CN112063181A - Mixing silicone rubber and preparation method thereof - Google Patents

Mixing silicone rubber and preparation method thereof Download PDF

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Publication number
CN112063181A
CN112063181A CN202010989994.XA CN202010989994A CN112063181A CN 112063181 A CN112063181 A CN 112063181A CN 202010989994 A CN202010989994 A CN 202010989994A CN 112063181 A CN112063181 A CN 112063181A
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parts
silicone rubber
vinyl
mixed
coupling agent
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李振平
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Dongguan Haizhilan Silicone Technology Co ltd
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Dongguan Haizhilan Silicone Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
    • C08K2003/387Borates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

Abstract

The invention belongs to the technical field of silicone rubber, and particularly relates to mixed silicone rubber which comprises the following components in parts by mass: 20-100 parts of methyl vinyl silicone rubber, 10-900 parts of vinyl-terminated polymethyl vinyl silicone rubber, 20-800 parts of fumed silica, 0.5-50 parts of platinum flame retardant, 0.3-50 parts of fatty acid, 1-80 parts of structural control agent, 0.1-10 parts of release agent, 0.1-50 parts of ammonium carbonate, 0.3-50 parts of triazole compound, 0.1-30 parts of nano titanium dioxide, 0.1-20 parts of coupling agent and 0.1-30 parts of zinc borate. In addition, the invention also provides a preparation method of the mixing silicone rubber. Compared with the prior art, the mixed silicon rubber has high transparency and high strength, and reaches the flame-retardant safety level.

