defining a vector spectrum s. Typically the elements of this vector will represent a well-defined region in the spectrum. To ensure that the system is defined, the number of integrals must be the same as the number of independent variables. The third step is to determine the distribution of the matrix M. the Matrix is drawn up through the discovery of deposits of carbon atoms from the level of the Central monomer in each triad (column) in the direction of each integral region (row). You need to follow the direction of the polymer when choosing which carbon atom belongs to the Central link. A useful property of such distribution matrix is that the sum of each row must be equal to the number of carbon atoms in the Central element of the triad, which is party to a number. This equality can be easily checked and, consequently, to prevent some of the common errors of data entry.
After making the distribution matrix it is necessary to test the statistical indefinability. In other words, the number of linearly independent columns must be greater than or equal to the number of independent p of the belt in the vector-product. If the matrix is not validated statistical indefinability, you need to go back to the second stage and the integral correction areas, and then again to determine the distribution of the matrix until you pass the test statistic indefinability.
In General, when the number of columns plus the number of additional restrictions or conditions imposed more than the number of rows of the matrix M, the system is overridden. More than overridden the system, the more matrix method can correct or identify inconsistent data that could be obtained from the integration of data with low signal-to-noise (S/N), or partial saturation of some resonance signals.
The final stage is the decision matrix. This is easily accomplished in Microsoft Excel by using the solver. The solver first calculates the approximate vector solution (molar relationships among the various triads) and then performs an iterative solution to minimize the sum of distances between the calculated vector product and the contribution of the vector product s. The solver also allows explicitly to impose restrictions or restrictive conditions.
P = propylene; E = ethylene; Q = 2,1-inserted propylene.Chemical shifts
The composition of the 1,2-inserted propylene calculated by summing all molar fractions of stereoregular propylene Central process sequences. The composition of 2,1-inserted propylene (Q) calculated by summation of all molar fractions of Q centered process sequences. Mole percent propylene determined by adding all R centered triads and multiplying the mole fraction of 100. The composition of the ethylene is determined by subtracting the molar percent P and Q of 100.
In a particularly preferred aspect of the present invention propylene-alpha-olefin copolymer used in the invention is a propylene-ethylene copolymer obtained demetallation catalyst with a Central metal and heteroaryl ligand, such as the catalyst described in U.S. patent No. V (Stevens et al, issued November 1, 2005), which is incorporated by reference in its entirety in parts of its guidance relating to the rolled is atorm. For such catalysts the definition of "heteroaryl" includes substituted heteroaryl. The most preferred demetallation catalyst with a Central metal and heteroaryl ligand is complex metal 4 groups as a catalytic component, which can be described by the following formula:
G1selected from alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroalkyl, geterotsiklicheskie, heteroaryl, heteroalkyl, heteroalkyl, Silla and inertly substituted derivatives containing from 1 to 40 atoms, not counting hydrogen atoms, preferably di-orthoaccel-substituted aryl; most preferably 2,6-diisopropylphenyl;
T is a divalent bridging group containing from 10 to 30 atoms, not counting hydrogen atoms, selected from mono - or di-aryl-substituted methylene or siljanoski groups or mono - or di-heteroarylboronic methylene or siljanoski groups. Most preferably, at least one aryl or heteroaryl Deputy substituted in one or both ortho-positions of the secondary or tertiary alkyl group, secondary or tertiary heteroalkyl group, cycloalkyl group or geteroseksualnoe group;
G2represents a C6-20-heteroaryl is inuu group, contains the base functionality Lewis, in particular pyridine-2-ilen or substituted pyridine-2-ilen group;
M represents a metal 4 groups, preferably hafnium;
X” is an anionic, neutral or dianion ligand group;
x” is a number from 0 to 5 indicating the number of groups X””;
communications optional communication and electron-electron interactions are represented by lines, dotted lines and arrows respectively.
In addition, the active catalyst may also include an activator capable of converting the specified range of metal into an active catalyst for the polymerization of accession, the carrier or substrate, a liquid solvent or diluent, the tertiary component, such as the acceptor, and/or one or more excipients or adjuvants, such as processing AIDS, absorber and/or a regulator of the degree of polymerization.
Propylene-alpha-olefin copolymers obtained by using such demetallizing catalyst with a Central metal and heteroaryl ligand, are unique Regio-error. Regio-error is determined using the peaks in the spectrum of13With NMR, corresponding approximately to 14.6 ppm and about a 15.7 ppm, In this particularly preferred aspect, these peaks have app is siteline equal intensity, and they usually approximately from 0.02 to 7 mol%. propylene insertions into the copolymer chain.
Comparison of some spectra13With NMR additionally illustrates the unique Regio-errors propylene-ethylene copolymers used in a particularly preferred aspect of the present invention. Figures 1 and 2 represent the spectra of propylene-ethylene copolymers, propylene similar-the ethylene copolymers used in the examples. Spectra of each polymer describe a high degree of isotacticity (isotactic triad (mm)measured13With NMR, more than 0,94) and unique Regio-errors of such propylene-ethylene copolymers. Range13With NMR figure 3 represents the spectrum of the propylene-ethylene copolymer obtained using a metallocene catalyst. This spectrum does not show Regio-error (about 15 ppm)characteristic of the preferred propylene-ethylene copolymers used in the present invention.
Preferably the propylene-alpha-olefin copolymers have a molecular mass distribution (MMD), defined as srednevekovaja molecular weight divided by srednecenovogo molecular weight (Mw/Mn)of 3.5 or less, preferably 3.0 or less.
The molecular weight and molecular weight distribution of the propylene-alpha-olefin the s copolymers determined using gel permeation chromatography (GPC, GPC) at high temperature chromatographic installing Polymer Laboratories PL-DSU-220, equipped with four linear columns with mixed layer (Polymer Laboratories (particle size 20 microns)). The oven temperature is at 160°C hot zone automatic sampler at 160°C and the warm zone at 145°C. the Solvent is 1,2,4-trichlorobenzene containing 200 hours/million 2,6-di-tert-butyl-4-METHYLPHENOL. The flow rate is 1.0 ml/minute, and the size of the injection of 100 microliters. About 0.2%wt. solution samples receive for injection by dissolving the sample is purged with nitrogen 1,2,4-trichlorobenzene containing 200 hours/million 2,6-di-tert-butyl-4-METHYLPHENOL, for 2.5 hours at 160°C under mild agitation.
Molecular weight distribution set using ten polystyrene standards with narrow molecular weight distribution (from Polymer Laboratories, EasiCal PS1, which is in the range from 580 to 7500000 g/mol) in conjunction with their elution volumes. Molecular weight equivalent to the propylene-alpha-olefin copolymer determined using a ratio of Mark-Houwink for polypropylene (as described in the publication Th.G. Scholte, N.L.J. Meijerink, H.M.Schoffeleers, A.M.G. Brands,J.Appl.Polym. Sci., 29, 3763-3782 (1984)) and polystyrene (as described in the publication EP Otocka, R.J.Roe, N.Y. Hellman, P.M. Muglia,Macromolecules, 4, 507, (1971)) in equation Mark-Houwink:
where Kpp=1,90E-04 andRR=0,725 and Kps=1,26E-0,4, aps=0,702.
Differential scanning calorimetry
Differential scanning calorimetry (DSC) is a standard technology that can be used to study the melting and crystallization of semi-crystalline polymers. General principles of measurement using DSC and application of DSC to study semi-crystalline polymers are described in standard textbooks (e.g., E.A. Turi, ed.,Thermal Characterization of Polymeric Materials, Academic Press, 1981). Analysis by differential scanning calorimetry performed using the model Q1000 DSC (TA Instruments, Inc.). Calibration of the DSC carried out as follows. First, the baseline is obtained by carrying out the DSC from -90 up to 290°C in the absence of any sample in an aluminum pan of the DSC. Then 7 milligrams of fresh sample India analyzed by heating the sample to 180°C., cooling the sample to 140°C at a cooling rate of 10°C/min; followed by keeping the sample isothermally at 140°C for 1 min, followed by heating the sample from 140 to 180°C at a heating rate of 10°C/min, Determine the heat of fusion and the beginning of melting of the sample India; they are determined to be within 0.5°C from of 156.6°C for the beginning of melting in the range of 0.5 j/g from 28,71 J./g for the heat of fusion. Then an is are lysed with deionized water by cooling a small drop of fresh sample in the pan of the DSC from 25 to -30°C at a cooling rate of 10°C/min The sample stand isothermal at -30°C for 2 minutes and heated to 30°C at a heating rate of 10°C/min, Determine the beginning of the melting; it is determined to be within 0.5°C from 0°C.
Samples of the propylene-alpha-olefin copolymer pressed into a thin film at a temperature of 190°C. About 5 to 8 g of sample is weighed and placed in a pan of DSC. The cover is fixed on the pallet to provide a closed atmosphere. The tray sample is placed in a cell of the DSC and then heated at a heating rate of approximately 10°C/min to a temperature of approximately 30°C above the melting temperature. The sample is maintained at this temperature for about 3 minutes Then the sample is cooled at a speed of 10°C/min to -40°C and maintained isothermally at this temperature for 3 min and Then the sample is heated at a rate of 10°C/min until complete melting. The resulting curve of enthalpy examined for the presence of a peak melting temperature (if present), the beginning of melting and the peak crystallization temperatures, heat of fusion and heat of crystallization, the temperature at which melting of the polymer ends (Tme), and any other interest of the quantitative characteristics of the respective images, as described in U.S. patent No. 6960635 B2. Coefficient, which is used to transfer heat is the notes melting in nominal wt.%. crystallinity is 165 j/g=100% crystallinity. With this conversion factor, the total crystallinity propylene-alpha-olefin copolymer (units: wt.%. crystallinity) calculated in the form of heat of fusion divided by 165 j/g and multiplied by 100%.
