CN106496563B - A kind of silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction and its preparation method and application - Google Patents

Abstract

The present invention relates to a silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction and its preparation method and application. The compatibilizer has a structure shown in formula (I): in formula (I), R is an alkyl group or a hydroxyl group, and M is an unsaturated hydrocarbon group. 10≤x+l+m≤3000, x/(l+m)>0, 0<l/(l+m)≤1, 2≤n≤30, x, y, l, m, n are integers . The invention also provides the preparation method and application of the compatibilizer. The compatibilizer of the present invention has an excellent compatibilizing effect, can significantly improve the tensile strength and tear strength of the combined system of silicone rubber/unsaturated carbon chain rubber, the amount of increase in tensile strength can reach 3.81MPa, and the amount of increase in tear strength can reach 2.45KN/m.

Description

A kind of silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction and Its preparation method and application

technical field

The invention relates to a silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction and its preparation method and application, belonging to the technical field of rubber additives.

Background technique

At present, unsaturated carbon chain rubber including butyl rubber, natural rubber, and nitrile rubber is the most widely used type of rubber. Taking butyl rubber (IIR) as an example, because the methyl group on the molecular chain is very dense, forming a worm-like structure, it has a high loss factor, and because there is a secondary transition near the glass transition temperature of butyl rubber , resulting in high and wide internal friction peaks, so butyl rubber has excellent shock absorption effect, and the damping materials prepared with it have been widely used in aerospace, automobile manufacturing and other fields. However, the temperature range in which butyl rubber plays a damping role is narrow, especially in low temperature environments, and it is difficult to meet the application requirements.

The organosilicon polymer represented by polysiloxane has good high and low temperature resistance, thermal stability, weather resistance and aging resistance. Its performance is quite stable in a wide temperature range, but its mechanical properties are relatively low. Difference.

Blending is an effective way to improve material properties, develop new materials and balance material prices. Therefore, the combination of silicone rubber and unsaturated carbon chain rubber can not only broaden the use temperature range of unsaturated carbon chain rubber, but also improve the mechanical properties of silicone rubber.

However, due to the difference in structure between silicone rubber and unsaturated carbon-chain butyl rubber, their compatibility is poor, and phase separation is prone to occur during blending, so that the prepared material cannot meet the expected requirements, and even the performance is reduced.

Chinese patent document CN 105906950A (application number: 201610377516.7) discloses a high-temperature-resistant ethylene-propylene rubber/silicone rubber compound glue and a preparation method thereof, in which ethylene-propylene rubber, silicone rubber, a compatibilizer, white carbon black, and a coupling agent After mixing, add anti-aging agent and vulcanizing agent to vulcanize to obtain the product; the compatibilizer used is a polysiloxane graft polymer with unsaturated carbon-carbon double bonds in the side chain, and unsaturated carbon-carbon double bonds in the main chain or side chain. One or more of polysiloxane block polymers with carbon-carbon double bonds. In this patent document, a compatibilizer prepared by molecular design reaction is added in the mixing process of ethylene-propylene rubber and silicone rubber. Since the designed polymer has unsaturated carbon-carbon double bonds, it can be used during the preparation and vulcanization of the mixed rubber. Realize the physical and chemical compatibilization of ethylene-propylene rubber and silicone rubber, further improve the heat resistance of the combined rubber, and can be used as materials that need to be exposed to high temperature environments for a long time and have certain strength requirements.

However, the compatibilizers used in this patent document all consume a certain amount of unsaturated bonds, which requires ethylene-propylene rubber and silicone rubber to have a higher vinyl content, which will lead to a high hardness of the blend rubber, making the combination The elasticity of the system is reduced, and properties such as system damping are sacrificed.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction and its preparation method and application. The compatibilizer of the invention has wide applicability, low raw material cost, simple process and good compatibilizing effect of the compatibilizer. The preparation reaction efficiency is high, the reaction is complete, the conversion rate is high, and the purity is high. It can be widely used in the combination system of silicone rubber and unsaturated carbon chain rubber.

Technical scheme of the present invention is as follows:

A kind of silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation, has the structure shown in formula (I):

In formula (I), R is an alkyl group or a hydroxyl group, and M is an unsaturated hydrocarbon group.

10≤x+l+m≤3000, x/(l+m)>0, 0<l/(l+m)≤1, 2≤n≤30, x, y, l, m, n are integers .

