Thermoplastic gel composition transformed in thermoactive gel under action of radiation

FIELD: chemistry.

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

 

Reference to related applications

This Application claims the priority filing date of March 25, 2004, provisional patent Application U.S., with registration number 60/556448.

The technical field

The present invention relates to gel compositions. In particular, the present invention relates to gel compositions for the manufacture of products such as candles, air fresheners, sealing parts (gaskets), elastic pads, mattresses, pillows and the like.

Prior art

Gel compositions are widely known in the art, is also known about their use in the manufacture of various kinds of products. For the purposes of the present invention the gel is firm and elastic material. The gels used for the manufacture of products such as transparent oil gel candles, if used in combination with oil, or air fresheners, if combined with a volatile solvent and aromatic substance. Another example of the use of such gels is the creation of soft products, such as sealing gaskets, elastic lining and toys.

In the patent US 5879694 disclosed a transparent gel candle containing hydrocarbon oil and one or more than one tribocorrosion, radial block copolymers or multiblock copolymer of thermoelastomer the and. Because the gels of this type are thermoplastic, they have a low viscosity at the temperature of the melt and, consequently, they are easy to mix and to give them the appearance of a product. However, one of the problems with the use of gels is that, despite good performance when used at room temperature, they can soften and deform or even be spread when heated. This drawback can be costly if the gel is thermoplastic at temperatures that are created, for example, in a cargo container on a hot day or in the engine compartment of the vehicle. For the manufacture of such products, it would be advisable to use gels, is not deformed and is not spreading at temperatures just above room temperature.

It would also be helpful in the manufacture of products such as gel candles, air fresheners, sealing gaskets, elastic lining (such as Bicycle tires, cushions for chairs and sofas and the like), mattresses, pillows and the like, to maintain ease of processing thermoplastic gel, but to improve the material so that it is not deformed or not flowed at elevated temperatures.

The invention

According to one aspect of the present invention is a thermo is plasticheskuyu gel composition, converted to thermosetting gel composition by ionizing or non-ionizing radiation, with thermoplastic gel composition comprises: (a) from about 40 to 5 wt.% stitched blockcopolymer selected from the group consisting of hydrogenated and negidrirovannah styrene/diene block copolymers and EPDM/diene copolymers; (b) from about 60 to 90 wt.% component selected from the group consisting of oils for filling, plasticizers and solvents; and (C) from about 1 to 20 wt.% at least one cross-linking agent selected from the group consisting of bifunctional or multifunctional acrylate or methacrylate monomers and vinyl ethers; (d) from 0 to about 10 wt.% expanding microspheres; and (e) from 0 to about 3.0 wt.% photoinitiator; where the total number of all components is 100 wt.%, and component (b) is compatible with stitched by blockcopolymers and liquid at room temperature.

According to another aspect of the present invention relates to a thermosetting product, which is a product made from thermoplastic gel composition, which is converted into thermosetting gel composition under the influence of ionizing or non-ionizing radiation, with termoplastic the Skye gel composition comprises: (a) from about 40 to 5 wt.% stitched blockcopolymer, selected from the group consisting of hydrogenated and negidrirovannah styrene/diene block copolymers and EPDM/diene copolymers; (b) from about 60 to 90 wt.% component selected from the group consisting of oils for filling, plasticizers and solvents; and (C) from about 1 to 20 wt.% at least one cross-linking agent selected from the group consisting of bifunctional or multifunctional acrylate or methacrylate monomers and vinyl ethers; (d) from 0 to about 10 wt.% expanding microspheres; and (e) from 0 to about 3.0 wt.% photoinitiator; where the total number of all components is 100 wt.%, and component (b) is compatible with stitched by blockcopolymers and liquid at room temperature.

According to another aspect of the present invention relates to a method of manufacturing a thermosetting product, in which thermoplastic product is exposed to ultraviolet radiation or electron beam radiation for a time and under conditions sufficient to convert thermoplastic products in thermosetting product, and the specified thermoplastic product is made from a thermoplastic gel composition, which can be converted to thermosetting gel composition under the influence of ioniziruushei is about, or non-ionizing radiation, and thermoplastic gel composition comprises: (a) from about 40 to 5 wt.% stitched blockcopolymer selected from the group consisting of hydrogenated and negidrirovannah styrene/diene block copolymers and EPDM/diene copolymers; (b) from about 60 to 90 wt.% component selected from the group consisting of oils for filling, plasticizers and solvents; and (C) from about 1 to 20 wt.% at least one cross-linking agent selected from the group consisting of bifunctional or multifunctional acrylate or methacrylate monomers and vinyl ethers; (d) from 0 to about 10 wt.% expanding microspheres; and (e) from 0 to about 3.0 wt.% photoinitiator; where the total number of all components is 100 wt.%, and component (b) is compatible with stitched by blockcopolymers and liquid at room temperature.

Information confirming the possibility of carrying out the invention

COMPONENT (a)

The present invention relates to thermoplastic gel composition which when exposed to ionizing or non-ionizing radiation can be converted to thermosetting gel composition. The composition of the present invention includes from about 40 to 5 wt.%, preferably approximately from 20 to 10 wt.%, stitched blockcopolymer you the security of a group, consisting of a selectively hydrogenated and negidrirovannah styrene/diene block copolymers and EPDM/diene copolymers. Used block copolymers can be linear triblock or multiplexability or multibeam or star-shaped symmetric or asymmetric copolymers. Can also be used diplomaprimary and mixtures of copolymers, such as a mixture of tribocorrosion with diplokaryon.

According to one implementation of block copolymers include digidrirovannye styrene-butadiene block copolymers having the General formula:

where S is a styrene polymer block, means butadiene polymer block having a content of 1,2 - vinyl groups ranging from 10 to 80 mol.%, Y is the residue of a coupling agent, x is an integer from 2 to 20, y is an integer from 0 to 20, the sum (x+y) is from 2 to 30. Preferably, the value of x was from 2 to 12, most preferably 2, and the value of y was from 0 to 12, most preferably 2. Such copolymers are disclosed in US patent 5777039, which is included in this description by reference. The actual molecular weight of the copolymers according to this variant of implementation will vary depending on the use end of the group,but may lie in the range from about 30 to 1000 kg/mol and preferably in the range of about 40 to 250 kg/mol and more preferably in the range from approximately 50 to 150 kg/mol. The term "actual molecular weight" in this context refers to the molecular weight, determined by the peak in the GPC chromatogram in kg/mol.

In blockcopolymer formula (I) styrene content preferably ranges from about 10 to 40 wt.%, more preferably from about 15 to 30 wt.%. Block copolymers of the formula (I) can be obtained by any known method, including a well-known method full sequential polymerization, optionally in combination with re-initiation, and method combination, as described, for example, in patent documents US 3231635, US 3251905, US 3390207, US 3598887, US 4219627, EP-A-0387671, EP-A-0636654 and WO 04/22931, which are included in this description by reference. Binding agents that can be used in the preparation of the copolymers according to the present implementation of the invention by a method combinations are, for example, dibromethane, silicon tetrachloride, diethylacetal, divinylbenzene, clear, methyldichlorosilane, although there may be other binding agents. This method of obtaining it is preferable to use binders that do not contain halogen, such as gamma glycidoxypropyltrimethoxysilane or diglycidyl ether of bisphenol A.

When using block copolymers of the formula (I) for the preparation of thermoplastic oil compo the way of the present invention, containing an expanding microspheres in the composition, it is preferable to add an additional polymer (hydrogenated block copolymers, is not cured under the action of UV radiation). Preferably, this additional polymer was a hydrogenated block copolymers, hydrogenated, at least 90% (hydrogenated polymer in which at least 90% 1,3-butadiene gidrirovanie with obtaining copolymers containing ethylene/butylene blocks, or block copolymers in which at least 90% of isoprene gidrirovanie with obtaining copolymers containing ethylene/propylene blocks). Preferably, these hydrogenated copolymers had a styrene content from about 5 to 40%, more preferably from about 15%to 30%. Examples of such polymers include, but are not limited to the above list, the polymers with the General structure that contains at least one polystyrene block and at least one hydrogenated polybutadiene block, hydrogenated branch, Rubezhnoe, Ukraine block or hydrogenated mixed block of polybutadiene and polyisoprene. Preferred commercially available block copolymers that can be used in the present invention together with blockcopolymers formula (I)include, but are not limited to the above list, polymers KRATON®, such as RATON® G1652, KRATON® G1726 or KRATON® G1657. When using blockcopolymer formula (I) together with gidrirovanny blockcopolymers they are preferably used in a ratio of from 3:1 to 1:3 (block copolymers of formula (1):hydrogenated block copolymers), so that the final quantity of the component (a) ranged from 5 to 40 wt.% from thermoplastic gel composition. According to a preferred variant of the invention, the ratio is from 2:1 to 1:2, most preferably 1:1.