Wide distribution of crystallinity
In a particularly preferred aspect of the present invention propylene-alpha-olefin copolymers exhibit a wide distribution of crystallinity. I believe that the use of the propylene-alpha-olefin copolymers (preferably propylene-ethylene copolymer), having a wide distribution of crystallinity will give compositions having lower specs tack/adhesion compared with compositions comprising copolymers made with metallocene catalysts and/or catalyst of Ziegler-Natta. Preferably nepetalactone catalysts with a Central metal and heteroaryl ligand (as described earlier) are used in the production of propylene-alpha-olefin copolymers due to their ability to produce copolymers exhibiting a broad distribution of crystallinity. Particularly preferred are propylene-alpha-olefin copolymers produced using such nepetalactone catalysts with the Central m is the thallus and heteroaryl ligand. I believe that the wide distribution of crystallinity propylene-alpha-olefin copolymers produced using such nepetalactone catalysts with a Central metal and heteroaryl ligand will crystallize faster than the propylene-alpha-olefin copolymers with a narrow distribution of crystallinity having equivalent percentage composition of units formed from ethylene.
Without being bound to any theory, a wider distribution of crystallinity can be translated in an increased upper limit of operating temperature, which can be measured by means of dynamic mechanical thermal analysis, more specifically, by using the dynamic modulus of elasticity, which is kept at a higher temperature. Faster crystallization can be translated in various benefits, including, but without limitation, the smaller the viscosity, the faster the setting (hardening) under cooling and the higher the productivity of the process line. Faster crystallization can be measured using methods known to experts in this field. These methods include, but are not limited to, differential scanning calorimetry (DSC), microscopy, radiography, measurement of the specific gravity and mechanical properties. Specific and processes who can benefit from the above advantages are, but are not limited to, film extrusion, blown film, injection molding, spinning fiber, extrusion profiles and sheets, extrusion tape and use in electric wires and cables.
In the case of propylene-alpha-olefin copolymers having a heat of fusion greater than about 20 j/g, the distribution of crystallinity is preferably determined from the analysis TREF/ATREF described below.
Determination of the allocation length is able to crystallization sequence can be carried out in laboratory scale by fractionation method elution with increasing temperature (TREF). The relative weight of the individual fractions can be used as the basis to estimate the distribution over constantly. L.Wild with co (Journal of Polymer Science. Polymer. Physics ed., 20, 441 (1982)) proportionally reduced the sample size and added the detector mass, to have permanent representation on the distribution as a function of temperature elution. This version of the analytical fractionation method elution with increasing temperature (ATREF) with a proportional reduction tied to the actual allocation fractions, but a more precise definition of the mass distribution of the fractions.
As TREF is usually used for copoly the development of ethylene and higher α-olefins, it can also be used in the case analysis isotactic copolymers of propylene with ethylene (or higher α-olefins). Analysis of copolymers of propylene requires higher temperatures for dissolution and crystallization of pure isotactic polypropylene, but most of the products copolymerization of interest, Loiret at the same temperature, which is observed in the case of ethylene copolymers. The following table shows the set of conditions used for the analysis of copolymers of propylene. Except as stated, the conditions for TREF comply with the terms of publications Wild et al., (ibid) and Hazlitt,Journal of Applied Polymer Science: Appl. Polym. Symp., 45, 25 (1990).
The parameters used for TREF
|The type and size columns||Bullet stainless steel with a volume of voids between the pellets 1.5 cm3|
|The detector mass||Single-beam infrared detector IR4 supplied PolymerChar of Valencia, Spain|
|The injection temperature||150°C|
|The temperature of the completed device||Oven GC|
|The flow velocity||1.0 ml/min|
|Concentration||0.1 to 0.3% (wt./wt.)|
|The cooling rate 1||From 140 to 120°C -6,0°/min|
|The cooling rate 2||From 120 to 44.5°C -0,1°/min|
|The cooling rate 3||From 44.5 to 20°C at -0,3°/min|
|The heating rate||From 20 to 140°C at a 1.8°/min|
|The speed of receiving data||12/min|
Data obtained from TREF, expressed as the normalized graph mass fraction as a function of temperature elution. The separation mechanism similar to the mechanism of separation of copolymers of ethylene, resulting in a molar content kristallicheskogo component (ethylene) is the primary factor that determines the temperature of the elution. In the case of copolymers of propylene, the temperature of the elution determines the molar content of isotactic units of propylene.
One of the statistical factors, to the which can be used to describe the distribution of crystallinity propylene-alpha-olefin copolymers, is skewed, representing statistics reflecting the asymmetry of the TREF curve for a particular polymer. Equation 1 mathematically expresses the coefficient of skewness, Sixas a measure of this asymmetry.
The value of TMaxis defined as the temperature of the largest mass fraction eluting between 50 and 90°C, at TREF curve. Tiand wirepresent the temperature of the elution and mass fraction relative to a randomly selected, the i-th fraction in TREF distribution. Distribution normalize (sum of wiequal to 100%) relative to the total area of the curve, eluting from about 30°C and up to less than 90°C. Therefore, the coefficient reflects only the configuration zakristallizuetsya polymer containing comonomer (ethylene), and any metacrystallographic polymer (polymer still in solution at 30°C or below) are excluded from the calculation presented in equation 1. In a particularly preferred aspect of the present invention used propylene-alpha-olefin copolymer has a wide distribution of crystallinity, determined by the coefficient of skewness for the propylene-alpha-olefin copolymer, more than (-1,2), preferably more than -1,0, more preferably more than -0,8 and also preferably greater than the a-0.7, and in some cases pain is better than -0,60. The coefficient of skewness indicates a propylene-alpha-olefin copolymer having a wide distribution of crystallinity.
In addition to the coefficient of skew another measure of the width of the TREF curve (and, hence, measure the width of the distribution of crystallinity of the copolymer) is the median temperature of the elution end eluting quartiles (TM4). The median temperature elution represents the median temperature elution of 25% mass fraction TREF distribution (polymer still in solution at 30°C or below are excluded from the calculation, as discussed above for the coefficient of skewness), which aluinum last or at the highest temperatures. Interval quartiles top temperature (TM4-TMaxdetermines the difference between the median temperature of the elution end eluting quartiles and the peak temperature TMax. In a particularly preferred aspect of the invention, the propylene-alpha-olefin copolymers have a wide distribution of crystallinity, which partially specifies the interval quartiles upper temperature greater than 4.0°C, preferably at least 4,5°C, more preferably at least 5°C, also more preferably at least 6°C, most preferably at least 7°C, and in some cases, at least 8°C, and D. the same at least 9°C. In General, higher values for the interval quartiles upper temperature relevant to a broader distribution of crystallinity of the copolymer. Propylene-alpha-olefin copolymers used in the present invention, preferably exhibit a wide distribution of crystallinity, satisfying the above-described interval quartiles top temperature.
In addition, in this preferred aspect, the used propylene-alpha-olefin copolymers include propylene-ethylene copolymers and show unusual and unexpected results using TREF. Distribution tend to cover a large temperature range elution, while simultaneously giving prominent narrow peak. In addition, covering the whole wide interval of the introduction of ethylene, the peak temperature TMaxis about 60-65°C. In conventional copolymers based on propylene for some levels the introduction of ethylene such a peak will mix to higher elution temperatures lower introduction of ethylene.
For conventional metallocene catalysts is the approximate ratio of the molar fraction of propylene, Xpto the temperature of the TREF elution for the maximum peak, TMaxis described by the following equation:
In the case of propylene-alpha-olefin copolymers used in a particularly preferred aspect, the natural Log molar fraction of propylene, LnP, is greater than the logarithm of the normal metallocenes, as shown in the following equation:
In the case of propylene-alpha-olefin copolymers exhibiting a heat of fusion of less than 20 j/g, a broad distribution of crystallinity is preferably installed or by defining a high crystalline fraction (FF, HCF) using DSC, or by determining the relative deviation of stock (OOS, RCD) using GPC-FTIR. This analysis is carried out as follows.
High crystalline fraction, FF, is defined in the form of a partial area on the melting curve of the DSC-propylene-alpha-olefin copolymer at a temperature above 128°C. To determine the partial area first, get a heat of fusion, then put a vertical line at 128°C and define a partial area above 128°C (relative to the same baseline, which is used for heat of fusion). Propylene-alpha-olefin copolymers used in a particularly preferred aspect of the present invention have a heat of fusion of less than 20 j/g, MCFs have more than about 1 j/g and an ethylene content bol is more than about 10 wt.%, particularly preferably MCFs will be more than 0.2 j/g and most preferably MCFs is greater than about 0.5 j/g, and also has an ethylene content greater than about 10% wt.
Figure 4 presents a comparison of wide and narrow distribution of crystallinity by DSC for propylene-ethylene copolymer (P-1), similar to the polymer R/S-4 examples, except that it has a melt flow index of 12 g/10 min, content of units derived from ethylene, 15% wt., the heat of fusion of approximately 9.6 j/g and MMP 2,46, and catalyzed by metallocene propylene-ethylene copolymer having approximately 13.7% of wt. units formed from ethylene and a melt flow index of approximately 150 g/10 min Figure 4 also shows a partial area of high crystalline fraction (FF) relative to the square that represents the heat of fusion.
