WO2023035283A1 - 一种超低粘度液体硅橡胶及其交联剂与制备方法 - Google Patents

一种超低粘度液体硅橡胶及其交联剂与制备方法 Download PDF

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WO2023035283A1
WO2023035283A1 PCT/CN2021/118308 CN2021118308W WO2023035283A1 WO 2023035283 A1 WO2023035283 A1 WO 2023035283A1 CN 2021118308 W CN2021118308 W CN 2021118308W WO 2023035283 A1 WO2023035283 A1 WO 2023035283A1
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monomer
silicone rubber
crosslinking agent
cross
independently selected
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French (fr)
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周传健
苏文禄
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山东大学
山东大学威海工业技术研究院
山东省工业技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Definitions

  • the application relates to a novel liquid silicone rubber, a crosslinking agent and a preparation method thereof, belonging to the technical field of silicone rubber.
  • Silicone rubber is one of the most important silicone products. Silicone rubber is usually made of linear polysiloxane, reinforcing fillers, crosslinking agents, catalysts, modified additives and other raw materials. After kneading (or mixing) and vulcanization under certain conditions, it can be changed from high viscosity to The plastic state transforms into an elastic state with a certain cross-linked network structure. Because silicone rubber has excellent high and low temperature resistance, ultraviolet resistance, radiation resistance, weather resistance, electrical insulation, high air permeability, physiological inertness, etc. and so on are widely used.
  • liquid silicone rubber is mainly divided into two types: condensation type and addition type.
  • addition type liquid silicone rubber is composed of hydrogen-containing silicone oil, vinyl silicone oil, fillers and catalysts that can catalyze the addition of silicon hydrogen.
  • Condensation type liquid silicone rubber It is mainly composed of hydroxy silicone oil, alkoxy silane and their condensation polymers; the main components of these two liquid silicone rubbers are silicone oils with different degrees of polymerization, which have high viscosity and poor fluidity, and are not suitable for potting in narrow spaces, ultra-thin coating, etc. , and cannot meet the needs of high-precision 3D printing.
  • catalysts such as Pt are used for hydrosilylation-type silicone rubber, which are easily poisoned during use; condensation-type liquid silicone rubber has a slow curing speed. Therefore, reducing the viscosity of liquid silicone rubber is of great significance for expanding the application of liquid silicone rubber.
  • the liquid silicone rubber is composed of cyclosiloxane, "dumbbell-shaped" polysiloxane crosslinking agent, catalyst and/or reinforcing filler, etc., wherein the "dumbbell-shaped" polysiloxane crosslinking agent can be combined with cyclosiloxane
  • cyclosiloxane is the basic raw material used in the production of liquid silicone rubber. This method directly uses basic raw materials as raw materials, which greatly reduces the viscosity of the system.
  • the polymerization speed can be effectively controlled, and the controllable crosslinking can be realized; at the same time, it also solves the problem of Pt-based catalysts for addition-type silicone rubber. And easily poisoned, condensation type liquid silicone rubber cross-linking speed is slow.
  • the silicone rubber elastomer obtained by the method has good environmental adaptability and thermal stability, and has better mechanical properties.
  • an ultra-low viscosity liquid silicone rubber is provided, and the silicone rubber includes cyclosiloxane, a crosslinking agent and a catalyst. Described cyclosiloxane structure is as shown in formula I:
  • R a , R b , R c , R d , Re , R f are independently selected from one of hydrogen, methyl, ethyl, trifluoropropyl, phenyl and vinyl, n is 1, 2 or 3.
  • the silicone rubber includes 80-120 parts of cyclosiloxane, 1-30 parts of crosslinking agent, 0.5-2 parts of catalyst and 0-100 parts of reinforcing agent, wherein the catalyst is selected from trifluoromethane At least one of sulfuric acid, sulfuric acid, hydrochloric acid, perchloric acid and solid acid, preferably trifluoromethanesulfonic acid.
  • the cyclosiloxane is octamethylcyclotetrasiloxane and hexamethylcyclotrisiloxane.
  • the solid acid catalyst is selected from at least one of oxide catalysts, sulfide catalysts, sulfate catalysts, phosphate catalysts, zeolite molecular sieve catalysts and heteropolyacid catalysts.
  • the silicone rubber includes 100 parts of octamethylcyclotetrasiloxane, 15 parts of crosslinking agent, 1 part of catalyst and 20 parts of reinforcing agent.
  • a cross-linking agent for ultra-low viscosity liquid silicone rubber is provided, the molecular structural formula of the cross-linking agent is shown in Formula II:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are independently selected from H , C1-C5 alkyl containing linear, branched or cyclic structure, C1-C5 haloalkyl containing linear, branched or cyclic structure, C1-C5 alkene containing linear, branched or cyclic structure A group, including a C1-C5 haloalkenyl group with a straight chain, branched chain or cyclic structure, one of phenyl and alkylphenyl;
  • the R', R" are independently selected from a C2-C5 alkyl group containing a straight chain or branched chain, and a C2-C5 haloalkyl group containing a straight chain or branched chain;
  • a and b are independently selected from 1, 2 or 3, and c is selected from an integer between 1-50.