According to another variant embodiment of the invention the copolymers selectively gidrirovanny and chosen from:

or

or

where a represents an aromatic hydrocarbon block having a molecular weight of from 4,000 to 30,000, HD is a hydrogenated conjugated diene block having a molecular weight of from 10000 to 100000, Y is a multifunctional linking agent, UD is a conjugated diene block having a molecular weight of from 1000 to 80000, or conjugated diene block having a molecular weight of from 1000 to 80000, partially hydrogenated, x is an integer from 1 to 20, y is 0 or 1, z is an integer from 1 to 20, and in formulas (II) and (III) the sum of (x+z) is from 2 to 30. Such copolymers are disclosed in US patent 5486574, which included the n in this description by reference.

In formulas (II), (III) and (IV) the blocks are polymer blocks of the vinyl aromatic hydrocarbon. Preferably, the vinyl aromatic hydrocarbon was styrene. Other useful vinyl aromatic hydrocarbons include, but are not limited to list, alpha methylsterol, various alkyl substituted styrene, alkoxy-substituted styrene, vinylnaphthalene, vinyltoluene and the like. Blocks HD and UD are polymer blocks of conjugated dienes. The preferred diene blocks HD is butadiene. For blocks UD preferred isoprene. Can also be used and other dieny, including but not limited to the above list, piperylene, methyl pentadiene, phenylbutazon, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like, are preferred conjugate diene containing from 4 to 8 carbon atoms. Preferably, the conjugated diene used in the block HD, differed from the conjugated diene used in the unit UD, especially in ease of selective hydrogenation.

Preferably, the diene in the block HD was gidrirovaniya faster and more completely than the diene in the block UD. As noted above, the block UD can be digidrirovanny or partially gidrirovanny. If the block UD partially gidrirovanny, the degree of hydrogenation of unsaturated (UD) blocks after the reaction can article shall be such what blocks UD will be up to 90% saturated, then there will be at least 10% unsaturated (unsaturated). Preferably, at least 50%, more preferably from 50 to 90% of the original unsaturation of the diene was preserved in blocks UD after partial hydrogenation. Generally, the increase of residual unsaturation viscosity of melts of such polymers is reduced.

As broadly described in the prior art, A-HD-rays or blocks can be gidrirovanny preferably, therefore, to have recovered at least 90% of the olefinic double bonds in the polymer chains. Accordingly, And in-HD-rays gidrirovanny at least 50%, preferably at least 70% and more preferably at least 90%, most preferably at least 95% of the original olefinic unsaturated bonds.

Preferably, in this invention were used dieny, which is mainly amorphous when used temperatures (typically from 10 to 40°C) and does not contain excessive amounts of crystalline forms, preventing elasticity. In the case of butadiene, for example, it is preferable that the percentage of 1,2-supplements ranged from 30 to 80% to prevent excessive crystallinity after hydrogenation to ethylene-butylene (EB) rubber.

Especially preferred option ASU is estline of the present invention is a thermoplastic oil composition, in which the copolymers are selected from:

or

or

where S is a polystyrene block, S is a block of polybutadiene polymer [poly(ethylene/butylene) block], the content of 1,2-vinyl butadiene polymer block prior to hydrogenation is from 30 to 80 mol.%, I branch, Rubezhnoe, Ukraine is a polymer block or partially gidrirovanny branch, Rubezhnoe, Ukraine polymer block Y is a residue of a coupling agent, x is an integer from 1 to 20, preferably from 2 to 12, y is 0 or 1, z is an integer from 1 to 20, preferably from 2 to 12, and in formulas (V) and (VII) the sum of (x+z) is from 2 to 30. Even more preferred variant implementation of the present invention are those which make use of the copolymers of formula (V), (VI) or (VII)for which value of x equal to 2 and the value of z is equal to 2. Under this option, the hydrogenation of the polybutadiene block with the formation of poly(ethylene/butylene) block is carried out in conditions that are selective for the reaction of polybutadiene and, in fact, exclusive, largely or completely, the hydrogenation of the isoprene block.

The polymers of formulas (II) through (VII), in General, have the content of the block a (the content of polystyrene, if a represents styrene) before the crystals from 4 to 35%, preferably from 12 to 25%. Preferably, these polymers had molecular weight in the range from about 35,000 to 300000. Units And have a molecular weight ranging from 4000 to 20000. Blocks HD should have a molecular weight in the range from 10000 to 100000. Blocks UD should have a molecular weight ranging from 1000 to 80000.

Molecular weight linear polymers or individual line segments of polymers such as mono-, di-, triblock etc. rays of star-shaped polymers, before joining determined by gel permeation chromatography (GPC), where the GPC system is calibrated accordingly. In the case of anionic polymerized linear polymers the polymer, as a rule, monodispersion that, on the one hand, conveniently, and with another - quite clearly to describe molecular weight "peak" observed the exact molecular mass distribution. Molecular weight peak is typically the molecular weight of the main fragments detected using chromatograph. As the substances used in the GPC columns, the most widely used styrene-divinylbenzene gels or silica, which is a good environment. A good solvent for the polymers described here is tetrahydrofuran. May apply UV or refractive detectors.

The actual measurement is the molecular weight of the linked star polymer is not as effective or it is not so easy to perform using GPC. The reason is that star-shaped molecules do not share and do not suiryudan filled GPC-columns as it happens with linear polymers, used for calibration, and therefore, the output time determined by UV or refractive detectors unsuitable as an indicator of molecular weight. A good method is applicable for a star polymer is a measurement of the average molecular weight by light scattering. The sample is dissolved in a suitable solvent at a concentration of less than 1.0 g sample in 100 ml of solvent and filtered using syringe filters with porous membranes with pore size less than 0.5 microns, directly in the cell for light scattering. Measurement of light scattering performed as a function of scattering angle and the concentration of the polymer using standard techniques. Differential refractive index (DPP) of the sample measured at the same wavelength and in the same solvent that was used to light scattering. The above-described methods of analysis refers to the following reference material:

1. Modern Size-Exclusion Liquid Chromatography (Modern size-exclusion chromatography), W.W.Yau, J.J.Kirkland, D.D.Blu, John Wiley&Sons, New York, NY, 1979.

2. Light Scattering from Polumer Solution (the Scattering of light in the polymer solution). ..Huglin, ed., Academic Press, New York, NY, 1972.

3. W.Kaye and A.J.Havlik, Applied Optics, 12, 541 (1973).

4. M.L.McConnel, American Laboratory, 63, May, 1978.

The preferred method of producing copolymers of formulas (II) - (VII) of this implementation, essentially, is described in European patent application No. 0314256 included in this description by reference, although you may be used and any other known methods such as described in patent documents US 3231635, US 3251905, US 3390207, US 3598887, US 4219627, EP-A-0413294, EP-A-0387671, EP-A-0636654 and WO 04/22931 included in this description by reference. In European patent application No. 0314256 described two-step method of obtaining asymmetric radial polymers, to avoid problems of undesirable hoopalicious polymer. The method includes separately polymerization of monomers with the formation of separately two different types of rays. Then one of the polymer beams attached to a binder agent, and when this reaction joining ends to the binding agent attached to the second block polymer rays. This ensures that the resulting polymer will contain only a small number of comopolitan. For example, according to the present invention isoprene rays will anionic polymerized and is connected through the binding agent. Such negidrirovannah predecessors, there are stability issues that are common to polim the ditch with a high degree of unsaturation (for example, (SB)2-Y-I2)). The polymer was then hydronaut in the conditions in which preferably hereroense only politian A-HD-beam (or block), leaving politian UD-beam (or block), essentially unsaturated.

