Acrylic mixtures

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of low molecular and high molecular acrylic polymers. The invention discloses an acrylic polymer composition for moulding or extrusion, which contains a mixture in molten thermoplastic high molecular acrylic material (HMAM) and thermoplastic low molecular acrylic material (LMAM). An alkyl(alk)acrylate based (co)polymer accounts for at least 70 wt % of the HMAM and LMAM. The HMAM is characterised by average molecular weight (Mw) between 40000 Da and 1000000 Da, and the LMAM is characterised by Mw ranging from molecular weight of entwinement (Me) (expressed in thousand daltons) to 250000 Da.The invention also discloses a method of preparing an acrylic polymer composition, versions of using and processing the acrylic polymer composition, as well as products made from said composition.

EFFECT: obtaining acrylic polymer compositions with improved processability.

36 cl, 4 dwg, 19 ex

 

The present invention relates to acrylic compounds, more specifically, to mixtures of low molecular weight acrylic polymers and high molecular weight acrylic polymers.

Improved processing AIDS, acrylic polymers for various applications is an important area of research, allowing to achieve many commercial advantages. The processability of polymers in General can be improved by increasing the melt flow index (MFI), and in the industry of acrylic polymers is carried out by adding to the macromolecular polymer PMMA various copolymers, such as copolymers of alkylacrylate or methacrylic acid. Despite the fact that thus you can increase MFI, it can also lead to a significant decrease in the glass transition temperature of the polymer PMMA, with the consequent reduction of the range of its applications, such as those that require resistance to temperatures in the range from moderate to high.

In document EP 0588147 describes a two-step blending method, mainly intended for use in the case of polyolefins. The use of two-stage blending method is aimed at solving problems of "fish eyes" in the final product. Specific m the molecular mass is not presented.

The authors Hwang and Cho, Department of Chemical Engineering, Pohang University, in the description on the web page entitled “Effect of chain entangled on the bulk strength of glass polymer”, report on the determination of the critical density weave circuits using estimates of the viscosity at the destruction. They concluded that the use of PMMA with low magnitude MM adversely affects the fracture energy of polymer.

In document WO 086/05503 describes a mixture of high and low molecular weight polymers of alkylacrylate, which is obtained from a given monomer. The alkyl(ALK)acrylates are mentioned only as comonomeric components are of high or low molecular weight copolymer. The document refers to the use of these mixtures for adhesives, bonding with pressure.

In the document JP 56-008476 describes the composition of the adhesive, bonding with pressure obtained by mixing (A) a low molecular weight acrylic polymer, such as PMMA, and (C) acrylic polymer. As stated, the composition achieves improved adhesion to rough surfaces.

In the document JP 07-174133 describes a mixture of low and high molecular components, including polymers of alkyl(ALK)acrylate as a high molecular weight component. The content of high molecular weight component is less value than the level containing the Oia low molecular weight component. The usefulness of mixtures connected with the sphere rolls low hardness. Low molecular weight additive can be chosen from:

a softener,

plasticizers,

additives that increase the stickiness,

oligomers

or residue.

In the document JP 07-174189 describes a system similar to that described in the document JP 07-174133, but it is used to enhance the performance of damping.

In the document JP 54-23539 describes a toner containing a coloring agent, an acrylic copolymer and optionally a vinyl polymer. The copolymer preferably contains (a) methacrylates such as methyl methacrylate, (b) vinyl monomer and (C) glycidylmethacrylate (2,3-epoxypropanol).

In document EP 0144140 describes a mixture for mixing with bentonite as drilling mud. The mixture contains a low molecular weight water-soluble nonionic or anionic polymer and a high molecular weight anionic polymer. The molecular weight of the low molecular weight component is less than approximately 50,000 (page 2, line 31), and the molecular weight of the high molecular weight component has a value greater than approximately 500000. Polymers of acrylic resin are cited as examples of low molecular weight components (page 2, line 18), characterized by a molecular weight that goes up to 40000. As General examples of PR what are the lower alkyl (C 1-4) acrylate, and acrylic acid and methacrylic acid are mentioned specifically. The presence of acid groups can facilitate solubility. The alkyl(ALK)acrylate mixtures are not described.

In document EP 1189987 B1 mentioned that when using impact-resistant high molecular weight acrylic polymers based on crosslinked poly(meth)acrylate, mixed with more low molecular weight acrylic polymers, it is possible to achieve a specific set of properties, including the desired heat resistance by Vika.

The document US 6388017 relates to a method for introduction of the ethylene polymer base with a narrow molecular weight distribution in contact with the high molecular weight polymer, such that there would be a 0.1%→10% (wt.) molecules with a molecular weight of >1 million. As a possible way mentioned mixing, although it is preferable copolymerization.

In documents US 5306775, US 5319029 and US 5380803 describes a mixture of high and low molecular weight polyolefins, with the aim of improving resistance to cracking, transparency and the like.

In the document FR 2749591 describes a cleaning composition to equipment for processing plastics. There are two components PMMA:

(a) 95%-25% (wt./wt.) high-molecular neuroplastic component PMMA; and

(b) 5-75% (wt./wt.) termoplastycznego the PMMA.

In the description, the term "high molecular weight" is defined as "the average molecular weight greater than 500[000], preferably greater than 1000[000] Dalton...".

Similarly, the description defines the term "thermoplastic [PMMA]... understood as [PMMA], characterized by an average molecular weight in the range from 50[000] to 200[000]...". Neuroplasticity PMMA during the cleaning process, apparently, is stored in the form of a solid phase.

In accordance with the first aspect of the present invention features an acrylic polymer composition containing the mixture in the melt of thermoplastic high molecular weight acrylic material (WMAM) and low molecular weight thermoplastic acrylic material (NMAM), with at least 70% (wt./wt.), when calculating the total mass of WMAM mentioned VMEM is (co)polymer based on alkyl(ALK)acrylate, and mentioned (co)polymer contains at least 80% (wt./wt.) the first polymer derived from monomer units C1-C12alkyl (C1-C8ALK)acrylate, and optionally up to 20% (wt./wt.), when calculating the above mentioned (co)polymer based on alkyl(ALK)acrylate, the first copolymer obtained from the monomer units C1-C12alkyl(C0-C8ALK)acrylate and/or (C0-C8ALK)acrylic acid, if e is ω-mentioned WMAM characterized by a mass-average molecular weight in the range from 40000 daltons to 1,000,000 daltons, moreover, at least 70% (wt./wt.), when calculating the total mass of NMAM mentioned NMAM is (co)polymer based on alkyl(ALK)acrylate, and mentioned (co)polymer contains at least 80% (wt./wt.) the second polymer derived from monomer units C1-C12alkyl (C1-C8ALK)acrylate, and optionally up to 20% (wt./wt.), when calculating the above mentioned (co)polymer based on alkyl(ALK)acrylate, the second copolymer obtained from the monomer units C1-C12alkyl(C0-C8ALK)acrylate and/or (C0-C8ALK)acrylic acid, these NMAM characterized by a mass-average molecular weight in the range of molecular weight weave (Me) (expressed in thousands of daltons) to 250,000 daltons, with the proviso that WMAM characterized by magnitude, Mw, of greater than Mw at NMAM.

Preferably the first polymer VMM and the second polymer NMAM constitute one and the same, that is, if the first polymer is a polymer based on methyl(meth)acrylate, and then the second polymer is a polymer based on methyl(meth)acrylate and the like. Similarly, preferably, the first copolymer and the second copolymer are the same, i.e. if the first copolymer is a copolymer based on acilac elata, then the second copolymer is a copolymer based on ethyl acrylate and the like. Preferably the ratio between the amounts of the first polymer, the first copolymer is a value within ±30% of the ratio of amounts of the second polymer, the second copolymer, more preferably within ±20%, most preferably within ±10%.

