阅读说明：本技术 一种热硫化硅橡胶组合料、橡胶及其制备方法 (Heat-vulcanized silicone rubber composite material, rubber and preparation method thereof ) 是由 黄灵智 杨秀生 安秋凤 于 2020-12-10 设计创作，主要内容包括：本发明公开了一种热硫化硅橡胶组合料与橡胶的制备方法。本发明的热硫化硅橡胶组合料由A、B两种胶料所组成；A胶料由100份环氧基封端的聚有机硅氧烷、5-25份3-4官能度环氧基低聚硅氧烷交联剂、5-10份气相白炭黑、20-40份纳米颜填料、20-30份环保型阻燃剂、0.5-2份脱模组分硬脂酸盐所组成；B胶料由100份POSS改性氨基硅混合料、5-10份气相白炭黑、20-40份纳米颜填料、20-30份环保型阻燃剂、0.5-2份脱模组分硬脂酸盐所组成。应用表明,用环氧基聚有机硅氧烷和氨基硅混合料作基胶组分,确能实现硅橡胶的热硫化,且此法制备的硅橡胶应用性能可达到现有热硫化硅橡胶的水平。(The invention discloses a preparation method of a heat-vulcanized silicone rubber composite material and rubber. The heat-vulcanized silicone rubber composite material consists of A, B rubber compounds; the A sizing material consists of 100 parts of epoxy-terminated polysiloxane, 5-25 parts of 3-4 functional epoxy-oligomeric siloxane cross-linking agent, 5-10 parts of fumed silica, 20-40 parts of nano pigment and filler, 20-30 parts of environment-friendly flame retardant and 0.5-2 parts of demoulding component stearate; the B sizing material consists of 100 parts of POSS modified amino-silicon mixture, 5-10 parts of fumed silica, 20-40 parts of nano pigment filler, 20-30 parts of environment-friendly flame retardant and 0.5-2 parts of demoulding component stearate. The application shows that the hot vulcanization of the silicone rubber can be realized by using the mixture of epoxy polyorganosiloxane and amino silicone as the base rubber component, and the application performance of the silicone rubber prepared by the method can reach the level of the existing hot vulcanization silicone rubber.)

1. A heat-vulcanized silicone rubber composition characterized by comprising:

the material A comprises the following components in percentage by mass: 100 parts of epoxy-terminated polysiloxane EPS, 5-25 parts of 3-4 functional epoxy-oligomeric siloxane cross-linking agent, 5-10 parts of fumed silica, 20-40 parts of nano pigment and filler, 20-30 parts of environment-friendly flame retardant and 0.5-2 parts of stearate;

the material B comprises the following components in mass: 100 parts of POSS modified amino-silicon mixture, 5-10 parts of fumed silica, 20-40 parts of nano pigment filler, 20-30 parts of environment-friendly flame retardant and 0.5-2 parts of stearate;

the structural formula of the 3-4 functional epoxy group oligosiloxane cross-linking agent is as follows:

or

In the formula (1), EP is 2, 3-glycidoxypropyl or 3, 4-epoxycyclohexylethyl, R is isobutyl, isooctyl or phenyl, and R ═ CH₃、-C₂H₅(ii) a a. b is an integer not less than zero;

the POSS modified amino-silicone mixture consists of 20-50 wt% of POSS modified amino-silicone polymer and 50-80 wt% of monoamine type amino-hydrocarbyl polysiloxane;

the POSS modified amino-silicon polymer has the structural formula:

or

In the formulae (2) and (3), n, m₁、m₂Taking a positive integer;

r 'and R' are the same or different, R 'and R' are-CH₃、-C₂H₅、-C₈H₁₇～-C₁₈H₃₇-ph and/or-CH₂CH₂CF₃；

A is methyl, hydroxy, methoxy or ethoxy;

the monoamine type aminoalkyl polysiloxane is gamma-aminopropyl terminated polyorganosiloxane, polyorganosiloxane with monoamine type aminoalkyl connected to side chain or polyorganosiloxane with monoamine type secondary amine alkyl on main chain block.

2. The composition of claim 1, wherein the 3-4 functional epoxy-oligomeric siloxane crosslinker is 1,3,5, 7-tetrakis (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1- (trimethoxysilylethyl) -3,5, 7-tris (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1- (triethoxysilylethyl) -3,5, 7-tris (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, caged tris (2, 3-glycidoxypropyl) pentahydrocarbyl POSS, caged tris (3, 4-epoxycyclohexylethyl) pentahydrocarbyl POSS, semi-closed cage type tri (2, 3-glycidoxypropyldimethylsilyl) heptahydrocarbyl POSS, semi-closed cage type tri (2, 3-glycidoxypropyl dimethylsilyl) heptahydrocarbyl POSS; the alkyl in the compound is one of isobutyl, isooctyl and phenyl; the polyether in the above compound is polyoxyethylene polyoxypropylene ether- (C)₂H₄O)_a(C₃H₆O)_b-or polyoxypropylene ether- (C)₃H₆O)_b-, in the formulaThe value range of a and b is an integer from 0 to 10.