Usually, this method is used to obtain an asymmetric radial or star polymers with any polymer containing reactive end group which will react with one or more functional groups available in the selected binding agent. The method is particularly suitable for obtaining asymmetric radial polymers of the so-called "living" polymers containing one terminal metal ion. As is well known in the prior art, "living" polymers are polymers containing at least one active group, such as a metal atom bound directly to the carbon atom. "Living" polymers are easily derived by anionic polymerization. Since the present invention is particularly well suited for obtaining asymmetric radial polymers, using their education rays "living" polymers, the invention will be described on the basis of such polymers. However, it should be understood that the invention is equally suitable for polymers having different reactive groups, provided that the bonding agent contains a functional group, REAG the tank with the reaction center, present in the polymer.

Living polymers containing one terminal group, of course, well known. Methods of obtaining such polymers are described, for example, in U.S. patent No. 3150209, 3496154, 3498960, 4145298 and 4238202. Methods for obtaining block copolymers, such as those that are preferred for use in the method of the present invention, also described, for example, in U.S. patent No. 3231635, 3265765 and 3322856. These patents are included in this description by reference. If a living polymer product is statistical or tapered copolymer, the monomers are usually added at the same time, although more reactive monomer in some cases, it may be added slowly, while if the product is blockcopolymers, the monomers used for the formation of separate blocks, add sequentially.

Typically, the polymers used as beams in the asymmetric radial polymers of this invention can be obtained by the interaction of the monomer or monomers 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. the Most effective polymerization initiators are organic lithium compounds having the General formula RLi, where R represents aliphatic the ski, cycloaliphatic, alkyl substituted cycloaliphatic, aromatic or alkyl substituted aromatic hydrocarbon radical containing from 1 to 20 carbon atoms.

In most cases, the living polymers are used as beams in the asymmetric radial polymer will interact with a bonding agent at a temperature in the range from 0 to 100°C. and a pressure in the range from 0 to 7 bar, and the interaction will continue to until the reaction between the rays and the linking agent is not completed or is at least essentially not complete, usually within 1 to 180 minutes.

Usually living polymers used as beams in the asymmetric radial polymers of this invention interact with a bonding agent in the form of a solution. Acceptable solvents include the solvents used for polymerization of the polymer in the solution and include aliphatic, cycloaliphatic, alkyl substituted cycloaliphatic, aromatic and alkyl substituted aromatic hydrocarbons, ethers and mixtures thereof. Thus, suitable solvents include aliphatic hydrocarbons, such as butane, pentane, heptane and the like, cycloaliphatic hydrocarbons such as cyclohexane, cyclopentane, Cycloheptane and the like, alkyl substituted cycloaliphatic hydrocarbons, such is how methylcyclohexane, methylcycloheptane and the like, aromatic hydrocarbons such as benzene and alkyl substituted aromatic hydrocarbons such as toluene, xylene and the like, and ethers such as tetrahydrofuran, diethyl ether, di-n-butyl ether and the like. Since the polymers used in the preparation of the asymmetric radial polymers of this invention will contain one terminal reactive group, the polymers used for preparing asymmetric radial polymers, after cooking will be kept in solution without decontamination reactive (living) centre. Typically, a binding agent can be added to the polymer solution or the polymer solution can be added to the binder.

To obtain the asymmetric radial polymers of this invention can be any binding agents which are suitable as is known in the prior art for the formation of radial polymer by reaction with the living polymer. Acceptable binders will contain three or more functional groups capable of interacting with the living polymer of the metal-carbon. Since the method of the present invention leads to improved mutual distribution of the various rays in the asymmetric radial polymer containing any number of rays, which is about an effective, when the binder contains from three to about twenty functional groups that react with the linking metal-carbon "living" polymer. In this case, acceptable binding agents include Si4, RSiX3, HSi3X3Si-SiX3, R x2Si-(CH2)x-SiX2R, RX2Si(CH2)x-SiX2-(CH2)x-SiX2R, X3Si-(CH2)x-Si3, R-C(Si3)3, R-C(CH2Si3)3,

C(CH2Si3)4and the like, particularly compounds containing from three to six functional groups. In the above formulas each variable X can independently be fluorine, chlorine, bromine, iodine, alkoxide group, carboxylate group, hydride, and the like; R represents hydrocarbonous group containing from 1 to about 10 carbon atoms, preferably from 1 to about 6 carbon atoms; and x is an integer from 1 to about 6. The most useful binding agents include tetrachloride silicon, such as tetraploid silicon, silicon tetrachloride, tetrabromide silicon and the like, and bis(trihalo)silanes such as bis(trihalo)cililitan and hexachlorodisilane, where the halogen can be fluorine, chlorine, bromine or iodine.

The way of interaction in pure form in detail about the description in the patent US 4096203, included in this description by reference. This patent describes specific multifunctional linking agents, however, there are other binding agents, which can also be used here.

Star-shaped polymers are polymer compound of the rays using a polyfunctional coupling agent or a binder monomer. The preferred binding agent is palearkticheskii binding agent, such as described in U.S. patent No. 4010226, 4391949 and 4444953 included in this description by reference. Patent US 5104921 included in this description by reference, contains the complete description of such polyalkanoates compounds in columns 12 and 13. Preferred are divinecaroline hydrocarbons containing in the molecule up to 26 carbon atoms and, in particular, divinylbenzene, in the form of its meta - or para-isomer, as well as technical divinylbenzene, representing a mixture of these isomers, also quite meet the requirements. The binding agent is preferably added to the living polymer after polymerization is essentially completed. The amount of bonding agent varies within wide limits, but preferably at least one equivalent was used for each equivalent of associate nenas the seal of the living polymer. In most cases the reaction of the compound is carried out in the same conditions as the reaction of polymerization. The temperature varies in a wide range, for example, from 25 to 95°C.

Hydrogenation of the polymer such rays can be performed using a variety of traditional methods including hydrogenation in the presence of such catalysts as Raney Nickel, noble metals such as platinum, palladium and the like, and soluble catalysts of transition metals. Suitable for use are the ways according to which diesterase polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane, and hydronaut hydrogen in the presence of a soluble hydrogenation catalyst. Such methods are described in U.S. patent No. 3113986, 4226952 and reissued patent 27145 described in this description by reference. Polymers hydronaut so that the obtained hydrogenated polymer had a residual unsaturation content in Polivanova block HD less than approximately 20%, and preferably, if possible, about 0%, of their original unsaturation content prior to hydrogenation, at the same time to Polivanova part blocks UD contained at least 10% residual unsaturation, preferably at least 50%. When the hydrogenation takemore to be used titanium catalyst, such as disclosed in US patent 5039755.

COMPONENT (b)

Thermoplastic gel composition comprises from about 60 to 90 wt.% component selected from the group consisting of oils for filling, plasticizers and solvents. The choice of any of these oils for filling, plasticizers and solvents for use depends on the end use for which it is intended composition. For example, if the target application is a candle, it will use the butter for the filling. If the target application is a gasket or a toy, often used plasticizer. If the target application is the air freshener will be used volatile solvent and aromatic substance.

Oil filling used to create products of the present invention, preferably are hydrocarbon oils. The preferred oils for filling are white mineral oils, such as oil DRAKEOL®sold by the company Penreco, Karns City, PA, oil TUFFLO®sold by the company Citgo, Tulsa, OK. Also meet the technological paraffinic/naphthenic oils with low content of aromatic compounds, such as oil SHELLFLEX®manufactured by Shell, Houston, TX, and oil CALAOL®, manufactured by Calumet. Suitable synthetic oils, such as the Oli-alpha-olefin oils, polypropylene oil, polybutene oil and the like. Any oil for filling, compatible with the copolymers of the present invention, a liquid at room temperatures and is used for the production of the target product are known to those of ordinary skill in this field can be used according to the present invention.

For manufacturing products of the present invention can be used a number of plasticizers. Acceptable plasticizers can be synthetic esters, ethers or alcohols, as well as natural fats and oils. Such plasticizers include plasticizers JAYFLEX®, branched alkalemia esters, manufactured by Exxon company, Houston, TX, and BENZOFLEX®, esters of benzoic acid, manufactured by Velsicol, Rosemont, IL. A fairly complete list of acceptable plasticizers described in the publication of the patent US patent US Patent Application Publication 2002/0055562 A1. Any plasticizer that is compatible with the copolymers of the present invention, a liquid at room temperatures and is used for the production of the target product are known to those of ordinary skill in this field can be used according to the present invention.

