CN110606986A - Silicone rubber cross-linking agent, and preparation method and application thereof - Google Patents

Silicone rubber cross-linking agent, and preparation method and application thereof Download PDF

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CN110606986A
CN110606986A CN201910891633.9A CN201910891633A CN110606986A CN 110606986 A CN110606986 A CN 110606986A CN 201910891633 A CN201910891633 A CN 201910891633A CN 110606986 A CN110606986 A CN 110606986A
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silicone rubber
crosslinking agent
preparing
catalyst
silicon rubber
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CN110606986B (en
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张才亮
吴坤红
王笛
洪东海
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Hangzhou Jufeng New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the field of polymer processing, and discloses a silicone rubber cross-linking agent which has the following structural formula, and the preparation method comprises the following steps: reacting nitroxyl radical piperidinol and styrene under the action of an initiator to prepare alkoxy amine diol; then adding the alkoxyamine diol into a catalyst, an acid-binding agent and a reaction medium, and then dropwise adding chlorosilane for reaction to obtain the catalyst. The silicon rubber cross-linking agent contains silicon hydrogen bonds, and can replace the traditional silicon rubber cross-linking agents such as peroxide or hydrogen-containing silicone oil and the like; and the cross-linking agent contains C-ON dynamic bonds which can be dissociated at high temperature and recombined at room temperature. The thermoplastic silicon rubber cross-linked network structure prepared by the method is gradually uncrosslinked into an original linear chain at high temperature, and the cross-linked network structure is reformed at room temperature, so that the repeated processability and mechanics of the silicon rubber are realizedExcellent performance, and can keep the mechanical property basically unchanged after repeated processing.

Description

Silicone rubber cross-linking agent, and preparation method and application thereof
Technical Field
The invention relates to the field of polymer processing, and particularly relates to a silicone rubber crosslinking agent, and a preparation method and application thereof.
Background
Silicone rubber refers to rubber having a backbone composed of alternating silicon and oxygen atoms with two organic groups attached to the silicon atoms. The silicon rubber has outstanding high temperature resistance, weather resistance, radiation resistance and good elasticity, can keep stable mechanical property between minus 40 ℃ and 200 ℃, keeps certain toughness, rebound resilience and hardness, and is widely applied to various fields. The excellent performance of the silicone rubber is mainly derived from a three-dimensional covalent cross-linked network structure formed by silicon-oxygen bonds. However, the highly irreversible crosslinked network structure also makes it impossible to thermoplastically machine and form again, and can only be used as a thermosetting material, thus limiting its wider application prospect.
At present, two main types of silicon rubber capable of realizing thermoplastic processing are available, one type is thermoplastic organosilicon dynamic vulcanized rubber which is a silicon rubber composite material and is a process of melting and blending unvulcanized rubber and a thermoplastic material under the action of high shear and simultaneously adding a cross-linking agent to vulcanize the unvulcanized rubber. In this process, the thermosetting rubber phase (dispersed phase) is uniformly dispersed in the thermoplastic material (continuous phase) in a certain particle size range, and is melt blended under the action of proper temperature and shearing, the rubber phase particles are completely crosslinked, and finally the thermoplastic dynamic vulcanized rubber (TPV) is obtained. The crosslinking of the rubber phase stabilizes the rubber particle morphology, preventing re-agglomeration of the rubber particles prior to crystallization or cooling of the thermoplastic continuous phase to a glassy state and during subsequent processing. The main characteristic of dynamic vulcanization is that the rubber phase which is thermosetting is loaded in the thermoplastic material, so that the characteristics of the thermosetting rubber and the thermoplastic plastic are combined, and the processing and recycling of the material are facilitated.