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are independently selected from One of C1-C5 alkyl groups containing straight chain or branched chains, C1-C5 alkenyl groups containing straight chains, branched chains or cyclic structures;
  • the a and b are independently selected from 1 or 2, and the c is selected from an integer between 1-10.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are independently selected from One of methyl, ethyl, phenyl and trifluoropropyl.
  • R 1 and R 6 are the same, R 2 and R 7 are the same, R 3 and R 8 are the same, R 4 and R 9 are the same, R 5 and R 10 are the same, R 15 and R 16 are the same.
  • the R 1 , R 3 , R 5 , R 6 , R 8 , and R 10 are all methyl groups, the R 2 , R 4 , R 7 , and R 9 are all vinyl groups, and the R 11 , R 12 , R 13 and R 14 are all methyl;
  • both a and b are 2, and c is 1.
  • a kind of preparation method of novel silicone rubber cross-linking agent which comprises the following steps:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are independently selected from H, including C1-C5 alkyl with straight chain, branched chain or cyclic structure, C1-C5 haloalkyl with straight chain, branched chain or cyclic structure, C1-C5 alkenyl with straight chain, branched chain or cyclic structure, One of C1-C5 haloalkenyl, phenyl and alkylphenyl containing straight chain, branched chain or cyclic structure;
  • the R 15 and R 16 are independently selected from one of straight-chain or branched C2-C5 alkenyl, and straight-chain or branched C2-C5 haloalkenyl;
  • a and b are independently selected from 1, 2 or 3, and c is selected from an integer between 1-50.
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are independently selected from One of C1-C5 alkyl groups containing straight chain or branched chains, C1-C5 alkenyl groups containing straight chains, branched chains or cyclic structures;
  • the R 15 and R 16 are independently selected from one of straight-chain or branched C2-C5 alkenyl groups,
  • the a, b are independently selected from 1 or 2, and the c is selected from an integer between 1-10;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are independently selected from One of methyl, ethyl, phenyl and trifluoropropyl.
  • R1 and R6 are the same, R2 and R7 are the same, R3 and R8 are the same, R4 and R9 are the same, R5 and R10 are the same.
  • the monomer A and the monomer B are independently selected from trimethyltrivinylcyclotrisiloxane or tetramethyltetravinylcyclotetrasiloxane, and the monomer C is 1, 1,3,3-Tetramethyldisiloxane, which is characterized by being common and inexpensive;
  • both the monomer A and the monomer B are tetramethyltetravinylcyclotetrasiloxane, which is characterized by being common and cheap.
  • the ratio of the weight sum of the monomer A and the monomer B to the molar ratio of the monomer C is 2-10:1, and the monomer A, the monomer B and the monomer C are The ratio of the sum of the weights to the weight of the organic solvent is 1-3:1;
  • the molar ratio of the sum of the weight of the monomer A and the monomer B to the mole of the monomer C is 2:1, 4:1, 6:1 or 8:1, more preferably 6:1 1.
  • the ratio of the sum of the weight of monomer A, monomer B and monomer C to the weight of the organic solvent is 2:1.
  • the catalyst is at least one of platinum-based catalysts, rhodium-based catalysts, iridium-based catalysts, cobalt-based catalysts, iron-based catalysts, nickel-based catalysts, palladium-based catalysts, ruthenium-based catalysts and zirconium-based catalysts, so
  • concentration of the catalyst in the reaction monomer is 1ppm-2500ppm.
  • the catalyst can be used as long as it can be used to catalyze the hydrosilylation reaction.
  • the catalyst is a Karstedt catalyst, and the concentration of the catalyst in the reaction monomer is 10ppm-100ppm.
  • the karstedt catalyst is platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane, which has high catalytic efficiency, faster reaction and higher conversion rate.
  • the organic solvent is one of dichloromethane, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, toluene, xylene, acetone, n-hexane, petroleum ether and pyridine, preferably toluene.
  • step 1) under the protection of an inert gas, the monomer A, monomer B and monomer C are dehydrated and dried separately to obtain the mixed reaction monomer, and the catalyst is added to After drying the treated organic solvent to obtain the dispersion liquid, add the dispersion liquid dropwise into the reaction monomer, and react at 40°C-80°C for 4-8h;
  • step 2) after the reaction is completed, the organic solvent is removed at a pressure not greater than -0.096MPa and a temperature of 40-80°C, and the organic solvent is removed at a pressure not greater than -0.096MPa and a temperature of 120°C to 160°C
  • the unreacted reaction monomer is cooled to room temperature to obtain the crosslinking agent.
  • the monomer A and the monomer B are dehydrated and dried at -0.096MPa, 40-60°C;
  • the solvent was dehydrated and dried using calcium hydride.
  • the inert gas is selected from nitrogen, argon or helium, preferably nitrogen.
  • the silicone rubber is the silicone rubber described in any one of the above.
  • a "dumbbell-shaped" polysiloxane crosslinking agent which can directly open and copolymerize with cyclosiloxane under the action of acid to form a crosslinked structure and become an elastomer.
  • the amount of the agent can adjust the cross-linking density of silicone rubber, greatly improving the heat resistance and mechanical properties of silicone rubber.
  • Cyclosiloxane is directly used as a raw material in the formula of the new ultra-low viscosity silicone rubber of this application, and the in-situ copolymerization method is adopted, polymerization and vulcanization occur simultaneously, the system viscosity is low, and the polymerization speed is controllable. Due to the direct use of cyclosiloxane, the use of silicone oil with a high viscosity is avoided, thereby greatly reducing the viscosity of silicone rubber.