In addition, in the manufacture of the products of the present invention can be used solvents. The choice of solvent also varies in the depending on the end use of the product. The solvent may function as a plasticizer, but preferably, it was a volatile compound, slowly evaporating from the gel and perform the same function as masking unpleasant odors or killing or repelling insects. The solvents used according to the present invention can also be volatile hydrocarbon solvents or oxygen-containing solvents, such as ethers or alcohols, slowly evaporating, and helps to release functional additives, such as repellent or flavoring. Any solvent that is compatible with the copolymers of the present invention, a liquid at room temperatures and is used for the production of the target product are known to those of ordinary skill in this field can be used according to the present invention.

As stated above, oil filling, plasticizers and solvents can be present in the gel composition of the present invention in amounts of from about 60 to 90 wt.%, preferably from about 80 to 90 wt.%.

COMPONENT (C)

Compositions of the present invention also include from about 1 to 20 wt.% at least one cross-linking agent selected from the group consisting of bifunctional or multifunctional acrylate or methacryloylamido, such as monomers, supplied by Sartomer company, Exton, PA, and vinyl esters, such as supplied by BASF, Mount Olive, NJ. The most preferred cross-linking agents for use according to the present invention are hexaniacinate and alkoxycarbonyl hexaniacinate.

COMPONENT (d)

In cases when you want to prepare gels with a lower density, to achieve this result may be added to another component of the present invention, the expansive microspheres, such as expanding microspheres EXPANCEL®, available from Akzo Nobel. In addition it is preferable that the data expanding microspheres contained in thermoplastic gel composition in the amount of approximately from 0.1 to 10 wt.%, preferably in quantities of from about 1 to 5 wt.%. Usually expanding microspheres consist of a polymer shell, inside of which is enclosed gas or volatile liquid. When heated, the gas inside the shell is an increase in pressure, resulting in a thermoplastic shell softens, causing a significant increase in the volume of the microspheres. At full extension the volume of the microspheres can be increased more than 40 times their original volume. The density of such polymeric microspheres to expand can l in order to reap in the range from 1.0 to 1.3 g/cm 3. Temperature expansion of such polymeric microspheres can vary from approximately 60 to 200°C. After the expansion, the density of the expanding microspheres falls to approximately 0.05 g/cm3. To prevent delamination of the upper part of the data expanded microspheres with a low density in the expansion process requires that the gel had integrity enough to prevent such delamination. Exfoliating microspheres inhibited by crosslinking of the gel polymers and crosslinking agents of the present invention.

COMPONENT (e)

If you need to convert thermoplastic compositions of the present invention in thermosetting composition under the influence of ultraviolet radiation in the composition should include photoinitiator in a concentration of from 0.1 to 3.0 wt.%. Used photoinitiator include:

- benzoic esters, such as benzoylmethylene ether and benzoylpropionic ether;

- substituted acetophenone and benzophenone, such as diethoxyacetophenone and DAROCURE™ BP sold by the company Ciba, Tarn/town, NY;

- benzyldimethylamine, such as IRGACURE® 651, sold by the company Ciba;

- alpha hydroxyketone, such as IRGACURE® 184, sold by the company Ciba;

and

bis-acylphosphatase, such as IRGACURE® 819, sold by the company Ciba.

For crosslinking of the compositions of the present invention when the hcpa is istii ultraviolet radiation is the most preferred photoinitiator type bis-allpotential.

Thermoplastic compositions of the present invention can be solidified under the influence of a number of sources of electromagnetic radiation. Can be used ionizing radiation, such as alpha, beta, gamma, x-ray and high-energy electrons, or non-ionizing radiation, such as ultraviolet radiation, visible radiation, infrared radiation, microwave radiation and radio frequency radiation. Preferred are the sources of electron beams, ultraviolet and visible radiation.

Electron beam equipment can be a high voltage type, in which the focused high-energy electron beams pass through a curing composition, or low-energy type, in which the flow of electrons passes through the hole of the cathode ray tube with a linear cathode, and the composition is held under the stream. Manufacturers of high voltage electron accelerators are High Voltage Engineering Corporation, Burlington, Mass. And Radiation Dynamics, Inc., Westbury, N.Y. To manufacturers of generators of low-energy electron beams are American International Technologies. Inc., Torrance, California; RPC Industries, Hayward, California; and Energy Sciences, Wilmington, Massachusetts.

The sources of UV light can also be high-intensity type, in which the used lamps in intervallet 200 to 300 watts/inch, or low-intensity type, in which the used lamps in the range from 5 to 20 watts/inch. The discharge is generated in the lamp by means of electrodes on one of the ends of the tubes or by means of microwave radiation, forming inside the lamp plasma. The material of the inner side of the lamp determines the wavelength of the electron emission lamp, while the lamp type can be selected so that the radiation emitted by the lamp, corresponded to the absorption characteristics of photoinitiator. High-intensity UV equipment there is, for example, in Fusion Systems Inc., Gaithersburg, MD. Low-intensity UV equipment there is, for example, Ultra-Violet Products, Los Angeles, CA.

In addition, using equipment of the same type as used to produce ultraviolet radiation, a simple application of lamps containing appropriate material, may be received radiation in the visible region. Can also be used in fluorescent lamps, tungsten halide lamps and lasers in the visible range.

In addition, the compositions of the present invention can contain up to 20 wt.% one or more auxiliary components selected from the group consisting of stabilizers, pigments, dyes, blowing agents, foaming agents, flavouring substances and substances to improve adhesiveness. With the according to the present invention can be any known additives, used in the manufacture of products using gels.

The components of thermoplastic compositions of the present invention can be combined and mixed with the formation of thermoplastic compositions in any way used for these purposes in the formation of thermoplastic gels. Typically, the components are mixed at a temperature high enough to ensure ease of mixing, and in the course of time, long enough for the formation of homogeneous composition, then the composition is cooled to room temperature, obtaining thermoplastic gel. If necessary, may be added the excess solvent, which is then removed by distillation at elevated temperature.

Thermoplastic compositions of the present invention can be produced by any method used for the manufacture of such products. Such methods include, but are not limited to the list, molding, casting, extrusion pressing, and the like.

Not wishing to be bound to any theory, however, suggest that crosslinking of the polymer by using a crosslinking agent transforms thermoplastic compositions of thermosetting composition. Once converted, thermosetting compositions of the present invention can be used when the comparator is on high temperatures without deformation or spreading, what makes these compositions are suitable for the stated applications, and other applications of gels, where such properties may be preferred.

EXAMPLES

The following examples are given to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be interpreted that way. If not specified, the number of mean mass parts or mass %.

For illustration of the invention used three polymer. Polymer a has the type described in patent US 5777039. Polymer a is a (S-B)2-Y-B2where S is a polystyrene-block - polybutadiene block with the content of 1,2 - vinyl 55%, a Y is the residue of a coupling agent. Polymers b and C are of the type described in the patent US 5486574. The polymer is a (S-EB)2Y(I)2where S is a polystyrene block, EB - almost completely hydrolyzed polybutadiene block with the content of 1,2 - vinyl 40%, I - partially hydrolyzed isoprene unit, and Y is the residue of a coupling agent. The polymer is a (I-S-EB)2-Y, where I, S, S have the same value as that of the polymer Century characteristics of the polymers are presented in Table 1.