CN 105885423A discloses a method for preparing silicone rubber/polyamide thermoplastic vulcanizate by reactive compatibilization, which comprises the steps of shearing and mixing silicone rubber, polyamide, self-made solubilizer and antioxidant at the high temperature of 170-260 ℃, adding vulcanizing agent and polymerization inhibitor to mix uniformly after cooling, and finally dynamically vulcanizing under high-temperature high-speed shearing to obtain the silicone rubber/polyamide thermoplastic vulcanizate. The thermoplastic vulcanized rubber can be reprocessed and molded at high temperature, but can only meet very limited silicon rubber application scenes due to the existence of the thermoplastic polymer matrix.
Another method for achieving silicone rubber reworking is dynamic covalent Chemistry, several silicone rubbers prepared by metal-ligand coordination interactions are currently disclosed, and Zhang et al, 2.20.2017, Vol.8, 218, Macro chemical and physical, disclose the synthesis and characterization of a Room temperature self-healing methyl phenyl silicone rubber based on metal-ligand crosslinking (synthesis and catalysis, Macromolecular Chemistry and physics volume 218, Issue8), which can achieve recycling but have poor mechanical properties far below commercially available non-thermoplastic silicone rubbers.
Disclosure of Invention
Aiming at the problems of poor repeatability and poor mechanical property of the thermoplastic silicone rubber in the prior art, the invention provides a silicone rubber cross-linking agent which is used for replacing the traditional silicone rubber cross-linking agent and converting the silicone rubber into the thermoplastic silicone rubber with high strength and repeatable processing.
In order to achieve the purpose, the invention adopts the technical scheme that:
a silicone rubber crosslinker having the structure:
wherein R is1And R2Is C1-C5Alkyl group of (1).
The invention also provides a preparation method of the silicon rubber crosslinking agent, which comprises the following steps:
(1) reacting nitroxyl radical piperidinol and styrene at 80-100 deg.C for 4-6h under the action of initiator, cooling to remove unreacted styrene, adding potassium hydroxide solution, reacting at room temperature for 10-14h, separating, and purifying to obtain alkoxyamine diol, wherein the reaction formula is as follows:
(2) adding the alkoxyamine diol prepared in the step (1) into a catalyst A, an acid binding agent and a reaction medium, dropwise adding chlorosilane at the speed of 0.5-3 drops/second under the protection of nitrogen, reacting for 8-14h in an ice bath or at room temperature, and separating and purifying to obtain the silicon rubber cross-linking agent, wherein the reaction formula is as follows:
wherein R is1And R2Is C1-C5Alkyl group of (1).
In the step (1), the raw materials are calculated according to molar ratio: the mol ratio of the nitroxide radical piperidinol to the styrene to the initiator to the potassium hydroxide is 1: 0.5-5: 0.1-1: 1.
the steps of separation and purification are as follows: adding an organic solvent and water into the reaction mixture for liquid separation, collecting an organic phase, drying the organic phase, and removing the organic solvent to obtain a crude product of the alkoxylamine diol; the crude product was separated by column chromatography to give the pure product of the alkoxyamine diol.
The initiator is a peroxide initiator or an azo initiator.
Further preferably, the peroxide initiator is dicumyl peroxide, benzoyl peroxide or tert-butyl hexane peroxide; the azo initiator is azo isobutyryl formamide, azo diisobutyronitrile, azo diisovaleronitrile or azo diisoheptanonitrile.
In the step (2), the dosage of each raw material is calculated according to molar ratio: the molar ratio of the alkoxyamine glycol to the chlorosilane to the acid-binding agent to the reaction medium is 1: 0.5-5: 1-5: 1-5, wherein the catalyst A accounts for 1-10 wt% of the total amount of reactants. It is further preferable that the acid-binding agent is in excess to absorb hydrogen chloride generated during the reaction.
The steps of separation and purification are as follows: and centrifuging after the reaction is finished to obtain supernatant of the reaction mixture, and distilling the supernatant under reduced pressure to remove the reaction medium, the acid-binding agent and the like to obtain the silicon rubber crosslinking agent.