According to the present invention, preferably, the alkyl group is a C1-C10 alkyl group, more preferably -CH ₃ , -CH ₂ CH ₃ or -CH ₂ CH ₂ CH ₃ .

According to the present invention, preferably, the number average molecular weight of the compatibilizer is 0.2-150,000.

According to the present invention, preferably, 20≤x+l+m≤2000, 9≤x<2000, 1≤l<1000, 1≤m<1000, x, l, m are all integers.

According to the present invention, preferably, the unsaturated hydrocarbon group is a C5-C20 alkenyl group, more preferably 1-octenyl, 1-nonenyl, 1-decenyl, 1,7-octadienyl, 1,8-nonadienyl, 1,9-decadienyl, 7-methyl-1,6-octadienyl, dihydromyrcenyl, myrcenyl or citronellyl.

According to the invention, the compatibilizer is prepared by a hydrosilylation reaction. Preferably, the preparation method of above-mentioned compatibilizer, comprises steps as follows:

Mix the unsaturated hydrocarbon and hydrogen-containing silicone oil and dissolve in the solvent, add catalyst and co-catalyst, and stir the reaction; after the reaction is completed, the product is washed with water, and then the small molecular low boiling substances in the material are removed under reduced pressure to obtain Compatibilizer.

According to the preparation method of the present invention, preferably, the unsaturated hydrocarbon is 1-octene, 1-nonene, 1-decene, 1,7-octadiene, 1,8-nonadiene, 1, 9-Decadiene, 7-methyl-1,6-octadiene, dihydromyrcene, myrcene or citronellene.

According to the preparation method of the present invention, preferably, the mixing ratio of the unsaturated hydrocarbon and the hydrogen-containing silicone oil is calculated by the ratio of the unsaturated hydrocarbon to Si—H, and the material ratio thereof is 0.001-10:1.

According to the preparation method of the present invention, preferably, the solvent is toluene, tetrahydrofuran, hexamethylphosphoric triamide, dimethylformamide, cyclohexane or ethanol.

According to the preparation method of the present invention, preferably, the catalyst is a metal complex or chelate, more preferably nickel, palladium, rhodium, platinum complex or chelate; preferably, the amount of catalyst added It is 0.01%-2% of the total mass of unsaturated hydrocarbon and hydrogen-containing silicone oil.

According to the preparation method of the present invention, preferably, the cocatalyst is 4-dimethylaminopyridine, triphenylchlorosilane, triphenylborane, triphenylphosphine, triphenylphosphine oxide, 1,3, 5-triphenylbenzene, triphenylamine or triphenylmethane; preferably, the amount of cocatalyst added is 0.01%-2% of the total mass of unsaturated hydrocarbon and hydrogen-containing silicone oil.

According to the preparation method of the present invention, preferably, the stirring reaction temperature is 10°C-150°C, more preferably 60°C-120°C; the stirring reaction time is 6-36h.

According to the preparation method of the present invention, preferably, the hydrogen-containing silicone oil has a structure shown in formula (II):

y=l+m, x, l, m, R are the same as in formula (I). Preferably, the number average molecular weight of the hydrogen-containing silicone oil is 0.1-100,000, and the hydrogen-containing molar content is 10-90% (molar content).

According to the preparation method of the present invention, preferably, the hydrogen-containing silicone oil is prepared as follows:

Mix D ₄ (octamethylcyclotetrasiloxane) and D ₄ ^H (tetramethylcyclotetrasiloxane), dehydrate first, replace the air with dry nitrogen, heat up to the polymerization temperature, add end-capping agent and catalyst, Atmospheric pressure polymerization reaction, after the polymerization reaction is completed, remove the small molecular low boilers in the material under reduced pressure to obtain hydrogen-containing silicone oil. The molecular weight of hydrogen-containing silicone oil is controlled by the amount of catalyst and end-capping agent.

According to the method for preparing hydrogen-containing silicone oil of the present invention, preferably, the amount ratio of D ₄ to D ₄ ^H is 0.1-20:1.

According to the method for preparing hydrogen-containing silicone oil of the present invention, preferably, the end-capping agent is water or hexamethyldisiloxane, and the amount of the end _- capping agent added is ^0.01-5 % of the total mass of D4 and _D4H .