  • the silicone rubber according to the present application has low viscosity, short curing time, good environmental adaptability and thermal stability, and has better mechanical properties.
  • Fig. 1 is the NMR spectrum of the crosslinking agent 1# involved in Example 1 of the present application.
  • crosslinking agent 1# 1,3-bis(tetrafluoroethylene Methyltrivinylcyclotetrasiloxane (silethylene) tetramethyldisiloxane, yield: 83%.
  • Embodiment 2 Cross-linking agent 2#
  • crosslinking agent 2# The difference between crosslinking agent 2# and crosslinking agent 1# is that monomer A of crosslinking agent 2# is tetramethyltetravinylcyclotetrasiloxane (30.8g, 0.09mol), and monomer B is Trimethyltrivinylcyclotrisiloxane (22.7g, 0.09mol), the solvent is 28.3g toluene, and other conditions are the same as crosslinking agent 1#.
  • cross-linking agent 3# The difference between cross-linking agent 3# and cross-linking agent 1# is that monomer A and monomer B of cross-linking agent 3# are both 1,3,5-trimethyl-1,3,5-tri( 3,3,3-trifluoropropyl)cyclotrisiloxane (118.8g in total, 0.18mol), the solvent is 60.9g toluene, and other conditions are the same as those of crosslinking agent 1#.
  • the yield of crosslinking agent 3# is 73%.
  • the characteristic peak of -CH 2 CF 3 is at 2.00-2.20 ppm
  • the characteristic peak of -CH 2 CF 3 is at 0.45 ppm.
  • the characteristic peak of -CH 2 -CH 2 -, and the characteristic peak of -CH(CH 3 )- at 1.60.
  • Embodiment 4 Cross-linking agent 4#
  • crosslinking agent 4# The difference between crosslinking agent 4# and crosslinking agent 1# is: monomer A and monomer B of crosslinking agent 4# are trimethyl trivinyl cyclotrisiloxane (45.4g in total, 0.18mol ), the solvent is 24.2g toluene, and other conditions are all the same as crosslinking agent 1#.
  • the yield of crosslinking agent 4# is 89%.
  • the characteristic peak of -CH 2 -CH 2 - is at 0.45 ppm
  • the characteristic peak at 1.60 is - Characteristic peak of CH(CH 3 )-.
  • Embodiment 5 Cross-linking agent 5#
  • crosslinking agent 5# The difference between crosslinking agent 5# and crosslinking agent 1# is: monomer A and monomer B of crosslinking agent 5# are tetramethyltetravinyl cyclotetrasiloxane (a total of 20.5g, 0.06mol ), the solvent is 11.75g toluene, and all the other conditions are the same as crosslinking agent 1#.
  • the yield of crosslinking agent 5# is 78%.
  • the characteristic peak of -CH 2 -CH 2 - is at 0.45ppm
  • the characteristic peak at 1.60 is-
  • the characteristic peak of CH(CH 3 )- the results of liquid phase showed that the polymer component containing three cyclosiloxanes appeared.
  • crosslinking agent 6# The difference between crosslinking agent 6# and crosslinking agent 1# is that the monomer C of crosslinking agent 6# is 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (9.98g, 0.03mol), the solvent is 35.8g toluene, and other conditions are the same as crosslinking agent 1#.
  • the yield of crosslinking agent 6# is 75%.
  • the characteristic peak of -C6H5 is at 7.40-7.80ppm
  • the characteristic peak of -C6H5 is at 0.45ppm.
  • the characteristic peak of -CH 2 -CH 2 -, and the characteristic peak of -CH(CH 3 )- at 1.60.
  • Embodiment 7 Cross-linking agent 7#
  • cross-linking agent 7# The difference between cross-linking agent 7# and cross-linking agent 1# is that the catalyst of cross-linking agent 7# is tetrakis(triphenylphosphine)palladium, and other conditions are the same as cross-linking agent 1#.
  • the yield of crosslinking agent 7# is 45%.
  • the characteristic peak of -CH 2 -CH 2 - is at 0.45 ppm
  • the characteristic peak at 1.60 is - Characteristic peak of CH(CH 3 )-.
  • crosslinking agent D1# and crosslinking agent 1# are 1,3-divinyltetramethyldisiloxane (total 33.55g, 0.18mol), solvent It is 18.3g toluene, and other conditions are the same as crosslinking agent 1#.
  • crosslinking agent D2# The difference between crosslinking agent D2# and crosslinking agent 1# is: monomer A and monomer B of crosslinking agent D2# are tetramethyltetravinyl cyclotetrasiloxane (10.3g in total, 0.03mol ), the solvent is 6.65g toluene, and all the other conditions are the same as crosslinking agent 1#.
  • cross-linking agent D3# is 0. Since the molar ratio of the sum of monomers A and B to monomer C is 1:1, it cross-links in the flask and becomes a transparent elastomer.
  • crosslinking agent D3# The difference between crosslinking agent D3# and crosslinking agent 1# is that the monomer C of crosslinking agent D3# is 1,3-divinyltetramethyldisiloxane (5.58g, 0.03mol), and the solvent It is 33.59g of toluene, and other conditions are the same as crosslinking agent 1#.