The chlorosilane is dimethylchlorosilane, diethylchlorosilane or methylethylchlorosilane.
The catalyst A is aminopyridine, and the structure of the catalyst A is shown as follows:
wherein R is1And R2Is C1-C5Alkyl group of (1).
The acid-binding agent is triethylamine, triethanolamine or tetrabutylammonium bromide.
The reaction medium is toluene, dimethyl sulfoxide, dimethylformamide or tetrahydrofuran.
The invention also provides a thermoplastic silicone rubber, wherein in the vulcanization process of the silicone rubber, 0.2-5 parts of the silicone rubber crosslinking agent, 0.01-0.1 part of the catalyst B and 0.01-0.1 part of the inhibitor are added to each 100 parts of the silicone rubber, and then the mixture is melted and blended in blending equipment to prepare the thermoplastic silicone rubber. The thermoplastic silicone rubber can be repeatedly processed, has excellent mechanical properties, and can still maintain good mechanical properties after repeated processing for many times.
The silicone rubber is a mixed rubber containing 0-50% of white carbon black, and the mixed rubber containing the white carbon black has excellent aging resistance, high and low temperature resistance, acid and alkali resistance and the like, so that the finally prepared thermoplastic silicone rubber has more excellent performance.
The catalyst B is a dispersion system or a complex of transition metal. Further preferably, the catalyst B is a platinum complex, and has excellent catalytic performance.
The inhibitor is a nitrogen heterocyclic inhibitor and comprises pyridine, imidazole or pyrazole.
The silicon rubber cross-linking agent contains a silicon hydrogen bond (-SiH), and can replace the traditional silicon rubber cross-linking agent such as peroxide or hydrogen-containing silicone oil; the cross-linking agent contains C-ON dynamic bonds which are dissociated at high temperature and recombined at room temperature, so that the cross-linked network structure of the prepared thermoplastic silicone rubber is gradually uncrosslinked into an original linear chain at high temperature, and the cross-linked network structure is reformed at room temperature, thereby realizing the repeated processability of the silicone rubber.
Compared with the prior art, the invention has the following beneficial effects:
(1) by adopting the silicon rubber cross-linking agent, the mechanical property of the prepared thermoplastic silicon rubber after vulcanization is equivalent to that of commercial non-thermoplastic silicon rubber after vulcanization.
(2) By adopting the silicon rubber crosslinking agent, the prepared thermoplastic silicon rubber can be repeatedly processed, and the mechanical property of the silicon rubber is basically kept unchanged after repeated processing.
(3) When the thermoplastic silicone rubber is applied, the thermoplastic silicone rubber is not influenced by other polymer matrixes, has wide application range, and can be used in various fields of aviation, instruments, metallurgy, medical treatment and the like.
Drawings
FIG. 1 is an infrared spectrum of an alkoxyamine diol used in example 1 and the resulting silicone rubber crosslinking agent.
FIG. 2 is a photograph showing the change of the thermoplastic silicone rubber obtained in application example 4 and the ordinary silicone rubber chips of comparative example 2 before and after hot pressing at 180 ℃ and 5MPa for 20 min.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following examples are all purchased from commercial places, wherein the silicone rubber is R230CN purchased from Wake chemical, and the addition amount of the white carbon black is 30%; reagents such as 4-hydroxy tetramethyl piperidine, benzoyl peroxide, styrene, methylene chloride, triethylamine and the like are commercially available from alatin. Reagents such as potassium hydroxide, 4-dimethylaminopyridine, toluene, tetrahydrofuran, and the like are purchased from Chinese medicines.
The adopted test method comprises the following steps:
and (3) hardness testing: tested according to GB/T531-1999 standard, 5 second reading.
And (3) tensile test: the tensile rate was 500mm/min as tested in GB 1040-2006 standard.