According to the preparation method of hydrogen-containing silicone oil of the present invention, preferably, the catalyst is tetramethylammonium hydroxide, potassium hydroxide, solid acid or concentrated sulfuric ^acid , and the addition amount of the catalyst is 0.5% of the total mass of D4 and _{D4H .} %-5%;

Further preferably, the solid acid is acid clay, sulfonic acid resin or heteropolyacid, and the mass concentration of the concentrated sulfuric acid is 90%-98%.

According to the method for preparing hydrogen-containing silicone oil of the present invention, preferably, the dehydration conditions are: -0.01-0.02MPa, 40-90°C, 0.5-5h.

According to the preparation method of the hydrogen-containing silicone oil of the present invention, preferably, the polymerization reaction temperature is 50-150° C., and the polymerization reaction time is 0.5-5 h. The polymerization reaction is under normal pressure.

According to the preparation method of the hydrogen-containing silicone oil of the present invention, preferably, after the polymerization reaction is completed, the temperature is raised to 50-200° C., and small molecular low boiling substances in the material are removed at 133-1330 Pa for 0.5-5 hours.

According to the present invention, the application of the above-mentioned compatibilizer is used for the combination system of silicone rubber/unsaturated carbon chain rubber, and the rubber is blended.

According to the application of the present invention, the preparation of the combined system of silicone rubber/unsaturated carbon chain rubber can be carried out on an open mill or an internal mixer. Preferably, the preparation method of silicone rubber/unsaturated carbon chain rubber and system raw materials is as follows:

Add compatibilizer to silicone rubber and unsaturated carbon chain rubber, add white carbon black, vulcanizing agent, vulcanization accelerator and auxiliary agent at the same time, knead evenly, vulcanize and mold at 140-180°C for 10-35min to obtain Silicone rubber/unsaturated carbon chain rubber combined system.

According to the application of the present invention, preferably, the unsaturated carbon chain rubber is butyl rubber, natural rubber or nitrile rubber;

Preferably, the silicone rubber has a number average molecular weight of 300,000 to 1 million, and a vinyl molar content of 0.05% to 0.5%;

Preferably, the white carbon black is fumed white carbon black or precipitated white carbon black;

Preferably, the auxiliary agent is a mixture of a lubricant and a reinforcing additive; further preferably, the lubricant is stearic acid, and the reinforcing additive is aluminum oxide or zinc oxide.

According to the application of the present invention, preferably, the vulcanizing agent is two 2,5, dicumyl peroxide (DCP), sulfur, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, A mixture of two or more of tert-butyl peroxybenzoate and di-tert-butyl peroxide;

Preferably, the vulcanization accelerator is 4,4'-dithiodimorpholine (DTDM), dithiocarbamate, xanthate, thiazole and tetramethylthiuram disulfide (TMTD ) in a mixture of two types in a mass ratio of 0.1 to 10:1.

According to the application of the present invention, preferably, the mass ratio of silicone rubber, unsaturated carbon chain rubber, white carbon black, vulcanizing agent, vulcanization accelerator, auxiliary agent, compatibilizer is 100: (10-1000): (20- 200):(0.05-5):(0.01-3):(0.01-3):(0.5-5).

Principle of the present invention and characteristics are as follows:

The present invention adopts hydrosilicon addition reaction to make hydrogen-containing silicone oil side chains graft unsaturated hydrocarbons to prepare compatibilizers to prepare hydrogen-containing silicone oils. Small will lead to insignificant compatibilizing effect of compatibilizer; the hydrogen content is between 10% and 90% (molar content), which is determined from factors such as the ease of synthesis and the compatibilizing effect of compatibilizer; specific end groups can be used in combination The system has specific properties, such as the terminal group being an alkyl group can play a physical compatibilizing effect and enhance the damping performance of the combined system; the hydroxyl group can make the compatibilizer have a certain polarity, which is suitable for the combined system with polar groups. The compatibilizer is obtained by grafting a certain amount of unsaturated hydrocarbons through hydrosilylation reaction, wherein the grafting rate of unsaturated hydrocarbon groups is preferably 10%-100%, that is, the mixing ratio of unsaturated hydrocarbons and hydrogen-containing silicone oil is in the range of The ratio of unsaturated hydrocarbons to Si-H is calculated, and the molar ratio of the substances is 0.001-10:1. The number of compatibilizers used should be 0.5-5 parts. Based on 100 parts of silicone rubber, too little will not achieve the effect of compatibilization, and too much will reduce the mechanical strength of the combined system.