Preferably the mass ratio of VMEM:NMAM in the composition exceeds 1:1, more preferably is at least 6:5, most preferably at least 7:3.

Preferably the acrylic polymer composition comprises, based on the weight of the acrylic polymeric composition, up to 55% (wt./wt.) NMAM and at least 40% (wt./wt.) VMAM, more preferably up to 15% (wt./wt.) NMAM and at least 50% (wt./wt.) VMAM, most preferably up to 10% (wt./wt.) NMAM and at least 60% (wt./wt.) material VMEM.

Under the mixture in the melt mean a composition which is received by way of mixing in the melt. Under the mixing in the melt, means the way of mixing in the melt, which leads to a reduction in the heterogeneity of double (or contains more components) composition of various polymers (including polymers which differ from each other only by its molecular weight). The mechanism of mixing bookmark is included initiating physical movement of ingredients at elevated temperature (preferably T> the glass transition temperature Tg for all polymer components). It includes providing distribution and dispersive mixing, sufficient to be able to read the ingredients into a homogeneous mixture. Therefore, it requires for polymers convective mixing under the action of laminar flow for a sufficiently long period of time, such that the residence time of the polymers in the process of mixing would exceed the time required to achieve homogenization using this process. (Preferably recommended practice work provides achievement in the broad sense of the similarity of the size and shape of the mixed polymer components, which thus contributes to the dispersive mixing). Suitable for use in the methods of mixing may include single or twin screw extrusion or pripuskanie through the method feeder screw feeder during injection molding.

This definition excludes the use of mixing only under pressure (even if the temperature will increase to a value considerably higher than the glass transition temperature) or mixing in the mixing in solution and subsequent evaporation (C Rauwedaal Polymer Extrusion Hanser Publishers, Munich (1994) ISBN 3-446-17960-7; page 322 and JM Deely and KF Wissbrun Melt Rheology and its role in plastics processing, Theory and Applications, Van Nostran Reinhold, New York (1990) ISBN 0-442-22099-5; page 480).

Links to Methis document should include determination upon receipt of the torsion characteristics of the rheology of the melt.

This characterization is carried out in accordance with ASTM D4440. Specifically, Memust be taken as the value determined for a polymer sample as follows:

before you install the torsion plastometer get a solid pre-formed disks, which is dried in a vacuum oven overnight at 70°C to remove residual moisture. After this they are placed between parallel plates with a diameter of 25 mm rotational plastometer Rheometrics RDAII.

The upper fixture for testing lowered so that it would touch the bottom of the fixture for testing at approximately the same normal force, the impact of which it is subjected during the test. After that, the indicator lumen set to zero. Then the upper fixture for testing raise and lower the fixture for testing include a sample in the form of a disk.

The plate is gently lowered to the surface of the disk, and then heated to a temperature equal to 140°C, p and simultaneously maintaining a predetermined installation space sample in the form of a disk with a thickness of 2 mm As soon as the disk of the polymer in the form of melts, the excess polymer sample, acting on the sides of the cone and plate is cut using a sharp knife. After that, the sample at a given fixed temperature using plastometer impact torsional vibrations with frequencies in the range from 0.01 to 100 rad/sec at a fixed amplitude of deformation of 5%. During this frequency sweep at each frequency to determine the storage modulus (elasticity) G'(ω) and loss modulus (viscosity) G"(ω).

After that, the melt temperature increased to values, usually at 20-30°C higher than the previous, this experimental technique is repeated. Measurements are generally performed at 230°C, up to the maximum temperature, usually 250°C.

Measurement modules accumulation and loss makes it possible to calculate the complex viscosity η*(ω) when using a standard ratio (reference: LA Utraki Polymer Alloys and Blends, p134 Hanser Publishers (1990)):

(4A)

After that, the modules accumulation and loss were subjected to time-temperature superposition shift to the reference temperature of 230°C. when using a computer program Shiftt.exe conceptually described and together with the source given by GV Gordon and Shaw MT Computer Programs for Rheologists, Hanser Publishers (1994).

Popucauses is in the "generalized curves were shifted to a reference temperature of 230°C under the assumption of equality of glass transition temperature of approximately 100°C. when used as reference spectra for blending or tan δ (G"(ω)/G'(ω)), or storage modulus G'(ω).

The following figures (1-3) represent an example of basic rheological data for a sample for testing before and after superposition with a generalized curve.

Fig.(1): Data on torsional rheometry for sample for testing, measured in the range from 0.01 to 100 Hz and in the range from 140 to 250°C.

Fig.(2): Data on torsional rheometry in the form of "generalized curve for the test pieces subjected to superposition with the shift to 230°C. In this case demonstrates the full range of rheological for this polymer in the frequency range from 10-2up to 107rad/sec.

Determination of molecular weight of weave of generalized curves

Molecular weight weave correlated with the shear modulus in the plateau, determined from data such as shown in Fig.(2)in accordance with addictions

(8)

where ρ is the density of the polymer at the temperature T. the values for the polymer PMMA at specific temperatures can be found in the work Cogswell FN Polymer Melt Rheology Appendix 9 p156,

Woodhead Publishing Ltd 1997, G0Nis a module on the plateau, and R is the gas constant (8,3144 J. mol-1To-1), and k is a constant, the value of which is 4/5 (definition of interval weave and constants in the tubular model is available in RG Larson et al Journal of Rheology 47 p809 (2003)).

The module on the plateau can be obtained from the generalized curve in the form of the values of the storage modulus G ω), where tan δ reaches a local minimum (see S Wu Chain Structure and entanglements” Journal of Polymer Science: Pt B Polymer Physics27p723 (1989)).

Thus, the retrieval of data from Fig.(2) and graphing according to tan δ makes possible the determination of the magnitude of G0N.

Fig.(3). The module on the plateau G0Ncalculated for G'(ω) at the minimum value of tan δ(=G"(ω)/G'(ω)) using the data set from Fig.(2). G0Nin accordance with this definition, equal 0,46 MPa.

Preferably the compositions of the present invention are thermoplastic, and heterooligomeric compositions. Preferably the mixture in the melt represent a homogeneous mixture in the melt.

The composition optionally can include a second or additional component VMEM (defined the same way as the aforementioned first VMM), which is characterized by a mass-average molecular mass greater than the mass-average molecular mass of NMAM, but which may be greater or lesser than the mass-average molecular weight of the other component (component) VMEM. This second or additional components may be present with the level of content, PR is based on the amount of acrylic polymer composition, equal to at least 5% (wt./wt.), more preferably, at least 10% (wt./wt.), most preferably, at least 15% (wt./wt.). Preferably, the aforementioned second or additional VMM characterized by a mass-average molecular mass less than the mass-average molecular weight of the first component VMEM. In another case, the second or additional VMM may include any of the preferred characteristics of the first VMM, including any correlative dependence with NMM, such as those that concern the nature and content of third polymer and copolymer in comparison with the second polymer and the copolymer NMAM.

In addition, preferably the first polymer VMEM and third or more second polymer or additional VMM constitute one and the same. Preferably, the first copolymer and the third copolymer constitute one and the same. Preferably the ratio between the amounts of the first polymer, the first copolymer is a value within ±30% from the ratio of the amounts of the third polymer, the third copolymer, more preferably within ±20%, most preferably within ±10%.

VMEM (including second or additional component WMAM if any) may be present, based on the total weight of the acrylic polymeric composition, the level of content, reaching up to 99% (wt./wt.), more preferably up to 96% (wt./wt.), most preferably up to 94% (wt./wt.).

NMAM may be present, based on the total weight of the acrylic polymeric composition with a content equal to at least 1% (wt./wt.), more preferably at least 2% (wt./wt.), most preferably at least 4% (wt./wt.).