And (3) infrared testing: the infrared test was performed on a Thermo Nicolet model 6700 infrared spectrometer. The test samples were coated on a KBr chip and dried under an infrared lamp before testing. The testing temperature is room temperature (25 ℃), and the scanning range is 4000--1Scanning frequency of 32s-1Resolution of 4cm-1。
Example 1
(1) Dissolving nitroxide radical piperidinol and benzoyl peroxide in styrene, wherein the molar ratio of the nitroxide radical piperidinol to the benzoyl peroxide to the styrene is 1: 0.2: 1, introducing argon gas, bubbling for 30min, reacting for 5h at 90 ℃ under the protection of argon gas, and cooling to room temperature; decompressing to remove unreacted styrene, adding potassium hydroxide solution with the same mol as the nitroxyl radical piperidinol, and continuing to react at room temperature for 12 hours;
adding dichloromethane and deionized water into the reaction mixture to separate the product, collecting an organic phase, and extracting the water phase with dichloromethane for 3 times; adding anhydrous sodium sulfate into the organic phase, drying for 24h to remove water, filtering to remove the anhydrous sodium sulfate, and removing dichloromethane under reduced pressure to obtain a crude product; separating and purifying the crude product by using column chromatography, and taking a mixed solvent of petroleum ether and ethyl acetate as a mobile phase to obtain alkoxylamine diol;
(2) putting the alkoxyamine diol obtained in the step (1) into a reaction bottle, adding 4-dimethylaminopyridine, triethylamine and tetrahydrofuran under the protection of nitrogen, dropwise adding dimethylchlorosilane at room temperature at a dropping speed of 1 drop/second, wherein the molar ratio of the alkoxyamine diol to the dimethylchlorosilane to the triethylamine to the tetrahydrofuran is 1: 1: 1: 1; 4-dimethylamino pyridine accounts for 1 percent of the total mass of reactants, after 12 hours of reaction, the mixture is centrifuged to obtain upper organic clear liquid, and the organic clear liquid is decompressed and distilled to remove reaction medium, acid-binding agent and the like, thus obtaining the silicone rubber crosslinking agent, which is marked as A1.
Example 2
(1) Dissolving nitroxide radical piperidinol and benzoyl peroxide in styrene, wherein the molar ratio of the nitroxide radical piperidinol to the benzoyl peroxide to the styrene is 1: 0.2: 1, introducing argon gas, bubbling for 30min, reacting for 5h at 90 ℃ under the protection of argon gas, and cooling to room temperature; decompressing to remove unreacted styrene, adding potassium hydroxide solution with the same mol as the nitroxyl radical piperidinol, and continuing to react at room temperature for 12 hours;
adding dichloromethane and deionized water into the reaction mixture to separate the product, collecting an organic phase, and extracting the water phase with dichloromethane for 3 times; adding anhydrous sodium sulfate into the organic phase, drying for 24h to remove water, filtering to remove the anhydrous sodium sulfate, and removing dichloromethane under reduced pressure to obtain a crude product; separating and purifying the crude product by using column chromatography, and taking a mixed solvent of petroleum ether and ethyl acetate as a mobile phase to obtain alkoxylamine diol;
(2) putting the alkoxyamine diol obtained in the step (1) into a reaction bottle, adding 4-dimethylaminopyridine, triethylamine and tetrahydrofuran under the protection of nitrogen, dropwise adding dimethylchlorosilane at room temperature at a dropping speed of 1 drop/second, wherein the molar ratio of the alkoxyamine diol to the dimethylchlorosilane to the triethylamine to the tetrahydrofuran is 1: 2: 1: 1; 4-dimethylamino pyridine accounts for 1 percent of the total mass of reactants, after 12 hours of reaction, the mixture is centrifuged to obtain upper organic clear liquid, and the organic clear liquid is decompressed and distilled to remove reaction medium, acid-binding agent and the like, thus obtaining the silicone rubber crosslinking agent, which is marked as A2.
Application example 1
100 parts of silicon rubber, 0.5 part of A1, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing machine at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B1.