  • crosslinking agent D4# is 0, because monomer C does not contain Si-H, the hydrosilylation reaction cannot proceed.
  • the fixed formula is: 15 parts of cross-linking agent, 100 parts of D Tetrasiloxane), 20 parts of reinforcing agent, 1 part of catalyst (trifluoromethanesulfonic acid), mixed uniformly with a 3D mixer and then cured to prepare silicone rubber 1#-7# and silicone rubber D1# respectively.
  • the cross-linking agent prepared by the scheme of the present invention is a new type of cross-linking agent for silicone rubber, which can be vulcanized by in-situ polymerization with cyclosiloxane.
  • the rubber has low initial viscosity, short curing time, good thermal stability and good mechanical properties.

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Abstract

一种超低粘度液体硅橡胶及交联剂与制备方法，特别适用狭缝浇筑、3D打印等超低粘度的应用场景，属于硅橡胶技术领域。所述的原位聚合型液体硅橡胶包括环硅氧烷、交联剂和催化剂，其中交联剂以含Si-CH＝CH 2的环硅氧烷与两端为Si-H的线型聚硅氧烷作为单体反应，进行硅氢加成制备出一种"哑铃形"的两端为环状硅氧烷的分子，该交联剂可以与环硅氧烷原位共聚直接成为交联弹性体，且可以通过调整交联剂用量、反应条件等控制硅橡胶的交联密度、交联速度等，整个体系具有粘度低、交联可控、操作方便等特点，同时，采用该方法制得的超低粘度液体硅橡胶粘度低，固化时间短，环境适应性和热稳定性好，具有较佳的力学性能。

Description

一种超低粘度液体硅橡胶及其交联剂与制备方法 技术领域
本申请涉及一种新型液体硅橡胶及其交联剂与制备方法，属于硅橡胶技术领域。
背景技术
硅橡胶是最重要的有机硅产品之一。硅橡胶通常是由线型聚硅氧烷、补强填料、交联剂、催化剂、改性添加剂等原料，经过混炼(或混合)后，在一定的条件下硫化，便可从高黏滞塑性态转变为具有一定交联网络结构的弹性态。由于硅橡胶具有优异的耐高低温、耐紫外、耐辐照、耐候、电绝缘、高透气性、生理惰性等，在航空、航天、电子电气、轻工、机械、建筑、化工、医学、日用品等方面应用广泛。
目前液体硅橡胶主要分为缩合型和加成型两种，其中加成型液体硅橡胶由不同分子量的含氢硅油、乙烯基硅油、填料以及能催化硅氢加成的催化剂组成，缩合型液体硅橡胶主要由羟基硅油和烷氧基硅烷及其缩聚物组成；这两种液体硅橡胶的主要成分都是不同聚合度的硅油，粘度大，流动性差，不适合狭窄空间灌封、超薄涂覆等，也不能满足高精度3D打印等需求。另外，硅氢加成型硅橡胶要用到Pt等催化剂，在使用过程中易中毒；缩合型液体硅橡胶的固化速度慢。因此，降低液体硅橡胶粘度，对拓展液体硅橡胶应用有重要意义。
发明内容
为了解决上述问题，提供了一种超低粘度液体硅橡胶配方及其交联剂的制备方法与应用。该液体硅橡胶由环硅氧烷、“哑铃型”聚硅 氧烷交联剂、催化剂及/或补强填料等组成，其中该“哑铃形”聚硅氧烷交联剂可以与环硅氧烷原位开环共聚直接交联，所谓的环硅氧烷就是生产液体硅橡胶所用的基础原材料。该方法直接使用基础原材料作原料，大幅降低了体系粘度，通过调整酸引发剂的用量和温度，可以有效控制聚合的速度，实现交联的可控；同时还解决了加成型硅橡胶Pt类催化剂及易中毒，缩合型液体硅橡胶交联速度慢的问题。另外，采用该方法的到硅橡胶弹性体环境适应性和热稳定性好，具有较佳的力学性能。
根据本申请的一个方面，提供了一种超低粘度液体硅橡胶，所述硅橡胶包括环硅氧烷、交联剂和催化剂。所述的环硅氧烷结构如式I所示：
Figure PCTCN2021118308-appb-000001
式I：环硅氧烷结构示意图；
其中，式I中，R a、R b、R c、R d、R e、R f独立的选自氢、甲基、乙基、三氟丙基、苯基和乙烯基中的一种，n为1、2或3。
可选地，所述硅橡胶包括80-120份环硅氧烷、1-30份交联剂、0.5-2份催化剂和0-100份补强剂，其中，所述催化剂选自三氟甲基磺酸、硫酸、盐酸、高氯酸和固体酸中的至少一种，优选为三氟甲基磺酸。
优选的，所述环硅氧烷为八甲基环四硅氧烷，六甲基环三硅氧烷。
可选地，所述固体酸催化剂选自氧化物类催化剂、硫化物类催化 剂、硫酸盐类催化剂、磷酸盐类催化剂、沸石分子筛类催化剂和杂多酸类催化剂中的至少一种。
优选的，所述硅橡胶包括100份八甲基环四硅氧烷、15份交联剂、1份催化剂和20份补强剂。