NMAM may be present, based on the total weight of the acrylic polymeric composition in amount in the range of 1-60% (wt./wt.), more preferably 2-55% (wt./wt.), most preferably 4-51% (wt./wt.), in particular 4-40% (wt./wt.), more particularly 4-30% (wt./wt.).

VMEM (including second or additional component WMAM if any) may be present, based on the total weight of the acrylic polymeric composition in amount in the range 99-40% (wt./wt.), more preferably 98-49% (wt./wt.), most preferably 98-70% (wt./wt.), in particular 98-45% (wt./wt.), more particularly 96-49% (wt./wt.), to the greatest extent, especially 96-60% (wt./wt.) or 96-70% (wt./wt.).

VMEM and NMAM together can be up to 90% (wt./wt.), more preferably 95% (wt./wt.), most preferably 99% (wt./wt.), in particular essentially 100% (wt./wt.) derived from acrylic mon the mayors of component acrylic polymer composition.

Preferably NMAM characterized by a mass-average molecular weight (Mw)in excess of 11,000 daltons, more preferably greater than 15000 daltons, most preferably in excess of 20,000 daltons. In some implementations, it may exceed 50000 or even 70000.

Preferably NMAM characterized by the value of Mw, less than 150,000, more preferably less than 70000, most preferably less than 65000. Especially preferred value of Mw for NMAM has a value less than 40,000, even more particularly preferred is a value less than 25000.

The upper limits and lower limits defined in this document for Mw NMAM and Mw VMAM, can be combined in any appropriate combination.

Preferably WMAM characterized by a magnitude Mw in excess of 50,000 daltons, more preferably greater than 70000 daltons, most preferably greater than 85000 Dalton.

The first component of VMM can be characterized by the value of Mw, exceeding 100,000, more preferably 120000, most preferably 140000, while the second or additional component VMEM can be characterized by the value of Mw greater than 50000, more preferably in excess of 60,000, most preferably in excess of 70000.

Preferably the first or second SOPs shall liner based on C 1-C12alkyl(C0-C8ALK)acrylate and/or (C0-C8ALK)acrylic acid, if any, is up to 15 wt.% copolymer based on alkyl(ALK)acrylate, more preferably up to 10 wt.%, most preferably up to 8 wt.%. The first or second copolymer may be a polymer based on C1-C12alkyl(C0-C8ALK)acrylate-based or (C0-C8ALK)acrylic acid or a combination thereof and may be present in NMAM or VMEM with independent levels. Preferably the corresponding (co)polymer based on alkyl(ALK)acrylate is more than 80 wt.% VMEM or NMAM, more preferably more than 90 wt.%, most preferably referred to the appropriate (co)polymer is more than 95 wt.% NMAM or VMM.

Preferably VMEM and NMAM together make up more than 80 wt.% acrylic polymer composition, more preferably at least 90 wt.% acrylic polymer composition, most preferably at least 95 wt.%, in particular, 99, or 100 wt.% acrylic polymer composition.

The residual part (i.e. up to 100%) acrylic polymer of the composition, and/or VMM, and/or NMAM may consist of suitable for use additives, preferably necrology additives. Preferably d is the additives comprise less than 30% (wt./wt.), more preferably less than 20% (wt./wt.), most preferably less than 10% (wt./wt.), and in particular less than 5% of said composition, and/or VMM, and/or NMM.

Additives may include stabilizers, UV stabilizers, dyes, controls Shine, regulators diffusion, flame retardants, and lubricants. Preferably the additive does not include staplers. Preferably the acrylate used in the present invention, do not have functional groups capable of passing a significant staple in the composition or in subsequent compositions containing composition. Preferably all parts of acrylic acid, having a free hydroxyl group present in the composition, does not serve as staple or not present in amounts sufficient to provide for the flow of essential staple. In particular, the compositions of the present invention preferably are characterized by significant levels in the polymer chains necrology or vinyl monomer unit (other than those of the vinyl monomer units which are derived from acrylic monomers). Preferred acrylic monomers and the like that are used in the present invention are not characterized by any or significant (e.g., larger than 1%) levels of Acrylonitrile the x monomers, but really include substituted or unsubstituted monomers based on the C1-C12alkyl(C0-C8ALK)acrylate and monomers based on (C0-C8ALK)acrylic acid. Preferably substituted acrylic monomers and the like do not have any (or if none is characterized by the significant levels of the monomers) of substituents capable of flowing stitching with the same or a different substituent in the acrylic monomer link adjacent or the same polymer chain. In particular, the acrylic monomer units of the polymers and copolymers of the present invention are not characterized by any significant levels of Monomeric units having substituents in the form of groups of glycidyl or hydroxyl (other than the group (ALK)acrylic acid). The term "significant"as used above, refers to a quantity that is smaller than 5% (wt./wt.) in VMM or NMAM, more preferably less than 1% (wt./wt.), most preferably less than 0.1%, in particular less than 0.01% (wt./wt.), more in particular 0.001% (wt./wt.).

Acrylic polymer composition may also form a polymer basis subsequent system that requires a polymer base, such as high-impact polymer or resin, dissolved sludge is dispersion in the solvent.

In accordance with this invention in the second aspect covers the acrylic composition containing

(a) an acrylic polymer composition that corresponds to the first aspect of the present invention, and

(b) suitable for use with solvent.

Preferably, the ratio (wt./wt.) the solvent (b): polymer (a) in the above-mentioned second aspect is in the range from 10:90 to 60:40, more preferably from 20:80 to 50:50, most preferably from 30:70 to 45:55.

Suitable for use with solvent is n-butyl acetate.

The modification of impact-resistant mixtures based on crosslinked poly(meth)acrylate of low molecular weight component is known for low levels of crosslinked poly(meth)acrylate. However, surprisingly, but the inventors have discovered advantageous properties such as high value of Tg at much larger levels of impact resistance modifiers.

In accordance with this third aspect, the invention extends to high impact acrylic polymer composition containing

(a) a polymer basis, the corresponding acrylic polymer composition of the first aspect of the present invention, and

(b) the impact resistance modifier with the structure of "core-shell", preferably mixed with it.

Preferably, the ratio (wt./wt.) (a):(b) in the third TSA is regarding subsection is in the range from 30:70 to 90:10, more preferably from 40:60 to 80:20, most preferably from 50:50 to 70:30.

Particularly preferred content of component (b) in impact-resistant acrylic resin composition are in the range of 7% to 50% (wt./wt.), more preferably 30-50% (wt./wt.), most preferably 32-40% (wt./wt.).

Suitable for use particles with the structure of "core-shell" represent discrete particles obtained by carrying out multi-stage graft copolymerization is usually in accordance with the methods of emulsion polymerization, each of which has a multilayer structure and is generally used to improve the impact strength of polymers, such as acrylic materials. Access to a wide range of these particles, which differ in the type of copolymers from which they are received, and the number and amount of shells that are available around the nucleus. Usually the core is obtained from methacrylate Homo - or copolymer, and the first shell provides kauchukopodobnoe material characterized by a low value of Tg and is usually formed of a copolymer of alkylacrylate/styrene. The formulation of this shell is often made with a view to making it kauchukopodobnoe character for modifying impact resistance while ensuring her compliance by pokazatel the refractive acrylic substrate, in which you must enter. The preferred type of copolymer, forming a shell, the core is n-butyl acrylate and aromatic comonomer, for example styrene or its derivative. Also can be a second or subsequent shell. Commercially there are many suitable for use particles with the structure of "core-shell", for example IR441 available in Mitsubishi Rayon Co., and some commercially available brands of acrylic molding materials include such materials, pre-blended with the polymer. One suitable for the particle with the structure of "core-shell" is described in document WO 96/37531, the content of which by reference is incorporated herein, and includes (meth)acrylic polymer core, the first shell containing polymer with a low Tg value, containing 0-25% (wt.) styrene monomer and 75-100% (wt.) acrylic monomer, (meth)acrylic monomer capable of forming a homopolymer characterized by the value of Tg in the range from -75 to -5°C, with the first shell is at least 65% (vol.) the combined volume of the core and the first shell (as defined by the method of transmission electron microscopy, identifying the shell as a result of contrast, and in the assumption of sphericity of the particles and when used in the research Institute of the expression 4/3πr 3to determine the amount of cores and patterns "core/shell"), and optional second membrane that contains the second (meth)acrylic polymer, which may be the same as the first (meth)acrylic polymer, or may be different, and the core and the first shell together contain 0.5 to 1.0% (wt.) grafting staple.

