CN111187511B - Thermoplastic elastomer and preparation method thereof - Google Patents
Thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN111187511B CN111187511B CN202010076674.5A CN202010076674A CN111187511B CN 111187511 B CN111187511 B CN 111187511B CN 202010076674 A CN202010076674 A CN 202010076674A CN 111187511 B CN111187511 B CN 111187511B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/128—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to reaction products of polysiloxanes having at least one Si-H bond and compounds having carbon-to-carbon double bonds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention provides a thermoplastic elastomer and a preparation method thereof, comprising the following steps: 1) Grafting a polar group on the surface of the organosilicon elastomer micron particle; 2) Dispersing the surface-modified silicone elastomer microparticles formed in step 1) in a polyamide to form a polyamide-silicone thermoplastic elastomer. By adopting the technical scheme, the polyamide-organic silicon thermoplastic elastomer can be conveniently obtained without being constrained by processing equipment and a processing technology, surface-modified organic silicon elastomer micron particles can be directly dispersed in polyamide by adopting common double-screw extrusion equipment, an internal mixer and the like in the prior art, the processing equipment is easy to obtain, the preparation process is easy to control, the production process is safe and environment-friendly, the formula is flexible and changeable, and the product performance is more outstanding.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer is a polymer material with both excellent elastomer performance and thermoplastic plasticity. Due to the thermoplastic characteristics, the thermoplastic elastomer has the repeatable processability, thereby greatly reducing or even avoiding the generation of waste materials, and having great advantages in the aspects of resource utilization and environmental protection compared with the conventional rubber chemically crosslinked. Polyamide thermoplastic elastomers have appeared later and to date have been produced by a few companies all over the world, whereas polyamide-silicone thermoplastic elastomers are less commercially available due to technical and technological obstacles. The current preparation method of polyamide-organosilicon thermoplastic elastomer mainly comprises a polyamide-organosilicon dynamic vulcanization method and two methods of directly copolymerizing functional end group organosilicon and polyamide monomer.
Patents CN01807264 and CN01808872 describe methods for preparing polyamide-silicone thermoplastic elastomers by a dynamic vulcanization process, in the dynamic vulcanization process, silicone which is initially liquid is uniformly dispersed in a polyamide continuous phase and is crosslinked and cured into silicone elastomer particles, and finally, a polyamide-silicone thermoplastic elastomer with a polyamide continuous phase and silicone elastomer particles dispersed phase is formed. The dynamic vulcanization process has high requirements on equipment, such as the length, meshing block proportion, torque and the like of a double-screw extruder are specially customized, in order to obtain good mechanical properties, final organic silicon elastomer particles are required to be completely cured in the process and uniformly dispersed in polyamide in a certain range of particle size, the dynamic vulcanization conditions such as processing temperature, vulcanization speed, shear strength and the like of each section are required to be accurately regulated, and the operation window range is narrow. And once the proportion of silicone is too high, the silicone itself will form a continuous phase, significantly reducing the thermoplasticity of the material. Meanwhile, the compatibility of the low-polarity organosilicon and the high-polarity polyamide is poor, so that macroscopic phase separation is easy to occur in a system, and the mechanical property is seriously influenced. The tensile strength of the polyamide-organic silicon thermoplastic elastomer produced by the general dynamic vulcanization method is difficult to exceed 20MPa.
Patents CN200480001598 and CN201310628391 describe methods for preparing polyamide-based silicone thermoplastic elastomers by direct copolymerization of functional end group-containing silicones and polyamide monomers, but such methods belong to pure chemical production, and not only have huge investment, but also require a large amount of toxic, flammable and explosive raw materials and solvents in the production process, and high-temperature and high-pressure production processes. The challenges encountered with such projects are now well understood with increasing emphasis on environmental protection and safety. And, to date, no commercial products have been available for producing polyamide-silicone thermoplastic elastomers using such chemical copolymerization processes.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a thermoplastic elastomer and a preparation method thereof, which finally form a thermoplastic elastomer material with polyamide as a continuous phase and silicone elastomer microparticles as a dispersed phase, and is used for solving the problems in the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of a thermoplastic elastomer, which comprises the following steps:
1) Grafting polar groups on the surface of the silicone elastomer micron particles;
2) Dispersing the surface-modified silicone elastomer microparticles formed in step 1) in a polyamide to form a polyamide-silicone thermoplastic elastomer.
According to the technical scheme of the preparation method, the organosilicon elastomer microparticles in the step 1) are spherical microparticles. Preferably, in step 1), the silicone elastomer microparticles have a diameter of 0.05 to 50 μm, more preferably, a diameter of 0.1 to 30 μm. More preferably, the silicone elastomer microparticles have a diameter of 0.8 to 3.0 μm.