The present invention has the following advantages:

1. In the preparation process of the compatibilizer of the present invention, the use of hydrosilylation reaction has high preparation efficiency, high conversion rate, high purity, low raw material cost and simple process;

2. During the application process of the compatibilizer of the present invention, the compatibilizer has a good compatibilizing effect, and can be widely used in the combination system of silicone rubber and unsaturated carbon chain rubber;

3. The compatibilizer of the present invention has excellent compatibilizing effects, and can significantly increase the tensile strength and tear strength of the combined system of silicone rubber/unsaturated carbon chain rubber. The increase in tensile strength can reach 3.81MPa, and the increase in tear strength can reach Up to 2.45KN/m.

Description of drawings

Fig. 1 is the infrared spectrogram of the compatibilizer prepared in the present invention.

Detailed ways

The present invention will be described in further detail below in conjunction with specific embodiments, but is not limited thereto.

The parts described in the examples are all parts by weight.

Example 1

(1) Preparation of hydrogen-containing silicone oil

Add 30g D ₄ and 48g D ₄ ^H into the polymerization reactor for dehydration. The dehydration conditions are -0.01~-0.02MPa, 40~80°C, 2h, dry nitrogen and ventilate, then raise the temperature to the polymerization temperature of 80~120°C, add Hexa Disiloxane-based end-capping agent, potassium hydroxide catalyst, normal pressure reaction for 24 hours, after the end of the polymerization, the temperature was raised to 150°C, and the small molecule low boiling substances in the material were removed at 133-1330Pa, and the time was 4 hours to obtain hydrogen-containing The molecular weight of silicone oil is controlled by the amount of hexamethyldisiloxane end-capping agent and potassium hydroxide catalyst, the number average molecular weight is about 7000, and the molar content of Si-H is about 66%.

The structural formula of the obtained hydrogen-containing silicone oil is as follows:

(2) Preparation of compatibilizer

Add 48g of 1-octene and 36g of hydrogen-containing silicone oil obtained in step (1) into 80g of cyclohexane solvent, add 0.15mL of chloroplatinic acid catalyst, 0.05mL of triphenylmethane cocatalyst, and stir at a temperature of 90°C. Reaction 12h.

The reaction product was washed with water for 3 to 4 times, heated to 120°C, and the small molecular low boilers in the material were removed under a reduced pressure of 133 to 1330 Pa to obtain 76 g of compatibilizer with a yield of 95% and a number average molecular weight of about 16,000.

The structural formula of the compatibilizer made is as follows:

(3) Preparation of silicone rubber/unsaturated carbon chain rubber combined system raw materials

100 parts of raw silicone rubber, 10 parts of butyl rubber, 30 parts of white carbon black, 1.5 parts of vulcanizing agent DCP, 0.1 part of sulfur, 0.14 parts of stearic acid, 0.35 parts of zinc oxide, 0.05 parts of DTDM, 0.05 parts of TMTD, phase Add 3 parts of compatibilizer in turn to the double-roller mill and knead evenly, and use the material to vulcanize and mold at 160°C for 20 minutes to obtain a silicone rubber/unsaturated carbon chain rubber combination system with good compatibilization effect.

Example 2

(1) Preparation of hydrogen-containing silicone oil

Add 30g D ₄ and 48g D ₄ ^H into the polymerization reactor for dehydration. The dehydration conditions are -0.01~-0.02MPa, 40~80°C, 2h, dry nitrogen and ventilate, then raise the temperature to the polymerization temperature of 80~120°C, add Hexa base disiloxane end-capping agent, tetramethylammonium hydroxide catalyst, reaction at normal pressure for 24h, after the polymerization is completed, the temperature is raised to 150°C, and small molecular low boiling substances in the material are removed at 133-1330Pa for 4h The hydrogen-containing silicone oil is obtained, the molecular weight of which is controlled by the amount of hexamethyldisiloxane end-capping agent and tetramethylammonium hydroxide catalyst, the number average molecular weight is about 5000, and the Si-H molar content is about 66%.

The structural formula of the obtained hydrogen-containing silicone oil is as follows:

(2) Preparation of compatibilizer

Add 56g of dihydromyrcene and 36g of hydrogen-containing silicone oil obtained in step (1) into 90g of toluene solvent, add 0.15mL of chloroplatinic acid catalyst, 0.05mL of triphenylphosphine oxide cocatalyst, and stir at a temperature of 80°C to react 12h.