Table 1
/td> Polymer AndThe polymer InThe polymer
The type of polymer(S-B)2-Y-B2(S-EB)2Y(I)2(I-S-EB)2-Y
Mass %
% S171820
%83
% S4644
% I3636
Molecular weight, kg/mol
Block S151010
Block In40
Block S2521
Block I2018
The efficiency of binding %909284
Viscosity @ 25%, SDR2000
Viscosity @ 20%, SDR5701300

Other ingredients used in the examples are defined as follows:

IngredientProviderDescription
KRATON G1652KRATONThe polymer of the form of S-EB-S, a polystyrene content of 30 wt.%
Drakeol 7PenrecoWhite mineral oil, 11 cSt @ 40°C
Irganox 1010CibaSterically hindered phenolic antioxidant
Irgacure 651CibaPhotoinitiator benzyldimethylamine type
Irgacure 819CibaPhotoinitiator bis-acylpolyamines type
SR238SartomerHexaniacinate crosslinking agent
CD560SartomerAlkoxycarbonyl hexaniacinate crosslinking agent
Expancel DU091/80Akzo NobelExpanding microspheres

Sample preparation: the Gels were mixed using a rotor/stator mixers Silverson at a temperature of 130°C. is First dissolved in the oil polymer and an antioxidant, stirring for about 1 hour. Then add photoinitiator and diacrylates Monomeric crosslinking agent and continued stirring for another 5 minutes before preparing samples for testing. Film thickness of about 0.6 cm were made by pouring approximately 60 g of gel on lined paper porcelain boat size 10×10 cm Candles with a diameter of approximately 3.3 cm and a height of 4.3 cm were made by pouring 60 ml of gel in a polypropylene Cup. Film and candles were removed from containers and irradiated on the device for irradiation of ULTRA-VIOLET PRODUCTS Model CL-1000, equipped with 5 UV lamp power 8 watts (F8T5BL 8W Black Light) for various time intervals from 30 seconds to 10 minutes. Some samples were subjected to fluorescent room lights for up to 1 week.

Testing: To assess the degree of crosslinking used three tests (although not all the tests were used for all samples).

Cross-linked gel: In this test a piece of film of gel thickness of 0.6 cm suspended in the vessel for 1 hour at a temperature of 100°C and measured the fraction of gel, slavyvshyesya on the bottom of the vessel. Originally stripe size 8,8×1.3 cm squeezed between the wooden spatula and suspended in the vessel. Later, the test was changed and the range of films with a diameter of 2.5 cm, mounted on 5-cell grid, was placed in the upper part of the vessel. If the gel was seamless, almost 100% of the gel melted and drops flowed into the vessel (cross-linked gel = 0%). If the gel was utverjdala across the thickness, it did not melt (cross-linked gel = 100%). It was found, especially when using IRGACURE 651, some gels had a drop of hardness; the side opposite the UV lamps are strongly utverzhdenii, and the reverse side has remained uncured.

Gel in toluene: In this test a piece of film of gel thickness of 0.6 cm was soaked in toluene overnight and qualitatively evaluated the appearance of the gel. If the sample was completely nessity is, gel in toluene was absent. If the sample was well utverzhdennym, gel swollen in toluene was neat, spongy, smooth appearance. If the gel there was a difference in hardness, the swollen gel was twisted, because the surface facing the lamps, was strongly utverzhdenii and, therefore, could only slightly swell, while the reverse side was overiden only slightly and, therefore, could swell all.

Deformation candles: In this test a candle with a diameter of 3.3 cm were placed in a chemical glass unexposed end up, the glass was placed in an oven for 1 hour at a temperature of 70°C, after which the deformation of the candles were evaluated as molten, strongly, weakly or undeformed. If the gel was uncured, candle melted and flowed smooth surface on the bottom of the glass. It is sometimes observed strong deformation, in which the candle was very obvious, but not completely melted. In other cases there was only a weak deformation, in which the candle was just a little more oil around the middle. If the gel was well utverzhdennym, there was no deformation of the candles, in this case, the deformation was assessed as absent.

Examples a, b and 1-4

Table 2 shows the nature of the crosslinking polymer A. the Samples a and b are outside the scope of this invention. The sample And not from the containing a series of photoinitiator or acrylic monomer, not crosslinks when exposed for up to 10 minutes and, therefore, he just melts at the temperature of 100°C and samovyrivnyuyucha on the bottom of the vessel, and dissolved while soaking in toluene. Sample partially crosslinks when exposed to UV radiation, but the content of the crosslinked gel is low. Samples 1-4 are included in the scope of this invention. Samples 1-4 showed that compositions containing and photoinitiator, and acrylic monomer, are bound, therefore, in the test for content of cross-linked gel more than half of the gel remains unmelted.

Table 2
Composition, wt.%AndIn1234
Drakeol 779,977,976,975,472,977,9
Polymer And20,020,020,020,020,020,0
Irganox 101 0,10,10,10,10,10,1
Irgacure 6512,02,02,02,02,0
Sartomer SR2381,02,55,01,0
The content of cross-linked gel, %, after exposure for
2 minutes731363242
5 minutes82741424259
10 minutes 102754525365
Gel in toluene after irradiation for
2 minutesflatflattwistedtwistedflat
5 minutesnoflatCL. twistedtwistedtwistedCL. twisted
10 minutesnoflatCL. twistedtwistedtwistedCL. twisted

Examples 5-9

The results in Table 3 show that as photoinitiator IRGACURE 819 t is aetsa even more effective than IRGACURE 651. The content of cross-linked gel in samples 5-8 were very high, and the deformation of the candles is very weak or absent. For sample 9, the content of the crosslinked gel was lower and deformation of the spark was weak, indicating that 0.1 wt.% IRGACURE 819 is the approximate minimum number required for the crosslinking of the gel.

td align="center"> 0,2
Table 3
Composition, wt.%56789
Drakeol 776,977,9 78,478,478,778,8
Polymer And20,020,020,020,020,0
Irganox 10100,10,10,10,10,1
Irgacure 8192,01,00,50,1
Sartomer SR2381,01,01,01,01,0
The content of cross-linked gel, %, after exposure for
0.5 minutes9610095-51
1 minute929599-33
2 minutes9296998951
Gel in toluene after irradiation for
0.5 minutesflatthe flat is th 2 coatsperfectnot tight
1 minuteflatflat2 coatsperfectfluid
2 minutesflatflat2 coatsperfectfluid
Deformation candles after irradiation for
0.5 minutesPTS. weaknononoweak
1 minutePTS. weakPTS. weaknonoweak
2 minutesPTS. weak nononoweak

Examples 10-12

Comparison of the results obtained for samples 7-9 in Table 3, with the results obtained for samples 10-12 in Table 4 shows that the effect of hexaniacinate, Sartomet SR238, is very close to the action alkoxysilanes of hexaniacinate, Sartomet SD560.

no
Table 4
Composition, wt.%101112
Drakeol 778,478,778,8
Polymer And20,020,020,0
Irganox 10100,10,10,1
Irgacure 8190,50,20,1
Sartomer SD5601,01,01,0
The content of cross-linked gel, %, after exposure for
0.5 minutes989750
1 minute979829
2 minutes979796
Gel in toluene after irradiation for
0.5 minutesperfect-loose
1 minuteperfect2 coatsfluid
2 minutesperfect2 coatsfluid
Deformation candles after irradiation for
0.5 minutesnono
1 minutenonono
2 minutesnonono

Examples 13-16

The results presented in Table 5, suggest that the effectiveness of partially hydrogenated polymers. The results show that both polymers at concentrations of 10 or 20 wt.% oil gel well stitched together with the formation of high concentrations of cross-linked gel and the correct structure of the gel swelling in toluene.

Table 5
Composition, wt.%13141516
Drakeol 784,474,484,474,4
The polymer In10,020,0
The polymer10,020,0
Irganox 10100,10,10,10,1
Irgacure 8190,50,50,50,5
Sartomer SR2385,05,05,05,0
The content of cross-linked gel, %, after exposure for
0.5 minutes746097100
1 minute747199100
2 minutes7473100100
Gel in toluene after irradiation for
0.5 minutesneatneatneatneat
1 minuteneatneatneatneat
2 minutesneatneatneatneat

Examples 17-19

Table 6 shows the effect of the concentration of Irgacure 819 on gels based on partially hydrogenated polymer. The results show that all samples from 17 to 19 are well custom made with high content of cross-linked gel and give the correct structure of the gel swelling in toluene. A slight increase in deformation candles lowering the concentration of photoinitiator.