Application example 2
100 parts of silicon rubber, 1 part of A1, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing instrument at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B2.
Application example 3
100 parts of silicon rubber, 3 parts of A1, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing instrument at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B3.
Application example 4
100 parts of silicon rubber, 0.5 part of A2, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing machine at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B4.
Application example 5
100 parts of silicon rubber, 1 part of A1, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing instrument at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B5.
Application example 6
100 parts of silicon rubber, 0.5 part of A2, 0.04 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing machine at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B6.
Application example 7
100 parts of silicon rubber, 1 part of A1, 0.04 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing machine at 160 ℃ under the condition of 5MPa to prepare the thermoplastic silicon rubber, which is marked as B7.
Comparative example 1
100 parts of silicon rubber, 1 part of commercial hydrogen-containing silicon oil, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing instrument at 160 ℃ under the condition of 5MPa to prepare the common silicon rubber which is marked as C1.
Comparative example 2
100 parts of silicon rubber, 3 parts of commercial hydrogen-containing silicon oil, 0.02 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing instrument at 160 ℃ under the condition of 5MPa to prepare the common silicon rubber which is marked as C2.
Comparative example 3
100 parts of silicon rubber, 3 parts of commercial hydrogen-containing silicon oil, 0.04 part of platinum catalyst and 0.01 part of pyridine are uniformly mixed on an open mill, and then vulcanized for 15min on a flat-plate vulcanizing instrument at 160 ℃ under the condition of 5MPa to prepare the common silicon rubber which is marked as C3.
The mechanical properties of the silicone rubbers obtained in the application examples and comparative examples are shown in table 1, and the thermoplastic silicone rubber B4 in application example 4 was repeatedly processed and tested for mechanical properties after each processing, and the results are shown in table 2.
From the results of mechanical properties in Table 1, the mechanical properties of the thermoplastic silicone rubber cross-linked and vulcanized using the silicone rubber cross-linking agent of example 1 or 2 are comparable to those of ordinary silicone rubber cross-linked and vulcanized using a commercial cross-linking agent.
The results in Table 2 show that the thermoplastic silicone rubber can be repeatedly processed and used, and the mechanical properties of the silicone rubber are basically kept unchanged after three times of repeated processing.
TABLE 1 mechanical Properties of Silicone rubbers of application examples and comparative examples
TABLE 2 mechanical Properties of thermoplastic Silicone rubber of example 4 after repeated processing
From FIG. 1, it can be seen that a characteristic peak of-OH is evident in the alkoxyamine diol and a characteristic peak of-SiH is evident in the thermoplastic silicone rubber crosslinking agent.
As can be seen from fig. 2, the general silicone rubber C2 of comparative example 2 was still broken after hot pressing and could not be repeatedly processed, since the silicone covalent bond was very stable at high temperature and thus could not be repeatedly heat-formed; and application example 4, the thermoplastic silicone rubber B4 is remolded after hot pressing, because at high temperature, the C-ON bond in the thermoplastic silicone rubber is deflected and dissociated, the linear chain segment of the silicone rubber is recovered, the thermoplastic silicone rubber can flow and plasticity, after cooling, the dissociated C-ON is recombined to be used as the cross-linking point of the silicone rubber, and a network structure is formed by vulcanization, so that the reworkability of the silicone rubber is realized.

Claims (10)

1. A silicone rubber cross-linking agent characterized by the following structural formula:
wherein R is1And R2Is C1-C5Alkyl group of (1).
2. The method for preparing a silicone rubber crosslinking agent according to claim 1, comprising the steps of:
(1) heating nitroxyl radical piperidinol and styrene to react under the action of an initiator, removing unreacted styrene after the reaction is finished, adding a potassium hydroxide solution to continue reacting at room temperature, and separating and purifying to obtain the alkoxyamine glycol, wherein the reaction formula is as follows:
(2) mixing the alkoxyamine diol prepared in the step (1) with a catalyst A, an acid-binding agent and a reaction medium, dropwise adding chlorosilane under the protection of inert gas, reacting at an ice bath or room temperature, and separating and purifying to obtain the silicon rubber cross-linking agent, wherein the reaction formula is as follows:
wherein R is1And R2Is C1-C5Alkyl group of (1).