Alternatively, or in addition to the way the DSC described above, the relative width of the distribution of crystallinity for lower crystalline copolymers can be represented using the methodology GPC-FRIR (for example, in the publications: R.P. Markovich, L.G. Hazlitt, L. Smith,ACS Symposium Series: Chromatography of Polymers, V.521, pp.270-276, 199; R.P. Markovich, L.G. Hazlitt, L. Smith,Polymeric Materials Science and Engineering, 65, 98-100, 1991; P.J. DesLauriers, D.C. Rohlfing, E.T. Hsieh “Quantifying Short Chain Branching in Ethylene 1-olefin Copolymers usng Size Exclusion Chromatography and Fourier Transform Infrared Spectroscopy (SEC-FTIR)”, Polymer, 43 (2002), 159-170). These methods, originally designed for copolymers based on ethylene, can be easily adapted to systems based on propylene to obtain the composition of the copolymer as a function of the molecular weight of the polymer. Propylene-ethylene copolymers, showing a wide distribution in composition (with regard to the introduction of ethylene), when they are measured in the following way DSU-FTIR), as installed, will also display a wide distribution of crystallinity, which indicate high values of FF in the above-described method DSK. For these reasons, for the purposes of the present invention the distribution of the composition and distribution of crystallinity will be considered as congruent in that the relative width of the distribution of crystallinity, which is indicated by the value of the MCFs for low crystalline in General, the copolymer (that is, the heat of fusion of less than 20 j/g), consistent with the broader distribution of the composition, as indicated by the value of environmental protection (RCD) (described below), measured using the TRU-FTIR.
Various technical specifications and parameters for the analysis of the GPC-FTIR are shown in tables C and D. From the system GPC-FTIR receive consecutive spectra, while the fraction of the dissolved copolymer elute from the column GPC (GPC) (in order of decreasing molecular weight) by appropriately issue Lenogo flow through the cell [Part # 0820-2000, Polymer Laboratories Inc., Amherst, MA]. The scope removals from 2750 to 3050 cm-1within each FTIR spectrum integrate, as shown in figure 5, written as functions of the number range or volume of elution and used as a very good approximation of the mass (or concentration) in each room of the spectrum or the volume of elution in the GPC chromatogram. This integrated area called total absorption spectrum and additionally normalized by dividing by the sum of all integrations other common areas for all other spectra. Normalized total area, thus, equal to the mass fraction of the whole polymer represented by the given range (for a given volume of elution). Therefore, the mass fraction lirovannomu polymer is a Gauss curve on each Fig.7-8, which is obtained from the normalized total area of each spectrum. The composition of the propylene/ethylene in each set of consecutive spectra (or at each subsequent elution volume) estimated by using the incomplete square acquisitions in the spectrum at more than 2940 cm-1as shown in figure 5, using the calibration curve (as, for example, figure 6). Calibration is obtained by integrating the averaged spectra for elution of several copolymers whose compounds tentatively identified the Lena using NMR methods, presented in this paper. Consequently, the composition (mass fraction of ethylene) can be determined for each spectrum and plotted on a graph as a function of the number range or volume of elution. Such distribution is depicted in Fig.7-8.
And, finally, the width of any particular distribution of the composition by GPC-FTIR (and any determination described above, the corresponding distribution of crystallinity) can be estimated by comparing the maximum and minimum ethylene content (or fractions) using only the spectrum with the highest total absorption (i.e. the highest concentration of polymer), which when summed gives 95% (wt.) lirovannomu polymer, and ignoring the spectra with the lowest absorption (or "wings" on the curve of GPC, as shown in Fig.7 and 8). This is necessary to avoid problems arising due to a low signal-to-noise. The maximum and minimum values is chosen as the average values of the three highest and the lowest calculated values of ethylene, respectively, of 95% (wt.) spectra, for which the calculated compositions. The difference between the maximum and minimum ethylene content divided by the calculated average full content of ethylene in the polymer, is defined as the relative deviation of the composition or OO is (RCD) and expressed in percentage. When eluting the sample with the highest content of ethylene, are found at higher molecular weight (i.e. in the earlier volumes of elution)than the samples with the lowest ethylene content, the value of EA is positive, and otherwise it is negative. Propylene-ethylene copolymers used in a particularly preferred aspect of the present invention, showing a wide distribution of crystallinity, which is defined using the environment more than about 15%, more preferably more than 30%, and most preferably greater than 45%. In addition, in the preferred aspect is OOS shown such propylene-ethylene copolymers, is positive. In this particularly preferred aspect, the propylene-alpha-olefin copolymers exhibit a broad distribution of crystallinity and the average to have a polymer chain, which have a higher introduction of ethylene and higher molecular weight relative to the polymer chains comprising lower amounts of ethylene.
Molecular weight calculated from the presented srednevekovoi molecular weight, Mw, and presents srednetsenovoj molecular weight, Mn, for each polymer. These data are obtained from the analysis, the written throughout the document. Each room subsequent spectrum (or elution volume) can be translated in molecular mass by solving the following simultaneous equations.
In both equations, S represents the number of the spectrum (which is similar to the elution volume) for each of N+1 (0≤S≤N) consecutive spectra FTIR, Msrepresents the molecular weight when the number of the spectrum, S, wsrepresents the normalized total area of the spectrum, S, and m and b are the necessary factors for the calculation of the molecular weight in each spectrum, S. These equations are easily solved using tools such as SOLVER* [Microsoft Corp., Redmond, WA], by, for example, minimize the following function for a and b:
The set of parameters FTIR [Thermo Electron Corp., Waltham, MA]
|DATA COLLECTION INFORMATION||DESCRIPTION of the SPECTROMETER|
|The number of scans of the sample: 32||Spectrometer: Magna System 560|
|Interval sampling: to 9.32 sec||Source: IR|
The beam splitter: KBr
|Levels at zero fill: 0||Space samples: 2,0000|
|The number of points scanning: 8480||Digital convert discharge: 20|
|The number of FFT points: 8192||The speed of the reflector: 3,1647|
|The frequency of laser: 15798,3 cm-1||Neckline: 95,00|
|The position of the tick interferogram: 4096||The gain of the sample: 1,0|
|Apodization: Happ-Genzel||The high-pass filter: 200,0000|
|The number of reverse scans: 0||Low-pass filter: 20000,0000|
|Background gain: 0,0||DYNAMICS DATA|
|DESCRIPTION DATA||Type of data collection: GC/IR|
|Number of points: 1738||The total collection time: 30,01|
|The X-axis: wave number (cm-1)||Final format: single beam|
|Y axis: single beam||The first value of X: 649,9036||From 649,9036 to 3999,7031|
|The last value of X: 3999,7031||DESCRIPTION SERIES|
|Data space: 1,928497||Minimum value: 0,1553|
|Maximum value: 30,0080|
|Step size: 0,1555|
|The number of spectra: 193|
|The amount of flow through the cell [Polymer Laboratories Inc., Amherst, MA] and the parameters of GPC [Waters Corp., Milford, MA]|
|Interface FTIR Polymer Labs (Part # 0820-2000) liquid connections on top of the Windows of the cells: calcium fluoride (idle volume: 70 μl, path length: 1 mm).|
|The GPC instrument: high-temperature GPC Waters 150C|
|Column: 4×300×7,5 mm Polymer Labs, 10 microns mixed In|
|Solvent: Perl ritilin (Sigma-Aldrich, grade HPLC)|
|Flow rate: 1 ml/min|
|Concentration: 2.5 mg/ml|
|Injection: 250 ál|
Figure 5 shows an example of an infrared spectrum of the propylene-ethylene copolymer. The spectrum obtained in the GPC-FTIR and shows the area of carbon-hydrogen extensions. The absorption at frequencies more than 2940 cm-1calculated as a proportion of total removals from 2750 to 3050 cm-1use to calculate the mass fraction of propylene.
Figure 6 presents the calculation used to calculate the mass fraction of propylene using the total area and partial area from the absorption at frequencies more than 2940 cm-1in the infrared spectrum, such as in figure 5.
7 shows the distribution of the composition by GPC-FTIR for propylene-ethylene copolymer (P-1) figure 4. Shows the key data are normalized total absorption in each spectrum (elution volume), mass fraction of ethylene for each spectrum (elution volume) and relative deviation of stock (OOS, RCD) for distribution in composition. With Tavi calculated only for 95% (wt.) spectra showing the highest concentrations of polymer, in order to exclude errors caused by low signal-to-noise.
On Fig shows the distribution of the composition by GPC-FTIR for metallocene propylene-ethylene copolymer having 13,5% wt. units formed from ethylene (calculated using NMR as described previously). Shows the key data are normalized total absorption in each spectrum (elution volume), mass fraction of ethylene for each spectrum (elution volume) and relative deviation of stock (OOS, RCD) for distribution in composition. The compositions are calculated for 95% (wt.) spectra showing the highest concentrations of polymer, in order to exclude errors caused by low signal-to-noise.
The melt flow index (engineers, MFR) of the propylene-alpha-olefin copolymer used for the present invention, has a value of at least 0.1 g/10 min, usually at least 0.2 g/10 min, preferably at least 1.0 g/10 min, more preferably at least 1.5 g/10 min, most preferably at least 3 g/10 min ITR propylene-alpha-olefin copolymer used for the present invention typically has a value of at most 100 g/10 min, preferably less than 75 g/10 min, more predpochtite is correctly less than 60 g/10 min, even more preferably less than 50 g/10 min, most preferably less than 40 g/10 min, and even more preferably less than 30 g/10 min Measurement of the melt flow index for the propylene-alpha-olefin copolymers is carried out in accordance with ASTM D-1238, condition 230°C/2,16 kg mass. The melt flow index is inversely proportional to the molecular weight of the polymer. Therefore, the higher the molecular weight, the lower the melt flow index, although the relationship is not linear.