According to the technical scheme of the preparation method, the silicone elastomer micron particles in the application can be prepared by the method in the prior art.
Furthermore, the preparation method of the silicone elastomer micron particles can adopt the patent with the domestic publication number of CN106543455A for production.
According to the technical scheme of the preparation method of the thermoplastic elastomer, in the step 1), the polar group comprises one or more selected from an acrylic group, an acrylate group, an acrylonitrile group, an epoxy group and an amino group.
According to the technical scheme of the preparation method of the thermoplastic elastomer, in the step 1), the method for grafting the polar group on the surface of the silicone elastomer micron particle is to add a polar modifier into a mixture of the silicone elastomer micron particle and water, then initiate polymerization, and perform solid-liquid separation on a polymerization product to obtain the surface-modified silicone elastomer micron particle.
The amount of the polar modifier added is preferably 0.1 to 45wt%, more preferably 1 to 25wt%, and still more preferably 5 to 25wt% of the mass of the silicone elastomer fine particles.
According to the above technical solution of surface grafting polar groups, the polar modifier contains at least one polar group. Preferably, the polar modifier is a monomer or oligomer containing at least one polar group. More preferably, the oligomer has a molecular weight of 150 to 100000.
More preferably, the monomer containing at least one polar group is selected from one or more of the following: acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, triallyl isocyanurate, cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4 butanediol diacrylate, 1,4 butanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1, 6 hexanediol diacrylate, 1, 6 hexanediol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1, 12-dodecyl diacrylate, 1, 12-dodecyl dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3 butanediol diacrylate, 1,3 butanediol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, neopentyl glycol propoxylated dimethacrylate, neopentyl glycol dimethacrylate; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, propoxylated glycerol triacrylate, propoxylated glycerol trimethacrylate; dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethylacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, diallyl maleate, diallyl terephthalate, diallyl phthalate, bisphenol a diallyl ether, diallyl bisphenol a; divinyl-1, 4-butanediol ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether.
More preferably, the oligomer of at least one polar group comprises one or more of: comprising an aliphatic urethane acrylate containing 1 to 20 acrylate groups; aliphatic polyurethane methacrylate containing 1-20 methacrylate groups; aromatic urethane acrylates containing 1 to 20 acrylate groups; aromatic urethane methacrylates containing 1 to 20 methacrylate groups; polyester acrylates containing 1 to 20 acrylate groups; polyester methacrylate containing 1 to 20 methacrylate groups; chlorinated polyester acrylates containing 1 to 20 acrylate groups; chlorinated polyester methacrylates containing 1 to 20 methacrylate groups; epoxy acrylates containing 1 to 20 acrylate groups; epoxy methacrylate containing 1-20 methacrylate groups; aliphatic epoxy acrylates containing 1 to 20 acrylate groups; aliphatic epoxy methacrylate containing 1-20 methacrylate groups; amino acrylates containing 1 to 20 acrylate groups; amino methacrylate containing 1-20 methacrylate groups; melamine acrylates containing 1 to 20 acrylate groups; melamine methacrylate containing 1-20 methacrylate groups; polybutadiene diacrylate; polybutadiene dimethacrylate; polyether acrylates containing 1 to 20 acrylate groups; polyether methacrylate containing 1-20 methacrylate groups; a metal acrylate containing 2 or more acrylate groups; metal methacrylate containing more than 2 methacrylate groups and metal polyester acrylate containing more than 2 acrylate groups; metal polyester methacrylate containing more than 2 methacrylate groups, metal polyurethane acrylate containing more than 2 acrylate groups, metal polyurethane methacrylate containing more than 2 methacrylate groups, epoxy soybean oil acrylate containing 1-20 acrylate groups, epoxy soybean oil methacrylate containing 1-20 acrylate groups, novolac epoxy acrylate containing 1-20 acrylate groups, novolac epoxy methacrylate containing 1-20 acrylate groups, hyperbranched polyester acrylate, hyperbranched polyester methacrylate, hyperbranched polyurethane acrylate, hyperbranched polyurethane methacrylate, phosphorus-containing hyperbranched polyurethane acrylate, phosphorus-containing hyperbranched polyurethane methacrylate, hyperbranched acrylic ester, hyperbranched methacrylic ester, fluorine-containing acrylic phosphate ester, fluorine-containing methacrylic phosphate ester, phosphorus-containing polyurethane acrylic ester, phosphorus-containing polyurethane methacrylic ester, phosphorus-containing epoxy polyurethane acrylic ester and phosphorus-containing epoxy polyurethane methacrylic ester.
According to the method for surface grafting of polar groups, the polymerization initiating mode is selected from one of high-energy radiation source irradiation, water-soluble persulfate initiator, water-soluble oxidation-reduction initiating system, water-soluble azo initiator and thermal initiation polymerization.