3. The method for preparing a silicone rubber crosslinking agent according to claim 2, wherein in step (1), the raw materials are, in terms of mole ratio: the mol ratio of the nitroxide radical piperidinol to the styrene to the initiator to the potassium hydroxide is 1: 0.5-5: 0.1-1: 1.
4. the method for preparing a silicone rubber crosslinking agent according to claim 2, wherein in step (1), the initiator is dicumyl peroxide, benzoyl peroxide, t-butylperoxyhexane, azoisobutyrylcyanamide, azodiisobutyronitrile, azodiisovaleronitrile, or azodiisoheptanonitrile.
5. The method for preparing a silicone rubber crosslinking agent according to claim 2, wherein in step (2), the raw materials are used in a molar ratio of: the molar ratio of the alkoxyamine glycol to the chlorosilane to the acid-binding agent to the reaction medium is 1: 0.5-5: 1-5: 1-5; the catalyst A accounts for 1-10 wt% of the total weight of reactants.
6. The method of preparing a silicone rubber crosslinking agent according to claim 2, wherein in step (2), the chlorosilane is dimethylchlorosilane, diethylchlorosilane, or methylethylchlorosilane.
7. The method for preparing a silicone rubber crosslinking agent according to claim 2 or 5, wherein in step (2), the catalyst A is aminopyridine, and the structure is shown as follows:
wherein R is1And R2Is C1-C5Alkyl group of (1).
8. The method for preparing a silicone rubber crosslinking agent according to claim 2, wherein in step (2), the acid-binding agent is triethylamine, triethanolamine, or tetrabutylammonium bromide.
9. The method for preparing a silicone rubber crosslinking agent according to claim 2, wherein in step (2), the reaction medium is toluene, dimethyl sulfoxide, dimethylformamide, or tetrahydrofuran.
10. A thermoplastic silicone rubber, characterized in that, in the vulcanization of silicone rubber, 0.2 to 5 parts of the silicone rubber crosslinking agent of claim 1, 0.01 to 0.1 part of catalyst B and 0.01 to 0.1 part of inhibitor are added per 100 parts of silicone rubber, and then melt-blended in a blending device to obtain the thermoplastic silicone rubber.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646354A (en) * 2020-12-22 2021-04-13 杭州聚丰新材料有限公司 Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1273241A (en) * 1999-02-25 2000-11-15 西巴特殊化学品控股有限公司 Hydroxy substituted N-alkoxy hindered amine
CN103627182A (en) * 2013-11-29 2014-03-12 浙江新安化工集团股份有限公司 Low compression set liquid silastic and preparation method thereof
CN105885423A (en) * 2016-05-25 2016-08-24 北京化工大学 Method for preparing silicone rubber/polyamide thermoplastic vulcanized rubber by virtue of reactive compatibilization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1273241A (en) * 1999-02-25 2000-11-15 西巴特殊化学品控股有限公司 Hydroxy substituted N-alkoxy hindered amine
CN103627182A (en) * 2013-11-29 2014-03-12 浙江新安化工集团股份有限公司 Low compression set liquid silastic and preparation method thereof
CN105885423A (en) * 2016-05-25 2016-08-24 北京化工大学 Method for preparing silicone rubber/polyamide thermoplastic vulcanized rubber by virtue of reactive compatibilization

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUAN, CE, ET AL.: "Application of alkoxyamine in self-healing of epoxy", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646354A (en) * 2020-12-22 2021-04-13 杭州聚丰新材料有限公司 Organic silicon-polyurethane thermoplastic elastomer and preparation method thereof

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