Suitable for use with the method and apparatus of transmission electron microscopy is a Philips CM12 TEM.

The present invention does not necessarily refers to acrylic polymer compositions, which essentially does not contain a modifier impact resistance, obtained from cross-linked poly(meth)acrylates, or pre-mixed to high molecular weight component, or otherwise United with him, and do not necessarily contain no such impact resistance modifier, pre-mixed to any of the components. Actually, in one implementation provides acrylic polymer composition essentially containing no modifier impact resistance. By "essentially no content" means the amount of acrylic polymer compositions of the impact resistance modifier, less than 1% (wt./wt.), more preferably less than 0.5% (wt./wt.), most preferably less than 0.1% (wt./wt.).

However, advantageously the case, add a component, forming an impact resistance modifier, if the use thereof in the present invention can be carried out in the framework of the one-stage method, i.e. VMAM, NMAM and the component constituting the impact resistance modifier, can be mixed with each other in the right quantities at the same stage of mixing in the melt, where the step of mixing in the melt, they are administered as separate components.

However, in alternative component, forming an impact resistance modifier, can be pre-mixed with NMM before mixing in the melt shockproof NMAM and WMAM. The advantage of this approach is that the properties of high impact NMAM will be more similar properties VMEM and thus will be easier to carry out the processing and mixing in the melt with him. By using this option, apparently, the closer will be the optimum mixing conditions, such as temperature for each component.

Therefore, in accordance with an additional aspect of the present invention proposes a method of mixing in the melt to produce impact-resistant acrylic resin composition corresponding to a third aspect of the invention, which includes stages:

mixing in the melt of the following individual components on a single stage mixing in the melt:

VMAM, corresponding to the first aspect is that the present invention;

NMAM, corresponding to the first aspect of the present invention;

and impact resistance modifier with the structure of "core-shell".

As an additional alternative, the impact resistance modifier can be mixed with a pre-mixed acrylic polymer composition of the first or any aspect of the invention. In the best case, this implies that the acrylic polymer composition of the invention can be subjected to a modifying impact resistance after receipt.

For the avoidance of doubt references to mixing or mixing in the melt in this document do not necessarily include the before phase of the melting phase mixing in a tumbling container.

VMEM and NMAM preferably represent a simple single-phase polymers, usually obtained by the same method of polymerization. Before mixing, they can be of any shape suitable for use when mixing, such as beads, lead shot or pellets. Suitable for use methods of obtaining VMEM or NMAM include polymerization in bulk and suspension polymerization. Although VMM and/or NMAM can be received and according to the method of emulsion polymerization, it is preferable not to get, since this method includes the process additional unnecessary stage, m which can lead to the inclusion neodnopodnykh polymers and not easy to get the size of the beads or granules, consistent with the appropriate dimensions for VMAM/NMAM were not obtained by the method of emulsion polymerization.

This is not surprising, but in comparison with the isolated WMAM polymer mixture in the melt corresponding to any of the aspects of the present invention, is characterized by a much higher melt flow index (MFI) and a comparable value of Tg.

Because the value of Tg is kept on a comparable level with the corresponding characteristic of VMM, the composition can be used in a wide range of such applications, but with improved processing AIDS due to the high values of MFI. For example, comparable processability can be maintained at low length cycles, which thus reduces the production cost. In the best case, the invention also offers advantages and processing, as a mixture with high Tg values require less time for processing, i.e. the cooling time during processing. Therefore, when using the invention can be used in high speed cooling parts in the device. In addition, a complete design can be achieved at elevated target temperatures of details, which effectively reduces the duration of the cycles of ohlord the deposits. One field of application in which it will be profitable, refers to applications in forming thick sections that require polymers with high fluidity of the melt. Such polymers with high fluidity of the melt can be quickly removed from the form, if the value of Tg of the polymer is higher.

In accordance with this invention in another aspect applies to the use of the polymers of the invention in methods of forming thick cross sections and extraction from the mold, and molded products with thick sections obtained from the compositions of the invention. Under molded products with thick section refers to the product with an average thickness of the molded product in the range from 3 mm to 100 mm, more preferably from 5 mm to 50 mm, most preferably from 5 mm to 20 mm, particularly preferred are cross-section in the range of 5-10 mm Thick cross-section can also be extended to products that have any part of the section are located at some distance from the nearest surface of the product, greater than 3 mm, more preferably greater than 4 mm, most preferably greater than 5 mm, especially greater than 6 mm, the Invention is also applicable to molded polymer products with thick sections obtained from the composition corresponding to any of the 1st, 2nd and 3rd aspects of the present is the first invention.

Another advantage of opportunities to increase MFI implies that there can be obtained new polymers with unique properties. Polymers with a high Tg value/high value MFI are particularly suitable for use in applications characterized by the presence of heat, such as applications in lighting. Applications characterized by the presence of heat, are applications in which the final molded product may be subjected to temperatures exceeding 50°C, more often greater than 70°C. Therefore, such polymer mixtures are suitable for use in achieving greater flexibility of design in applications with light or other applications in which the polymer is exposed to nearby heat source.

Therefore, in accordance with the fourth aspect of the present invention features a molded polymer product containing acrylic polymer composition corresponding to the first, second or third aspect of the present invention. Mentioned molded product can be obtained by methods of injection molding or extrusion molding.

The increase in MFI should also lead to a reduction in viscosity in Arah use in the coating in the sense of without increasing the viscosity can be used more polymer, or the same quantity of polymer can be obtained with lower viscosity.

In accordance with this fifth aspect of the present invention provides the use of acrylic compositions corresponding to any of the aspects of the present invention, to obtain mixed in the melt composition or a molded polymer product with high MFI value (in comparison with VMEM, not mixed with NMAM).

Preferably the invention also provides mixed in the melt composition or a molded polymer product with high Tg value.

Tests to determine high value of Tg and/or a higher MFI values can be performed by using the following further method. The values of Tg and MFI for conventional polymer install using commonly used ways. For the avoidance of doubt references to the MFI in this document are references to the MFI values, expressed in units of grams/10 minutes, determined at 230°C. using a weight of 3.8 kg in accordance with ASTM D1238-98, Procedure A.

Low molecular weight additives are mixed with the conventional polymer with the same level of content, which preferably leads to an increase of the melt flow index of conventional polymer, for example, equal to 15 minutes g If the value of Tg measure to increase the MFI of 15 g/10 min, it is found experimentally that in this embodiment, the value of Tg will usually undergo a reduction only in the range from 1 to 15°C., more often 2-12°C, the most commonly 4-10°C. Even in the case of increase in MFI of 25 g/10 min, the value of Tg is usually will decrease only 1-20°C, more often 2-15°C, most often 4-12°C. Preferably for each increase in MFI of 5 g/10 min, the decrease in Tg will be less than 5°C, usually this will be observed up to very high values of MFI, for example, goes up to 35 g/10 min, 40 or 45 g/10 minutes

This option improvements distinguishes the invention from alternative way to increase the melt flow index on the same value (for example, 15 g/10 min). This is done by the conservation of molecular weight constant, but increase the content of acrylate co monomer used in the copolymer. This alternative strategy leads to an increase in MFI of 15 g/10 min due to the suppression of the glass transition temperature on the order of more than 15°C.