Preferably, the high-energy radiation source irradiates one selected from cobalt source, X-ray, ultraviolet ray and high-energy electron accelerator, and more preferably from cobalt source; the irradiation dose is selected in the range of 0.1Mrad to 30Mrad, more preferably 1Mrad to 10Mrad.
Preferably, the water-soluble persulfate initiator is selected from one or more of potassium persulfate, sodium persulfate, and ammonium persulfate in combination, more preferably from ammonium persulfate; the addition amount of the water-soluble persulfate initiator is 0.001-30 wt%, more preferably 0.1-10 wt% of the weight of the polar modifier.
Preferably, the water-soluble redox initiating system is selected from the group consisting of ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-ferrous sulfate, hydrogen peroxide-ferrous sulfate, ammonium persulfate-ferrous chloride, hydrogen peroxide-ferrous chloride, potassium persulfate-silver nitrate, persulfate-thiol in combination of one or more thereof, more preferably from the group consisting of ammonium persulfate-sodium bisulfite; the water-soluble redox system is 0.001wt% to 30wt%, more preferably 0.1wt% to 10wt% of the weight of the polar modifier.
Preferably, the water-soluble azo initiator is selected from one or more of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride, azodicyano valeric acid and azodiisopropyl imidazoline, more preferably from azodicyano valeric acid, and the water-soluble azo initiator is 0.001-30 wt%, more preferably 0.1-10 wt% of the weight of the polar modifier.
Preferably, the thermal initiation temperature is from 70 ℃ to 100 ℃, more preferably from 90 ℃ to 100 ℃.
Preferably, the means for separating the polymerization product comprises drying to obtain the surface-modified silicone elastomer microparticles.
More preferably, in some embodiments, further comprising oxygen scavenging the mixture of silicone elastomer microparticles and water.
More preferably, in some embodiments, if the polar modifier contains a polymerization inhibitor, the method further comprises removing the polymerization inhibitor in the polar modifier, so that the reaction can be smoothly carried out.
The surface of the surface-modified organic silicon elastomer micron particles is polymerized with a certain proportion of polar polymers, so that the surface polarity and tension are improved, and the problems of compatibility, dispersion, adhesion and precipitation of pure organic silicon micron balls in the polar polymers are effectively solved; the problems that the pure organic silicon elastomer microspheres are easy to agglomerate and influence the fluidity are solved.
According to the technical scheme of the preparation method of the thermoplastic elastomer, the surface modified silicone elastomer microparticles are dispersed in the polyamide by a double-screw extruder and/or an internal mixer to form the polyamide-silicone thermoplastic elastomer.
Preferably, an antioxidant is added during dispersion. Antioxidants are used to prevent the polyamides themselves from oxidative degradation during processing or from yellowing. More preferably, the antioxidant is Irganox1098, an antioxidant Irgafos 168. More preferably, the antioxidant is added in a mass percentage of 0.1wt% to 1wt% based on the total mass of the surface-modified silicone elastomer micron particles and the polyamide.
Preferably, the polyamide is contained in an amount of 15 to 65wt%, preferably 20 to 60wt%, and more preferably 40 to 60wt%, based on the total mass of the surface-modified silicone elastomer microparticles and the polyamide.
The invention also discloses a thermoplastic elastomer prepared by the method.
The technical idea of the preparation method of the thermoplastic elastomer disclosed by the invention is that surface-modified organosilicon elastomer microparticles with specific particle diameters are divided into cases to form a polyamide-organosilicon thermoplastic elastomer in polyamide, polar groups of acrylic groups, acrylate groups, acrylonitrile groups, epoxy groups, amino groups and the like are grafted on the surface-modified organosilicon elastomer microparticles, and the polar groups enable the surface-modified organosilicon elastomer microparticles and the polar groups of the polyamide to form a chemical action, so that the compatibility problem of the organosilicon elastomer microparticles and the polyamide is changed, the microparticles can be well dispersed in a polyamide continuous phase.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
The preparation method of the silicone elastomer microparticles in the embodiment of the application can be produced by adopting a patent with domestic publication number CN106543455A to obtain silicone elastomer microparticles with different particle sizes, different crosslinking densities and different strengths.
Grafting polar groups on the surface of the organosilicon elastomer microparticles to form surface-modified organosilicon elastomer microparticles, and drying to remove moisture. Specific embodiments are shown in table 1.
TABLE 1
The silicone elastomer microparticles with different particle diameters and different polar groups grafted on the surfaces are dispersed in polyamide by screw extrusion equipment to form the polyamide-silicone thermoplastic elastomer, and the specific embodiment and the properties of the finally obtained polyamide-silicone thermoplastic elastomer are shown in table 2 below.