Table 6
Composition, wt.%17 1819
Drakeol 773,974,474,7
The polymer20,020,020,0
Irganox 10100,10,10,1
lrgacure 8191,00,50,2
Sartomer SR2385,05,05,0
The content of cross-linked gel, %, after exposure for
0.5 minutes10010049
1 minute10010080
2 minutes10010098
Gel in toluene after exposure in those who tell
0.5 minutesperfectperfectperfect
1 minuteperfectperfectperfect
2 minutesperfectperfectperfect
Deformation candles after irradiation for
0.5 minutesnoPTS. weakweak
1 minutenoPTS. weakweak
2 minutesnoPTS. weakweak

Examples 20-24

Table 7 shows the importance of UV curing oil gel in the preparation of oil gels low density improvement and using the expanding microspheres. These gels were prepared by mixing polymer and antioxidant in oil using a Silverson mixer for about 1 hour at a temperature of 130°C. was Added expanding microspheres and was stirred for approximately 5 minutes. Then added a crosslinking agent and photoinitiator and was stirred for another 5 minutes, after which the prepared samples for testing. It is important to admix expanding microspheres in a gel at a temperature below the temperature at which the skin is softened and they increase in volume, in these examples, this temperature is approximately 165°C. In these examples, the compositions were poured from the mixer hot at a temperature of 130°C in molds to obtain films with a thickness of approximately 12.5 mm Gels were subjected to UV lamp for 5 minutes. Then they were heated to a temperature of 175°C for 15 minutes for the expansion of the microspheres. Thickness was measured before and after heating and expected percentage increases in thickness.

The results in Table 7 show that the unstitched gel, the sample 20, just melted when heated to a temperature of 175°C for the expansion of the microspheres. Sample 21 was so much overiden that was split into 2 parts with the expansion of the microspheres. In the sample 22 the degree of cure was limited to using a 50/50 mixture of KRATON G1652, which is not cured under attack by the AI UV, and polymer that cures when exposed to UV. The results showed that the gel has increased in volume by 27% when heated to expand the microspheres. Sample 23, which used a mixture of 75/25 inactive/active polymers, was not overide, as he melted when heated to a temperature of 175°C. the Sample 24 shows a gel with the polymer, when heated, the increase in volume by 20%.

Table 7
Composition, wt.%2021222324
Drakeol 782,782,782,782,782,4
KRATON G165215,07,5to 12.0
Polymer And15,07,53,0
The polymer 15,0
Irganox 10100,10,10,10,10,1
Irgacure 8190,20,20,20,5
Sartomer SR2381,01,01,01,0
Expancel DU091/801,01,01,01,01,0
Increase height %meltedbusted27melted20

Examples 25-27

Table 8 presents (approved when exposed to UV radiation oil gels with higher concentrations of expanding microspheres. These gels were prepared as in Examples 20-24 except samples for testing were a candle with a diameter of 3.3 cm and a height of 3 see Candles were utverjdali under the action of fluorescent indoor lamps within 1 week. Cured gels were heated for 30 minutes at a temperature of 165°C for the expansion of the microspheres. After the expansion candles hold their shape, but it became somewhat more. Candle carved cubes, we measured their size and weight and calculate the density.

The density calculated for the unexpanded gel is about 0,86 g/cm3. The results presented in Table 8, show that the enhanced density gels have decreased by approximately 40%.

Table 8
Composition, wt.%252627
Drakeol 786,286,276,2
KRATON G16526,75,010,0
Polymer And3,35,010,0
Irganox 1010 0,10,10,1
Irgacure 8190,20,20,2
Sartomer SR2380,50,50,5
Expancel DU091/803,03,03,0
Density, g/cm30,540,560,48

1. Thermoplastic gel composition that can be crosslinked under the action of radiation, including:
(a) from about 5 to 40 wt.% stitched block copolymer selected from the group consisting of
or
or
or
where a represents vinylaromatic hydrocarbon block having a molecular weight of from 4,000 to 30,000, HD is a hydrogenated conjugated diene block having a molecular weight of from 10000 to 100000, Y is a multifunctional linking agent, UD is a conjugated diene block having a molecular weight of from 1000 to 80000, or conjugated diene block, iluminacao weight of 1000 to 80000, which is partially gidrirovanny, x is an integer from 1 to 20, y is 0 or 1, z is an integer from 1 to 20, and in formulas (II) and (III) the sum of (x+z) is from 2 to 30;
(b) from 60 to 90 wt.% the liquid component selected from oils for filling, plasticizers and solvents that are compatible with stitched block copolymer;
(c) from 1 to 20 wt.% at least one crosslinking agent selected from bifunctional or multifunctional acrylate or methacrylate monomers and vinyl esters;
(d) optionally from 0 to 10 wt.% expanding microspheres; and
(e) optionally from 0 to 3 wt.% photoinitiator,
where the total number of all components is 100 wt.%.

2. Thermoplastic gel composition according to claim 1, characterized in that the block copolymer chosen from:
or
or
,
where S is a polystyrene block, EB is a hydrogenated polybutadiene polymer block, the content of 1,2-vinyl butadiene polymer block prior to hydrogenation is from 30 to 80 mol.%, I branch, Rubezhnoe, Ukraine is a polymer block or partially gidrirovanny branch, Rubezhnoe, Ukraine polymer block Y is a residue of a coupling agent, x is an integer from 1 to 20, y is 0 or 1, z is an integer h is scrapped from 1 to 20, and in formulas (V) and (VII) the sum of (x+z) is from 2 to 30.

3. Thermoplastic gel composition according to claim 1 or 2, wherein x is 2 and z is 2.

4. Thermoplastic gel composition according to claim 1 or 2, characterized in that the component (b) selected from white mineral oils, paraffinic/naphthenic oils for filling, synthetic or natural esters, ethers or alcohols, and hydrocarbon and oxygen-containing hydrocarbon solvents, preferably paraffinic/naphthenic oils for filling.

5. Thermoplastic gel composition according to claim 1 or 2, characterized in that the crosslinking agent is a bifunctional acrylate monomer, preferably hexaniacinate.

6. Thermoplastic gel composition according to claim 1 or 2, characterized in that it contains an expanding microspheres in an amount of from 0.1 to 10 wt.%, preferably from 1 to 5 wt.%.

7. Thermoplastic gel composition according to claim 1 or 2, characterized in that it contains photoinitiator in the amount of from 0.1 to 3 wt.%, selected from benzoic esters, substituted acetophenone and benzophenone, substituted benzylacetone, bis-allpotential, alpha hydroxyketones, alpha aminoketones and mixtures thereof, preferably bis-allpotential.

8. Thermosetting product containing thermoplastic gel composition is Yu according to any one of claims 1 to 7, exposed to ionizing radiation, preferably electron beam radiation or non-ionizing radiation, preferably ultraviolet radiation or visible light, for a time and under conditions sufficient to convert thermoplastic products in thermosetting product.

9. Thermoset product of claim 8, wherein selected from the group including candles, air fresheners, soft rubber sealing elements, elastic pads, mattresses and pillows.

10. Thermoplastic gel composition that can be crosslinked under the action of radiation, including:
(a) from 5 to 40 wt.% the mixture stitched block copolymer of the formula

where S represents a polystyrene polymer block, means polybutadiene polymer block having a content of 1,2-vinyl groups ranging from 10 to 80 mol.%, Y is the residue of a coupling agent, x is an integer from 1 to 20, preferably 2, y is an integer from 0 to 20, preferably 2, and the sum (x+y) is from 2 to 30; and the block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene), the ratio (a block copolymer of the formula (I)): (block-copolymer type polystyrene-hydrogenated polybutadiene-polystyrene) is from 3:1 to 1:3;
(b) from 60 to 90 wt.% Zhidkov the component, selected from oils for filling, plasticizers and solvents that are compatible with stitched block copolymer;
(c) from 1 to 20 wt.% at least one crosslinking agent selected from bifunctional or multifunctional acrylate or methacrylate monomers and vinyl esters;
(d) from 0.1 to 10 wt.% expanding microspheres; and
(e) from 0 to 3 wt.% photoinitiator, where the total number of all components is 100 wt.%.



 

Same patents:

FIELD: chemistry.

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

FIELD: chemistry.