Therefore, a high value of Tg can be considered as the value of Tg under test (co)polymer of the invention, which exceeds the relevant value of the comparative copolymer characterized by the same value of the MFI, which we who are of the same type and equivalent amount of monomer (monomers) based on the C 1-C12alkyl(C1-C8ALK)acrylate, but the increased amount of monomer (monomers) based on the C1-C12alkylacrylate with achievement thus necessary increase in MFI, and which is not mixed in the melt VMEM and NMAM corresponding to the invention, where "equivalent number" C1-C12alkyl With1-C8alkalidata represents the same amount, reduced by the proportional increase in the comparative copolymer number1-C12alkylacrylate, for example, if the comparative copolymer contains 5% (wt./wt.) With1-C12alkylacrylate greater than the polymer under test, then the number With1-C12alkyl With1-C8alkalidata in comparative copolymer is reduced by 5% (wt./wt.).

Preferably, when the value of the MFI of the polymer mixture in the range of 30-50 g/10 min, the value of Tg is preferably in the range 80°C-110°C, more preferably 85°C-110°C, most preferably 90°C.-110°C.

Links to Tg in this document should refer to the definition using the methods of DSC in accordance with ASTM E1356-98 as extrapolated temperature at the start of transition for the 2nd re-heating, unless other specified.

In accordance with the pole is m aspect of the present invention proposes a method of obtaining the acrylic polymer composition, incorporating the following stages:

a) introducing a thermoplastic high molecular weight acrylic material (UMAM) in contact with thermoplastic low molecular weight acrylic material (NMAM); and

b) mixing the said VMM and NMAM at an elevated temperature until obtaining a mixture in the melt;

where mentioned elevated temperature exceeds the glass transition temperature as VMM and NMM.

Stages a) and b) can be performed sequentially or simultaneously. Preferably the acrylic polymer composition is consistent with what is defined in any of the other aspects of the present invention.

Mixing in the melt can be carried out in accordance with the methods of extrusion or injection molding.

Hereinafter the invention will be illustrated by the accompanying examples. Figure 1 shows the comparative results when equivalent quantities of additives on the basis of alkylacrylate and methacrylic acid. These results are also shown in table 1.

Experimental section

Polymerization

Polymer samples were obtained according to the method of conventional free-radical suspension polymerization, which in result led to obtaining beads of polymer, characterized by a defined chemical composition and molecular weight distribution. Beads of polymer drying is whether in a vacuum oven overnight at 70°C to remove all residual moisture.

Mixing in the melt

A mixture of beads of polymers, characterized by different homogeneous molecular masses were received in the first otoshiana known amounts of each polymer when used as pan of the balance. The proper amount of each polymer constituting the composition of the mixture, was stirred tumbling plastic bag for approximately five minutes to ensure thorough dispersion of the components. Then the mixture is subjected to mixing in a tumbling vessel, was placed in a clean metal container and dried in a vacuum oven overnight at 70°C to remove any residual moisture.

The dried mixture is subjected to mixing in a tumbling vessel, condensed to obtain an extrudable continuous flow of melt through the use of twin-screw mixer in the form of extruder DSM micro (volume 15 cm3), heated in all areas at 230°C (much more than the glass transition temperature of approximately 100°C)operating at a screw speed equal to at least 60 rpm Times stay when passing through the extruder was chosen to ensure the homogenization of the melt flow. Polymer "tape" was taken out of the extruder and mechanically crushed into pieces by a length, avnoj approximately 5 mm, when using conventional dezintegriruetsja device for polymer processing.

Description test method for determination of MFI

The melt flow index measures the rate of extrusion of thermoplastics through a circular extrusion head at a prescribed temperature and a fixed load. The amount of polymer that ekstragiruyut for a specified time, selected as a sample and determine the mass of the cooled extrudate. From these data, determine the melt flow index. This is a simple method of measuring the fluidity of the molten polymer and thus processing AIDS polymer at a fixed temperature.

Approximately 5-8 g of the polymer is loaded into the cylinder apparatus for determining the melt flow (Davenport 730A/77CR), which is heated to a specified temperature. After this affect the mass of the plunger, which forces the molten polymer through a circular extrusion head. The test begins as soon as the pressure applied load to drive the plunger past the drawn risks, and ends the test after a specified time interval. The polymer, which ekstragiruyut from the extrusion head during this specified period of time, allow to cool and carry it to the scales.

Test method and equipment used by the traveler in the test, described in more detail in the document ASTM D1238 - procedure A. the Values used in this test for samples of PMMA and mixtures, was a

Temperature (at 10 mm above the extrusion head)=230°C

The attached load = 3.8 kg

The diameter of the circular extrusion head = 2,0955+/-0,0051 mm

Test duration = 10 minutes

Mass = grams

Velocity = grams/10 minutes

Determination of molecular weight

The molecular weight Mw was characterized using size-exclusion chromatography (also called gel chromatography - GPC) using Polymer Laboratory Caliber together with PMMA standards.

The GPC calibration required implementation of the following further method. Standard solutions of PMMA was obtained using 15 mg or Mr 10300 or Mr 107000 dissolved in 10 ml of chloroform containing 5-10 ál of the marker MMA. Approximately 5 mg of each standard were placed in a vial, dissolved in 10 ml of chloroform containing 5-8 μl of token flow of MMA was filtered and the amount of 1-2 ml was transferred into ampoules automatic sampler to estimate.

The analysis shall be tested polymers was carried out as follows. In a vial was weighed 25-30 mg of polymer was added 10 ml of chloroform. The mixture was stirred until dissolution. The samples were filtered is via the 0.2-micron syringe filter PTFE without using excessive pressure prior to analysis.

The polymer sample was dissolved in chloroform at 30°C. the Volume injected for analysis by GPC method was value in the range from 1 to 5 microliters. Used a flow rate of 1 ml/min Determination of molecular weight Mw was performed automatically using the analytical software used in the device.

Molecular weight was measured in chloroform in comparison with standard PMMA using equipment for GPC, equipped with an infrared detector configured on the optical absorption of the carbonyl in the field 5,90 microns. The levels of residual monomers was determined in the re-processing of the source data using software LG/GC. Equipment and software for GPC were supplied by Polymer Laboratories Limited.

SolventChloroform
Velocity1 ml min-1
Concentration sample25 mg/10 ml
Temperature30°C
PCCompatible with computer IBM

Calculation of volume for the structure of "core-shell"

Samples (high impact polymer) was cut to obtain surfaces of the blocks are suitable for thin slices. After that, they were placed in a fresh solution of trichloride ruthenium in aqueous sodium hypochlorite. Flowing in the reaction resulted in the receipt of ruthenium tetroxide and caused the emergence of preferred contrast any unsaturation present in the system. The contrast has led to improved contrast in transmission electron microscope (TEM), which thus contributed to the interpretation of the results. The blocks were soaked contrasting environments within one hour prior to their excavation, washing with distilled water and the provision of drying at room temperature. After alignment ultramicrotome Reichert Ultracut E received slices with a thickness of approximately 50 nm, which were examined using a Philips CM12 TEM.

The characterization of glass transition temperature

Characteristics of glass transition temperature Tg of each polymer was obtained by using differential scanning calorimetry (DSC) in accordance with the methodology described in the document ASTM E1356-98. The method used to characterize Tg represents the methods of the extrapolated temperature at the start of the transition for the second re-heating.

The equipment used was a controller Mettler Toledo TC15 TA, characterized by the geometry of the round Cup with a diameter of approximately 5 mm, and a depth of 1 mm, made of aluminum with a nominal thickness of 15 μm. Samples were heated at a scan rate of 20°C/min, Measurements were carried out with the use of nitrogen with purity of >99.9%, and the rate of flow of 50 ml/min during the measurement of glass transition temperature no signs of passing any adverse reactions were noted. Upon completion of the first heating a Cup of cooled using liquid nitrogen prior to re-heating when using the previously described conditions.