Double-screw extrusion equipment is adopted during dispersion, the length-diameter ratio is 48, the rotating speed is 300 r/min, and the temperature of each area is as follows: 60 ℃, 70 ℃, 195 ℃, 260 ℃, 265 ℃, 269 ℃, 267 ℃, 265 ℃.
The polyamide is polyamide 6 which is Yueyangshi 3400 and is dried for 10 hours at 80 ℃ before use.
Antioxidant Irganox1098: n, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, pasfu corporation;
antioxidant Irgafos 168: phenyl tris (2, 4-di-tert-butyl) phosphite, basf corporation.
Test method for tensile strength reference ISO527-2;
the method for testing the elongation is according to ISO527-2.
TABLE 2
The test effect data show that the polyamide-organosilicon thermoplastic elastomer prepared in the above embodiments of the present application has rubber appearance and characteristics, and the thermoplastic elastomer formed in the above embodiments is suitable for processing by plastic processing, is convenient to process, can effectively eliminate waste materials, and has great advantages in resource utilization and environmental protection compared with the conventional chemically crosslinked rubber.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (6)
1. A method of preparing a thermoplastic elastomer comprising the steps of:
1) Grafting polar groups on the surface of the silicone elastomer micron particles;
2) Dispersing the surface-modified silicone elastomer microparticles formed in step 1) in a polyamide to form a polyamide-silicone thermoplastic elastomer;
the elastomer micron particles comprise the following raw material components in parts by weight:
100-110 parts by weight of liquid organic silicon composition
0.01 to 5 parts by weight of curing retarder
0.01 to 20 parts by weight of a surfactant;
the liquid silicone composition comprises a polysiloxane containing a silicon-hydrogen bond and a polysiloxane containing an unsaturated carbon-carbon bond; the raw material components also comprise an effective catalytic amount of a platinum group metal-containing catalyst; the diameter of the silicone elastomer micron particles is 0.05 to 50 microns; the polyamide is 52-65 wt% in percentage by mass based on the total mass of the surface-modified silicone elastomer micron particles and the polyamide; the polar group comprises one or more selected from acrylic group, acrylate group, acrylonitrile group, epoxy group and amino group; the surface-modified silicone elastomer microparticles are dispersed in the polyamide using a twin screw extruder and/or internal mixer to form a polyamide-silicone thermoplastic elastomer.
2. The method for preparing the surface-modified silicone elastomer micro particles according to claim 1), wherein the step 1) of grafting the polar groups on the surface of the silicone elastomer micro particles is carried out by adding a polar modifier to a mixture of the silicone elastomer micro particles and water, then initiating polymerization, and separating the polymerization product to obtain the surface-modified silicone elastomer micro particles.
3. The method of claim 2, wherein the polar modifier is a monomer or oligomer containing at least one polar group; and/or the polymerization initiating mode is selected from one of high-energy radiation source irradiation, water-soluble persulfate initiator, water-soluble oxidation-reduction initiating system, water-soluble azo initiator and thermal initiation polymerization; and/or further comprising the step of oxygen scavenging the mixture of silicone elastomer microparticles and water.
4. The method according to claim 2, wherein an antioxidant is added during the dispersion in the step 2).
5. The preparation method of claim 4, wherein the antioxidant is added in an amount of 0.1wt% to 1.0wt% based on the total mass of the surface-modified silicone elastomer microparticles and the polyamide.
6. A thermoplastic elastomer prepared by the preparation method according to any one of claims 1 to 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011148887A (en) * | 2010-01-21 | 2011-08-04 | Kaneka Corp | Thermoplastic elastomer composition |
| CN106543455A (en) * | 2016-11-03 | 2017-03-29 | 涌奇材料技术（上海）有限公司 | Method that is a kind of continuous and preparing organosilicon micron ball without discharge |
| CN109836545A (en) * | 2019-02-01 | 2019-06-04 | 涌奇材料技术（上海）有限公司 | A kind of preparation method and applications of surface modified organic silicon micron ball |
| CN110234681A (en) * | 2017-01-31 | 2019-09-13 | 玛尔提贝斯股份有限公司 | Thermoplastic copolymer block polyamide elastomer silicone |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011148887A (en) * | 2010-01-21 | 2011-08-04 | Kaneka Corp | Thermoplastic elastomer composition |
| CN106543455A (en) * | 2016-11-03 | 2017-03-29 | 涌奇材料技术（上海）有限公司 | Method that is a kind of continuous and preparing organosilicon micron ball without discharge |
| CN110234681A (en) * | 2017-01-31 | 2019-09-13 | 玛尔提贝斯股份有限公司 | Thermoplastic copolymer block polyamide elastomer silicone |
| CN109836545A (en) * | 2019-02-01 | 2019-06-04 | 涌奇材料技术（上海）有限公司 | A kind of preparation method and applications of surface modified organic silicon micron ball |
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