Various increases the adhesiveness of the resin, known to specialists in this field can be used in the present invention. Such increase the adhesiveness of the resin to be used when it is desirable to attach the product containing the inventive composition to another product or component of a product. For example, when the inventive composition is used as one component of a layered product, and when it is desirable that such a component has been attached to one or more than one layer. (For example, when applied, where the inventive composition is used as effective at short-term pressing of the adhesive layer to attach the elastomeric sheet or film to another sheet or layer of material).
Examples of increasing the adhesion of resins that can be entered in Appl who controls the composition are hydrogenated hydrocarbon resins such as hydrocarbon resins REGALREZ (fully gidrirovanny low molecular weight hydrocarbon resin α-methylstyrene type produced by polymerization and hydrogenation of pure monomer hydrocarbon raw materials that are sourced Hercules Incorporated), and a series of increasing the adhesion of substances ARKON P (gidrirovanny resin supplied AK Elastomers, Tokyo, Japan); and terpene hydrocarbon resin. Oil filling can also be added to the formulations of the inventive compositions. Typical oil filling is a white mineral oil, supplied under the trade designation Drakeol 34 company Pennzoil Company Pennreco Division. Drakeol 34 has a density 0,864-of 0.878 at 15°C flash point 238°C and viscosity 370-420 SUS at 38°C. Suitable vegetable oils and animal oils or their derivatives can also be used as oil for filling.
The definition of "consisting essentially..." indicates that in addition to the specific items, materials, or stages, optional elements, materials or stage, not having an actual impact on the basic and novel characteristics of the object of the invention. For example, additives which are usually used with polymer based on propylene in concentrations known to specialists in this field, neobyazatelnoe to be added within the scope of the present invention. The definition of "consisting essentially of" for the purposes of the present invention includes a composition comprising a propylene-alpha-olefin copolymer, styrene block copolymer, and may also include increasing the adhesiveness of the resin described above, and additional components that do not have a negative effect on the physical properties of the object of the invention. Typical additional components include, but without limitation, pigments, antioxidants, stabilizers, surfactants, waxes, activators, solvents, oils, materials in the form of particles and materials added to improve the workability of the composition and capabilities of working with it.
The MIXTURE of COMPONENTS:
The composition can be made by: (a) dry mixing the components; (b) direct feed components through the system mixer (volumetric or gravimetric)mounted on the extruder; (C) mixing the components in a mixing extruder to obtain a mixed product; and/or (d) by any other mixing techniques known in this field. Preferably the composition is formed into pellets with the aim of easier moving and handling in the main thread of production equipment.
The END USE AND INDUSTRIAL PRODUCTS:
The composition can be successfully used in RA is personal technological processes, in order to produce useful products. Some examples of such products and processes are: (1) film obtained by casting and extrusion blown tempered air and water; the corresponding film obtained by casting, and hardened air film obtained by extrusion-blow process, described, for example, in the publication:The Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, John Wiley & Sons, New York, 1981, Vol.16, pp.416-417 and Vol.18, pp.191-192. Suitable methods of extrusion and requirements known to experts in the field; (2) use in injection molding, such as described, for example, Injection Molding Handbook, T.A. Osswald, T. Turng, P. Gramann, Hanser Gardner Publications, ISBN # 1569903182, 2001; (3) use in thermoforming, such as described, for example, Technology of Thermoforming, J.L. Throne, Hanser Gardner Publications, ISBN # 1569901988, 1996; (4) applications in fiber and non-woven material obtained by extrusion blow from the melt, as described, for example, in the publication ofThe Nonwovens Handbook, Association of the Nonwovens Fabrics Industry, Cary NC and Principles of Nonwovens, INDA, Cary NC.; and (5) predanie from the melt fibers and nonwovens spunbond production, for example, as described in the publication ofNonwoven Fabrics: Raw Materials, Manufacture, Applications, Characteristics, Testing Processes, W. Albrecht, H. Fuchs, W. Kittelmann, ISBN # 3527304061, Wiley-VCH, 2003.
In the case of the present invention elongation at break, 2% secant modulus p and the elongation and ultimate tensile strength (load at break) measured by method described below, and the sample geometry ASTM D1708 with the basic length of the sample 22,25 mm and a speed of stretching 111,25 mm/min (strain-rate of 500%/min).
The examples use the following tar.
P/E-1 is a propylene-ethylene of plastomer made with the use of the catalyst in the polymerization method, the same method of polymerization as described below. P/E-1 has srednevekovoy molecular weight other 153.9 kg/mol, srednecenovogo molecular weight 69,9 kg/mol, a molecular weight distribution of 2.2, the melt flow index of 26.4 g/10 min, the regularity of the molecular structure of at least 90% of the triads, the ethylene content of 8.9 wt.%, density 0,8746 grams per cubic centimeter (g/cm3), the heat of fusion of 47.1 j/g, shows the modulus of elasticity in bending of 80.3 MPa in accordance with ASTM D790, shows the modulus of tensile elasticity (2% secant modulus) 82,9 MPa, determined using the geometry of ASTM D1708 tensile strength tensile 22,8 MPa, which is determined using the geometry of ASTM D1708, elongation at break 875% and has a wide distribution of crystallinity as determined in accordance with the methods described above.
R/E-2 is a propylene-ethylene elastomer, manufactured using Catalyst And SP is the property of polymerization, the same method of polymerization as described below. R/E-2 has srednevekovoy molecular weight of 152.5 kg/mol, srednecenovogo molecular weight 69,8 kg/mol, a molecular weight distribution of 2.2, the melt flow index of 23.8 g/10 min, the regularity of the molecular structure of at least 90% of the triads, the ethylene content of 11.3 wt.%, density 0,8668 g/cm3the heat of fusion of 28.5 j/g, shows the modulus of elasticity in bending of 38.1 MPa in accordance with ASTM D790, shows the modulus of tensile elasticity (2% secant modulus) of 37.8 MPa, determined using the geometry of ASTM D1708 tensile strength tensile 18,8 MPa, which is determined using the geometry of ASTM D1708, elongation at break 960% and has a wide distribution of crystallinity as determined in accordance with the methods described above.
P/E-3 is a propylene-ethylene elastomer, manufactured using Catalyst And the polymerization method, the same method of polymerization as described below. P/E-3 has srednevekovoy molecular mass of 290 kg/mol, srednecenovogo molecular weight 118,4 kg/mol, a molecular weight distribution of 2.5, the melt flow index of 1.8 g/10 min, the regularity of the molecular structure of at least 90% of the triads, the ethylene content of 12.3% by weight, density 0,8652 g/cm3, heat is the melting point of 22 j/g, shows the modulus of elasticity in bending of 28.0 MPa in accordance with ASTM D790, shows the modulus of tensile elasticity (2% secant modulus) of 27.2 MPa, determined using the geometry of ASTM D1708 tensile strength tensile 17,1 MPa, which is determined using the geometry of ASTM D1708, elongation at break 990% and has a wide distribution of crystallinity as determined in accordance with the methods described above.
P/E-4 is a propylene-ethylene elastomer, manufactured using catalyst And the polymerization method, the same method of polymerization as described below. P/S-4 is srednevekovoy molecular weight to 274.9 kg/mol, srednecenovogo molecular weight 113,8 kg/mol, molecular weight distribution 2,42, the melt flow index of 1.8 g/10 min, the regularity of the molecular structure of at least 90% of the triads, the ethylene content of 15.2% wt., density 0,8588 g/cm3the heat of fusion of 0 j/g, shows the modulus of elasticity in bending of 11.4 MPa in accordance with ASTM D790, shows the modulus of tensile elasticity (2% secant modulus) of 7.3 MPa, determined using the geometry of ASTM D1708, ultimate tensile strength 12 MPa, which is determined using the geometry of ASTM D1708, elongation at break 1130% and has a wide RA is the distribution of crystallinity, determined in accordance with the methods described above.
RCPP has a melt flow index of 5.0 g/10 min and is a statistical propylene-ethylene copolymer made with a catalyst of the Ziegler-Natta, which is supplied by The Dow Chemical Company under the designation grade DS6D81 and which has a 1% secant modulus in bending 550 MPa (ASTM D790), 5.7% by weight. units formed from ethylene and a density of 0.9.
G-1657 is a linear SEBS styrene block copolymer, supplied by Kraton Polymers (Houston, Texas, United States), which has a density of 0.9 g/ml, from 12 to 14% wt. polystyrene links, is the viscosity of the solution from 1200 to 1800 centipoise (SDR), with the content iblokov 30% and the mass ratio of styrene to rubber 13:87.
The catalyst And
Synthesis of catalyst And
a) 2-Formyl-6-bromopyridin. This compound is synthesized in accordance with methods described in the literature (Tertahedron Lett., (2001) 42, 4841).
b) 6-Bromo-2-(2,6-diisopropylphenyl)aminopyridin. In a dry 3-necked round bottom flask 500 ml upload a solution of 2-formyl-6-bromopyridine (72,1 g, 383 mmol) and 2,6-diisopropylaniline (72.5 g, 383 mmol) in 500 ml be the water toluene, containing molecular sieves with a pore size of 0.3 nm (6 g) and 80 mg of p-TsOH. A reactor equipped with a reflux condenser, head mechanical stirrer and a cell thermocouple. The mixture is heated to 70°C in an atmosphere of N2within 12 hours. After filtration and removal of volatile components under reduced pressure to produce a brown oil. The output is 109 g, 81.9 percent.
GC/MS 346 (M+), 331, 289, 189, 173, 159, 147, 131, 116, 103, 91, 78.