3. The composition of claim 1, wherein the epoxy-terminated polyorganosiloxane is 2, 3-glycidoxypropyl-terminated polydimethylsiloxane, 2, 3-glycidoxypropyl-terminated polytrifluoropropylmethylsiloxane, 2, 3-glycidoxypropyl-terminated poly (trifluoropropylmethylsiloxane-co-dimethylsiloxane), 2, 3-glycidoxypropyl-terminated poly (dimethylsiloxane-co-C)_2-18Alkyl methyl siloxane), 2, 3-glycidoxypropyl terminated poly (dimethyl siloxane-co-phenyl methyl siloxane) and 2, 3-glycidoxypropyl terminated poly (dimethyl siloxane-co-diphenyl siloxane), wherein the epoxy group content of the epoxy group terminated polyorganosiloxane is 0.003-0.05mol/100g, and the viscosity of the epoxy group terminated polyorganosiloxane is 200-10000 mPa.s.

4. The composition of claim 1, wherein the POSS modified aminosilicone polymer has a viscosity of 1000-30000mpa.s, an ammonia value of 0.04-0.15 mmol/g; the POSS modified amino-silicon polymer is obtained by carrying out aminolysis ring-opening reaction on terminal group type or side chain type gamma-aminopropyl polysiloxane and single-arm type 2, 3-epoxypropoxy propyl POSS.

5. The composition of claim 4, wherein the aminolysis ring-opening reaction comprises the steps of: reacting gamma-aminopropyl polysiloxane with single-arm 2, 3-epoxypropoxy propyl POSS at 60-70 ℃ for 4-6 h;

the gamma-aminopropyl polysiloxane is gamma-aminopropyl terminated polydimethylsiloxane, gamma-aminopropyl terminated polytrifluoropropylmethylsiloxane, gamma-aminopropyl terminated poly (trifluoropropylmethylsiloxane-co-dimethylsiloxane), gamma-aminopropyl terminated poly (dimethylsiloxane-co-C)_2-18Alkyl methylsiloxane), gamma-aminopropyl terminated poly (dimethylsiloxane-co-diphenylsiloxane), gamma-aminopropyl methylsiloxane-co-dimethylsiloxane copolymer, gamma-aminopropyl methylsiloxane-co-dimethylsiloxane-co-methylphenylsiloxane copolymer, gamma-aminopropyl methyl siloxaneOne or more of a siloxane-co-dimethylsiloxane-co-diphenylsiloxane copolymer;

the single-arm 2, 3-glycidoxypropyl POSS is one of 2, 3-glycidoxypropyl heptaisobutyl POSS and 2, 3-glycidoxypropyl heptaisooctyl POSS.

6. The composition of claim 1, wherein the monoamine type aminoalkyl silicone is one or more of γ -aminopropyl terminated polydimethylsiloxane, γ -aminopropyl methylsiloxane-co-dimethylsiloxane copolymer, N-cyclohexyl- γ -aminopropyl methylsiloxane-co-dimethylsiloxane copolymer, γ -aminopropyl methylsiloxane-co-trifluoropropylmethylsiloxane copolymer, γ -aminopropyl methylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane copolymer, γ -aminopropyl methylsiloxane-co-dimethylsiloxane-co-methylphenylsiloxane copolymer, the monoamine type aminoalkyl silicone has an ammonia value of 0.01 to 0.25mmol/g, the viscosity is 1000-20000 mPa.s.

7. The composition of claim 1, wherein the nano pigment filler is one or more of metal oxide, carbon black, graphene, silica micropowder, ceramsite, calcium carbonate, barium sulfate, Ag powder and copper-coated silver nanoparticles; the metal oxide is titanium dioxide, ZnO and Al₂O₃One or more of; the environment-friendly flame retardant is one or more of zinc borate, aluminum hydroxide, magnesium hydroxide, antimony trioxide and the like; the stearate is one or more of zinc stearate, magnesium stearate and aluminum stearate.

8. A method for preparing a heat-vulcanized silicone rubber from the composition of any one of claims 1 to 7, comprising the steps of:

taking the material A and the material B as defined in any one of claims 1 to 7, according to the mole number of epoxy groups in the material A: and B, stirring and uniformly mixing the amino N-H bonds and the rubber material with the mol number of 1:1, pouring the mixture into a mold, heating to the temperature of 120-.

9. The method as claimed in claim 8, wherein before the materials A and B are mixed, the materials A and B are respectively stirred uniformly by a kneader, ground for 3-4 times by a three-roll grinder, vacuumized and defoamed for 0.5-3h at 120-130 ℃, cooled to room temperature, and then stored in a sealed package for later use.

10. A silicone rubber obtained by the method of any one of claims 8 or 9.

Technical Field

The invention belongs to the field of silicone rubber, and particularly relates to a silicone rubber composite material and a preparation method of silicone rubber, wherein the silicone rubber composite material is composed of an epoxy group polyorganosiloxane rubber material and a POSS modified amino silicone rubber material.

Background

The main chain of the silicon rubber is a Si-O-Si bond which is continuously and repeatedly appeared, and the side group of the silicon rubber is an organic group such as methyl and phenyl, so that the silicon rubber has the characteristics of good high and low temperature resistance, electric insulation, radiation resistance, weather resistance, strong rebound resilience, excellent compression resilience and the like, and is widely applied to the fields of aerospace, aircraft carriers, deep sea submarines, airplanes, automobiles, mobile phones, computers, electronic appliances and the like. If fluorine-containing groups are continuously introduced into the structure of the silicone rubber, the silicone rubber is expected to have improved oil resistance, solvent resistance and other properties, so that the silicone rubber can play a role in oil pipelines, oil-resistant sealing elements, gaskets, diaphragms and the like.

