CN103160130B - Organic silicon thermoplastic elastomer and preparation method for same - Google Patents
Organic silicon thermoplastic elastomer and preparation method for same Download PDFInfo
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Abstract
The invention discloses an organic silicon thermoplastic elastomer material and a preparation method for the same. The organic silicon thermoplastic elastomer material is characterized in that a thermoplastic elastomer is composed of organic silicon rubber, organic silicon resin and a crosslinking system; and the thermoplastic elastomer is prepared according to the following process steps of: preparing the thermoplastic elastomer by enabling the organic silicon rubber, the organic silicon resin and the crosslinking system to achieve intermolecular blending in solution, or uniformly mixing the organic silicon rubber, the organic silicon resin and the crosslinking system via a kneader or a double-screw extruder in a temperature condition of greater than 100 DEG C, and then preparing the high-performance dynamically-vulcanized organic silicon thermoplastic elastomer. Compared with other thermoplastic elastomers, the material is more capable of exerting the high-temperature resistance and ultraviolet resistance of organic silicon materials, excellent in optical transmission, and capable of being widely applied to the fields of solar energy, buildings, automobiles and medical treatment.
Description
Technical field:
The present invention relates to a kind of Organic silicon thermoplastic elastomer material and preparation method thereof, belong to the preparation field of organosilicon macromolecule material.
Technical background:
Thermoplastic elastomer has the use properties of elastic caoutchouc and the processing characteristics of plastics concurrently, repeatedly can repeat processing, in prospective material development, have economic worth.Current, widely used thermoplastic elastic material comprises polystyrene type, polyolefins and polyurethanes.Organosilicon material owing to having the excellent ability such as weathering resistance, high-low temperature resistant for all conglomeraties such as building, electronics, water treatment, space flight and the energy.Existing organosilicon material adopts room temperature or hot crosslinked method once shaped usually, and cannot repeat processing, thus Organic silicon thermoplastic elastomer material extensively receives publicity due to easy molding mode and excellent use properties.
1970, John C S, David J G and Sarah Lindsey publishes an article in " Macromolecules " magazine the 3rd volume, and " Block Copolymers of polydimethylsiloxane and Polystyrene " progressively causes styrene monomer and hexamethyl cyclotrisiloxane monomer generation active anionic polymerization by n-Butyl Lithium, prepare the two component blocks multipolymer of polysiloxane-polystyrene, molecular weight is usually 10
5below g/mol, whole polymerization process is carried out under anhydrous and oxygen-free condition, severe reaction conditions.
Calendar year 2001, Brown D A and Price G J publishes an article on " Polymer " magazine the 42 volume " Preparation and thermal properties of block copolymer of PDMS with styrene and methyl methacrylate usingATRP ", then caused the active free radical polymerization of vinylbenzene or methacrylic acid monomer further containing polyorganosiloxane segment macromole evocating agent by preparation, prepare the thermoplastic elastic material containing silicone segments, the method needs previously prepared macromole evocating agent and controls the efficiency of initiation of initiator, the thermoplastic elastomer prepared is worth segment by silicone segments and vinylbenzene or methacrylic acid and jointly forms.
US 6362287 discloses and a kind ofly uses Organosiliconpolymermodified modified nylon for the method for thermoplastic elastomer, in preparation process, adopt Dynamic Thermal sulfuration method to prepare the thermoplastic elastic material that massfraction 35%-85% is nylon by twin screw extruder under the condition of at least 210 DEG C.Similar, US 6479580, US6649704, US20060229417 individually disclose and use Organosiliconpolymermodified modified polyolefine, polymeric amide and polyphenyl thioether material, prepare the method mainly consisting of the thermoplastic elastic material of polyolefine, polyamine and polyphenylene sulfide that can repeat to process.CN 102153853A discloses a kind of thermoplastic elastic material using polyurethane/silicon rubber and preparation method thereof.In the material prepared by above-mentioned method, one of composition of the thermoplastic material that organosilicon material is just finally formed, can not play the resistance toheat of organosilicon material completely, resistance to elevated temperatures on using.And prepare silicone elastomer material at present once just not reproducible processing after cross moulding, the full thermoplastic elastomer for organosilicon material of polymkeric substance composition that can reuse yet there are no relevant report.