C) 6-(1-Naphthyl)-2-[(2,6-diisopropylphenyl)imino]pyridine.Attelboro acid (54,5 g, 316 mmol) and Na2CO3(83.9 g, 792 mmol) is dissolved in 200 ml obezvozhennoy mixture of N2O/Et (1:1). The resulting solution was added to a solution in toluene (500 ml) of 6-bromo-2-(2,6-diisopropylphenyl)aminopyridine (109 g, 316 mmol). Inside the box with dried and purified atmosphere in 50 ml obezhirennogo toluene dissolve 1 g (0.86 mmol) of tetrakis(triphenylphosphine)palladium(0). The solution extracted from Boxing with dried and purified atmosphere and loaded into the product of N2the reactor. Two-phase solution was intensively stirred and heated at 70°C for 4-12 hours. After cooling to room temperature the organic phase is separated, the aqueous layer was washed with toluene (3×75 ml), the combined organic extracts washed with N2About (3×200 ml) and dried over MgSO4. After removal of volatile components under reduced pressure, the obtained light-yellow m the slo purified by recrystallization from methanol, receives a yellow solid. The output is 109 g, 87.2%of total; TPL 142-144°C.
1H-NMR (DCl3) δ 1,3 (d, 12H), 3,14 (m, 2H), 7,26 (m, 3H), 7.5 to about 7.6 (m, 5H), 7,75 one-7.8 (m, 3H), 8,02 (m, 1H), 8,48 (m, 2H).
13C-NMR (DCl3) δ 23,96, 28,5, 119,93, 123,50, 124,93, 125,88, 125,94, 126,49, 127,04, 127,24, 128,18, 128,94, 129,7, 131,58, 134,5, 137,56, 137,63, 138,34, 148,93, 154,83, 159,66, 163,86.
GC/MS 396 (M+), 380, 351, 337, 220, 207, 189, 147.
d) 2-Isopropylaniline.Inside Boxing gloves with an inert atmosphere to a solution in ether (50 ml) of 2-isopropylphenol (9,8 g, and 49.2 mmol) via a dropping funnel within 35-45 min add n-utility (52,5 mmol, 21 ml of 2.5 M solution in hexano). At the end of the addition the mixture is stirred at room temperature for 4 hours. Then the ether solvent is removed in vacuum over night. The next day the remaining white solid substance add hexane, washed with additional hexane and then dried in vacuum. 2-Isopropylaniline (to 4.98 g, 39,52 mmol) collected in the form of a brilliant white powder. The second portion of the product (0,22 g) receive later after the second initial filtering hexane filtrate.
1H-NMR (d8-THF) δ 1,17 (d, J=6.8 Hz, 6H), 2.91 in (s, J=6,8, 1H), 6,62-6,69 (m, 2H), 6,77 (d, J=7,3 Hz, 1H), 7,69 (m, 1H).
13C-NMR (d8-THF) δ 25,99, 41,41, 120,19, 122,73, 122,94, 142,86, 160,73, 189,97.
e) N-[2,6-bis(1-methylethyl)phenyl]-α-[2-(1-methylethyl)phenyl]-6-(1-naphthalenyl)-2-pyridylmethylamine. -(1-Naphthyl)-2-[(2,6-diisopropylphenyl)imino]pyridine from step C) (2.20 g, 5,6 mmol) mechanically stirred suspension of 60 to 70 ml of dry ether under nitrogen atmosphere. Using the syringe slowly for 4-5 minutes add an ethereal solution of 2-isopropylaniline (1,21 g, 9,67 mmol in 25 ml dry ether). At the end of the add selected a small sample, quenched with 1N NH4Cl and the organic layer is analyzed by high performance liquid chromatography (HPLC)to confirm complete consumption of the starting material. The remainder of the reaction mixture is quenched by careful, slow addition of 1N solution of NH4Cl (10 ml). The mixture is diluted with ether, and the organic layer washed twice with brine, dried (Na2SO4), filtered and the solvent is distilled off under reduced pressure. The crude product is obtained as a thick red oil (2,92 g, theoretical yield 2,87 g), used without further purification.
1H-NMR (DCl3) δ of 0.96 (d, J=6.6 Hz, 3H), 1,006 (d, J=6.8 Hz, 3H), 1,012 (d, J=6.8 Hz, 6H), 1,064 (d, J=6.8 Hz, 6H), 3,21-to 3.34 (m, 3H), 4,87 (users, NH), 5,72 (s, 1H), 6,98 (d, J=7,6 Hz, 1H), 7,00-7,20 (m, 7H), 7.23 percent-7,29 (m, 4H), 7,51 (d, J=7,1 Hz, 1H), 7,60-the 7.65 (m, 2H), to 7.75 (m, 1H), 8,18 (m, 1H).
13C-NMR (DCl3) δ 23,80, 24,21, 24,24, 24,36, 28,10, 28,81, 67,08, 120,20, 122,92, 123,96, 124,42, 125,35, 125,81, 126,01, 126,28, 126,52, 126,58, 126,65, 127,80, 128,52, 128,62, 129,25, 131,82, 134,52, 136,81, 138,82, 140,94, 143,37, 143,41, 146,66, 159,05, 162,97.
f) [N-[2,6-bis(1-Methylethyl)phenyl]-α-[2-(1-methylethyl)phenyl]-6-(1-naphthalenyl-κ-From2)-2-pyrid methanamine(2-)-κN 1that κN2]dimethylamine
In a glass vessel load 8,89 mmol of the ligand from step (e), dissolved in 30 ml of toluene. To the resulting solution with a syringe add 8.98 mmol n-BuLi (2.5 M solution in hexano). The solution is stirred for 1 hour, then add 8,89 mmol hard HfCl4. The vessel is closed with an air reflux condenser, and the mixture is heated at the boil under reflux for 1 hour. After cooling with a syringe type of 31.1 mmol MeMgBr (3.5 EQ., 3.0 M solution in diethyl ether) and the resulting mixture is stirred over night at room temperature. The solvent (toluene, hexane and dimethyl ether) are removed from the reaction mixture using a vacuum system attached to the box with reclaimed and refined atmosphere. To the residue is added toluene (30 ml) and the mixture is filtered, the residue (magnesium salt) was washed with additional toluene (30 ml). The solvent from the combined toluene solution is removed using a vacuum, add hexane, then removed in vacuum. Again add hexane, and the resulting suspension is filtered, the product washed with pentane, get the target product as a yellow powder.
1H NMR (C6D6): δ 8,58 (d, J=7.8 Hz, 1H), 8,25 (d, J=8,4 Hz, 1H), 7,82 (d, J=7.5 Hz, 1H), 7,72 (d, J=6,9 Hz, 1H), 7,50 (d, J=8,1 Hz, 1H), was 7.36-7,27 (m, 3H), 7,19-6,99 (m, 7H), PC 6.82 (t, J=8,1 Hz, 1H), to 6.57 (s, 1H), 6,55 (d, J=7.8 Hz, 1H), 3,83 (s, J=6,9 Hz,1H), 3,37 (s, J=6,9 Hz, 1H), 2,89 (s, J=6,9 Hz, 1H), 1,38 (d, J=6.6 Hz, 3H), of 1.37 (d, J=6.9 Hz, 3H), of 1.17 (d, J=6.9 Hz, 3H)and 1.15 (d, J=7.2 Hz, 3H), of 0.96 (s, 3H), 0.70 and (s, 3H), 0.69 (d, J=5.4 Hz, 3H), 0,39 (d, J=6.9 Hz, 3H).
A General method of continuous propylene-ethylene copolymerization in solution circulation
Propylene-ethylene copolymers receive in accordance with the following procedure using catalyst A.
The polymerization process is exothermic. Approximately 900 British thermal units (BTU) released per pound polymerized propylene and about 1500 BTU released per pound of polymerized ethylene. The main issue in the development process is the question of the discharge of the heat of reaction. Propylene-ethylene copolymers produced in the rector circulation low pressure polymerization in a solution consisting of 3”-howl of the circulation tube plus two heat exchanger, the total volume of which is 50.3 per gallon. The solvent and the monomer (propylene) injected into the reactor in liquid form. Comonomer (ethylene) in the form of gas is completely dissolved in a liquid solvent. The raw material is cooled to 10°C before entry into the reactor. The reactor operates at concentrations of polymer 20% wt. The adiabatic temperature rise of the solution due to a certain abstraction of heat from the polymerization reaction mixture. The heat exchangers within the reactor used in esults to lead the rest of the heat of reaction, providing temperature control of the reactor at 105°C.
Used solvent is an isoparaffin fraction of high purity, supplied by Exxon, which is called Isopar E. Fresh propylene is passed through a layer of Selexsorb COS to clean before mixing with the recycle stream (contains solvent, propylene, ethylene and hydrogen). Recycle stream is passed through a layer of 75% wt. Molecular Sieves H and 25% wt. Selexsorb CD to clean before using the pump for raw materials high-pressure (700 psi)to serve the content in the reactor. Fresh ethylene is passed through a layer of Selexsorb COS to clear before compression flow up to 750 psi. Hydrogen (telogen used to reduce the molecular weight) is mixed with the compressed ethylene before mixing/dissolving both in the liquid raw material. The total stream is cooled to the appropriate temperature of the raw material (10°C). The reactor operates at 525 psi, and the control temperature is 105°C. the Conversion of propylene in the reactor is maintained by controlling the rate of injection of the catalyst. The reaction temperature is maintained by controlling the temperature through the side wall of the heat exchanger at 85°C. the residence Time in the reactor is short, 10 minutes Conversion of propylene in a single pass reactor is 60% wt.