According to the curing mechanism and action mode, the existing hot vulcanized silicone rubber mainly comprises two types, one is hot vulcanized silicone rubber prepared by radical copolymerization (the initiator is peroxide vulcanizing agents such as bis-tetra, bis-penta and the like) based on vinyl silicone rubber (base rubber) (see CN105419338, CN101717581, CN104262971, CN109486201 and the like), and the other is addition type silicone rubber prepared by hydrosilylation addition reaction (see CN101717583, CN 109852073, CN 109919227, CN106751907 and the like) based on hydrogen-containing silicone oil and vinyl silicone oil (double components). In the former system, however, the thermal vulcanization process of the silicone rubber needs to use bis-tetra-vulcanizing agent, namely bis (2, 4-dichlorobenzoyl) peroxide as a vulcanizing agent, and the agent is decomposed by heating to generate toxic chloride; the later system sulfurizing process needs to use expensive and poisoned chloroplatinic acid or complex platinum as catalyst. In addition, there are few reports of preparing heat-vulcanized silicone rubber by other methods.

As is known, epoxy resin can be cured at room temperature and also cured by heat under the action of an organic amine curing agent (see CN102796439, CN107459612, CN 104497271); then, by means of similar principles, whether the epoxy group polyorganosiloxane (A) and the amino alkyl polysiloxane (B) can be respectively used as A, B-base rubber components or not can be respectively prepared, then the two components are respectively blended with the nano pigment filler, the flame retardant and the like to prepare the two-component A, B rubber material, the two components are independently stored at room temperature and are blended when in use, and the two components are heated to generate thermosetting reaction similar to that of epoxy resin and organic amine so as to form the silicone rubber elastomer, which is not reported yet.

Disclosure of Invention

Aiming at the defects that the existing hot vulcanized silicone rubber system is only in addition type or free radical copolymerization type and has relatively single curing reaction, the invention discloses a rubber composite material prepared based on epoxy polyorganosiloxane (A rubber material component), POSS modified amino silicone mixture (B rubber material component) and the like and a preparation method of hot vulcanized silicone rubber developed based on the rubber composite material.

Therefore, the invention adopts the following technical scheme:

a preparation method of a heat-vulcanized silicone rubber composite material and rubber is characterized in that: the heat-vulcanized silicone rubber composite material is composed of A, B two rubber components.

The A glue material component consists of 100 parts of epoxy-terminated polyorganosiloxane (EPS, A-based glue main component), 5-25 parts of 3-4 functional epoxy-based oligosiloxane cross-linking agent, 5-10 parts of fumed silica, 20-40 parts of nano pigment and filler, 20-30 parts of environment-friendly flame retardant and 0.5-2 parts of demoulding component stearate according to the parts by weight;

the B glue material component comprises, by weight, 100 parts of POSS modified amino-silicon mixture (B-based glue main component), 5-10 parts of fumed silica, 20-40 parts of nano pigment and filler, 20-30 parts of environment-friendly flame retardant and 0.5-2 parts of demoulding component stearate.

When in use, the amount of A, B sizing material is controlled as follows: the molar number of epoxy groups in the size A component to the molar number of amino N-H bonds in the size B component is about 1: 1.

The epoxy-terminated polyorganosiloxane (EPS) is prepared from 2, 3-glycidoxypropyl-terminated polydimethylsiloxane, 2, 3-glycidoxypropyl-terminated polytrifluoropropylmethylsiloxane and 2, 3-glycidoxypropylEnd-capped poly (trifluoropropylmethylsiloxane-co-dimethylsiloxane), 2, 3-glycidoxypropyl end-capped poly (dimethylsiloxane-co-C)_2-18Alkyl methyl siloxane), 2, 3-glycidoxypropyl terminated poly (dimethylsiloxane-co-phenylmethyl siloxane), 2, 3-glycidoxypropyl terminated poly (dimethylsiloxane-co-diphenylsiloxane), etc., the epoxy group content (in terms of moles of epoxy groups contained in one hundred grams of polysiloxane) is about 0.003-0.05% (i.e., 0.003-0.05mol/100g), and the viscosity is about 200-;

the 3-4 functional epoxy group oligosiloxane cross-linking agent has a structure shown in formulas (A) - (D), is oligosiloxane with a structure of ring, cage and semi-closed cage, wherein 3-4 epoxy groups are contained in a molecule, 1,3,5, 7-tetra (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1- (trimethoxysilylethyl) -3,5, 7-tri (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1- (triethoxysilylethyl) -3,5, 7-tri (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane and cage type tri (2, 3-glycidoxypropyl) pentahydrocarbyl POSS are selected, cage type tri (3, 4-epoxy cyclohexyl ethyl) penta-alkyl POSS, semi-closed cage type tri (2, 3-epoxy propoxy propyl dimethyl silicon base) hepta-alkyl POSS and semi-closed cage type tri (2, 3-epoxy propoxy polyether propyl dimethyl silicon base) hepta-alkyl POSS, wherein the alkyl is one of isobutyl, isooctyl and phenyl, and the polyether is polyoxyethylene polyoxypropylene ether- (C)₂H₄O)_a(C₃H₆O)_b-or polyoxypropylene ether- (C)₃H₆O)_b-wherein a and b are positive integers in the range of 0 or 1-10.