Summary of the invention
The object of the invention is to provide a kind of Organic silicon thermoplastic elastomer and preparation method thereof for the deficiencies in the prior art, what be characterized in the Organic silicon thermoplastic elastomer polymkeric substance that preparation method of the present invention prepares consists of full stress-strain silicon polymer; There is certain second-order transition temperature, can machine-shaping be repeated.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is parts by weight.
The starting raw material of Organic silicon thermoplastic elastomer is composed of the following components:
Organo-silicone rubber 100 parts
Silicone resin 50-2000 part
Cross-linking system 0.08-30 part.
Organo-silicone rubber is organopolysiloxane that is linear or branching, its chemical structural formula:
(R
1 3SiO
1/2)
x(R
2 2SiO
2/2)
y(R
3SiO
3/2)
z
Wherein, x and y is the positive integer of 1 to 1000, and z is the positive integer of 0 or 1 to 1000;
R
1, R
2and R
3for hydrogen, amino, phenyl, C
1-20alkyl, C
1-20alkyl phenyl, C
1-20alkoxyl group or containing C
2-8identical or different organic group in thiazolinyl.
Abovementioned alkyl group preferably from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, more preferably in methyl, ethyl, propyl group;
The above-mentioned organic group containing thiazolinyl is selected from vinyl, allyl group, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, norbornylene and tetrahydrobenzene, more preferably vinyl, allyl group;
The chemical structural formula of silicone resin is:
R
4 3siO
1/2unit and SiO
4/2unit MQ resin, or containing R
5siO
3/2unit and R
6 2siO
2/2the TD resin of unit, or containing R
4 3siO
1/2unit and R
5siO
3/2the MT resin of unit, or containing R
4 3siO
1/2unit, R
5siO
3/2unit and R
6 2siO
2/2at least one in the MTD resin of unit; Wherein M, D, T, Q are term conventional in organosilicon industry, represent simple function respectively, two senses, trifunctional, four sense link units.
Wherein R
4, R
5and R
6for hydrogen, amino, phenyl, C
1-20alkyl, C
1-20alkyl phenyl, C
1-20alkoxyl group or containing C
2-8identical or different organic group in thiazolinyl;
Abovementioned alkyl group is selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, more preferably in methyl, ethyl, propyl group;
The above-mentioned organic group containing thiazolinyl is selected from vinyl, allyl group, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, norbornylene and tetrahydrobenzene, more preferably vinyl, allyl group;
In the mixture of described organo-silicone rubber and silicone resin composition, at least need comprise 2 organic groups containing thiazolinyl;
The described organic group containing thiazolinyl can be provided by organo-silicone rubber or be provided by silicone resin or jointly provided by the two, organic group containing thiazolinyl and organo-silicone rubber mass ratio are 0.0005 ~ 0.20: 1, be preferable over 0.0008 ~ 0.20: 1, more preferably in 0.001 ~ 0.15: 1;
Described cross-linking system is organo-peroxide or/and at least one or two in organic hydrogen polysiloxanes;
Described organo-peroxide is 1,1
"-bis-(t-butyl peroxy) 3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2, at least one in 5 two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-bis-(t-butyl peroxy) acetylene.
Described organic hydrogen polysiloxanes is the organopolysiloxane at least containing two silicon-hydrogen bonds.
Also can comprise catalyzer in described cross-linking system, described catalyzer is the complex compound of Platinic chloride or Platinic chloride and vinylsiloxane, four (triphenylphosphines) close at least one in palladium and three (triphenylphosphine) rhodium chloride; Wherein, catalyzer: the mass values of organo-silicone rubber is 0 ~ 0.03: 1, is preferable over: 0 ~ 0.02: 1, if add urge body agent quality on the low side, the elastic properties of materials prepared is not enough, and the higher meeting of catalyst system quality added causes material cost greatly to increase.