根据本申请的又一方面，提供了一种超低粘度液体硅橡胶用交联剂，所述交联剂的分子结构式如式Ⅱ所示：
Figure PCTCN2021118308-appb-000002
式Ⅱ：“哑铃型”交联剂结构示意图；
式Ⅱ中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自H，包含直链、支链或环状结构的C1-C5烷基，包含直链、支链或环状结构的C1-C5卤代烷基，包含直链、支链或环状结构的C1-C5烯基，包含直链、支链或环状结构的C1-C5卤代烯基，苯基和烷基苯基中的一种；
所述R’、R”独立的选自包含直链或支链的C2-C5烷基、包含直链或支链的C2-C5卤代烷基中的一种；
a和b独立的选自1、2或3，c选自1-50之间的整数。
可选地，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自包含直链或支链的C1-C5烷基，包含直链、支链或环状结构的C1-C5烯基中的一种；
所述a、b独立的选自1或2，所述c选自1-10之间的整数。
可选地，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自甲基、乙基、苯基和三氟丙基中的一种。
可选地，R 1和R 6相同，R 2和R 7相同，R 3和R 8相同，R 4和R 9相同，R 5和R 10相同，R 15和R 16相同。
可选地，所述R 1、R 3、R 5、R 6、R 8、R 10均为甲基，所述R 2、R 4、R 7、R 9均为乙烯基，所述R 11、R 12、R 13、R 14均为甲基；
优选的，所述a、b均为2，所述c为1。
根据本申请的另一个方面，提供了一种新型硅橡胶交联剂的制备方法，其包括以下步骤：
1)将单体A、单体B和单体C作为反应单体在有机溶剂中混合，加入催化剂进行反应；
2)反应结束后，脱除未反应的所述反应单体及所述有机溶剂，得到所述交联剂；
其中，所述单体A的分子结构式如式Ⅲ所示：
Figure PCTCN2021118308-appb-000003
式Ⅲ：单体A结构示意图；
所述单体B的分子结构式如式Ⅳ所示：
Figure PCTCN2021118308-appb-000004
式Ⅳ：单体B结构示意图；
所述单体C的分子结构式如式Ⅴ所示：
Figure PCTCN2021118308-appb-000005
式Ⅴ：单体C结构示意图；
其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自H，包含直链、支链或环状结构的C1-C5烷基，包含直链、支链或环状结构的C1-C5卤代烷基，包含直链、支链或环状结构的C1-C5烯基，包含直链、支链或环状结构的C1-C5卤代烯基，苯基和烷基苯基中的一种；
所述R 15、R 16独立的选自包含直链或支链的C2-C5烯基、包含直链或支链的C2-C5卤代烯基中的一种；
a和b独立的选自1、2或3，c选自1-50之间的整数。
可选地，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自包含直链或支链的C1-C5烷基，包含直链、支链或环状结构的C1-C5烯基中的一种；
所述R 15、R 16独立的选自包含直链或支链的C2-C5烯基中的一种，
所述a、b独立的选自1或2，所述c选自1-10之间的整数；
可选地，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自甲基、乙基、苯基和三氟丙基中的一种。
可选地，R 1和R 6相同，R 2和R 7相同，R 3和R 8相同，R 4和R 9相同，R 5和R 10相同。
优选的，所述单体A和所述单体B独立的选自三甲基三乙烯基环三硅氧烷或四甲基四乙烯基环四硅氧烷，所述单体C为1,1,3,3-四甲基二硅氧烷，其特点在于常见且价格低廉；
更优选的，所述单体A和所述单体B均为四甲基四乙烯基环四 硅氧烷，其特点在于常见且价格低廉。
可选地，所述单体A与所述单体B的重量之和与所述单体C的摩尔之比为2-10:1，所述单体A、单体B及单体C的重量之和与所述有机溶剂的重量之比为1-3:1；
优选的，所述单体A与所述单体B的重量之和与所述单体C的摩尔之比为2﹕1、4﹕1、6﹕1或8﹕1，更优选为6﹕1，所述单体A、单体B及单体C的重量之和与所述有机溶剂的重量之比为2:1。
可选地，所述催化剂为铂系催化剂、铑系催化剂、铱系催化剂、钴系催化剂、铁系催化剂、镍系催化剂、钯系催化剂、钌系催化剂和锆系催化剂中的至少一种，所述催化剂在所述反应单体中的浓度为1ppm-2500ppm。所述催化剂只要能够用于催化硅氢加成反应即可。
优选的，所述催化剂为karstedt催化剂，所述催化剂在所述反应单体中的浓度为10ppm-100ppm。karstedt催化剂为铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷，催化效率高，反应更快，且转化率更高。
所述有机溶剂为二氯甲烷、四氢呋喃、二甲亚砜、乙酸乙酯、甲苯、二甲苯、丙酮、正己烷、石油醚和吡啶中的一种，优选为甲苯。
可选地，步骤1)中，在非活性气体的保护下，将所述单体A、单体B及单体C分别除水干燥处理，得到混合后的所述反应单体，将催化剂加入至干燥处理后的所述有机溶剂后得到所述分散液，将所述分散液逐滴加入至所述反应单体内，于40℃-80下反应4-8h；