In the formulae (A) to (D), EP is 2, 3-glycidoxypropyl or 3, 4-epoxycyclohexylethyl, R ═ isobutyl, isooctyl, phenyl, R ═ CH₃、C₂H₅。

The POSS modified amino-silicone mixture consists of 20-50 wt% of POSS modified amino-silicone Polymer (POSA) and 50-80 wt% of monoamine-type amino-hydrocarbyl polysiloxane (MAPS);

the POSS modified amino-silicon Polymer (POSA) has a structure shown in formulas (I) - (II), is polysiloxane with POSS amino-hydrocarbon groups connected to two ends of a molecule or with POSS amino-hydrocarbon groups hung on side chains, has the viscosity of about 1000-00 mPa.s and the ammonia value (AV, millimole number of amino groups contained in each gram of polysiloxane) of about 0.04-0.15mmol/g, and is prepared by aminolysis ring-opening reaction of end group or side chain type gamma-Aminopropyl Polysiloxane (APS) and single-arm type 2, 3-glycidoxypropyl POSS (E-POSS).

In the formulae (I), (II):

r ', R ' may be the same or different, R ' ═ CH₃、C₂H₅、C₈H₁₇～C₁₈H₃₇Isoalkyl or ph, CH₂CH₂CF₃Etc.; a ═ CH₃OH, methoxy or ethoxy, and the like.

The gamma-Aminopropyl Polysiloxane (APS) and the single-arm E-POSS are subjected to aminolysis ring-opening reaction at the temperature of 60-70 ℃ for 4-6 h; the gamma-aminopropyl polysiloxane comprises two types of terminal groups and side chains, and is selected from gamma-aminopropyl terminated polydimethylsiloxane, gamma-aminopropyl terminated polytrifluoropropylmethylsiloxane, gamma-aminopropyl terminated poly (trifluoropropylmethylsiloxane-co-dimethylsiloxane), and gamma-aminopropyl terminated poly (dimethylsiloxane-co-C)_2-18Alkyl methyl siloxane), gamma-aminopropyl terminated poly (dimethyl siloxane-co-diphenyl siloxane), or poly (dimethyl siloxane) with gamma-aminopropyl attached to its side chain [ i.e. gamma-aminopropyl methyl siloxane-co-dimethyl siloxane copolymer)]Polymethylphenylsiloxane having gamma-aminopropyl attached to its side chain [ e.g. gamma-aminopropylmethylsiloxane-co-dimethylsiloxane-co ]-methylphenylsiloxane copolymer, gamma-aminopropylmethylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane copolymer]One of the like; the single-arm 2, 3-glycidoxypropyl POSS is one selected from 2, 3-glycidoxypropyl heptaisobutyl POSS, 2, 3-glycidoxypropyl heptaisooctyl POSS and the like.

The monoamine type aminoalkyl polysiloxane comprises two types of end groups and side chains, wherein the terminal groups and the side chains are selected from gamma-aminopropyl terminated polyorganosiloxane (the same as above) or polyorganosiloxane with monoamine type aminoalkyl groups such as gamma-aminopropyl, N-cyclohexyl-gamma-aminopropyl and the like connected to the side chains, or the polyorganosiloxane with monoamine type secondary amine alkyl groups blocked on the main chain, the ammonia value is about 0.01-0.25mmol/g, and the viscosity is about 1000-20000 mPa.s; preferably, gamma-aminopropyl terminated polydimethylsiloxane, polydimethylsiloxane having gamma-aminopropyl groups attached to side chains [ i.e., gamma-aminopropyl methylsiloxane-co-dimethylsiloxane ], polydimethylsiloxane having N-cyclohexyl-gamma-aminopropyl groups attached to side chains [ i.e., N-cyclohexyl-gamma-aminopropyl methylsiloxane-co-dimethylsiloxane copolymer ], polytrifluoropropylmethylsiloxane having gamma-aminopropyl groups attached to side chains [ i.e., gamma-aminopropyl methylsiloxane-co-trifluoropropylmethylsiloxane copolymer ], polymethylphenylsiloxane having gamma-aminopropyl groups attached to side chains [ i.e., gamma-aminopropyl methylsiloxane-co-dimethylsiloxane-co-diphenylsiloxane copolymer, poly (methyl siloxane-co-dimethylsiloxane copolymer), poly (methyl siloxane-co-diphenylsiloxane copolymer), poly (methyl siloxane-co-dimethylsiloxane, Or gamma-aminopropylmethylsiloxane-co-dimethylsiloxane-co-methylphenylsiloxane copolymer ], and the like.