SUBSTANCE: present invention relates to the method of producing functionalised, linked or star block copolymer, used in rubber compositions, cross-linked with sulphur and with low hysteresis in the cross-linked state. Described is a method of producing the said copolymer, containing soot and with low hysteresis in the cross-linked state. At least one or the above mentioned blocks consists of a diene elastomer, distinct from polyisoprene, the molar content of branches of one or several conjugate dienes of which exceeds 15%. The method is distinguished by that it involves: (i) copolymerisation of one or several monomers, containing at least one conjugated diene, distinct from isoprene, using a catalyst system, containing a hydrocarbon solvent, halogenation or non-halogenated organo-metal compound A of a group IIIA metal, compound B of an alkali-earth metal and a polymer initiator C, containing C-Li bond, which is formed from non-functionalised mono-lithium containing polyisoprene, meant for forming the said or each polyisoprene block; the said one or several polyisoprene blocks have average molecular mass Mn1 from 2500 to 20000 g/mol, in effect that, one or several blocks, containing diene elastomer, distinct from polyisoprene, contains 70% or more 1,4-trans-branches and has average molecular mass Mn2 from 65000 to 350000 g/mol, and (ii) addition into the copolymerisation product of a functionalised, linking or star structure forming agent, containing one, two or at least three epoxy groups, respectively, for functionalising, linking or forming a star structure of the given block, consisting of diene elastomer, distinct from polyisoprene. Description is also given a functionalised, linked or star block-copolymer, cross-linkable or cross-linked rubber composition, containing the said functionalised, linked or star block-copolymer, and description is also given of a pneumatic tyre tread and a pneumatic tyre.

EFFECT: obtaining a block-copolymer, which is used in compositions for pneumatic tyre treads, and which reduces hysteresis of the given composition in cross-linked state.

40 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention refers to making a moulded product for handling clean-room materials, intermediate products or end products, such as a container, a tray and a tool. The moulded product is made of resin compound prepared by mixing in melt cycloolefine polymer (A) 100 weight fractions chosen from the group including bicyclo[2.2.1]-2-heptene and its derivatives, tricyclo [4,3,0,12,5]-3-decene and its derivatives, and tetracyclo[4,4,0,12,5,17,10]-3-dodecene and its derivatives of vitrification temperature within 60 to 200°C, and amorphous or low-crystalline elastic copolymer (B(b1)) 1 to 150 weight fractions. Copolymer (B(b1)) is polymerised from at least two monomers chosen from the group including ethylene and a-olefin with 3 to 20 carbon atoms and vitrification temperature 0°C or lower. The compound contains radical polymerisation initiator 0.001 to 1 weight fractions containing peroxide, and polyfunctional compound (D) 0 to 1 weight fractions. The compound (D) has at least two radical-polymerised functional groups chosen from the group including vinyl group, allylic group, acrylic group and methacrylic group in a molecule.

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19 cl, 1 tbl, 2 dwg, 12 ex

FIELD: chemistry.

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13 cl, 6 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to a method of obtaining a resin composition. Description is given of the method of obtaining a resin composition through mixture in a molten mass of 100 weight parts of cyclic olefin polymer (A), whose glass transition temperature ranges from 60 and 200°C, and 1-150 weight parts of elastic polymer (B), with glass transition temperature 0°C or lower. Part of the cyclic olefin polymer (A) is first mixed in a molten mass with elastic polymer (B) and 0.001-1 weight parts of radical polymerisation initiator (C). The remaining cyclic olefin polymer (A) is then added and mixed in the molten mass. The ratio of the quantity of cyclic olefin polymer (A), initially added, to the quantity of the same polymer added later (initially added/added later) ranges from 1:99 to 70:30. Cyclic olefin polymer (A) is divided into two parts and added separately twice, such that, the mixture with a cross-linked structure can be diluted with cyclic olefin polymer (A), without a cross-linked structure. As a result, increase in the viscosity of the molten resin composition can be prevented.

EFFECT: good abrasion resistance and good moulding properties of the molten mass.

15 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention refers to rubber-processing industry, in particular to development of thermoplastic elastomeric rubber materials that can be used for manufacturing of various extrusion profiles and moulded flexible parts for automotive, cable, light industry and construction engineering. Thermoplastic elastomeric material is made of composition including, wt. fraction: rubber - 100, polyolefin - 2-150, vulcanising agent 1-15, vulcanisation activator 3-10, stearic acid - 0.75-2.0, oil - 25-500 and bulk additive - 1-100, modified diene-containing thermoplastic elastomer, such as hydrooxylated, halogenated, hydrogenated or hydrohalogenated dienevinylaromatic thermoplastic elastomer - 5-150, release agent - zinc stearate, calcium stearate or their mixture - 0.1-2.0. As oil additive the material contains paraffine-naphthene oils, as bulk additive is contains powder filler with particle size 100 nanometers to 20 microns, selected from the group: schungite, kaolin, chalk, talcum powder or carbon white, as well as mixed mineral additive with 0.04-4.0 mass % of industrial carbon. Thus as rubber thermoplastic elastomeric material contains ethylene-propylene-diene rubber with propylene chains 27 to 40 mass %, and as the third comonomer is contains ethylidene norbornene or dicyclopentadiene in amount 2-10 mass %, as well as butyl rubber, chlorbutyl rubber, brominated butyl rubber, polyisoprene rubber, butadiene-styrene rubber, or polybutadiene rubber. As polyolefin it contains isotactic polypropylene, polyethylene or their mixture at ratio of polyethylene mixed with isotactic polypropylene in amount of 5-95 mass %.

EFFECT: production of material possessing high technological and physical-mechanical properties, melt processability to products without vulcanisation by moulding under pressure or extrusion, low density, high fullness by oil.

5 cl, 2 tbl

FIELD: polymer production.

SUBSTANCE: invention provides elastomeric polymer composition comprising at least polymers and copolymers obtained from substituted and unsubstituted vinylaromatic monomers and from diene monomers and including 15 to 85% copolymer containing (i) at least one block formed by 10 to 5000 mainly syndiotactic structural sequences of monomer units derived from at least one substituted or unsubstituted vinylaromatic monomer and (ii) at least one block formed by 10 to 4000 monomer units derived from at least one diene monomer with predominant 1,4-cis structure, wherein 15-85 wt % of polymer obtained from diene monomers has molecular weight between 6000 and 600000 with content of 1,4-cis monomer units constituting at least 90%, while up to 70% of polymer obtained from substituted and unsubstituted vinylaromatic monomers has molecular weight between 10000 and 500000 and degree of syndiotacticity (expressed through syndiotactic pentads) at least 95%, a part formed by monomer units derived from diene monomer is optionally partially or completely hydrogenised. Method of preparing such elastomeric composition is also described.

EFFECT: extended temperature range for elastomeric performance of composition.

42 cl, 5 tbl, 27 ex

FIELD: manufacture of building materials.

SUBSTANCE: invention relates to heat- and hydroinsulation materials suitable for making and repairing various-type roofings, in particular to gluing roll bitumen and bitumen-polymer materials to brick, concrete, metal, wood, ceramic, and other surfaces, as well as for mastic hydroinsulation of construction units of buildings and installations. Bitumen-polymer mastic is composed of. wt %: toluene 31-34, bitumen 30.5-37, thermoelastoplastic 5-11.5, mineral filler (talc) 21-23, resin-colophony 2.5-3.5. Mastic preparation method is also described.

EFFECT: simplified composition and simplified mastic preparation method, achieved compatibility of mastic with a variety of materials, in particular with roofing materials.

4 cl

FIELD: manufacture of building materials.

SUBSTANCE: invention relates to heat- and hydroinsulation materials suitable for making and repairing various-type roofings, in particular to gluing roll bitumen and bitumen-polymer materials to brick, concrete, metal, wood, ceramic, and other surfaces, as well as for mastic hydroinsulation of construction units of buildings and installations. Bitumen-polymer mastic is composed of. wt %: toluene 27-29, bitumen 31-33, thermoelastoplastic 11-13, mineral filler (talc) 23-25, resin-colophony 3-5. Mastic preparation method is also described.

EFFECT: simplified composition and simplified mastic preparation method, achieved compatibility of mastic with a variety of materials, in particular with roofing materials.

4 cl

FIELD: manufacture of building materials.

SUBSTANCE: invention relates to heat- and hydroinsulation materials suitable for making and repairing various-type roofings, in particular to gluing roll bitumen and bitumen-polymer materials to brick, concrete, metal, wood, ceramic, and other surfaces, as well as for mastic hydroinsulation of construction units of buildings and installations. Bitumen-polymer mastic is composed of. wt %: toluene 48-50, bitumen 19-21, thermoelastoplastic 12.5-14,5, mineral filler (talc) 13-15, resin-colophony 2.5-4.5. Mastic preparation method is also described.

EFFECT: simplified composition and simplified mastic preparation method, achieved compatibility of mastic with a variety of materials, in particular with roofing materials.