Description

Mixing silicone rubber and preparation method thereof
Technical Field
The invention belongs to the technical field of silicone rubber, and particularly relates to mixed silicone rubber and a preparation method thereof.
Background
The organosilicon mixed silicone rubber is prepared by adding a reinforcing material and other additives on the basis of raw rubber, kneading and mixing the raw rubber to prepare mixed rubber, and then processing, crosslinking and curing the mixed rubber by processes such as mould pressing/extrusion/calendering and the like to prepare various silicone rubber products, and is an organosilicon high polymer material with the most extensive application. However, the organosilicon high molecular material is easy to burn, which is not favorable for the safe, environment-friendly and sustainable development.
The traditional organic silicon flame-retardant rubber compound achieves the flame-retardant effect by adding a large amount of inorganic flame retardants such as aluminum hydroxide and the like or organic nitrogen-phosphorus flame retardants, so that the traditional flame-retardant rubber compound (in white and other colors) loses the natural color transparency of organic silicon, subsequent adjustment processes such as color mixing and dyeing and the like are influenced, the traditional flame-retardant rubber compound is not beneficial to wide expansion of application, flame-retardant silicon rubber is further not beneficial to wide popularization, the popularization of high polymer materials in the aspect of safe flame retardance is hindered, and the requirements of the state on safe, environment-friendly and sustainable development of the high polymer materials are;
therefore, transparent flame-retardant rubber compound appears in the market, and although the transparency of the transparent flame-retardant rubber compound is greatly improved compared with that of the traditional organic silicon flame retardant, part of the transparent flame-retardant rubber compound still cannot reach the flame-retardant safety level of the rubber compound; some parts of the silicone rubber products reach the safety level by adding halogen flame retardant, but are not beneficial to environmental protection, and some parts of the silicone rubber products are not high in mechanical strength and are not beneficial to wide application in downstream silicone rubber product industries.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the provided mixed silicone rubber has high transparency and high strength and can reach the flame-retardant safety level.
In order to achieve the purpose, the invention adopts the following technical scheme:
the mixing silicone rubber comprises the following components in parts by mass: 20-100 parts of methyl vinyl silicone rubber, 10-900 parts of vinyl-terminated polymethyl vinyl silicone rubber, 20-800 parts of fumed silica, 0.5-50 parts of platinum flame retardant, 0.3-50 parts of fatty acid, 1-80 parts of structural control agent, 0.1-10 parts of release agent, 0.1-50 parts of ammonium carbonate, 0.3-50 parts of triazole compound, 0.1-30 parts of nano titanium dioxide, 0.1-20 parts of coupling agent and 0.1-30 parts of zinc borate.
As an improvement of the mixed silicone rubber, the average molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, wherein the mass percentage of vinyl is 0.03-8%.
As an improvement of the mixed silicone rubber, the average molecular weight of the vinyl-terminated polymethyl vinyl silicone rubber is 40-80 ten thousand, wherein the mass percentage of vinyl is 0.03-8%.
As an improvement of the mixing silicone rubber, the specific surface area of the fumed silica is 100-400 m2/g。
As an improvement of the mixed silicone rubber of the invention, the platinum flame retardant comprises at least one of chloroplatinic acid and a platinum complex.
In the improved mixed silicone rubber, the fatty acid comprises at least one of aliphatic hydrocarbon carboxylic acids with 10-18 carbon atoms. Such as stearic acid, lauric acid, and the like.
As an improvement of the mixing silicon rubber, the structural control agent comprises at least one of hydroxyl silicone oil, diphenyl silanediol, alkoxy silane, low-molecular polysilane and silazane.
As an improvement of the mixing silicon rubber, the triazole compound comprises at least one of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole and benzotriazole.
As an improvement of the mixed silicone rubber of the present invention, the release agent is a stearate-based release agent such as zinc stearate; the coupling agent is an organosilicon coupling agent or a titanate coupling agent, such as organosilicon coupling agent 171.
As an improvement of the mixed silicone rubber, the particle size D50 of the nano titanium dioxide is 15-25 nm. Preferably, the particle size D50 of the nano titanium dioxide is 20 nm.
The second purpose of the invention is: the preparation method of the mixed silicone rubber comprises the following steps:
adding methyl vinyl silicone rubber, vinyl-terminated polymethyl vinyl silicone rubber, fumed silica, a structural control agent and a release agent into a kneader according to parts by mass, kneading for 1-4 h at 130-200 ℃, and discharging to obtain a sizing material A; preferably, kneading at 150-170 ℃ for 2-3 h;
naturally cooling the rubber material A to 25 ℃, and standing for 24h at 25 ℃;
adding the rubber material A, a platinum flame retardant, fatty acid, ammonium carbonate, a triazole compound, nano titanium dioxide, a coupling agent and zinc borate into a kneader, heating to 100 ℃, stirring for 1.5 hours, and discharging to obtain the mixed silicone rubber.
Compared with the prior art, the invention at least has the following beneficial effects:
1) in the invention, two crude rubbers of methyl vinyl silicone rubber and vinyl-terminated polymethyl vinyl silicone rubber are compounded to form a stronger ethylene crosslinking network, so that the mixed silicone rubber has stronger mechanical strength.