In order to make the Organic silicon thermoplastic elastomer material prepared, there are better mechanical property, ageing resistance, flame retardant properties and processing characteristics etc., corresponding reinforcement, toughness reinforcing filler can also be added (such as in this elastomer material, carbon black, silicon-dioxide etc.), antiaging agent (as sterically hindered phenol), fire retardant (as nitrogen, phosphine compound) and fluidizer etc., the add-on of related auxiliaries is depending on material applications.
The preparation method of described Organic silicon thermoplastic elastomer comprises the following steps:
(1) organo-silicone rubber 100 parts, silicone resin 50-2000 parts, cross-linking system 0.08-30 part are mixed in solvent or mixing machine;
(2) mix 2 – 300 minutes temperature 20-250 DEG C, obtain organic plastic elastomeric second-order transition temperature 70 – 150 DEG C;
Wherein organic solvent is at least one in toluene, dimethylbenzene, tetrahydrofuran (THF), methylene dichloride.
Performance test:
1, the molecular weight of organo-silicone rubber and silicone resin is measured by gel permeation chromatograph (GPC) under 25 DEG C of conditions, take polystyrene molecular weight as standard;
2, tensile strength and elongation at break are with reference to GB/T 528-2009 standard test;
3, softening temperature is measured by ring and ball method.
Tool of the present invention has the following advantages
1, by the preparation-obtained Organic silicon thermoplastic elastomer of the present invention, its polymer architecture is entirely organosilicon polymer, can give full play to the performance advantages such as heat-resisting, cold-resistant, weather-proof, the resistance to ozone of organosilicon polymer material, ventilative, biologically inert;
2, this elastomerics can also carry out injecting, extrudes, mold pressing etc. is shaping, can reprocessabilty, and material can be used as the numerous areas such as building adhesive glue, LED immobilization material, solar panel encapsulation material, coating adhesive, pressure sensitive adhesive;
3, preparation technology is simple, efficiently, easily amplifies and carries out suitability for industrialized production.
Embodiment
Be specifically described the present invention below by embodiment, what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention, but can not be interpreted as limiting the scope of the invention.The person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
Under 25 DEG C of conditions, the methyl silicone rubber that 50 grams contain vinyl is dissolved in 250 milliliters of toluene and methylene dichloride mixing solutions, add the MQ resin 100 grams of molecular weight 5500 again, add hydrogen containing siloxane 0.15 gram and Platinic chloride 0.05 gram after mixing, the mass ratio of its medium vinyl and organo-silicone rubber is 0.011: 1.Be warming up to 80 DEG C of reactions 50 minutes after adding catalyst system, then decompression is heated up in a steamer desolvation and is prepared Organic silicon thermoplastic elastomer, products therefrom softening temperature 84 DEG C, tensile strength 2.18 MPa, elongation at break 314%.
Embodiment 2
Under 25 DEG C of conditions, the methyl silicone rubber that 50 grams contain vinyl is dissolved in the mixing of 250 milliliters of toluene and tetrahydrofuran (THF), add the TD resin 120 grams containing vinyl of molecular weight 8500 again, add after mixing containing 1, two (t-butyl peroxy) 3 of 1-, 3,5-trimethyl-cyclohexane 0.3 gram, its medium vinyl and organo-silicone rubber mass ratio are 0.002: 1.Stir desolvation after 30 minutes after adding superoxide, then be warming up to 150
oc reacts 30 minutes, prepares Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.11MPa, elongation at break 216%.
Embodiment 3
Under 25 DEG C of conditions, 20 grams are dissolved in the mixing of 250 milliliters of tetrahydrofuran (THF)s containing the methyl silicone rubber of vinyl and the phenyl siloxane rubber of 20 grams, add the MQ resin 120 grams containing vinyl of molecular weight 11500 again, the TD silicone resin of molecular weight 9,000 30 grams, add containing two (t-butyl peroxy) 3,3 of 1,1-after mixing, 5-trimethyl-cyclohexane 0.8 gram, its medium vinyl and organo-silicone rubber mass ratio are 0.012: 1.Stir desolvation after 30 minutes after adding superoxide, then be warming up to 150
oc reacts 10 minutes, prepares Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.41 MPa, elongation at break 200%.