步骤2)中，反应结束后，在压力不大于-0.096MPa，温度为40-80℃下脱除所述有机溶剂，并在压力不大于-0.096MPa、温度为120℃～160℃下脱除未反应的所述反应单体，冷却至室温得到所述交联剂。
可选地，在-0.096MPa，40-60℃下，对所述单体A和所述单体B进行除水干燥处理；
使用分子筛对所述单体C进行除水干燥处理；
使用氢化钙对所述溶剂进行除水干燥处理。
可选地，所述非活性气体选自氮气、氩气或氦气，优选为氮气。
根据本申请的新型硅橡胶交联剂的结构特征为“哑铃形”，其制备路径不仅限于本申请公开的方法，也可以采用其他从事合成研究的可以实现的路径，例如：采用含有Si-H的环硅氧烷与两端为Si-CH＝CH 2的线型聚硅氧烷作为单体反应，进行硅氢加成制备出的“哑铃形”的聚硅氧烷交联剂。
根据本申请的又一方面，提供了一种上述任一项所述的交联剂或上述任一项所述的制备方法得到的交联剂在制备硅橡胶中的应用；
优选的，所述硅橡胶为上述任一项所述的硅橡胶。
本申请的有益效果包括但不限于：
1.根据本申请的新型硅橡胶交联剂，以含Si-CH＝CH 2的环硅氧烷与两端为Si-H的线型聚硅氧烷作为单体反应，进行硅氢加成制备出一种“哑铃形”的聚硅氧烷交联剂，该交联剂在酸的作用下可以直接与环硅氧烷开环共聚，形成交联结构而成为弹性体，通过调整交联剂的用量可以调整硅橡胶的交联密度，大大提升硅橡胶的耐热性和力学性能。
2.本申请的新型超低粘度硅橡胶的配方中直接使用环硅氧烷作为原料，采用原位共聚方法，聚合和硫化同时发生，体系粘度低、聚合速度可控。由于直接使用环硅氧烷，避免使用粘度较大的硅油，从而大大降低了硅橡胶的粘度。同时不使用Pt等催化剂，可以避免加成型硅橡胶使用过程中催化剂“中毒”而不硫化的问题；原位聚合速度快，极大改善了缩合型液体硅橡胶固化时间长的问题。
3.根据本申请的新型硅橡胶交联剂的制备方法，原料易得，工 艺简单，条件温和，操作简便，成本低，无污染，便于产业化。
4.根据本申请的硅橡胶，粘度低，固化时间短，环境适应性和热稳定性好，具有较佳的力学性能。
附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本申请实施例1涉及的交联剂1#的核磁谱图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
实施例1交联剂1#的制备
1)在N 2保护下，向装有搅拌器的250ml干燥的烧瓶中加入单体A和单体B(单体A和单体B相同，合计为61.6g四甲基四乙烯基环四硅氧烷，共0.18mol)，在40℃-60℃、-0.096Mpa下脱除单体A和单体B中的水分；然后加入干燥后的单体C(3g 1,1,3,3-四甲基二硅氧烷，0.03mol)；然后加入干燥后的32.3g甲苯。然后向烧瓶中加入karstedt催化剂(100ppm)，在N 2保护下，70℃下搅拌反应8h。
2)反应结束后，逐渐降温至60℃，减压至-0.096Mpa脱除溶剂，升温至140℃，脱除未反应的单体，得到交联剂1#，即1,3-二(四甲基三乙烯基环四硅氧烷硅乙烯)四甲基二硅氧烷，产率为：83％。
核磁谱图如图1所示，其中，5.75-6.30ppm处为-CH＝CH 2的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。
实施例2交联剂2#
交联剂2#与交联剂1#的不同之处在于：交联剂2#的单体A为四甲基四乙烯基环四硅氧烷(30.8g，0.09mol)，单体B为三甲基三乙烯基环三硅氧烷(22.7g，0.09mol)，溶剂为28.3g甲苯，其他条件与交联剂1#均相同。
交联剂2#的产率为87％，核磁结果中，5.75-6.30处为-CH＝CH 2的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。
实施例3交联剂3#
交联剂3#与交联剂1#的不同之处在于：交联剂3#的单体A和单体B均为1,3,5-三甲基-1,3,5-三(3,3,3-三氟丙基)环三硅氧烷(共118.8g，0.18mol)，溶剂为60.9g甲苯，其他条件与交联剂1#均相同。
交联剂3#的产率为73％，核磁结果中，5.75-6.30ppm处为-CH＝CH 2的特征峰，2.00-2.20ppm处为-CH 2CF 3的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。
实施例4交联剂4#
交联剂4#与交联剂1#的不同之处在于：交联剂4#的单体A和单体B均为三甲基三乙烯基环三硅氧烷(共45.4g，0.18mol)，溶剂为24.2g甲苯，其他条件与交联剂1#均相同。
交联剂4#的产率为89％，核磁结果中，5.75-6.30ppm处为-CH＝CH 2的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。4.68ppm处属于Si-H处的特征峰消失，以及-CH 2-CH 2-和-CH(CH 3)-特征峰的出现，证明交联剂4#成功合成。
实施例5交联剂5#
交联剂5#与交联剂1#的不同之处在于：交联剂5#的单体A和单体B均为四甲基四乙烯基环四硅氧烷(共20.5g，0.06mol)，溶剂为 11.75g甲苯，其余条件与交联剂1#均相同。