Some samples (as indicated) were analyzed to determine the Tg using the deformation heat resistance (HDT) in terms of the deformation is 1.82 MPa in accordance with ASTM D648.

Polymer basics 1Polymer basics 2Polymer basics 3
The basic monomerMMAMMAMMA
% (wt./wt.) 979797
The second monomerEAEAEA
% (wt./wt.)333
Mw (in thousands of daltons)9014222,1
Mn (in thousands of daltons)41679,4
Product formPowderPowderPowder
Tg° (C) according to the method of DSC106,7110,396,3
MFI (g/10 min at 230°C/3,8 kg/die 2,095 mmof 5.41,2Immeasurable

Polymers fundamentals 1-3 are used in the following examples of mixing.

Examples of comparative polymers fundamentals 4-8

Polymer basics 4Polymer basics 5Polymer basics 6
The basic monomerMMAMMAMMA
% (wt./wt.)9998,595
The second monomerEAEAEA
% (wt./wt.)11,55
Mw (in thousands of daltons)909090
Mn (in thousands of daltons)454545
Product formCompositionCompositionComposition
Tg° (C) according to the method of DSCto 100.498,592,8
MFI (g/10 min at 230°C/3,8 kg/extrusion what I head 2,095 mm 3,64,36,0

Polymer basics 7Polymer basics 8
The basic monomerMMAMMA
% (wt./wt.)9086
The second monomerEAEA
% (wt./wt.)1014
Mw (in thousands of daltons)8890
Mn (in thousands of daltons)4145
Product formCompositionComposition
Tg° (C) according to the method of HDT 82,875,9
MFI (g/10 min at 230°C/3,8 kg/die 2,095 mm15,527,0

Part 9Part 10Part 11
Polymer basics111
Part959085
Polymer basics333
Part51015
Polymer basics---
Part---
Mw (in thousands of daltons) 85,082,577,4
Mn (in thousands of daltons)32,831,929,1
Product formCompositionCompositionComposition
Tg° (C) according to the method of DSC106,1104,2102,4
MFI (g/10 min at 230°C/3,8 kg/die 2,095 mm6,17,48,5
CommentsThe composition obtained from the dual of a mixture of polymers fundamentals (1 and 3)The composition obtained from the dual of a mixture of polymers fundamentals (1 and 3)The composition obtained from the dual of a mixture of polymers fundamentals (1 and 3)

12Composition 13Composition 14
Polymer basics12 2
Part505033
Polymer basics331
Part505034
Polymer basics--3
Part--33
Mw
(in thousands of daltons)
68,383,998,0
Mn
(in thousands of daltons)
22,921,130,4
Product formCompositionCompositionComposition
Tg° (C) according to the method of DSC105,1100,7104,7
MFI (g/10 min at 230°C/3,8 kg/extrusion th the transportation 2,095 mm 32,5119,811,53
CommentsThe composition obtained from the dual of a mixture of polymers fundamentals (1 and 3)The composition obtained from the dual of a mixture of polymers fundamentals (2 and 3)The composition obtained from the dual of a mixture of polymers fundamentals (1, 2 and 3)

15Part 16Part 17
Polymer basics222
Part206090
Polymer basics113
Part602010
Polymer basics33-
Part 2020-
Mw (in thousands of daltons)82,397,2115,6
Mn (in thousands of daltons)24,026,336,8
Product formCompositionCompositionComposition
Tg° (C) according to the method of DSC103,9104,8104,3
MFI (g/10 min at 230°C/3,8 kg/die 2,095 mm9,144,351,82
CommentsThe composition obtained from ternary mixtures of polymers fundamentals (1, 2 and 3)The composition obtained from ternary mixtures of polymers fundamentals (1, 2 and 3)The composition obtained from ternary mixtures of polymers fundamentals (2 and 3)

The polymer compositions of examples 9-17 are double or triple mixture of polymers fundamentals 1-3 and ensure the achievement of improved melt flow no matter what inogo reduce the glass transition temperature (as measured by the method DSC).

18Part 19
Polymer basics11
Part6054
Polymer basics-3
Part-6
The impact resistance modifierYesYes
Part4040
Mw (in thousands of daltons)9090
Mn (in thousands of daltons)4141
Product form CompositionComposition
Tg° (C) according to the method of HDT67,368,0
MFI (g/10 min at 230°C/3,8 kg/die 2,095 mm0,891,11
CommentsThe composition obtained from the dual of a mixture of polymer bases 1 and impact resistance modifierThe composition obtained from ternary mixtures of polymers fundamentals 1 and 3 and of the impact resistance modifier

The polymer composition from example 19 are shockproof dual blend of polymers fundamentals 1 and 3 and ensure the achievement of improved melt flow without a significant reduction in the glass transition temperature (as measured by the method DSC) in comparison with example 18.

Measured values of MFI and Tg data for the examples and the results are shown in figure 4. As you can see, the level of Tg for mixed polymers with high/low value of MM is significantly greater than the corresponding characteristic of the copolymers with a corresponding improvement of the MFI.

Figure 4: Graph of dependencies MFI Tg for polymers, perejil is the R in the above examples. The values of Tg were measured by the methods DSK or HDT (see the examples for more details).

Attention is drawn to all articles and documents associated with this application that have been submitted simultaneously with this description, or before him and which are publicly available together with the description of the invention, and the contents of all such papers and documents by reference is incorporated herein.

All the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all steps of any method or process disclosed in this way can be combined in any combination, except combinations where at least some of such features and/or stages are mutually exclusive.

Each characteristic disclosed in this specification (including any accompanying claims, abstract and drawings)may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly will not be declared another. Thus, unless explicitly will not be declared to each other and the open sign will represent only one example of x the characteristic series of equivalent or similar features.

The invention is not limited to the details of the above options (option) implementation. The invention extends to any new one or any combination of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any one or any combination of the steps of any method or process disclosed in this way.

1. Acrylic polymer composition for molding or extruding, representing an acrylic polymer composition essentially containing no modifier impact resistance, containing a mixture of molten thermoplastic high molecular weight acrylic material (WMAM) and low molecular weight thermoplastic acrylic material (NMAM), while at least 70 wt.%, when calculating the total mass of WMAM mentioned VMEM is (co)polymer based on alkyl(ALK)acrylate, and mentioned (co)polymer contains at least 80 wt.% the first polymer derived from monomer units C1-C12alkyl (C1-C8ALK) acrylate, and optionally up to 20 wt.%, when calculating the above mentioned (co)polymer based on alkyl(ALK)acrylate, the first copolymer obtained from the monomer unit C1-C12alkyl(C0-C8ALK)acrylate and/or (C0C 8ALK)acrylic acid, these WMAM characterized by a mass-average molecular weight in the range from 40000 daltons to 1,000,000 daltons, and at least 70 wt.%, when calculating the total mass of NMAM mentioned NMAM is (co)polymer based on alkyl(ALK)acrylate, and mentioned (co)polymer contains at least 80 wt.% the second polymer obtained from the monomer unit C1-C12alkyl (C1-C8ALK) acrylate, and optionally up to 20 wt.% when calculating the above mentioned (co)polymer based on alkyl(ALK)acrylate, the second copolymer obtained from the monomer unit C1-C12alkyl(C0-C8ALK)acrylate and/or (C0-C8ALK) acrylic acid, these NMAM characterized by a mass-average molecular weight in the range from 11,000 daltons to 250,000 daltons, with the proviso that WMAM characterized by magnitude, Mw, of greater than Mw at NMAM, where the first polymer VMM and the second polymer NMAM constitute one and the same.