Embodiment 4
Under 25 DEG C of conditions, 20 grams are dissolved in the mixing of 250 milliliters of toluene and tetrahydrofuran (THF) containing the methyl/ethyl silicon rubber of vinyl and the phenyl/propyl group silicon rubber of 20 grams, add the MQ resin 20 grams containing vinyl of molecular weight 11500 again, the TD silicone resin of molecular weight 9,000 20 grams, add containing two (t-butyl peroxy) 3,3 of 1,1-after mixing, 5-trimethyl-cyclohexane 0.5 gram, its medium vinyl and organo-silicone rubber mass ratio are 0.06: 1.Stir desolvation after 30 minutes after adding superoxide, then be warming up to 155
oc reacts 20 minutes, prepares Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.12MPa, elongation at break 210%.
Embodiment 5
Under 25 DEG C of conditions, 20 grams are dissolved in the mixing of 250 ml toluene and tetrahydrofuran (THF) containing the methyl/ethyl silicon rubber of vinyl and the phenyl/propyl group silicon rubber of 20 grams, add the MQ resin 400 grams containing vinyl of molecular weight 11500 again, the TD silicone resin of molecular weight 9,000 30 grams, add containing hydrogen containing siloxane 4 grams and Platinic chloride 0.5 gram and 1 after mixing, two (t-butyl peroxy) 3 of 1-, 3,5-trimethyl-cyclohexane 1.5 grams, its medium vinyl and organo-silicone rubber mass ratio are 0.12: 1.Stir desolvation after 30 minutes after adding superoxide, then be warming up to 150
oc reacts 10 minutes, prepares Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.85MPa, elongation at break 150%.
Embodiment 6
200 grams are contained the methyl silicone rubber of vinyl, 10 grams of methyl silicone rubbers containing propenyl, 20 grams of phenyl siloxane rubbers and the MQ resin of 500 gram molecular weights 11000 containing vinyl, the TD resin of 25 gram molecular weights 4600 and hydrogen containing siloxane 12 grams join in twin screw extruder with Platinic chloride 0.1 gram, be wherein 0.05: 1 containing thiazolinyl organic group and organo-silicone rubber mass ratio, extrude under 150 DEG C of conditions and prepare Organic silicon thermoplastic elastomer, the time that material stops in twin screw extruder is 3 minutes, products therefrom softening temperature 100 DEG C, draw high intensity 2.5 MPa, elongation at break 300%
Embodiment 7
By 220 grams containing vinyl methyl machine silicon rubber, 10 grams of methyl silicone rubbers containing propenyl, 20 grams of phenyl siloxane rubbers and the MQ resin of 1000 gram molecular weights 9000 containing vinyl, and hydrogen containing siloxane 5 grams and Platinic chloride 0.02 gram and 2, 5-dimethyl-2, 5 two (t-butyl peroxy) hexane 1.5 grams joins in twin screw extruder, be wherein 0.035: 1 containing the organo-functional group of thiazolinyl and the mass ratio of organo-silicone rubber, Organic silicon thermoplastic elastomer is directly extruded and is prepared under 150 DEG C of conditions, products therefrom softening temperature 77 DEG C, draw high intensity 1.6 MPa, elongation at break 320%.
Embodiment 8
300 grams are contained the methyl silicone rubber of vinyl thiazolinyl, 40 grams of phenyl siloxane rubbers and the MQ resin of 1500 gram molecular weights 7000 containing vinyl, the MT resin of 15 gram molecular weights 5000, the MTD resin of 15 gram molecular weights 8 000 and hydrogen containing siloxane 12 grams and Platinic chloride 0.01 gram and 2, 5-dimethyl-2, 5 two (t-butyl peroxy) hexane 1.5 grams joins in kneader, be wherein 0.085: 1 containing the organo-functional group of thiazolinyl and the mass ratio of organo-silicone rubber, Organic silicon thermoplastic elastomer is mediated and is prepared for 2 hours under 120 DEG C of conditions, products therefrom softening temperature 90 DEG C, draw high intensity 2.8 MPa, elongation at break 260%.