At the outlet of the reactor in solution polierautomat water and additive. Water hydrolyzes the catalyst, breaking the polymerization reaction. Supplements consist of antioxidants, 500 hours/million IrganoxTM1010 and 1000 hours/million IrgafosTM168, which remain in the polymer and act as stabilizers, preventing the destruction of the polymer during storage before subsequent production equipment consumers. The solution after reactor overheat from the reactor temperature up to 230°C in preparation for the two-stage removal of volatile components. During the process of removal of volatile components remove the solvent and unreacted monomers. The polymer melt is served by the pump in the die plate for cutting into pellets under water.
A couple of solvent and monomer, leaving the upper part of the evaporator, served in the coagulator. In the coagulator is displayed polymer pairs captured when removing volatile components. The net flow of vapor coming out of the coagulator, partially condensed in the cascade heat exchanger. A two-phase mixture enters the separator drum. The condensed solvent and monomers clean (they form the above-described recycle stream and reuse in the reactor. The pair emerging from the separating drum, mainly containing propylene and ethylene is fed to a flare and burn. Propylene-ethylene comonomers, made in accordance with the set is built above process, can be used for the propylene-alpha-olefin copolymers of the present invention.
A mixture of propylene-ethylene copolymers of the P/E-1 to P/E-4) and SEBS are mixed together dry in the rheometer torque Haake Rheocord 9000. The temperature during mixing is 210°C. while mixing add the set of antioxidants from 1000 hours/million Irganox 1010 and 1000 hours/million Irgafos 168. Mixing components continue approximately 5 to 10 minutes before until measurement of the torque rheometer reach a stable state. The mixture is then extracted from the mixing hopper and subjected to direct pressed into plates with a thickness of 1-2 mm at 210°C and at a pressure of from 100 to 300 psi. The plate is then immediately removed and immediately cooled by insertion in another form, located at 25°C for 3-5 min at a pressure of 100-300 psi. Molded plates allowed to grow under normal conditions (23°C, 50%relative humidity) for at least 2 days. Formulations of the mixtures are presented in table I.
Ripe plate is prepared for mechanical testing as follows.
The test is based strain-voltageSamples for measurement of mechanical properties are prepared in accordance with ASTM D1708 (geometry microbacteria), and the samples have an initial base length 22,25 mm and initial widths of the 4,8 mm Tensile test is carried out at a stretching using Instron machine (Model 5564), clamping the samples using a pneumatic gripper and then stretching them at a strain rate of 500%/min (111,25 mm/min until rupture of the specimen. Elongation at break (%) are obtained in the form of changes in the speed of traverse of the testing machine, divided by the initial separation capture 22,25 mm and multiplied by 100. The modulus of tensile elasticity (2% secant modulus) obtained as the slope of a line passing from 0% to a voltage corresponding to 2% elongation. The voltage is calculated by dividing the force on the cross-sectional area at the narrowest part of the sample (width 4.8 mm, multiplied by the initial thickness of the sample). Ultimate tensile strength is measured as the force at break, normalized to the cross-sectional area of the narrowest part of the base length (4.8 mm) in the beginning of the experiment. Tensile properties are summarized in table I.
Tensile properties of mixtures and control mixtures
|Example No.||And:||And||In||2% secant modulus, tensile (MPa)||Tensile strength (MPa)|
|Example 1-2||20:80||P/S-2||G-1657||of 5.4||960||to 12.0|
|Example 2-1||30:70||P/S-3||G-1657||the 5.7||960||14,0|
|CS 2-1||30:70||RCPP||G-1657||5,1||820||of 17.5|
As can be seen from table I, comparative mixture CS 1-1 - CS 2-3 do not provide the necessary elongation. In addition, as can be seen from table I, a mixture made with a P/E-2, 3 and 4, have a much lower modulus of tensile elasticity, when SEBS is less than fifty weight percent (50 weight percent (% wt.)) the composition of the mixture than the comparative the mixture, made with a statistical propylene-ethylene copolymer having to 5.7 wt.%. units formed from ethylene. Preferably the modulus of tensile elasticity (2% secant), the solidity of the composition is less than 20 MPa, preferably less than 17 MPa, more preferably less than 15 MPa, also more preferably less than 13 MPa, most preferably less than 10 MPa, and in some embodiments of the invention less than 8 MPa.
Plate thickness of one to two millimeters, described above, have to determine elastic properties. Testing elastic properties carried out as follows.
Elastic properties determined using measurement 2-cycle hysteresis. Samples for microbacteria pull up to a predetermined deformation (100, 200, 300, 400 or 500%) at a strain rate of 500%/min, return to the deformation of 0%, and then pull until then, until it is measured positive load. The deformation corresponding to this beginning exercise during the second pull (0.05 MPa), take immediate shrinkage. In the case of 2-cycle tests at strain of 100%, measure the load at 30%strain for the first pulling and sucking. The ratio of the voltage being drawn in the first draw to the load pulling the first pull when 30%is iformatsii, multiplied by 100%, is defined as R (see equation 2).
R is a measure of hysteresis. When the limit R equal to 1, the retracting force at 30%deformation is equal to the force of the retracting at 30%strain. A value of 0 for R indicates a lack of effort retracting at 30%strain. R is preferably at least 20%, more preferably at least 25%, even more preferably at least 40%, and most preferably at least 50%.
Test results of elastic properties, including values immediate shrinkage at different strain, are presented below in table II.
As can be seen from table II, the comparative mixture CS 1-1 - CS 2-3 do not provide the necessary elongation at break (i.e. do not provide more than 900% elongation at break). In addition, examples of CS 2-1, CS 2-2 and CS 2-3 all give values immediate shrinkage of more than 120% after test 2-cycle hysteresis at 500%. This behavior makes these compositions are unacceptable for use in application forms at high deformation, requiring elastic properties of the formulations of modern styrene block copolymers.
As can be seen from table II, a mixture containing a propylene-ethylene copoly the EP, having a high ethylene content, function well at different ratios of a mixture of from 70:30 to 30:70 components A:C. a Mixture containing a propylene-ethylene copolymers having a lower ethylene content and having at least a heat of melting of 22 j/g (P/E-2 and P/E-3)are more elastic (i.e. shows lower values immediate shrinkage) when used at levels less than 50% wt. based on the mixture.
(57) 1. Composition to obtain a film containing:
(a) from 30 wt.% to less than 50 wt.% propylene-alpha-olefin copolymer having, essentially, the isotactic sequence of propylene, and at least 70 wt.% links formed from propylene and from 10 to 25 wt.% links formed from C2 - or C4-C10-alpha-olefin and propylene-alpha-olefin exhibits a heat of fusion by DSC analysis from 1 to 37 j/g and a melt flow index from 0.1 to 100 g/10 min; and
(b) from more than 50 to 70 wt.% styrene block copolymer, where the mass ratio of propylene-alpha-olefin copolymer to styrene block copolymer is from 3:7 to 7:3, and
where the composition exhibits the following:
(1) 2% secant modulus, tensile, as measured using the sample geometry ASTM D1708 at strain rate of 500%/min less than 20 MPa;
(2) elongation at rupture of at least 900%;
(3) the Affairs of tensile strength, at least 5 MPa when measured using the sample geometry ASTM D1708 and strain rate of 500%/min;
(4) immediate relative shrinkage after the initial application 400% strain of less than 2X, where X represents the shrinkage shown as a single component (C) after the initial application 400% strain.
2. The composition according to claim 1, where the ratio of (a) to (b) is at least 4:6.
3. The composition according to claim 1, where the composition comprises from 30 wt.% propylene-alpha-olefin copolymer and 70 wt.% styrene block copolymer.
4. The composition according to claim 1, where the composition exhibits a 2% secant modulus, tensile of less than 7 MPa.
5. The composition according to claim 1, where the composition exhibits a 2% secant modulus, tensile of less than 6 MPa.
6. The composition according to claim 1, where the composition exhibits a tensile elongation at break of at least 950%.
7. The composition according to claim 1, where the composition exhibits a tensile elongation at break of at least 1000%.
8. The composition according to claim 1, where the composition exhibits a tensile strength of at least 10 MPa.
9. The composition according to claim 1, where the composition exhibits a tensile strength of at least 15 MPa.
10. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer contains a propylene-ethylene copolymer having from 11 to 17 wt.% units formed from ethylene.
11. Compo is ice according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer contains a propylene-ethylene copolymer having from 12 to 16 wt.% units formed from ethylene.
12. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer contains a propylene-ethylene copolymer having from 13 to 15 wt.% units formed from ethylene.
13. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer exhibits a heat of fusion from 2 to 37 j/g
14. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer exhibits a heat of fusion of from 4 to 25 j/g
15. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer exhibits a heat of fusion of from 4 to 19 j/g
16. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer exhibits a broad distribution of crystallinity.
17. Composition according to any one of claims 1 to 6, where the propylene-alpha-olefin copolymer obtained using demetallizing catalyst with a Central metal and heteroaryl ligand.
18. The composition according to item 16, where the propylene-alpha-olefin copolymer obtained using demetallizing catalyst with a Central metal and heteroaryl ligand.
19. The composition according to claim 1, which essentially contains:
(a) from 30 wt.% to less than 50 wt.% propylene-alpha-olefin copolymer having, essentially, from the tactical sequence propylene, and, at least 70 wt.% links formed from propylene and from 10 to 25 wt.% links formed from C2 - or C4-C10-alpha-olefin and propylene-alpha-olefin exhibits a heat of fusion by DSC analysis from 2 to 30 j/g and a melt flow index of 0.2 to 50 g/10 min; and
(b) from more than 50 to 70 wt.% styrene block copolymer, where the mass ratio of propylene-alpha-olefin copolymer to styrene block copolymer is from 3:7 to 7:3, and
where the composition exhibits the following:
(1) 2% secant modulus, tensile, as measured using the sample geometry ASTM D1708 at strain rate of 500%/min less than 10 MPa;
(2) elongation at rupture of at least 950%;
(3) ultimate tensile strength of at least 5 MPa when measured using the sample geometry ASTM D1708 and strain rate of 500%/min less than 10 MPa;
(4) immediate relative shrinkage after the initial application 400% strain of less than 2X, where X represents the shrinkage shown as a single component (C) after the initial application 400% strain.