2. The composition according to claim 1, where the first copolymer and the second copolymer are one and the same.

3. The composition according to claim 1, where the mass ratio of the first polymer, the first copolymer is a value within ±30% of the ratio of amounts of the second polymer, the second copolymer.

4. The composition according to claim 1, where the mass of zootoxin the s VMEM: NMAM in the composition exceeds 1:1.

5. The composition according to claim 1 where the acrylic polymer composition comprises, based on the weight of the acrylic polymeric composition, up to 55 wt.% NMAM and at least 40 wt.% VMEM.

6. The composition according to claim 1, where the mixture in the melt is homogeneous blends in the melt.

7. The composition according to claim 1, where the composition optionally includes a second or additional component VMEM (defined the same way as the first VMM), which is characterized by a mass-average molecular mass greater than the mass-average molecular mass of NMAM, but which is greater or lesser than the mass-average molecular weight of the other component (component) VMEM.

8. The composition according to claim 7, where the second or additional component is present with the level of content, when calculating the amount of acrylic polymer composition, is equal to at least 5 wt.%.

9. The composition according to claim 7 or 12, where the second or additional VMM characterized by a mass-average molecular weight (Mw)less than the mass-average molecular weight of the first component VMEM.

10. The composition according to claim 7, where the first polymer VMEM and third or more second polymer or additional VMM constitute one and the same.

11. The composition according to claim 7, where the first copolymer and the third copolymer constitute one and the same.

12. Composition p is 7, where the ratio between the amounts of the first polymer, the first copolymer is a value within ±30% from the ratio of the amounts of the third polymer, the third copolymer.

13. The composition according to claim 1 or 7, where VMM, including second or additional component WMAM if any, is present, based on the total weight of the acrylic polymer composition, with the level of content that goes up to 99% (wt./wt.).

14. The composition according to claim 1 or 7, where NMM is present, based on the total weight of the acrylic polymeric composition with a content equal to at least 1 wt.%.

15. The composition according to claim 1 or 7, where the ratio of the amounts of VMEM: NMAM is at least 6:5.

16. The composition according to claim 1 or 7, where VMEM and NMAM together comprise essentially 100 wt.% derived from the acrylic monomer components of the acrylic polymer composition.

17. The composition according to claim 1 or 7, where VMEM and NMAM unite to obtain essentially 100 wt.% acrylic polymer composition.

18. The composition according to claim 1 or 7, where the remaining portion of the acrylic polymer composition comprises suitable for use additives.

19. Acrylic composition containing
a) acrylic polymer composition according to any one of claims 1 to 18; and
b) suitable for use with solvent.

20. Acrylic composition according to claim 19, where the ratio (wt./wt.) rest ritel (b): polymer (a) is in the range from 10:90 to 60:40.

21. The method of obtaining the acrylic resin composition according to any one of claims 1 to 18, which includes stages
a) introducing a thermoplastic high molecular weight acrylic material (UMAM) in contact with thermoplastic low molecular weight acrylic material (NMAM); and
b) mixing the said VMM and NMAM at an elevated temperature until obtaining a mixture in the melt;
where mentioned elevated temperature exceeds the glass transition temperature as VMM and NMM.

22. The use of acrylic polymer composition according to any one of claims 1 to 18 to get mixed in the melt composition with increased index value melt flow MFI (in comparison with VMEM, not mixed with NMAM).

23. The application of the acrylic composition according to any one of claims 1 to 18 to get mixed in the melt composition with a high value of glass transition temperature Tg.

24. The use of acrylic polymer composition according to any one of claims 1 to 18 for receiving the molded polymer product.

25. Impact-resistant acrylic polymer composition containing
a) the polymer base, the corresponding acrylic polymeric composition according to claims 1 to 18; and
b) an impact resistance modifier with the structure of "core-shell".

26. Impact-resistant acrylic polymer composition according A.25, where the ratio (wt./wt.) (a):(b) is in the range from 30:70 to 90:10.

27. The use of songs by l is the Boma one of claims 1 to 18, 19, 20, or 25, 26 in the ways of forming products with a thick cross section and demolding.

28. Molded product with a thick cross-section of the composition according to any one of claims 1 to 18, 19, 20, or 25, 26.

29. Molded polymer product containing acrylic polymer composition according to any one of claims 1 to 18, 19, 20, or 25, 26.

30. The method of mixing in the melt to produce impact-resistant acrylic resin composition according PP, 26, which includes stages
mixing in the melt of the following individual components on a single stage mixing in the melt:
1a) BMAM as he described in claim 1;
1b) HMAM as he described in claim 1; and
1C) of the impact resistance modifier with the structure of "core-shell"; or
2A) BMAM as he described in claim 1; and
2b) HMAM as he described in claim 1, a pre-mixed with the impact resistance modifier with the structure of "core-shell"; or
3A) BMAM and HMAM, mixed according to claim 1; and
3b) of the impact resistance modifier with the structure of "core-shell".

31. The use of a composition according to any one of claims 1 to 18, 19, 20, or 25, 26 as a composition for reducing the duration of the molding cycle of the product.

32. The use of a composition according to any one of claims 1 to 18, 19, 20, or 25, 26 as compositions with reduced duration of the cooling cycle in the formation of the product.

33. Composition with a reduced cycle time of molding articles containing com is ositio according to any one of claims 1 to 18, 19, 20, or 25, 26.

34. Composition with reduced duration of the cooling cycle in the formation of the product containing the composition according to any one of claims 1 to 18, 19, 20, or 25, 26.

35. A method of reducing the duration of the molding cycle for molding compositions, comprising a stage of injection molding or extrusion molding composition according to any one of claims 1 to 18, 19, 20, or 25, 26.

36. A method of reducing the duration of the cooling cycle molding for molding compositions, comprising a stage of injection molding or extrusion molding composition according to any one of claims 1 to 18, 19, 20, or 25, 26.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention concerns curable thermoplastic elastomer mixes, their obtaining and application in production of items by cast or extrusion moulding. Curable thermoplastic elastomer mix includes: (a) 15 to 60 wt % of polymer or copolymer represented by complex polyalkylenephthalate polyether, and (b) 40 to 85 wt % of linked poly(met)acrylate or polyethylene/(met)acrylate curing resin combined with free radical peroxide initiation agent and organic diene co-agent in effective amount for linking the resin during extrusion or cast moulding of curable thermoplastic elastomer mix. After linkage the polymer or copolymer represented by complex polyalkylenephthalate polyether is present in the form of continuous phase, while the resin is present in dispersed phase. Such compositions are fit for production of rubber parts with excellent resistance to effect of oil lubricants and greases.

EFFECT: optimised residual compression deformation and Shore hardness, increased elastic constant during curing.

12 cl, 3 dwg, 2 tbl, 22 ex

FIELD: copolymers meant for usage in polymer binding agents for covers prone to swelling during heating.

SUBSTANCE: copolymer is described for usage in binding agent or as polymer binding agent in covers prone to swelling during heating, including a mixture of Newton copolymer and network copolymer, selected from a group including thixotropic and pseudo-plastic copolymers, while aforementioned Newton and network copolymers consist of links of substituted styrene and substituted acrylate and contain links of at least p-methylstyrene and 2-ethylhexylacrylate, with grammolecule ratio of p-methylstyrene and 2-ethylhexylacrylate ranging from 100/0 to 50/50. Also described is the cover prone to swelling during heating and method for producing the same, which cover includes polymer binding agent, foam-forming substances, carbon-forming substances and other normally used admixtures, featuring aforementioned copolymer as polymer binding agent.

EFFECT: optimized creation of coal and improved isolating properties of cover.

3 cl, 2 tbl, 8 dwg, 4 ex

FIELD: polymer materials.