The reaction product was washed with water for 3 to 4 times, heated to 120°C, and the small molecular low boilers in the material were removed under a reduced pressure of 133 to 1330 Pa to obtain 83 g of compatibilizer with a yield of 92% and a number average molecular weight of about 11,000.

The structural formula of the compatibilizer made is as follows:

(3) Preparation of silicone rubber/unsaturated carbon chain rubber combined system raw materials

Add 30 parts of raw silicone rubber, 70 parts of natural rubber, 30 parts of white carbon black, 1 part of sulfur, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of DTDM, 0.5 parts of TMTD, and 3 parts of compatibilizer to the Mix evenly on a two-roll mill, and use this material to vulcanize and press at 160°C for 20 minutes to obtain a silicone rubber/unsaturated carbon chain rubber combination system with good compatibilization effect.

Example 3

(1) Preparation of hydrogen-containing silicone oil

Add 30g D ₄ and 24g D ₄ ^H into the polymerization reactor for dehydration. The dehydration conditions are -0.01~-0.02MPa, 40~80°C, 2h, dry nitrogen and ventilate, then raise the temperature to the polymerization temperature 80~120°C, add Hexa base disiloxane end-capping agent, concentrated sulfuric acid catalyst, react at normal pressure for 24 hours, after the polymerization, raise the temperature to 150°C, and remove small molecular low boiling substances in the material at 133-1330Pa, and the time is 4 hours to obtain hydrogen-containing silicone oil , its molecular weight is controlled by the amount of hexamethyldisiloxane end-capping agent and concentrated sulfuric acid catalyst, the number average molecular weight is about 5000, and the Si-H molar content is about 50%.

The structural formula of the obtained hydrogen-containing silicone oil is as follows:

(2) Preparation of compatibilizer

Add 38g of 1-decene and 36g of the hydrogen-containing silicone oil obtained in step (1) into 90g of tetrahydrofuran solvent, add 0.15mL of chloroplatinic acid catalyst, 0.05mL of triphenylchlorosilane cocatalyst, and stir at a temperature of 90°C to react 12h.

The reaction product was washed with water for 3 to 4 times, heated to 120° C., and the small molecular low boilers in the material were removed under a reduced pressure of 133 to 1330 Pa to obtain 69 g of compatibilizer with a yield of 94% and a number average molecular weight of about 10,000.

The structural formula of the compatibilizer made is as follows:

(3) Preparation of silicone rubber/unsaturated carbon chain rubber combined system raw materials

The specific operation mode is the same as that of embodiment 1.

Example 4

(1) Preparation of hydrogen-containing silicone oil

Add 60g D ₄ and 24g D ₄ ^H into the polymerization reactor for dehydration. The dehydration conditions are -0.01~-0.02MPa, 40~80°C, 2h, dry nitrogen and ventilate, then raise the temperature to the polymerization temperature of 80~120°C, add Hexa base disiloxane end-capping agent, solid acid catalyst, react at normal pressure for 24 hours, after the polymerization is completed, raise the temperature to 150°C, and remove small molecular low boiling substances in the material at 133-1330Pa, and the time is 4 hours to obtain hydrogen-containing silicone oil , its molecular weight is controlled by the amount of hexamethyldisiloxane end-capping agent and solid acid catalyst, the number average molecular weight is about 20,000, and the Si-H molar content is about 33%.

The structural formula of the obtained hydrogen-containing silicone oil is as follows:

(2) Preparation of compatibilizer

Add 22g of 1,8-nonadiene and 36g of the hydrogen-containing silicone oil obtained in step (1) into 70g of ethanol solvent, add 0.15mL of chloroplatinic acid catalyst, 0.05mL of 1,3,5-triphenylbenzene cocatalyst, The temperature was 90°C, stirred, and reacted for 12 hours.

The reaction product was washed with water for 3 to 4 times, heated to 120° C., and the small molecular low boilers in the material were removed under a reduced pressure of 133 to 1330 Pa to obtain 52 g of compatibilizer with a yield of 91% and a number average molecular weight of about 40,000.

The structural formula of the compatibilizer made is as follows:

(3) Preparation of silicone rubber/unsaturated carbon chain rubber combined system raw materials

The specific operation mode is the same as that of embodiment 1.