20. The composition according to claim 19, where the propylene-alpha-olefin copolymer exhibits a coefficient of skew is greater than -1,2.
21. Composition according to any one of p, 20, where the propylene-alpha-olefin copolymer obtained using demetallizing catalyst with the Central metal is om and heteroaryl ligand.
SUBSTANCE: invention relates to a composition of a hot melt pressure-sensitive adhesive (HMSPA), a laminated system and a pressure sensitive label containing said adhesive. The HMSPA composition contains: a) 30-50% mixture of styrene diblock- and triblock-copolymers, total content of the styrene monomer in the said mixture between 14 and 40%; b) 40-55% tackifying resin with melting point between 70 and 150°C, obtained through hydrogenation, polymerisation or copolymerisation of mixtures of aliphatic unsaturated hydrocarbons containing approximately 5, 9 or 10 carbon atoms; c) 4-20% hydrocarbon coil containing less than 15% aromatic compounds; d) 1-6% filler selected from calcium carbonate or a homopolymer or a copolymer polyethylene with low molecular weight. The laminated system includes an adhesive layer consisting of HMPSA and a paper front material. The pressure sensitive label is made from the laminated system.
EFFECT: HMPSA composition provides low susceptibility to decolouration during storage of articles.
15 cl, 11 ex
SUBSTANCE: invention relates to production of shrinkable polymer labels, particularly to preparation of a film composition. The composition contains (a) a high-impact polystyrene component (HIPS) with a block-copolymer grafted to the polystyrene, (b) 10-50 wt % general purpose polystyrene (GPPS) and (c) approximately 2-80 wt % styrene block-copolymer. Component (a) contains a grafted rubber component which is a styrene block-copolymer and a rubber-like diene with conjugated double bonds from 1 to 7 wt % of the weight of the HIPS; less than 10 wt % concentration of gel, defined by extraction of the methylethylketone/methanol mixture. The average particle size of the rubber is less than 1 mcm and 0.01 mcm or more. Approximately 40-90 vol % of the rubber particles have diametre approximately less than 0.4 mcm and approximately 10-60 vol % of the rubber particles have diametre of approximately 0.4-2.5 mcm. Most of the rubber particles have a nucleus-shell morphology and said particles are in concentration of 10-70 wt % of the total weight of the polymer composition, and 1-5 wt % of the rubber-like diene of the total weight of the polymer composition.
EFFECT: film made from said composition has ratio of directed length to non-directed length in the direction of the greatest drawing at least equal to 3:1 and enable increase in size by 20% in the direction of less stretching at 110°C.
10 cl, 3 tbl, 7 ex
SUBSTANCE: described is a composition of bound high molecular weight block copolymers for making compounds, moulded articles and oil gels, containing: (a) a linear di-block copolymer (I) of general formula (A-B), having maximum apparent molecular weight between 230000 and 275000, (b) a linear double-beam block copolymer (II) of general formula (A-B)2X, (c) a three-beam block copolymer (III) of general formula (A-B)3X, (d) greater than the three-beam block copolymer (IV) of general formula (A-B)n>3X, (e) secondary polymer structures mainly based on monovinylaromatic hydrocarbons having maximum apparent molecular weight less than that of the linear di-block copolymer (I), where A is a block of mainly poly(monovinylaromatic hydrocarbons), and where content of poly(monovinylaromatic hydrocarbons) lies between 20 and 35 wt %; where B is a block of mainly poly(conjugated diene); where X is a residue of a trifunctional and/or tetrafunctional binding agent; where the composition of block copolymers has weight-average molecular weight Mw between 450000 and 800000, and where relative amounts of block copolymers are as follows: I between 5 and 15 wt %; II and III together between 70 and 90 wt %, where III is more than 10 wt %; IV ranges from more than 0 to less than 10 wt % and secondary polymer structures range from more than 0 to less than 10 wt %, respectively, relative the weight of the all the composition of block copolymers, in which the sum of the components is equal to 100%. The invention also describes a method of obtaining the composition of bound block copolymers. Described also are moulded articles and gels, obtained from the composition of bound block copolymers.
EFFECT: obtaining a composition of bound block copolymers with high molecular weight and low viscosity.
12 cl, 13 tbl, 6 ex
SUBSTANCE: invention relates to a composition of an oil-containing gel, which contains a block copolymer with controlled link distribution and at least one non-aromatic ester oil. The block copolymer is formed from monoalkenyl and a conjugated diene. The block copolymer undergoes selective hydrogenation and contains block A from monoalkenylarene homopolymer and block B with controlled link distribution in form of a medial block formed from monoalkenylarene and a conjugated diene. The non-aromatic ester oil is natural oil, eicosyl erucate or C12-15 alkyloctanoate. Oil content is equal to 250-2000 pts. wt per 100 pts. wt of the hydrogenated block copolymer.
EFFECT: invention enables to obtain stable transparent gels with improved properties.
14 cl, 13 tbl, 9 ex
SUBSTANCE: invention relates to polyester compositions containing oxygen-absorbing polydienes and used in packing food products and drinks. The invention describes a composition which contains a combination or a reaction product (i) resins based on aromatic polyester and (ii) hydrogenated polydiene with terminal hydroxyl groups, where 30-70 mol % monomer links of said polydiene are vinyl links or their hydrogenated residues, and in which 60-80% of initial double bonds remain after hydrogenation. Described also is a method of preparing the composition, involving anionic polymerisation of conjugated diene monomer to form polydiene with terminal hydroxyl groups and mixing the aromatic polyester to obtain polydiene.
EFFECT: good oxygen-absorbing properties and prevention of colouring of polyester compositions during secondary processing.
21 cl, 2 ex
FIELD: physics; photography.
SUBSTANCE: invention relates to a photosensitive polymer composition, preferably used in a flexographic printing plate. A photosensitive polymer composition is proposed, which contains a thermoplastic elastomer (a), which contains at least a vinyl aromatic hydrocarbon link, a butadiene link and an alkylene link, where content the alkylene link is not less than 10 wt % and not more than 60 wt % of the total amount of butadiene and alkylene links; a photopolymerisable unsaturated monomer (b) and a photopolymerisation initiator (c).
EFFECT: photosensitive polymer composition provides for high reproducibility of thin lines, resistance to ether solvent and prevention of formation of cracks on the surface of the plate.
15 cl, 1 tbl, 7 ex
SUBSTANCE: thermoplastic elastomer material contains: (a) from 10 to 100 wt % of at least one thermoplastic elastomer based on styrene; (b) from 0 to 90 wt % of at least one thermoplastic homopolymer or copolymer of α-olefin, different from (a); where amount of (a)+(b) equals 100; (c) from 2 to 90 pts. wt of vulcanised rubber in crushed state; (d) from 0.01 to 10 pts. wt of at least one coupling agent which contains at least one unsaturated ethylene; where amounts (c) and (d) are expressed in ratio to 100 pts. wt of (a)+(b).
EFFECT: improved mechanical properties, specifically breaking stress and breaking elongation, increased wear resistance.
60 cl, 6 tbl, 6 ex
SUBSTANCE: invention relates to a thermoplastic elastomer composition with high melt strength, to a method of making moulded elastomer objects and to moulded elastomer objects, made from the said composition. The composition contains at least one linear crystalline polyolefin and at least one compatible thermoplastic elastomer or a mixture of one or more styrene block copolymers with a thermoplastic and/or plasticiser. The polyolefin has melting point of at least 100° C and polydispersity index (PI) greater than 20, determined through isothermal dynamic frequency sweep at 190°C and calculated from the equation PI = 100000/Gc, where Gc is expressed in pascals and is the modulus at the point of intersection (Gc=G'=G"), and the thermoplastic elastomer or mixture has compression set below 50%, determined at ambient temperature 24 hours after compression on ASTM D395-03.
EFFECT: obtaining a composition which can be used in processes which include a stage for unsupported stretching while the composition is molten, such as foaming, film blowing, fibre drawing, blow moulding, profile extrusion and hot moulding.