The nano pigment filler is one or a combination of a plurality of metal oxides, carbon black, graphene, silicon micropowder, ceramsite, calcium carbonate, barium sulfate, Ag powder, copper-coated silver nanoparticles and the like; the metal oxide is titanium dioxide, ZnO and Al₂O₃Etc.; the environment-friendly flame retardant is selected from one of zinc borate, aluminum hydroxide, magnesium hydroxide, antimony trioxide and the like;

the stearate serving as the demolding component is divalent or trivalent metal salt of stearic acid, and one of zinc stearate, magnesium stearate, aluminum stearate and the like is selected;

the preparation method of the heat vulcanized silicone rubber comprises the following steps:

(1) a, B formulation of the compound: weighing the components in the A or B rubber material in turn according to the composition and the metering ratio, uniformly stirring in a kneader, grinding for 3-4 times on a three-roll grinder, vacuumizing and defoaming at the temperature of 120-130 ℃ for 0.5-3h, cooling to room temperature, and storing in a close packing manner for later use.

(2) Preparation of heat vulcanized silicone rubber: based on the number of moles of epoxy groups in compound A: and (3) sequentially weighing A, B rubber materials according to the molar number of amino N-H bonds in the rubber material B being about 1:1, uniformly stirring the A, B rubber materials and the rubber materials, pouring the mixture into a mold, heating to the temperature of 120-180 ℃, vulcanizing for 20-30min, and heating to the temperature of 150-180 ℃, and vulcanizing for 30-120min to obtain the solid elastomer, namely the heat-vulcanized silicone rubber.

The application performance of the silicon rubber sample is tested and evaluated according to the following method: tear strength: testing is carried out according to the GB/T529-2008 standard; tensile strength and elongation at break: testing with dumbbell type I test specimens, referred to GB/T528-2009 standard; flame retardant rating: the test was carried out with reference to the GB/T13489-2008 standard.

The invention has the beneficial effects that:

aiming at the defects that the existing heat-vulcanized silicone rubber system is only limited to addition type or free radical copolymerization type and the curing reaction is relatively single, the invention uses epoxy-terminated polysiloxane combined with 3-4 functionality epoxy-oligomeric siloxane cross-linking agent as the A-based rubber component of the silicone rubber composition, then uses POSS-typed steric hindrance amine type amino alkyl Polysiloxane (POSA) combined with monoamine or secondary amine type amino alkyl polysiloxane with larger steric hindrance as the B-based rubber component of the silicone rubber composition (the steric hindrance amine has the function of prolonging the application period of A + B mixed rubber), fully utilizes the characteristic that epoxy in the A rubber and amino in the B rubber are easy to react, can realize the heat curing of A, B silicone rubber composition, and not only can realize the heat curing of the silicone rubber composition, but also can realize the accurate control of the ratio of the epoxy to the N-H bond in A, B rubber and combined with the epoxy-based oligomeric silsesquioxane in the A rubber, The POSS amino alkyl polysiloxane in the rubber material B has the reinforcing effect on the silicon rubber, and the application performance of the silicon rubber can reach the level of the existing heat vulcanized silicon rubber. The method can provide a new variety for the existing hot vulcanization system of the silicon rubber, and is expected to make up for or improve the defects that the addition type silicon rubber needs a noble metal catalyst for vulcanization, and the double-four vulcanization system can release toxic chloride, and the like, thereby opening up a new way for obtaining safe and environment-friendly high-performance silicon rubber.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

(1) Preparation of POSS-modified aminosilicone polymer (POSA-1)

100g of polydimethylsiloxane (containing NH, with a side chain of approximately 20000 mPa.s) having 0.1mmol/g of AV and a side chain connected with gamma-aminopropyl was sequentially added to a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer₂0.01mol), 9.32g 2, 3-glycidoxypropyl heptaisobutyl POSS (0.01mol) and 46.85g Isopropanol (IPA) solvent, stirring, heating to 60 deg.C, reacting for 6h, evaporating IPA solvent at 80-85 deg.C, and reacting at 80 deg.C and P_{Watch (A)}Removing low boiling point under reduced pressure at 0.8MPa for 10min to obtain total 109.32g of transparent slightly turbid viscous liquid with structure shown in formula (II) and R ═ CH-₃The side-chain type POSS aminopropyl polydimethylsiloxane having an Amino Value (AV) of about 0.091mmol/g, wherein R is isobutyl, a is OH or methoxy, and is referred to as POSA-1.

(2) Preparation of heat-vulcanized rubber composite material

And (2) preparing a sizing material component A: 100 parts of 2, 3-glycidoxypropyl terminated polydimethylsiloxane (EPS-1) with the epoxy group content of about 0.01 percent and the viscosity of about 550mPa.s, 5 parts of 1,3,5, 7-tetra (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane cross-linking agent, 10 parts of fumed silica, 20 parts of nano calcium carbonate, 25 parts of zinc borate and 0.5 part of zinc stearate; mixing the above components with kneader, grinding and mixing for 3 times, and mixing at 120 deg.C and P_{Watch (A)}Vacuumizing and defoaming for 0.5h under the condition of 0.6MPa, cooling to room temperature, and hermetically packaging and storing to obtain about 160.5 parts of rubber (marked as A1 rubber) in total, wherein the epoxy group content (the mole number of epoxy groups in each hundred grams of silicone rubber, the same applies below) is about 0.024%.