Example 5

(1) Preparation of hydrogen-containing silicone oil

Add 30g D ₄ and 24g D ₄ ^H into the polymerization reactor for dehydration. The dehydration conditions are -0.01～-0.02MPa, 40～80℃, 2h, dry nitrogen and ventilate, then raise the temperature to the polymerization temperature of 80～120℃, add water seal Terminal agent, potassium hydroxide catalyst, react at normal pressure for 24 hours, after the polymerization is completed, heat up to 150°C, remove small molecular low boiling substances in the material at 133-1330Pa, and obtain hydrogen-containing silicone oil for 4 hours, the molecular weight of which is passed through water The amount of end-capping agent and potassium hydroxide catalyst is controlled, the number average molecular weight is about 1000, and the molar content of Si-H is about 50%.

The structural formula of the obtained hydrogen-containing silicone oil is as follows:

(2) Preparation of compatibilizer

Add 35g of 1-decene and 36g of hydrogen-containing silicone oil obtained in step (1) into 90g of tetrahydrofuran solvent, add 0.15mL of chloroplatinic acid catalyst, 0.05mL of triphenylphosphine co-catalyst, stir at 90°C, and react for 12h .

The reaction product was washed with water for 3 to 4 times, heated to 120° C., and the small molecular low boilers in the material were removed under a reduced pressure of 133 to 1330 Pa to obtain 67 g of compatibilizer with a yield of 94% and a number average molecular weight of about 2000.

The structural formula of the compatibilizer made is as follows:

(3) Preparation of silicone rubber/unsaturated carbon chain rubber combined system raw materials

The specific operation mode is the same as that of embodiment 1.

Example 6

(1) Preparation of hydrogen-containing silicone oil

Add 30g D ₄ and 24g D ₄ ^H into the polymerization reactor for dehydration. The dehydration conditions are -0.01～-0.02MPa, 40～80℃, 2h, dry nitrogen and ventilate, then raise the temperature to the polymerization temperature of 80～120℃, add water seal Terminal agent, concentrated sulfuric acid catalyst, react at normal pressure for 24 hours, after the polymerization is completed, raise the temperature to 150°C, and remove small molecular low boiling substances in the material at 133-1330Pa, and the time is 4 hours to obtain hydrogen-containing silicone oil, the molecular weight of which is sealed by water The amount of terminal agent and concentrated sulfuric acid catalyst is controlled, the number average molecular weight is about 60,000, and the molar content of Si-H is about 50%.

The structural formula of the obtained hydrogen-containing silicone oil is as follows:

(2) Preparation of compatibilizer

Add 40g of 1,9-decadiene and 36g of hydrogen-containing silicone oil obtained in step (1) into 90g of hexamethylphosphoric triamide solvent, add 0.15mL of chloroplatinic acid catalyst, 0.05mL of triphenylchlorosilane Catalyst, temperature 90°C, stirring, reacting for 12h.

The reaction product was washed with water for 3 to 4 times, heated to 120°C, and the small molecular low boilers in the material were removed under a reduced pressure of 133 to 1330 Pa to obtain 68 g of compatibilizer with a yield of 90% and a number average molecular weight of about 120,000.

The structural formula of the compatibilizer made is as follows:

(3) Preparation of silicone rubber/unsaturated carbon chain rubber combined system raw materials

The specific operation mode is the same as that of embodiment 1.

Comparative example 1

The specific mode of operation is the same as in Example 1, except that the addition of the compatibilizer in step (3) is 0 parts.

Comparative example 2

The specific mode of operation is the same as in Example 2, except that the addition amount of the compatibilizer in step (3) is 0 parts.

Comparative example 3

The specific mode of operation is the same as in Example 1, except that the addition of the compatibilizer in step (3) is 0.5 parts.

Comparative example 4

The specific mode of operation is the same as in Example 1, except that the step (3) compatibilizer add-on is 5 parts.

Comparative example 5

The specific operation mode is the same as that of Example 1, except that the molecular weight of the compatibilizer obtained in step (2) is 1000.

Comparative example 6

The specific mode of operation is the same as in Example 1, except that the molecular weight of the compatibilizer obtained in step (2) is 210,000.

Test case

The silicone rubber/unsaturated carbon chain rubber obtained in Examples 1-6 and Comparative Examples 1-6 were used for performance testing, and the results are shown in Tables 1, 2, and 3.