Embodiment 9
150 grams are contained the phenyl siloxane rubber of vinyl thiazolinyl, 10 grams contain the MQ resin of vinyl containing allylic methyl silicone rubber and 500 gram molecular weights 8800, the MT resin and 2 of 200 gram molecular weights 7600, 5-dimethyl-2, 5 two (t-butyl peroxy) hexane 6 grams and 2, 5-dimethyl-2, 5-bis-(t-butyl peroxy) acetylene 0.2 gram joins in kneader, be wherein 0.075: 1 containing the organo-functional group of thiazolinyl and the mass ratio of organo-silicone rubber, Organic silicon thermoplastic elastomer is mediated and is prepared for 2 hours under 150 DEG C of conditions, products therefrom softening temperature 140 DEG C, draw high intensity 3.8 MPa, elongation at break 210%.
Claims (8)
1. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: under 25 DEG C of conditions, the methyl silicone rubber that 50 grams contain vinyl is dissolved in 250 milliliters of toluene and tetrahydrofuran (THF), add the TD resin 120 grams containing vinyl of molecular weight 8500 again, add containing two (t-butyl peroxy) 3,3 of 1,1-after mixing, 5-trimethyl-cyclohexane 0.3 gram, its medium vinyl and organo-silicone rubber mass ratio are 0.002: 1; Stir desolvation after 30 minutes after adding superoxide, then be warming up to 150 DEG C of reactions 30 minutes, prepare Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.11MPa, elongation at break 216%.
2. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: under 25 DEG C of conditions, 20 grams are dissolved in the mixing of 250 milliliters of tetrahydrofuran (THF)s containing the methyl silicone rubber of vinyl and the phenyl siloxane rubber of 20 grams, add the MQ resin 120 grams containing vinyl of molecular weight 11500 again, the TD silicone resin of molecular weight 9,000 30 grams, add after mixing containing 1, two (t-butyl peroxy) 3 of 1-, 3,5-trimethyl-cyclohexane 0.8 gram, its medium vinyl and organo-silicone rubber mass ratio are 0.012: 1; Stir desolvation after 30 minutes after adding superoxide, then be warming up to 150 DEG C of reactions 10 minutes, prepare Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.41MPa, elongation at break 200%.
3. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: under 25 DEG C of conditions, 20 grams are dissolved in the mixing of 250 milliliters of toluene and tetrahydrofuran (THF) containing the methyl/ethyl silicon rubber of vinyl and the phenyl/propyl group silicon rubber of 20 grams, add the MQ resin 20 grams containing vinyl of molecular weight 11500 again, the TD silicone resin of molecular weight 9,000 20 grams, add after mixing containing 1, two (t-butyl peroxy) 3 of 1-, 3,5-trimethyl-cyclohexane 0.5 gram, its medium vinyl and organo-silicone rubber mass ratio are 0.06: 1; Stir desolvation after 30 minutes after adding superoxide, then be warming up to 155 DEG C of reactions 20 minutes, prepare Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.12MPa, elongation at break 210%.
4. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: under 25 DEG C of conditions, 20 grams are dissolved in the mixing of 250ml toluene and tetrahydrofuran (THF) containing the methyl/ethyl silicon rubber of vinyl and the phenyl/propyl group silicon rubber of 20 grams, add the MQ resin 400 grams containing vinyl of molecular weight 11500 again, the TD silicone resin of molecular weight 9,000 30 grams, hydrogen containing siloxane 4 grams and Platinic chloride 0.5 gram and 1 is added after mixing, two (t-butyl peroxy) 3 of 1-, 3, 5-trimethyl-cyclohexane 1.5 grams, its medium vinyl and organo-silicone rubber mass ratio are 0.12: 1, stir desolvation after 30 minutes after adding superoxide, then be warming up to 150 DEG C of reactions 10 minutes, prepare Organic silicon thermoplastic elastomer, products therefrom softening temperature 90 DEG C, tensile strength 3.85MPa, elongation at break 150%.
5. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: the methyl silicone rubber 200 grams being contained vinyl, 10 grams of methyl silicone rubbers containing propenyl, 20 grams of phenyl siloxane rubbers and the MQ resin of 500 gram molecular weights 11000 containing vinyl, the TD resin of 25 gram molecular weights 4600 and hydrogen containing siloxane 12 grams join in twin screw extruder with Platinic chloride 0.1 gram, be wherein 0.05: 1 containing thiazolinyl organic group and organo-silicone rubber mass ratio, extrude under 150 DEG C of conditions and prepare Organic silicon thermoplastic elastomer, the time that material stops in twin screw extruder is 3 minutes, products therefrom softening temperature 100 DEG C, draw high intensity 2.5MPa, elongation at break 300%.
6. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: the methyl silicone rubber 220 grams being contained vinyl, 10 grams of methyl silicone rubbers containing propenyl, 20 grams of phenyl siloxane rubbers and the MQ resin of 1000 gram molecular weights 9000 containing vinyl, and hydrogen containing siloxane 5 grams and Platinic chloride 0.02 gram and 2, 5-dimethyl-2, 5 two (t-butyl peroxy) hexane 1.5 grams joins in twin screw extruder, be wherein 0.035: 1 containing the organo-functional group of thiazolinyl and the mass ratio of organo-silicone rubber, Organic silicon thermoplastic elastomer is directly extruded and is prepared under 150 DEG C of conditions, products therefrom softening temperature 77 DEG C, draw high intensity 1.6MPa, elongation at break 320%.
7. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: the methyl silicone rubber 300 grams being contained vinyl, 40 grams of phenyl siloxane rubbers and the MQ resin of 1500 gram molecular weights 7000 containing vinyl, the MT resin of 15 gram molecular weights 5000, the MTD resin of 15 gram molecular weights 8000 and hydrogen containing siloxane 12 grams and Platinic chloride 0.01 gram and 2, 5-dimethyl-2, 5 two (t-butyl peroxy) hexane 1.5 grams joins in kneader, be wherein 0.085: 1 containing the organo-functional group of thiazolinyl and the mass ratio of organo-silicone rubber, Organic silicon thermoplastic elastomer is mediated and is prepared for 2 hours under 120 DEG C of conditions, products therefrom softening temperature 90 DEG C, draw high intensity 2.8MPa, elongation at break 260%.
8. an Organic silicon thermoplastic elastomer, it is characterized in that by following processing step and processing parameter preparation: the phenyl siloxane rubber 150 grams being contained vinyl, 10 grams contain the MQ resin of vinyl containing allylic methyl silicone rubber and 500 gram molecular weights 8800, the MT resin and 2 of 200 gram molecular weights 7600, 5-dimethyl-2, 5 two (t-butyl peroxy) hexane 6 grams and 2, 5-dimethyl-2, 5-bis-(t-butyl peroxy) acetylene 0.2 gram joins in kneader, be wherein 0.075: 1 containing the organo-functional group of thiazolinyl and the mass ratio of organo-silicone rubber, Organic silicon thermoplastic elastomer is mediated and is prepared for 2 hours under 150 DEG C of conditions, products therefrom softening temperature 140 DEG C, draw high intensity 3.8MPa, elongation at break 210%.
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| CN108865053B (en) * | 2018-08-01 | 2021-01-29 | 深圳日高胶带新材料有限公司 | High-low temperature resistant conductive organic silicon pressure-sensitive adhesive and preparation method and application thereof |
| CN109651822B (en) * | 2018-12-29 | 2021-01-12 | 山东百多安医疗器械股份有限公司 | Medical silicone rubber with high mechanical property and preparation method thereof |
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