SUBSTANCE: invention concerns amorphous light-sensitive cross-linked polymeric structure and provides structure including (i) amorphous cross-linked structure formed from matrix based on acrylate and/or methacrylate compound and cross-linking agent and (ii) photoreactive component capable of undergoing reversible photodimerization reaction. Cross-linked structures are characterized by good properties with shape-memory effect.

EFFECT: increased mechanical strength of material with desired property profile.

21 cl, 4 dwg, 2 tbl, 12 ex

The invention relates to ionomer polymer mixture, in particular the partially crosslinked thermoplastic and elastomeric polyolefin blends having a low hardness
The invention relates to dispersible in water material, which can be used as wipes

The invention relates to a composition for the manufacture of materials such as artificial leather, in particular, for the impregnation of textile bases in the production of fancy material

FIELD: polymer materials.

SUBSTANCE: invention concerns amorphous light-sensitive cross-linked polymeric structure and provides structure including (i) amorphous cross-linked structure formed from matrix based on acrylate and/or methacrylate compound and cross-linking agent and (ii) photoreactive component capable of undergoing reversible photodimerization reaction. Cross-linked structures are characterized by good properties with shape-memory effect.

EFFECT: increased mechanical strength of material with desired property profile.

21 cl, 4 dwg, 2 tbl, 12 ex

FIELD: copolymers meant for usage in polymer binding agents for covers prone to swelling during heating.

SUBSTANCE: copolymer is described for usage in binding agent or as polymer binding agent in covers prone to swelling during heating, including a mixture of Newton copolymer and network copolymer, selected from a group including thixotropic and pseudo-plastic copolymers, while aforementioned Newton and network copolymers consist of links of substituted styrene and substituted acrylate and contain links of at least p-methylstyrene and 2-ethylhexylacrylate, with grammolecule ratio of p-methylstyrene and 2-ethylhexylacrylate ranging from 100/0 to 50/50. Also described is the cover prone to swelling during heating and method for producing the same, which cover includes polymer binding agent, foam-forming substances, carbon-forming substances and other normally used admixtures, featuring aforementioned copolymer as polymer binding agent.

EFFECT: optimized creation of coal and improved isolating properties of cover.

3 cl, 2 tbl, 8 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention concerns curable thermoplastic elastomer mixes, their obtaining and application in production of items by cast or extrusion moulding. Curable thermoplastic elastomer mix includes: (a) 15 to 60 wt % of polymer or copolymer represented by complex polyalkylenephthalate polyether, and (b) 40 to 85 wt % of linked poly(met)acrylate or polyethylene/(met)acrylate curing resin combined with free radical peroxide initiation agent and organic diene co-agent in effective amount for linking the resin during extrusion or cast moulding of curable thermoplastic elastomer mix. After linkage the polymer or copolymer represented by complex polyalkylenephthalate polyether is present in the form of continuous phase, while the resin is present in dispersed phase. Such compositions are fit for production of rubber parts with excellent resistance to effect of oil lubricants and greases.

EFFECT: optimised residual compression deformation and Shore hardness, increased elastic constant during curing.

12 cl, 3 dwg, 2 tbl, 22 ex

Acrylic mixtures // 2418828

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of low molecular and high molecular acrylic polymers. The invention discloses an acrylic polymer composition for moulding or extrusion, which contains a mixture in molten thermoplastic high molecular acrylic material (HMAM) and thermoplastic low molecular acrylic material (LMAM). An alkyl(alk)acrylate based (co)polymer accounts for at least 70 wt % of the HMAM and LMAM. The HMAM is characterised by average molecular weight (Mw) between 40000 Da and 1000000 Da, and the LMAM is characterised by Mw ranging from molecular weight of entwinement (Me) (expressed in thousand daltons) to 250000 Da.The invention also discloses a method of preparing an acrylic polymer composition, versions of using and processing the acrylic polymer composition, as well as products made from said composition.

EFFECT: obtaining acrylic polymer compositions with improved processability.

36 cl, 4 dwg, 19 ex

Laminate // 2428315

FIELD: process engineering.

SUBSTANCE: invention relates to laminate used in glass panels, lenses etc. Proposed laminate comprises base made up of polycarbonate resin, first layer resulted from hardening acrylic resin hardening, second layer produced by thermal hardening of organosiloxane resin. Acrylic resin composition comprises (A) acrylic copolymer containing at least 70 mol % of repeating link of formula (A)

,

where X is hydrogen or methyl, Y is methyl, ethyl, cycloalkyl or hydroxyalkyl with the number of atoms of 2 to 5, or residue of UV radiation absorber based on triazine; blocked polyisocyanate compound; hardening catalyst; and (D) UV radiation absorber based on triazine. Note here that total content of UV radiation absorber based on triazine in formula (A) and as component (D) varies from 1 to 40 wt %. Composition of organosiloxane resin in proposed laminate comprises (E) colloidal silicon dioxide and (F) hydrolytic condensate of alkoxy silane. Invention covers also window glass made based on said laminate.

EFFECT: higher strength and longer life.

25 cl, 15 tbl, 50 ex

FIELD: physics.

SUBSTANCE: disclosed is use of a) polyalkyl(meth)acrylate and b) a compound of formula (I), wherein residues R1 and R2 independently denote an alkyl or cycloalkyl with 1-20 carbon atoms, to make solar cell modules, primarily for making light concentrators of solar cell modules. (I). Also disclosed is a solar cell module and a version of said module. The solar cell module has operating temperature of 80°C or higher; full light transmission of moulding compounds in the wavelength range from 400 to 500 nm is preferably at least 90%; full light transmission of moulding compounds in the wavelength range from 500 to 1000 nm is preferably at least 80%.

EFFECT: improved properties of the module.

16 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer obtained via condensation polymerisation. The polymer is obtained from at least two monomers: acrylic monomer and alkylamine. Said polymer is modified such that it contains a dithiocarbamate salt group capable of cleaning one or more compositions containing one or more metals. The polymer has molecular weight of 500-200000.

EFFECT: obtaining polymers for various media as means of purification from metals, including waste water systems.

13 cl, 5 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: described is use of a composition containing a polymer obtained from at least two monomers: acryl-x and alkylamine, where said polymer is modified such that it contains more than 55 mol % dithiocarbamic acid, capable of purifying one or more compositions containing one or more of the described metals.

EFFECT: polymers have multiple applications in different media, including sewage treatment systems.

12 cl, 1 dwg, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a composition for making articles. Composition contains at least one polyaromatic polyamide and at least one cross-linked polyolefin. Cross-linked polyolefin is obtained from at least one product (A) containing unsaturated epoxide, and at least one product (B) containing unsaturated carboxylic acid anhydride. According to invention, weight content of (A) and (B), designated respectively as [A] and [B], are such that ratio [B]/[A] varies from 3 to 14, preferably from 4 to 9. Invention also describes a method of producing a composition and use thereof for making a single-layer or multilayer structure.

EFFECT: technical result is smooth and glossy surface products, in particular, pipes, with very small amount or even complete absence of "adapter saliva".

34 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a composition for making articles containing, wt%: from 33 to 40 at least one cross-linked polyolefin, where polyolefin is obtained from at least one product (A) containing unsaturated epoxide, and at least one product (B), including unsaturated carboxylic acid anhydride, and from 3 to 10 at least one plasticiser, and remaining part consisting of at least one polyaromatic polyamide. Weight content of (A) and (B), designated as [A | and [B] is such that ratio [B]/[A | ranges from 3 to 14. Described also is a method for preparing composition, as well as use thereof.

EFFECT: technical result is providing compositions for making articles having heat resistance, ageing resistance, Charpy impact strength at -40 °C higher than or equal to 7 kJ/m, modulus of elasticity in flexure less than 800 MPa, combined with uniform or smooth appearance of surface.

39 cl, 2 tbl, 1 ex

Up!