交联剂5#的产率为78％，核磁结果中，5.75-6.30ppm处为-CH＝CH 2的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰，液相结果显示，出现含有三个环硅氧烷的聚合物组分。
实施例6交联剂6#
交联剂6#与交联剂1#的不同之处在于：交联剂6#的单体C为1,1,5,5-四甲基-3,3-二苯基三硅氧烷(9.98g，0.03mol)，溶剂为35.8g甲苯，其余条件与交联剂1#相同。
交联剂6#的产率为75％，核磁结果中，5.75-6.30ppm处为-CH＝CH 2的特征峰，7.40-7.80ppm处为-C 6H 5的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。
实施例7交联剂7#
交联剂7#与交联剂1#的不同之处在于：交联剂7#的催化剂为四(三苯基膦)钯，其余条件与交联剂1#相同。
交联剂7#的产率为45％，核磁结果中，5.75-6.30ppm处为-CH＝CH 2的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。
对比例1交联剂D1#
交联剂D1#与交联剂1#的不同之处在于：单体A和单体B均为1,3-二乙烯基四甲基二硅氧烷(共33.55g，0.18mol)，溶剂为18.3g甲苯，其余条件与交联剂1#相同。
交联剂D1#的产率为72％，核磁结果中，5.75-6.30ppm处为-CH＝CH 2的特征峰，0.45ppm处为-CH 2-CH 2-的特征峰，1.60处为-CH(CH 3)-的特征峰。
对比例2交联剂D2#
交联剂D2#与交联剂1#的不同之处在于：交联剂D2#的单体A和单体B均为四甲基四乙烯基环四硅氧烷(共10.3g，0.03mol)，溶剂为6.65g甲苯，其余条件与交联剂1#均相同。
交联剂D3#产率为0，由于单体A、B之和与单体C的摩尔比为1:1，在烧瓶中交联，变为透明弹性体。
对比例3交联剂D3#
交联剂D3#与交联剂1#的不同之处在于：交联剂D3#的单体C为1,3-二乙烯基四甲基二硅氧烷(5.58g，0.03mol)，溶剂为33.59g的甲苯，其余条件与交联剂1#相同。
交联剂D4#的产率为0，由于单体C中不含有Si-H，硅氢加成反应无法进行。
实验例
取15份实施例1-7制备的交联剂与对比例D1制得的交联剂，制备相应的硫化胶，固定配方为：15份交联剂，100份D 4(即八甲基环四硅氧烷)，20份补强剂、1份催化剂(三氟甲基磺酸)，用3D混合机混合均匀后固化，分别制得硅橡胶1#-7#、硅橡胶D1#。
对比例4加成型硅橡胶E1#
将100份107-Vi胶(乙烯基硅油)(M＝10000)、10份含氢硅油、20份补强剂、5份催化剂、3份抑制剂用3D混合机混合均匀后固化。
对比例5加成型硅橡胶E2#
将100份107-Vi胶(乙烯基硅油)(M＝30000)、10份含氢硅油、20份补强剂、5份催化剂、3份抑制剂用3D混合机混合均匀后固化。
对比例6缩合型硅橡胶E3#
将100份107胶(羟基硅油)(M＝10000)、5份交联剂MeSi(OMe) 3、 20份补强剂、5份催化剂用3D混合机混合均匀后固化。
对比例7缩合型硅橡胶E4#
将100份107胶(羟基硅油)(M＝30000)、5份交联剂MeSi(OMe) 3、20份补强剂、5份催化剂用3D混合机混合均匀后固化。
分别测试硅橡胶1#-7#、D1#以及对比例硅橡胶E1～E4的初始粘度、固化时间、拉伸强度、拉断伸长率、硬度及最大热失重温度，测试结果如表1所示。
表1
Figure PCTCN2021118308-appb-000006
由表1可以看出，采用本发明的方案制备得到的交联剂，是一种新型的硅橡胶的交联剂，可以与环硅氧烷以原位聚合的方式实现硫化，该新型液体硅橡胶的初始粘度低，固化时间短，热稳定性好，具有较佳的力学性能。
以上所述，仅为本申请的实施例而已，本申请的保护范围并不受这些具体实施例的限制，而是由本申请的权利要求书来确定。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的技术思想和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (17)

  1. 一种超低粘度液体硅橡胶，其特征在于，所述硅橡胶包括环硅氧烷、交联剂和催化剂，所述环硅氧烷结构如式I所示：
    Figure PCTCN2021118308-appb-100001
    环硅氧烷结构示意图；
    其中，式I中，R a、R b、R c、R d、R e、R f独立的选自氢、甲基、乙基、三氟丙基、苯基和乙烯基中的一种，n为1、2或3。
  2. 根据权利要求1所述的硅橡胶，其特征在于，所述硅橡胶包括80-120份环硅氧烷、1-30份交联剂、0.5-2份催化剂和0-100份补强剂，其中，所述催化剂选自三氟甲基磺酸、硫酸、盐酸、高氯酸和固体酸中的至少一种。
  3. 一种超低粘度液体硅橡胶用交联剂，其特征在于，所述交联剂的分子结构式如式II所示：
    Figure PCTCN2021118308-appb-100002
    “哑铃型”交联剂结构示意图；
    式II中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自H，包含直链、支链或环状结构的C1-C5烷基，包含直链、支链或环状结构的C1-C5卤代烷基，包含直链、支链或环状结构的C1-C5烯基，包含直链、支链或环状结构的C1-C5卤代 烯基，苯基和烷基苯基中的一种；