4 cl

FIELD: chemistry.

SUBSTANCE: there is disclosed foam thermoplastic gel composition containing (a) block copolymer containing at least one polymer block A made of monovinyl aromatic compound, and at least one polymer block B made of conjugated diene; (b) liquid component chosen from the group including filling oils, plasticiser and solvents compatible with said block copolymer (a); (c) thermoplastic particles foam when heated containing gas extended when heated or condensed gas, and optionally (d) photoinitiator characterised that block copolymer (a) represents a block copolymer cross-linked when irradiated and contains monovinyl aromatic compound 7 to 35 wt % of total polymer with total apparent molecular weight 50 to 1500 kg/mol and vinyl content in block B 10 to 80 mole %, where blocks B are probably hydrogenated thus residual initial ethylene unsaturation is at least 25 %. There is also disclosed production process of said foam elastic thermoplastic gel composition (versions), as well as application of said foam elastic gel composition.

EFFECT: production of low-density oil gels of improved hear resistance.

13 cl, 6 tbl, 7 ex

FIELD: textile industry, in particular, processes for manufacture of non-woven materials.

SUBSTANCE: method involves producing filled non-woven material obtained by combined process on the basis of physicochemical technology including impregnation with liquid phase composition exposed to wave action, with liquid phase composition containing low-emulsifier and emulsifier-free polyacrylic latexes; providing exposure to wave action in resonance mode after mechanical mixing of components; subjecting material to squeezing, drying and thermal processing.

EFFECT: reduced washing away of components used in production of non-woven materials during utilization of said materials, improved uniformity in distribution of filler and provision for keeping sorption capacity of materials with regard to admixtures in liquid media.

1 tbl, 4 ex

FIELD: petrochemical industry; rubber industry; other industries; methods of production of the rubber compound on the basis of the chloroprene rubber.

SUBSTANCE: the invention is pertaining to the field of rubber industry, in particular, to the method of production of the rubber compound on the basis of the chloroprene rubber, which is characterized by the heightened adhesiveness metrics. Production of the rubber compound on the basis of the chloroprene rubber includes mixing of magnesium oxide, zinc oxide, the stearic acid and carbon. At that during the mixing process additionally introduce the modifying agent, which has been preliminary produced as a result of interaction of the epoxy dianresin -ED-20 with the vat wastes of the residue of phenylamine production in the mass ratio of 2:1 at 150°С within 5 hours. At that the vat waste contain 15-18 mass share of phenylamine. The vulcanizates of the rubber compound based on the chloroprene rubber are characterized by the improved physical-mechanical metrics and the heightened adhesion to the metal. The method allows to salvage of the phenylamine (other name aniline) - the waste of the petrochemical industry.

EFFECT: the invention ensures production of the rubber compound based on the chloroprene rubber characterized by the improved physical-mechanical metrics and the heightened adhesion to the metal.

4 tbl

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

FIELD: medicine.

SUBSTANCE: method involves exposing silicon composition with microwave field of 70-90 W for 8-10 min.

EFFECT: accelerated production process; high microbiological cleanness of the articles.

FIELD: chemical industry; biotechnology; production of the new biopolymers by irradiation in the solid phase.

SUBSTANCE: the invention is pertaining to the new products produced on the basis of the biopolymers. The method of modification of the existing in the nature biocompatible biopolymer, which is characterized by the lack of any functional groups, provides for the treatment of the indicated biopolymer being in the solid or the dry state with the source of the ionizing radiation at the presence of the mediating gas. The mediating gas represents the unsubstituted alkene or alkyne gas, in capacity of which may be ethylene, propylene or acetylene and the annealing of the obtained product in the absence of oxygen at the temperature from nearby 40°C up to 120°C, with the subsequent removal of the all remained mediating gas. The modified biopolymer is produced by the above-stated method. The present in the nature modified biocompatible biopolymer produced by the above-stated method is sampled from the group consisting of polysaccharides of the vegetable or animal origin and the protein produced from the connective tissue of an animal, the protein produced from the other tissues of an animal, the combinations of at least of one of the indicated polysaccharides and at least of one other protein of the vegetable origin, or the demineralized bone ("DMB"). The method of modification of the tissue of the animal origin includes switches the treatment of the sample of the indicated tissue or its component in the solid or the dry state with the source of the ionizing radiation at the presence of the mediating gas and the annealing of the obtained product in the absence of the oxygen at the temperature from around 40 up to 120°C, with the subsequent removal of the all remained mediating gas. The invention allows to obtain the biopolymers possessing the good biocompatibility. At that into the source biopolymer do not introduce neither new, nor additional functional groups.

EFFECT: the invention allows to obtain the biopolymers possessing the good biocompatibility.

35 cl, 6 ex, 12 tbl, 43 dwg

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to radiation modification of polymers, in particular, to a method of radiation cross-linking articles made of polyolefins. Method involves irradiation of articles in unsaturated hydrocarbon medium comprising the length chain C2-C12. Method enhances the effectiveness of cross-linking polyolefins at relatively low absorbed doses of ionizing radiation. Invention can be used in manufacture of heat-stable petroleum-plunged cables, pipelines, thermally shrinking films and tubes.

EFFECT: improved method for radiation cross-linking.

3 cl, 2 tbl, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to radiation method for preparing grafted copolymers from material based on olefin polymer. Method involves carrying out the following stages in non-oxidizing atmosphere: (1) irradiation of material particles based on olefin polymer by high-energetic ionizing radiation; (2) treatment of prepared material based on olefin polymer with at least one grafting vinyl monomer that is able to form side chains on material based on olefin polymer in the presence of at least one additive regulating the molecular mass of side chains of polymerizing grafting vinyl monomer, and (3) deactivation of residual free radicals in prepared material based on olefin polymer subjected for grafting and removing unreacted vinyl monomer from the material. Additive regulating the molecular mass of side chains of polymerizing grafting vinyl monomer is chosen from: (a) at least one polymerization inhibitor based on halogen-substituted aliphatic or aromatic compound or aliphatic or aromatic derivative of phosphine. Prepared grafted polymers with low-molecular chains possess improved morphology of internal regions and surface and alleviated processing without negative effect on aggregate of physical properties of the grafted copolymer.

EFFECT: improved preparing method.

10 cl, 4 tbl, 4 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to plastics processing, in particular to fabrication of thermally shrinkable electronically and chemically modified tape designed for use in composite coatings based on mastic materials for anticorrosive insulation of various-destination steel main pipelines and in repair of pipeline coating. Fabrication of tape comprises extrusion of polyethylene composition, calendaring, electronic-chemical modification involving irradiation by accelerated electron stream (effected to absorption of dose 5-10 Mrad) and longitudinal orientation by 3-10% at 60-85°C. Wrap tape is characterized by content of gel fraction 40-54%, degree of shrinkage 3-6%, rupture strength 14.9-15.7 MPa, and breaking elongation 335-380%.

EFFECT: improved performance characteristics of tape.

1 tbl, 11 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for preparing thermoshrinkage polypropylene films based on the cross-linking polypropylene composition. Method involves preliminary preparing a modifier by mixing. A modifier comprises polypropylene of sort "Kaplen", dicumene peroxide, sulfur and a hydroxybenzophenone derivative. Then a modifier is granulated at temperature 190-210°C on granulating head and mixed in the amount 5.0-15.0 wt.-% with polypropylene of sort "Kaplen". Film is prepared by the hose blowing method and treated by UV-radiation. The combination of components of modifier taken in the definite ratio provides photochemical cross-linking the polypropylene composition in preparing the hose thermoshrinkage film. Prepared films show the enhanced resistance against tearing.

EFFECT: improved preparing method, enhanced properties of film.

3 tbl, 5 ex

FIELD: molecular biology, bio-organic chemistry, possible use for producing cellular microchips.

SUBSTANCE: in accordance to suggested method for forming alginate gel with its simultaneous holding on the surface of solid phase, alginate gel is formed on the surface of solid phase which contains metal oxide with free valences, in presence of polyamine connection. Current method is used in the method for producing a cellular microchip. Cellular microchip is produced by forming and holding micro-cells of gel, containing immobilized cells, on the surface of the solid phase.

EFFECT: possible production of alginate gel, reliably held on the surface of solid phase.

3 cl, 1 tbl, ex

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