17 cl, 6 ex, 9 tbl
SUBSTANCE: thermoplastic gel composition which can be cured under the action of radiation includes: (a) approximately from 5 to 40 wt % of cured block-copolymer selected from the group consisting from compounds of formula (II) or (III) or (IV), whereat A is vinyl aromatic hydrocarbon block with molecular mass from 4000 to 30000, HD is hydrogenated conjugated diene block with molecular mass from 10000 to 100000, Y is multifunctional binding agent, UD is conjugated diene block with molecular mass from 1000 to 80000 or conjugated diene block with molecular mass from 1000 to 80000 which is partially hydrogenated, x is integer number from 1 to 20, y is equal to 0 or 1, z is integer number from 1 to 20 and in the formulas (II) and (III) the sum (x+z) is in the range from 2 to 30; (b) from 60 to 90 wt % of the liquid component selected from the filling oils, plasticisers and solvents compatible with the curable copolymer; (c) from 1 to 20 wt % at least one curative agent selected from bifunctional or multifunctional acrylate or metaacrylate monomers or vinyl ethers; d) optionally from 0 to 10 wt % of the expanding microspheres; and (e) optionally from 0 to 3 wt % of the photoinitiator whereat total component amount is equal 100 wt %. The thermoreactive article containing the thermoplastic gel composition subjected to the action of radiation is described as well as the thermoplastic gel composition which can be cured under the action of radiation and includes: (a) from 5 to 40 % w/w of the mixture of curable block-copolymer with formula (I) whereat S is polystyrol block, B is polybutadiene polymer block having the content of 1,2-vinyl groups in the range from 10 to 80 mole %, Y is the radical of the binding agent, x is integer number from 1 to 20, preferably 2, y - integer number from 0 to 20, preferably 2, with sum (x+y) being in the range from 2 to 30; and block-copolymer of the (polystyrol -hydrogenated polybutadiene -polystyrol ) type with ratio (block-copolymer of formula (I): (block-copolymer of (polystyrol -hydrogenated polybutadiene -polystyrol ) type being in the range from 3:1 to 1:3; (b) from 60 to 90 wt % of the liquid component selected from the filling oils, plasticisers and solvents compatible with the curable copolymer; (c) from 1 to 20 wt % of at least one curative agent selected from bifunctional or multifunctional acrylate or metaacrylate monomers or vinyl ethers; (d) from 0.1 to 10 wt % of expanding microspheres; and (e) from 0 to 3 wt % of photoinitiator whereat total component amount is equal 100 wt %.
EFFECT: increase of high-temperature shrinkage resistance.
10 cl, 8 tbl, 30 ex
SUBSTANCE: method for preparation of functionalised, bound or star-block copolymer used in sulphur-cured rubber composition containing carbon char and having in cured state decreased hysteresis with at least one of said blocks containing polyisoprene and at least one other block consisting of diene elastomer different from polyisopren with mole content of repeating units of one or more of conjugated dienes exceeding 15% includes: copolymerisation of one or more monomers containing at least one conjugated diene different from polyisoprene with catalitycal system containing hydrocarbon solvent halogenated or unhalogenated metal-organic compound A of the group IIIA metal, alkaline-earth metal compound B and polymer initiator C containing bound C-Li formed by unfunctionalised monolythium-containing polyisopren intended for formation of the said block or every polyisoprene block and (ii) adding to the product of the said polymerisation of the functionalising, binding or star-shape forming agent containing acetoxy group of formula Rn-Sn-(O-CO-R')4n> whereat n is integer natural number from 0 to 4 and R and R' each represents following groups: alkyl, cycloalkyl, aryl, aralkyl, same or different, for functionalisation or binding or forming of star-shape structure of the said block consisting of dien elastomer different from polyisopren. The said one or more polyisopren blocks have number average molecular mass Mn1 from 2500 to 20000 g/mole, the said one or more dien elastomer blocks have number average molecular mass Mn2 from 65000 to 350000 g/mole. Functionalised, bound or star-block copolymer, curable or cured rubber composition with lowered hysteresis in cured state, containing reinforcing filler completely or partially consisting of carbon char and containing aforementioned functionalised, bound or star-block copolymer are described also. Pneumatic tyre tread containing aforementioned rubber composition is described as well as pneumatic tyre containing described above tread.
EFFECT: hysteresis decrease of cured the rubber composition.
36 cl, 5 ex
SUBSTANCE: described is a dispersion composition which is in form of an oil based suspension containing the following in wt % (per total weight of the dispersion composition): plant oil 50-90, UV-light absorber 0.001-0.1, bactericidal agent 0.001-0.1, ultrahigh molecular α-olefin-styrene polymer which lowers liquid flow resistance 5-40 and lubricant 2-25. To obtain the dispersion composition, the UV-light absorber and bactericidal agent are added to plant oil and a first mixture is obtained. The mixture is stirred to homogeneous state for use as a dispersant. The lubricant is then added to the polymer and a second mixture is obtained. The second mixture is crushed at temperature equal to lower than -90°C. The obtained powder is added to the dispersant and the mixture is stirred to obtain a suspension.
EFFECT: obtaining high content of dry composition substance, improved stability of the composition with the polymer.
14 cl, 7 tbl, 7 ex
SUBSTANCE: elastomeric polymer moulding composition can be used for making capacitor insulating layers, medical devices and fuel element seals. An elastomeric polymer moulding composition is described, which contains an elastomeric polymer, which can be cured by peroxide, is completely soluble (i.e. does not contain gel), does not contain divinyl benzene and extracting impurities. Material made based on the said composition is safe during production and use. The composition is an alternative to XL-10000 based compositions (butyl rubber, partially cross linked with divinyl benzene).
EFFECT: increased effectiveness of the composition.
7 cl, 1 tbl, 5 ex, 2 dwg
SUBSTANCE: described is a foaming polystyrene composition in form of granules, containing: (1) 100 pts. wt polystyrene, preferably with average molecular weight Mw ranging from 150000 to 400000 Da, (2) 3 to 20 pts. wt of foaming agent, which is water or a mixture of water and at least one other foaming agent, for example, hydrocarbon, (3) 0.1 to 12 pts. wt of at least one modified clay, with at least a partial lipophilic property. Also described is a method of producing a foaming polystyrene composition in form of granules, which involves polymerisation of styrene and optionally at least one comonomer, which is brought into an aqueous suspension and mixing by reacting 100 pts. wt styrene and optionally a comonomer or comonomers with at least one radical polymerisation initiator and at least one suspension agent. This method is characterised by that, the reaction process is also carried out in the presence of (a) 4 to 23 pts. wt of foaming agent, which is water or a mixture of water and at least one other foaming agent, for example hydrocarbon foaming agent, and (b) 0.5 to 12 pts. wt of at least one modified clay, with at least a partial lipophilic property. Described also is use of the said foaming polystyrene composition in form of granules in making moulded and foamed objects, preferably with bulk density ranging from 5 to 50 kg/m3, preferably from 5 to 30 kg/m3.
EFFECT: increased effectiveness of the composition.
17 cl, 6 ex
SUBSTANCE: invention refers to technology of hull-kernel particles which can be used to modify impact strength of poly(met)akrylate moulding compositions. According to method a) water and emulsifier b) are added with 25.0 to 45.0 mass fractions of the first composition containing A) alkylmetacrylate 50.0 to 99.9 mass fractions, B) alkylakrylate 0.0 to 40 mass fractions, C) cohesive monomers 0.1 to 10.0 mass fractions, and D) styrene monomers 0.0 to 8.0 mass fractions, and polymerised, c) added 35.0 to 55.0 mass fractions of the second composition containing E) (met)akrylates 80.0 to 100.0 mass fractions, F) cohesive monomers 0.05 to 10.0 mass fractions, and G) styrene monomers 0.0 to 20.0 mass fractions, and polymerised, d) added 10.0 to 30.0 mass fractions of the third composition containing H) alkylmetakrylates 50.0 to 100.0 mass fractions I) alkylakrylates 0.0 to 40.0 mass fractions and J) styrene monomers 0.0 to 10.0 mass fractions, and polymerised. Method is distinctive in that e) each polymerisation cycle is performed at temperature within 60 to 90°C and f) fractional content of all substances is selected so that total weight A) to J) per total weight of aqueous dispersion exceeds 50.0 mass %. Presented method is used to produce impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.
EFFECT: production of impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.
17 cl, 8 tbl
FIELD: manufacture of rubber articles on base of butadiene styrene rubber; manufacture of ebonite battery monoblocks.
SUBSTANCE: ebonite mix on base of butadiene styrene rubber contains reclaim, sulfur, diphenyl guanidine, magnesium oxide, kaolin, paraffin, phthalic anhydride with synthetic fatty acid, soap-surfactant, petrolatum oil and filler. Used as filler is ion-exchange resin -cationite KY-2 ground preliminarily to fraction of 1-40 mcm and taken in the amount of 180-360 parts by mass.
EFFECT: improved physico-mechanical parameters of vulcanizers; reduction of deficiency of rubber phase in ebonite; utilization of used ion-exchange resins.
FIELD: textile industry.
SUBSTANCE: invention relates to manufacture of nonwoven fabrics possessing sorption ability and can be used in making various-modification filters suitable for cleaning liquid media. Impregnating composition contains blend constituted by latexes based on rigid chain- and flexible chain-nature copolymers taken at ratio between 95:5 and 50:5, respectively, solid filler, and water, wherein ratio of all components is expressed as 1:(2.5-3.0):1. Composition is obtained by mixing and vibration action in resonance mode at frequency 50-150 Hz and action time 5-15 min.
EFFECT: increased aggregative stability of composition and physicomechanical properties of material with no additional components added.
2 cl, 2 tbl, 6 ex
SUBSTANCE: composition consists of copolymer of propylene, of first copolymer of ethylene with at least one linear or branched alpha-olefine having 3-8 carbon atoms and of second copolymer of ethylene with at least one linear or branched alpha-olefine having 3-8 carbon atms. Copolymer of propylene has value of poly-dispersity index within ranges from 4.5 to 10 and contents of isotactic penthalogy above 97.5 mol %. Also, said copolymer contains at least 95 wt % (relative to copolymer) links derivative from propylene. The first copolymer - copolymer of ethylene contains from 25 to less, than 40 wt % relative to this copolymer) links derivative from ethylene and is soluble in xylol at 25°C within the ranges from over 85 to 95 wt %, while the second copolymer of ethylene contains from 50 to less 75 wt %relative to this copolymer) links derivative from ethylene and is soluble in xylol at 25°C within the ranges from over 50 to 85 wt %, and possesses characteristic viscosity of fraction soluble in xylol below 1.8 sh/g.
EFFECT: composition possesses good resistance to stress causing whitening, and lustre combined with good balance of mechanical properties.
8 cl, 3 tbl, 2 ex