2) Compared with the traditional precipitation-process white carbon black, the gas-phase white carbon black has stronger mechanical complementary performance, can assist two raw rubbers of methyl vinyl silicone rubber and vinyl-terminated polymethyl vinyl silicone rubber to reinforce, and further improves the mechanical performance of the mixed silicone rubber; in addition, the coupling agent and the white carbon black prepared by the gas phase method are subjected to chemical reaction to form a chemical bond, so that the physical properties of the mixed silicon rubber are greatly improved; the structural control agent and the white carbon black prepared by the gas phase method are subjected to chemical reaction to form a chemical bond, so that the silicon rubber is prevented from being structured, and the mechanical property of the silicon rubber is prevented from being reduced.
3) In the invention, a platinum flame retardant is adopted instead of a halogen flame retardant or an inorganic oxide flame retardant, which can pass the ROHS test and does not influence the transparency of the mixed silicon rubber; in addition, the fatty acid, the ammonium carbonate and the triazole compound play a role in assisting flame retardance and further improving flame retardance, and the zinc borate plays a role in increasing transparency, so that the mixed silicone rubber is high in transparency and reaches a flame-retardant safety level.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
The mixing silicone rubber comprises the following components in parts by mass: 20 parts of methyl vinyl silicone rubber, 80 parts of vinyl-terminated polymethyl vinyl silicone rubber, 40 parts of fumed silica, 1.5 parts of chloroplatinic acid (platinum flame retardant), 35 parts of stearic acid (fatty acid), 3.5 parts of hydroxy silicone oil (structural control agent), 0.5 part of zinc stearate (mold release agent), 2 parts of ammonium carbonate, 40 parts of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (triazole compound), 0.8 part of nano titanium dioxide, 1 part of organosilicon coupling agent 171 (coupling agent) and 0.9 part of zinc borate. Wherein the average molecular weight of the methyl vinyl silicone rubber is 40-80 ten thousand, and the mass percentage of the vinyl is 4%; the average molecular weight of the vinyl-terminated polymethyl vinyl silicone rubber is 40-80 ten thousand, and the mass percentage of the vinyl is 4%; the specific surface area of the fumed silica is 100-400 m2(ii) in terms of/g. The particle size D50 of the nano titanium dioxide is 20 nm. Ammonium carbonate and zinc borate are of more than industrial purity.
The preparation method of the mixed silicone rubber comprises the following steps:
1) adding methyl vinyl silicone rubber, vinyl-terminated polymethyl vinyl silicone rubber, fumed silica, a structural control agent and a release agent into a kneader according to parts by mass, kneading for 1-4 h at 130-200 ℃, and discharging to obtain a sizing material A;
2) naturally cooling the rubber material A to 25 ℃, and standing for 24h at 25 ℃;
3) adding the rubber material A obtained in the step 2), a platinum flame retardant, fatty acid, ammonium carbonate, a triazole compound, nano titanium dioxide, a coupling agent and zinc borate into a kneader, heating to 100 ℃, stirring for 1.5h, and discharging to obtain the mixed silicone rubber.
Example 2
The difference from example 1 is:
the mixed silicone rubber of the embodiment comprises the following components in parts by mass: 20 parts of methyl vinyl silicone rubber, 90 parts of vinyl-terminated polymethyl vinyl silicone rubber, 45 parts of fumed silica, 2 parts of chloroplatinic acid (platinum flame retardant), 35 parts of lauric acid (fatty acid), 4 parts of hydroxy silicone oil (structural control agent), 0.5 part of zinc stearate (mold release agent), 2 parts of ammonium carbonate, 35 parts of benzotriazole (triazole compound), 0.9 part of nano titanium dioxide, 1 part of organosilicon coupling agent 172 (coupling agent) and 1 part of zinc borate.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is:
the mixed silicone rubber of the embodiment comprises the following components in parts by mass: 20 parts of methyl vinyl silicone rubber, 100 parts of vinyl-terminated polymethyl vinyl silicone rubber, 50 parts of fumed silica, 2 parts of chloroplatinic acid (platinum flame retardant), 30 parts of stearic acid (fatty acid), 4.5 parts of hydroxy silicone oil (structural control agent), 0.6 part of zinc stearate (mold release agent), 2.2 parts of ammonium carbonate, 35 parts of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (triazole compound), 0.1-30 parts of nano titanium dioxide, 1 part of organosilicon coupling agent 171 (coupling agent) and 1.2 parts of zinc borate.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is:
the mass percentage of vinyl in the methyl vinyl silicone rubber is 0.03 percent; the mass percentage of vinyl in the vinyl-terminated polymethyl vinyl silicone rubber is 4 percent.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is:
the mass percentage of vinyl in the methyl vinyl silicone rubber is 4 percent; the mass percentage of vinyl in the vinyl-terminated polymethyl vinyl silicone rubber is 0.03 percent.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is:
the mass percentage of vinyl in the methyl vinyl silicone rubber is 4 percent; the mass percentage of vinyl in the vinyl-terminated polymethyl vinyl silicone rubber is 8 percent.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is:
the mass percentage of vinyl in the methyl vinyl silicone rubber is 8 percent; the mass percentage of vinyl in the vinyl-terminated polymethyl vinyl silicone rubber is 4 percent.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is:
the mass percentage of vinyl in the methyl vinyl silicone rubber is 0.03 percent; the mass percentage of vinyl in the vinyl-terminated polymethyl vinyl silicone rubber is 8 percent.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is:
the mass percentage of vinyl in the methyl vinyl silicone rubber is 8 percent; the mass percentage of vinyl in the vinyl-terminated polymethyl vinyl silicone rubber is 0.03 percent.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is:
no vinyl terminated polymethylvinylsiloxane rubber was added.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 2
The difference from example 1 is:
the flame retardant is a halogen flame retardant.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 3
The difference from example 1 is:
the flame retardant is an inorganic oxide flame retardant.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 4
The difference from example 1 is:
stearic acid (fatty acid), ammonium carbonate and 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (triazole-based compound) were not added.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 5
The difference from example 1 is:
no zinc borate was added.
The rest is the same as embodiment 1, and the description is omitted here.
Performance testing
The silicone rubber compounds obtained in examples 1 to 9 and comparative examples 1 to 5, and commercial compound 1 (non-transparent), compound 2 (transparent) and compound 3 (transparent) were subjected to performance tests, and the results are shown in table 1.
TABLE 1 test results
Figure BDA0002690544620000071
As can be seen from the test results of table 1:
1) as can be seen by comparing examples 1-9 with comparative examples 1-5 and rubber mixtures 1-3, the mixed silicone rubber prepared by the formula provided by the invention is transparent in appearance, the flame retardant grade can reach 94VO, and the mechanical strength can be more than twice that of other silicone rubbers through ROHS.
2) As can be seen from the comparison of examples and comparative example 1, when the system contains only one raw rubber of methyl vinyl silicone rubber, the mechanical strength of the prepared mixed silicone rubber is poor, and when the system adopts two raw rubbers of methyl vinyl silicone rubber and vinyl-terminated polymethyl vinyl silicone rubber, the mechanical strength of the obtained mixed silicone rubber is greatly improved. The reason is that the methyl vinyl silicone rubber and the vinyl-terminated polymethyl vinyl silicone rubber are compounded to form a stronger ethylene crosslinking network, so that the mechanical strength of the mixed silicone rubber is improved. In particular, the compounded silicone rubber obtained in example 1 was the most excellent in mechanical strength.
3) Compared with halogen flame retardants and inorganic oxide flame retardants, the platinum flame retardant used in the invention can reach a flame retardant rating of 94VO, and can pass ROHS test, so that the platinum flame retardant has environmental protection and safety, and the platinum flame retardant does not affect the color of the mixed silicone rubber, so that the mixed silicone rubber can keep natural color and transparency.
4) As can be seen from the comparison between the examples and the comparative example 4, when the fatty acid, the ammonium carbonate and the triazole compound are also added into the formula, the oxygen index of the prepared mixed silicon rubber is higher, which shows that the flame retardant effect is better, because the three materials play a role in assisting flame retardance, thereby further improving the flame retardant property.
5) As can be seen from the comparison of examples and comparative example 5, when zinc borate was further added to the formulation, the resulting compounded silicone rubber was more transparent, indicating that it had an effect of increasing transparency.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. The mixing silicone rubber is characterized by comprising the following components in parts by mass: 20-100 parts of methyl vinyl silicone rubber, 10-900 parts of vinyl-terminated polymethyl vinyl silicone rubber, 20-800 parts of fumed silica, 0.5-50 parts of platinum flame retardant, 0.3-50 parts of fatty acid, 1-80 parts of structural control agent, 0.1-10 parts of release agent, 0.1-50 parts of ammonium carbonate, 0.3-50 parts of triazole compound, 0.1-30 parts of nano titanium dioxide, 0.1-20 parts of coupling agent and 0.1-30 parts of zinc borate.
2. The mixing silicone rubber according to claim 1, wherein the average molecular weight of the methyl vinyl silicone rubber is 40 to 80 ten thousand, and the mass percentage of vinyl groups is 0.03 to 8%.
3. The mixing silicone rubber according to claim 1, wherein the average molecular weight of the vinyl-terminated polymethylvinyl silicone rubber is 40 to 80 ten thousand, and the mass percentage of vinyl is 0.03 to 8%.
4. The mixing silicone rubber according to claim 1, wherein the fumed silica has a specific surface area of 100 to 400m2/g。
5. The compounded silicone rubber according to claim 1, wherein the platinum flame retardant comprises at least one of chloroplatinic acid and a platinum complex.
6. The compounded silicone rubber according to claim 1, wherein the fatty acid comprises at least one of aliphatic hydrocarbon carboxylic acids having 10 to 18 carbon atoms.
7. The compounded silicone rubber according to claim 1, wherein the structural control agent comprises at least one of a hydroxy silicone oil, a diphenylsilanediol, an alkoxysilane, a low molecular polysilane, and a silazane.
8. The compounded silicone rubber according to claim 1, wherein the release agent is a stearate-based release agent, and the coupling agent is an organosilicon coupling agent or a titanate coupling agent.
9. The mixed silicone rubber according to claim 1, wherein the particle diameter D50 of the nano titanium dioxide is 15 to 25 nm.
10. A method for producing the mixed silicone rubber according to any one of claims 1 to 9, characterized by comprising the steps of:
adding methyl vinyl silicone rubber, vinyl-terminated polymethyl vinyl silicone rubber, fumed silica, a structural control agent and a release agent into a kneader according to parts by mass, kneading for 1-4 h at 130-200 ℃, and discharging to obtain a sizing material A;
naturally cooling the rubber material A to 25 ℃, and standing for 24h at 25 ℃;
adding the rubber material A, a platinum flame retardant, fatty acid, ammonium carbonate, a triazole compound, nano titanium dioxide, a coupling agent and zinc borate into a kneader, heating to 100 ℃, stirring for 1.5 hours, and discharging to obtain the mixed silicone rubber.
CN202010989994.XA 2020-09-18 2020-09-18 Mixing silicone rubber and preparation method thereof Pending CN112063181A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115491038A (en) * 2022-09-16 2022-12-20 广州市矽友新材料科技有限公司 Halogen-free platinum flame retardant for silicone rubber and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115491038A (en) * 2022-09-16 2022-12-20 广州市矽友新材料科技有限公司 Halogen-free platinum flame retardant for silicone rubber and preparation method thereof

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Application publication date: 20201211