And B, sizing material component and preparation: 20 parts of POSA-1 with an AV of about 0.091mmol/g, 80 parts0.15mmol/g AV, 20000mPa.s viscosity, polydimethyl siloxane with gamma-aminopropyl connected to side chain, 10 portions of fumed silica, 20 portions of nano calcium carbonate, 25 portions of zinc borate and 0.5 portion of zinc stearate are stirred and mixed uniformly in a kneading machine, ground and mixed for 4 times in a three-roll grinding machine, and then the mixture is ground and mixed for 4 times at 120 ℃ and P_{Watch (A)}Vacuumizing and defoaming for 2H under the condition of 0.6MPa, cooling to room temperature, and storing in a close packing way to obtain about 155.5 parts of B rubber (marked as B1 rubber) in total, wherein the N-H content (the mole number of N-H bonds contained in each hundred grams of silicone rubber, the same below) is about 0.0166 percent.

(3) Preparation of heat-vulcanized silicone rubber

According to the proportion that the mole number of epoxy groups in the rubber material A is about 1:1 to the mole number of amino groups N-H in the rubber material B, 100 parts of rubber material A1 and 144.58 parts of rubber material B1 are sequentially weighed, are uniformly stirred and mixed, are vacuumized and defoamed, are poured into a mold, are heated to 120 ℃ for hot vulcanization for 30min, are heated to 180 ℃ for hot vulcanization for 60min, and the obtained solid elastomer, namely the hot vulcanization silicone rubber (Si-1) has the tearing strength: 16.2KN/m, tensile Strength: 8.15MPa, elongation at break: 296 percent; flame retardancy of the coil material, in T₁(first afterflame time), T₂(second afterflame time) represents T₁Is 1s, T₂Is 2 s.

Example 2

(1) Preparation of POSS modified amino silicon (POSA-2)

100g of terminal gamma-aminopropyl terminated polydimethylsiloxane (containing NH) having a viscosity of 1000mPa.s and an AV of 0.05mmol/g were put into a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer in this order₂0.005mol), 6.62g 2, 3-glycidoxypropyl heptaisooctyl POSS (0.005mol) and 18.80g IPA solvent, mechanically stirring, heating to 70 deg.C, reacting for 4 hr, evaporating IPA solvent at 80-85 deg.C, and reacting at 80 deg.C and P_{Watch (A)}Removing low boiling point under reduced pressure of 0.8MPa for 10min to obtain transparent viscous liquid with structure shown as formula (I), wherein R ═ CH-₃And a terminal-type POSS aminopropyl polydimethylsiloxane having an ammonia value of about 0.0469mmol/g and an iso-octyl group, and is referred to as POSA-2.

(2) Preparation of heat-vulcanized rubber composite material

And (2) preparing a sizing material component A: 100 parts of 2, 3-glycidoxypropyl terminated polydimethylsiloxane with the epoxy group content of about 0.005% and the viscosity of about 2000mPa.s, 25 parts of 1- (trimethoxysilylethyl) -3,5, 7-tris (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 5 parts of fumed silica, 30 parts of hydrophobic nano TiO₂20 parts of zinc borate and 2.0 parts of zinc stearate, the components are stirred and mixed evenly in a kneader, ground and mixed for 3 times in a three-roll grinder, and then the mixture is further ground and mixed at the temperature of 130 ℃ and the temperature of P_{Watch (A)}Vacuumizing and defoaming for 1h under the condition of 0.7MPa, cooling to room temperature, and storing in a close packing manner to obtain about 182 parts of sizing material (marked as A2 sizing material) with the epoxy group content of about 0.0591 percent.

And B, sizing material component and preparation: 50 parts of POSA-2 with AV of about 0.0469mmol/g, 50 parts of polydimethylsiloxane with AV of about 0.25mmol/g, viscosity of about 10000mPa.s and N-cyclohexyl-gamma-aminopropyl connected with a side chain, 5 parts of fumed silica and 30 parts of hydrophobic nano TiO₂20 parts of zinc borate and 2 parts of zinc stearate, the components are uniformly stirred in a kneader, ground and mixed for 3 times in a three-roll grinder, and then the mixture is further ground at 120 ℃ and P_{Watch (A)}Vacuumizing and defoaming for 1H under the condition of 0.6MPa, cooling to room temperature, and storing in a close packing manner to obtain about 157 parts of rubber (marked as B2 rubber) in total, wherein the N-H content is about 0.0094%.

(3) Preparation of heat-vulcanized silicone rubber

According to the proportion that the mole number of epoxy groups in the rubber material A and the mole number of N-H in the rubber material B are about 1:1, 10.0 parts of rubber material A2 and 62.87 parts of rubber material B2 are sequentially weighed, are uniformly stirred and mixed, are vacuumized and defoamed, are poured into a mold, are heated to 120 ℃ for hot vulcanization for 20min, are heated to 180 ℃ for hot vulcanization for 60min, and a solid elastomer is obtained, namely the hot vulcanized silicone rubber (Si-2) provided by the invention, the tear strength is 17.6KN/m, the tensile strength is 8.32MPa, the elongation at break is about 309%, and the flame retardance of a coiled material is T-shaped₁(first afterflame time), T₂(second afterflame time) represents T₁、T₂All for 2 s.