Tensile strength and elongation are tested according to GB/T 528-1998; tear strength is tested according to GB/T 529-1999; hardness is tested according to GB/T 531-1999.

Table 1 Silicone rubber/unsaturated carbon chain rubber vulcanization system proportioning embodiment (parts by weight)

Table 2 Silicone rubber/unsaturated carbon chain rubber vulcanization system ratio comparison ratio (parts by weight)

Table 3 Silicone rubber/unsaturated carbon chain rubber sulfur performance data

It can be seen from Table 3:

Comparative example 1 and comparative example 1 know that under the same conditions, adding compatibilizer of the present invention can obviously improve the tensile strength and tear strength of silicone rubber/unsaturated carbon chain rubber (butyl rubber) and system, The increase in tensile strength reaches 1.93MPa, and the increase in tear strength reaches 1.39KN/m.

Comparing Example 2 and Comparative Example 2 as can be seen, under the same conditions, adding compatibilizer of the present invention can obviously improve the tensile strength and tear strength of silicone rubber/unsaturated carbon chain rubber (natural rubber) and system, tensile The increase in tensile strength reaches 3.81MPa, and the increase in tear strength reaches 1.0KN/m.

Comparative example 1 and comparative example 3, comparative example 1 and comparative example 3 know that under the same conditions, adding the compatibilizer of the present invention too little can make the compatibilizing effect of silicone rubber/unsaturated carbon chain rubber combined system not obvious.

Comparing Example 1 and Comparative Example 4, Comparative Example 1 and Comparative Example 4, it can be seen that under the same conditions, adding too much compatibilizer of the present invention will make the compatibilization effect of the silicone rubber/unsaturated carbon chain rubber combined system decline.

Comparing Example 1 and Comparative Example 5, Comparative Example 1 and Comparative Example 5, it can be seen that under the same conditions, adding the compatibilizer of the present invention with too small molecular weight will make the compatibilization effect of the silicone rubber/unsaturated carbon chain rubber combined system Not obvious.

Comparing Example 1 and Comparative Example 6, Comparative Example 1 and Comparative Example 6, it can be seen that under the same conditions, adding the compatibilizer molecular weight of the present invention is too large to make the compatibilization effect of the silicone rubber/unsaturated carbon chain rubber combined system not good. obvious.

Comparing Example 3 and Example 4, it can be seen that under the same conditions, the hydrogen content of the silicone oil used in the compatibilizer of the present invention is too small to make the compatibilization effect of the silicone rubber/unsaturated carbon chain rubber combination system not obvious.

Comparing Example 3 and Example 5, it can be seen that under the same conditions, the addition of too much hydrogen content in the silicone oil used in the compatibilizer of the present invention will make the compatibilization effect of the silicone rubber/unsaturated carbon chain rubber combination system not obvious.

Comparing Example 1, Example 4 and Example 6, it can be seen that under the same conditions, adding the different end groups of the compatibilizer of the present invention will make the compatibilization effect of the silicone rubber/unsaturated carbon chain rubber combined system different, and the compatibilization The effect varies with the end group of the compatibilizer being the alkyl group greater than the hydroxyl group.

Claims (10)