    所述R’、R”独立的选自包含直链或支链的C2-C5烷基、包含直链或支链的C2-C5卤代烷基中的一种；
    a和b独立的选自1、2或3，c选自1-50之间的整数。
  4. 根据权利要求3所述的新型硅橡胶交联剂，其特征在于，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自包含直链或支链的C1-C5烷基，包含直链、支链或环状结构的C1-C5烯基中的一种；
    所述a、b独立的选自1或2，所述c选自1-10之间的整数。
  5. 根据权利要求4所述的新型硅橡胶交联剂，其特征在于，所述R 1、R 3、R 5、R 6、R 8、R 10均为甲基，所述R 2、R 4、R 7、R 9均为乙烯基，所述R 11、R 12、R 13、R 14均为甲基。
  6. 根据权利要求5所述的新型硅橡胶交联剂，其特征在于，所述a、b均为2，所述c为1。
  7. 一种超低粘度硅橡胶用交联剂的制备方法，其特征在于，包括以下步骤：
    1)将单体A、单体B和单体C作为反应单体在有机溶剂中混合，加入催化剂进行反应；
    2)反应结束后，脱除未反应的所述反应单体及所述有机溶剂，得到所述交联剂；
    其中，所述单体A的分子结构式如式Ⅲ所示：
    Figure PCTCN2021118308-appb-100003
    单体A结构示意图；
    所述单体B的分子结构式如式Ⅳ所示：
    Figure PCTCN2021118308-appb-100004
    单体B结构示意图；
    所述单体C的分子结构式如式Ⅴ所示：
    Figure PCTCN2021118308-appb-100005
    单体C结构示意图；
    其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自H，包含直链、支链或环状结构的C1-C5烷基，包含直链、支链或环状结构的C1-C5卤代烷基，包含直链、支链或环状结构的C1-C5烯基，包含直链、支链或环状结构的C1-C5卤代烯基，苯基和烷基苯基中的一种；
    所述R 15、R 16独立的选自包含直链或支链的C2-C5烯基、包含直链或支链的C2-C5卤代烯基中的一种；
    a和b独立的选自1、2或3，c选自1-50之间的整数。
  8. 根据权利要求7所述的制备方法，其特征在于，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13、R 14独立的选自 包含直链或支链的C1-C5烷基，包含直链、支链或环状结构的C1-C5烯基中的一种；
    所述R 15、R 16独立的选自包含直链或支链的C2-C5烯基中的一种，
    所述a、b独立的选自1或2，所述c选自1-10之间的整数。
  9. 根据权利要求8所述的制备方法，其特征在于，所述单体A和所述单体B独立的选自三甲基三乙烯基环三硅氧烷或四甲基四乙烯基环四硅氧烷，所述单体C为1,1,3,3-四甲基二硅氧烷。
  10. 根据权利要求9所述的制备方法，其特征在于，所述单体A和所述单体B均为四甲基四乙烯基环四硅氧烷。
  11. 根据权利要求7-10任一项所述的制备方法，其特征在于，所述单体A与所述单体B的重量之和与所述单体C的摩尔之比为2-10:1，所述单体A、单体B及单体C的重量之和与所述有机溶剂的重量之比为1-3:1。
  12. 根据权利要求11所述的制备方法，其特征在于，所述单体A与所述单体B的重量之和与所述单体C的摩尔之比为2:1、4:1、6:1或8:1，所述单体A、单体B及单体C的重量之和与所述有机溶剂的重量之比为2:1。
  13. 根据权利要求7-10任一项所述的制备方法，其特征在于，所述催化剂为铂系催化剂、铑系催化剂、铱系催化剂、钴系催化剂、铁系催化剂、镍系催化剂、钯系催化剂、钌系催化剂和锆系催化剂中的至少一种，所述催化剂在所述反应单体中的浓度为1ppm-2500ppm；
    所述有机溶剂为二氯甲烷、四氢呋喃、二甲亚砜、乙酸乙酯、甲苯、二甲苯、丙酮、正己烷、石油醚和吡啶中的一种。
  14. 根据权利要求13所述的制备方法，其特征在于，所述催化 剂为karstedt催化剂，所述催化剂在所述反应单体中的浓度为10ppm-100ppm；
    所述有机溶剂为甲苯。
  15. 根据权利要求7-10任一项所述的制备方法，其特征在于，
    步骤1)中，在非活性气体的保护下，将所述单体A、单体B及单体C分别除水干燥处理，得到混合后的所述反应单体，将催化剂加入至干燥处理后的所述有机溶剂后得到所述分散液，将所述分散液逐滴加入至所述反应单体内，于40℃-80下反应4-8h；
    步骤2)中，反应结束后，在压力不大于-0.096MPa，温度为40-80℃下脱除所述有机溶剂，并在压力不大于-0.096MPa、温度为120℃～160℃下脱除未反应的所述反应单体，冷却至室温得到所述交联剂。
  16. 权利要求3-6任一项所述的交联剂或权利要求7-15任一项所述的制备方法得到的交联剂在制备硅橡胶中的应用。
  17. 根据权利要求16所述的应用，其特征在于，所述硅橡胶为权利要求1或2所述的硅橡胶。
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