Example 3

(1) Preparation of POSS modified amino silicon (POSA-3)

A reflux condenser pipe is arranged,100g of polytrifluoropropylmethylsiloxane [ namely gamma-aminopropylmethylsiloxane-co-trifluoropropylmethylsiloxane copolymer ] with a side chain connected with gamma-aminopropyl and a viscosity of 10000mPa.s are sequentially added into a three-necked flask with a thermometer and a stirrer](containing NH)₂0.015mol), 13.97g 2, 3-glycidoxypropyl heptaisobutyl POSS (0.015mol) and 38.0g IPA solvent, mechanically stirring and uniformly mixing, heating to 60 ℃, continuously reacting for 4.5h, after the reaction is finished, evaporating the IPA solvent at 80-85 ℃, and then carrying out continuous reaction at 80 ℃ and P_{Watch (A)}Removing low boiling point under reduced pressure of 0.8MPa for 10min to obtain transparent and slightly turbid viscous liquid with structure shown as formula (II) and R ═ CH₃、R＂＝CH₂CH₂CF₃Poly [ (N-POSS-gamma-aminopropyl) methylsiloxane-co-trifluoropropylmethylsiloxane-co, wherein R is isobutyl, a is OH or ethoxy, and the amino number is about 0.1316mmol/g]And is designated as POSA-3.

(2) Preparation of heat-vulcanized rubber composite material

And (2) preparing a sizing material component A: 100 parts of 2, 3-glycidoxypropyl terminated polytrifluoropropylmethylsiloxane with the epoxy group content of about 0.015 percent and the viscosity of about 300mPa.s, 10 parts of semi-closed cage type tri (2, 3-glycidoxypropyl dimethyl silicon base) heptaisobutyl POSS, 10 parts of fumed silica, 30 parts of nano Al₂O₃30.0 parts of environment-friendly flame retardant aluminum hydroxide and 1.0 part of magnesium stearate; mixing the above components with kneader, grinding and mixing for 3 times, and mixing at 120 deg.C and P_{Watch (A)}Vacuumizing and defoaming for 2h under the condition of 0.6MPa, cooling to room temperature, and storing in a close packing manner to obtain 181 parts of sizing material (marked as A3 sizing material) with the epoxy group content of about 0.0209%.

And B, sizing material component and preparation: 25 parts of POSA-3 with AV of about 0.1314mmol/g, 75 parts of polytrifluoropropylmethylsiloxane (namely gamma-aminopropyl methylsiloxane-co-trifluoropropylmethylsiloxane copolymer) with AV of about 0.15mmol/g and viscosity of about 20000mPa.s and with gamma-aminopropyl connected with SiOH-terminated side chain, 10 parts of fumed silica and 30 parts of nano Al₂O₃30.0 parts of environment-friendly flame retardant aluminum hydroxide and 1.0 part of magnesium stearate; mixing the above components in kneading machine, and grinding with three-roller grinderGrinding and mixing for 4 times, and then at 130 deg.C and P_{Watch (A)}Vacuumizing and defoaming for 2H under the condition of 0.6MPa, cooling to room temperature, and storing in a close packing manner to obtain a total of 171 parts of rubber (marked as B3 rubber) with the N-H content of about 0.0151%.

(3) Preparation of heat-vulcanized silicone rubber

And (2) sequentially weighing 100 parts of A3 rubber and 138.67 parts of B3 rubber according to the ratio of the mole number of epoxy groups in the rubber A to the mole number of N-H in the rubber B of about 1:1, uniformly stirring the A3 rubber and the B3 rubber, vacuumizing and defoaming, pouring the mixture into a mold, heating to 130 ℃ for heat vulcanization for 30min, and then heating to 170 ℃ for heat vulcanization for 60min to obtain a solid elastomer, namely the heat vulcanized silicone rubber (Si-3) disclosed by the invention. Tear strength: 17.5KN/m, tensile Strength: 8.65MPa, elongation at break: 286%; flame retardancy of the coil material, in T₁(first afterflame time), T₂(second afterflame time) represents T₁Is 1s, T₂Is 1 s.

Example 4

(1) Preparation of POSS modified amino silicon (POSA-4)

100g of poly (dimethylsiloxane-co-diphenylsiloxane) (containing NH) was sequentially added to a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, wherein AV was 0.13mmol/g and the viscosity was 690 mPa.s. gamma. -aminopropyl terminated poly (dimethylsiloxane-co-diphenylsiloxane)₂0.013mol), 17.21g 2, 3-glycidoxypropyl heptaisooctyl POSS (0.013mol) and 30g IPA solvent, mechanically stirring, heating to 65 deg.C, reacting for 5 hr, evaporating IPA solvent at 80-85 deg.C, and adding water at 80 deg.C and P_{Watch (A)}The mixture is decompressed and boiled for 10min under the pressure of 0.6MPa to obtain transparent and slightly turbid viscous liquid, namely end group type POSS aminopropyl poly (dimethyl siloxane-co-diphenyl siloxane) with the structure shown in formula (I), R ═ ph, R ═ isooctyl and ammonia value of about 0.1113mmol/g, which is marked as POSA-4.