1. A silicone rubber/unsaturated carbon chain rubber compatibilizer based on a hydrosilylation reaction, having a structure shown in formula (I): (I), In formula (I), R is alkyl or hydroxyl, M is 1-octenyl, 1-nonenyl, 1-decenyl, dihydromyrcenyl, myrcenyl or citronellyl; 10≤x+l+m≤3000, x/(l+m)>0, 0 < l/(l+m)≤1, 2 ≤m ≤30, x, l, m are integers; The number average molecular weight of the compatibilizer is 0.2-150,000. 2. The silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction according to claim 1, characterized in that, the alkyl group is a C1-C10 alkyl group. 3. The silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction according to claim 2, characterized in that, the C1-C10 alkyl group is -CH ₃ , -CH ₂ CH ₃ or _{- CH2CH2CH3 .} 4. the preparation method of the silicone rubber/unsaturated carbon chain rubber compatibilizer based on hydrosilylation reaction described in any one of claim 1-3, comprises steps as follows: Mix unsaturated hydrocarbons with hydrogen-containing silicone oil and dissolve them in a solvent, add catalysts and cocatalysts, and stir for reaction; the unsaturated hydrocarbons are 1,7-octadiene, 1,8-nonadiene, 1,9 - decadiene, dihydromyrcene, myrcene or citronellene; After the reaction is finished, the product is washed with water, and then the small molecular low boilers in the material are removed under reduced pressure to obtain a compatibilizer. 5. The preparation method according to claim 4, characterized in that, the mixing ratio of the unsaturated hydrocarbon and the hydrogen-containing silicone oil is calculated based on the ratio of the unsaturated hydrocarbon to Si-H, and the amount ratio of the substances is 0.001-10 :1; The solvent is toluene, tetrahydrofuran, hexamethylphosphoric triamide, dimethylformamide, cyclohexane or ethanol; The catalyst is a metal complex or chelate, and the amount of catalyst added is 0.01%-2% of the total mass of unsaturated hydrocarbon and hydrogen-containing silicone oil; The cocatalyst is 4-dimethylaminopyridine, triphenylchlorosilane, triphenylborane, triphenylphosphine, triphenylphosphine oxide, 1,3,5-triphenylbenzene, triphenylamine or Triphenylmethane; the amount of co-catalyst added is 0.01%-2% of the total mass of unsaturated hydrocarbon and hydrogen-containing silicone oil. 6. The preparation method according to claim 4, characterized in that, the stirring reaction temperature is 10°C-150°C, and the stirring reaction time is 6~36h. 7. the preparation method according to claim 4 is characterized in that, described hydrogen-containing silicone oil is prepared as follows: Mix D ₄ (octamethylcyclotetrasiloxane) and D ₄ ^H (tetramethylcyclotetrasiloxane), dehydrate first, replace the air with dry nitrogen, heat up to the polymerization temperature, add end-capping agent and catalyst, Atmospheric pressure polymerization reaction, after the polymerization reaction is completed, remove the small molecular low boiling matter in the material under reduced pressure to obtain hydrogen-containing silicone oil; the molecular weight of hydrogen-containing silicone oil is controlled by the amount of catalyst and end-capping agent; _The substance ratio of D4 to ^D4H is 0.1-20: ₁ ; The end-capping agent is water or hexamethyldisiloxane, and the amount of the end _- capping agent is ^0.01-5 % of the total mass of D4 and _D4H ; _The catalyst is tetramethylammonium hydroxide, potassium hydroxide, solid acid or concentrated sulfuric ^acid , and the amount of catalyst added is 0.5%-5% of the total mass of D4 and _D4H ; The polymerization reaction temperature is 50-150°C, and the polymerization reaction time is 0.5-5h; the polymerization reaction is under normal pressure. 8. the application of the silicone rubber/unsaturated carbon chain rubber compatibilizer based on the hydrosilylation reaction described in any one of claim 1-3, for the combined use system of silicone rubber/unsaturated carbon chain rubber, blending Rubber mixing. 9. according to the described application of claim 8, it is characterized in that, the preparation method of silicone rubber/unsaturated carbon chain rubber and system raw material is as follows: Add compatibilizer to silicone rubber and unsaturated carbon chain rubber, add white carbon black, vulcanizing agent, vulcanization accelerator and auxiliary agent at the same time, knead evenly, vulcanize and mold at 140-180°C for 10-35min to obtain Silicone rubber/unsaturated carbon chain rubber combined system. 10. application according to claim 9, is characterized in that, described unsaturated carbon chain rubber is butyl rubber, natural rubber or nitrile rubber; The number average molecular weight of the silicone rubber is 300,000 to 1,000,000, and the vinyl molar content is 0.05% to 0.5%; Described white carbon black is fumed white carbon black or precipitated white carbon black; The auxiliary agent is a mixture of lubricant and reinforcing additive; The vulcanizing agent is bis-2,5, dicumyl peroxide (DCP), sulfur, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, peroxide A mixture of two or more of di-tert-butyl oxides; The vulcanization accelerator is 4,4'-dithiodimorpholine (DTDM), dithiocarbamate, xanthate, thiazole and tetramethylthiuram disulfide (TMTD) Two mixtures in a mass ratio of 0.1 to 10:1; The mass ratio of silicone rubber, unsaturated carbon chain rubber, white carbon black, vulcanizing agent, vulcanization accelerator, auxiliary agent and compatibilizer is 100: (10-1000): (20-200): (0.05-5): (0.01-3): (0.01-3): (0.5-5).