(2) Preparation of heat-vulcanized rubber composite material

And (2) preparing a sizing material component A: 100 parts of 2, 3-glycidoxypropyl terminated poly (dimethylsiloxane-co-diphenylsiloxane) having an epoxy group content of about 0.013 mol% and a viscosity of about 550mPa.s, 10 parts of semi-closed cage tris (2, 3-glycidoxypropyldimethylsilyl) heptaiso-propylButyl POSS, 8.5 parts of fumed silica, 20 parts of nano silicon powder, 20 parts of nano Ag powder, 25 parts of antimony trioxide and 1.5 parts of aluminum stearate; mixing the above components with kneader, grinding and mixing for 3 times, and mixing at 120 deg.C and P_{Watch (A)}Vacuumizing and defoaming for 2h under the condition of 0.6MPa, cooling to room temperature, and densely packing and storing to obtain 185 parts of sizing material (marked as A4 sizing material), wherein the epoxy group content is about 0.0111%.

And B, sizing material component and preparation: 20 parts of POSA-4 with ammonia value of about 0.1113mmol/g, 80 parts of AV of 0.13mmol/g, viscosity of about 15000mPa.s, SiOH-terminated side chain gamma-aminopropyl methyl siloxane-co-dimethyl siloxane-co-diphenyl siloxane copolymer, 8.5 parts of fumed silica, 20 parts of silicon micropowder, 20 parts of nano Ag powder, 25 parts of antimony trioxide flame retardant and 1.5 parts of aluminum stearate; mixing the above components with kneader, grinding and mixing for 4 times, and mixing at 120 deg.C and P_{Watch (A)}Vacuumizing and defoaming for 2H under the condition of 0.6MPa, cooling to room temperature, and storing in a close packing manner to obtain about 175 parts of rubber (marked as B4 rubber) in total, wherein the N-H content is about 0.0131 mol%.

(3) Preparation of heat-vulcanized silicone rubber

And (2) sequentially weighing 100 parts of A4 rubber and 84.80 parts of B4 rubber according to the ratio of the molar weight of epoxy groups in the rubber A to the molar weight of N-H in the rubber B of about 1:1, uniformly stirring the rubber A and the rubber B, pouring the mixture into a mold, heating to 120 ℃ for hot vulcanization for 25min, then heating to 150 ℃ for hot vulcanization for 120min, and obtaining the solid elastomer, namely the silicon rubber sample (Si-4) disclosed by the invention. Tear strength: 16.9KN/m, tensile Strength: 8.02MPa, elongation at break: 278 percent; flame retardancy of the coil material, in T₁(first afterflame time), T₂(second afterflame time) represents T₁、T₂All for 1 s.

Example 5 control group 1

The procedure and the amount were the same as in example 1, except that monofunctional 2, 3-glycidoxypropyltrimethoxysilane KH-560 was used in place of the 4-functional epoxy-based oligosiloxane crosslinker 1,3,5, 7-tetrakis (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane used in example 1, and that POSA-1 was replaced with 0.15mmol/g AV and a side chain γ -aminopropylpolydimethylsiloxane having a viscosity of about 20000 mPa.s. A heat-vulcanizable silicone rubber (Si-5) was prepared in the same manner as in example 1.

As a result, it was found that: under the same conditions, the hot vulcanized silicone rubber prepared by using the mono-functional polysiloxane or the bifunctional polysiloxane or the silane in the control group of the example 5 has the advantages of slower vulcanization speed, 2h prolonged vulcanization time and poorer vulcanization effect, the tearing strength of Si-5 is only 10.31KN/m, the tensile strength is about 5.36MPa, the elongation at break is about 267 percent, and the flame retardance T of a rubber roll material is₁About 3s, T₂Approximately 6 s. Obviously, the performance of the heat-vulcanized silicone rubber prepared by combining epoxy-terminated polysiloxane with monofunctional KH-560, monoamine gamma-aminopropyl polydimethylsiloxane and the like in the control group of example 5 is obviously inferior to that of the silicone rubber prepared by combining EPS-1 with 4-functional epoxy-based oligosiloxane cross-linking agent, POSS modified amino-silicone (having reinforcing and reinforcing effects on rubber) and the like in example 1 because the cross-linking density in the rubber is low and the reinforcing and flame-retardant effects of POSS are not provided.

Example 6-control 2

In order to compare the performances of the heat-vulcanized silicone rubber prepared by the patent of the invention, the heat-vulcanized silicone rubber is prepared by taking the heat-vulcanized silicone rubber methyl vinyl silicone rubber which is commonly used in industry as a reference, bis-tetra-peroxide (2, 4-dichlorobenzoyl) as a vulcanizing agent and pigment and filler as in example 2: namely, 100 parts of methyl vinyl silicone rubber with the vinyl content of about 0.23 percent and the viscosity of about 200 ten thousand mPa.s, 5 parts of fumed silica and 30 parts of hydrophobic nano TiO₂20 parts of zinc borate, 2.0 parts of zinc stearate and 2.0 parts of bis-2, 4 vulcanizing agent are kneaded and mixed uniformly in a kneading machine, then rolled for 4-6 times by a hot vulcanizing machine, and then placed in a mold to be heated to 180 ℃ for hot vulcanization for 60min, so that the solid elastomer, namely the control hot vulcanized silicone rubber (Si-6) prepared in example 6 of the invention, is obtained.

Tear strength: 15.9KN/m, tensile Strength: 8.61MPa, elongation at break: 291%; flame retardancy of coil materials, T₁(first afterflame time), T₂(second afterflame time) was 3 s.

The comparison shows that the performance of the heat vulcanized silicone rubber prepared by the method can basically reach the level of the existing heat vulcanized silicone rubber.