CN105585734A - 1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof - Google Patents

1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof Download PDF

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Publication number
CN105585734A
CN105585734A CN201510946502.8A CN201510946502A CN105585734A CN 105585734 A CN105585734 A CN 105585734A CN 201510946502 A CN201510946502 A CN 201510946502A CN 105585734 A CN105585734 A CN 105585734A
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sich
silane crosslinking
crosslinking agents
trialkoxy silane
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CN201510946502.8A
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Chinese (zh)
Inventor
翁祝强
张彬
孙鹏
陈天广
陈军
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Dongguan Million Shun's Organosilicon Science And Technology Co Ltd
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Dongguan Million Shun's Organosilicon Science And Technology Co Ltd
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Priority to CN201510946502.8A priority Critical patent/CN105585734A/en
Publication of CN105585734A publication Critical patent/CN105585734A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/541Silicon-containing compounds containing oxygen
    • C08K5/5415Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • C07F7/1872Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages

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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 provides a 1,2-ditrialkoxy silane crosslinking agent and a preparation method and application thereof. The 1,2-ditrialkoxy silane crosslinking agent has the structure as follows: (R1O)3SiCH2CH2(CH2)nSi(R2O)3, wherein the R1 and the R2 are independently any one of -CH3, -CH2CH3 or -CH2CH2CH3, and the n is an integer of 0-3. The 1,2-ditrialkoxy silane crosslinking agent prepared by means of the preparation method can strengthen the compatibility of a crosslinking agent and siloxane and has wide application prospect, deep curing is fast, the curing depth within 24 hours can reach 3-7 mm, and the shortcoming that a domestic dealcoholization type sealant is slow in deep curing can be overcome.

Description

Two trialkoxy silane crosslinking agents of a kind of 1,2-and its preparation method and application
Technical field
The invention belongs to silicon rubber field, relate to two trialkoxy silane crosslinking agents of a kind of 1,2-and preparation method thereof and answerWith.
Background technology
Organosilicon cross-linking agent is the active group that contains two kinds of different in kinds on same silicon atom, and a kind of is functionalized siliconReactive group, can there is chemical reaction with the surface of inorganic filler and generate Si-O-Si chemical bond in it; Another kind is that carbon official canReactive group, can react with organic polymer, becomes the active ingredient of polymer, thereby can make two kinds of nature differences veryLarge material is well bondd. Organosilicon cross-linking agent plays bridging action at two kinds of material interface places, the chemical bond handle of formationThe material coupling of two kinds of different in kinds is got up.
Conventional organosilicon cross-linking agent is methyl trimethoxy oxygen radical siloxane or vinyl trimethoxy siloxanes on the market, byThe sulphurated siliastic deep layer curing rate that this crosslinking agent prepares is slow, has limited its application.
Therefore, in the art, expect a kind of obvious organosilicon friendship that improves sulphurated siliastic deep layer curing rate of exploitationConnection agent.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide the two trialkoxy silane crosslinking agents of a kind of 1,2-andIts preparation method and application.
For reaching this object, the present invention by the following technical solutions:
On the one hand, the invention provides the two trialkoxy silane crosslinking agents of a kind of 1,2-, described crosslinking agent has following structure:(R1O)3SiCH2CH2(CH2)nSi(R2O)3, wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any oneKind; N is 0~3 integer, and for example n is 0,1,2 or 3.
Of the present invention 1, the compatibility of the two trialkoxy silane crosslinking agents of 2-and siloxanes is good, and deep layer quick solidifying, can improveDomestic dealcoholized type fluid sealant deep layer is solidified slow shortcoming.
Preferably, of the present invention 1, the two trialkoxy silane crosslinking agents of 2-are to have in the compound of following structureA kind of or the combination of at least two kinds:
(CH3O)3SiCH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2Si(OCH2CH3)3、(CH3CH2O)3SiCH2CH2Si(OCH3)3、(CH3CH2O)3SiCH2CH2Si(OCH2CH3)3、(CH3CH2O)3SiCH2CH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2CH2CH2CH2Si(OCH3)3、(CH3CH2O)3SiCH2CH2CH2CH2Si(OCH2CH3)3、(CH3CH2CH2O)3SiCH2CH2Si(OCH2CH3)3Or (CH3CH2CH2O)3SiCH2CH2Si(OCH2CH2CH3)3
Preferably, of the present invention 1, the two trialkoxy silane crosslinking agents of 2-are prepared into by the raw material of following weight portionArrive:
(R1O)3SiH80~100 weight portion
CH2=CH(CH2)nSi(R2O)380~100 weight portions
Catalyst 0.01~0.3 weight portion;
Wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer, for exampleN is 0,1,2 or 3.
Preferably, described catalyst is chloroplatinic acid, Pt/C or Pt/Al2O3In the combination of any one or at least two kinds,Preferably chloroplatinic acid. .
On the other hand, of the present invention 1, the preparation method of the two trialkoxy silane crosslinking agents of 2-, described method is:
(1) by raw material (R1O)3SiH and CH2=CH(CH2)nSi(R2O)3Mixing and stirring;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid to stir;
(3) be heated to 50~80 DEG C of reactions obtain described 1, the two trialkoxy silane crosslinking agents of 2-;
Wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer, for exampleN is 0,1,2 or 3.
Preferably, described in step (1) and step (2), be stirred in 20-30 DEG C (for example 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25DEG C, 26 DEG C, 27 DEG C, 28 DEG C or 29 DEG C) under carry out.
Preferably, the time of the described stirring of step (1) is 1~3 hour, for example 1.2 hours, 1.4 hours, 1.5 hours,1.7 hours, 1.9 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 2.9 hours.
Preferably, the time of the described stirring of step (2) is 0.5~1 hour, for example 0.55 hour, 0.6 hour, 0.65 littleTime, 0.7 hour, 0.75 hour, 0.8 hour, 0.85 hour, 0.9 hour or 0.95 hour.
Preferably, the time of the described reaction of step (3) is 3-8 hour, for example 3.5 hours, 4 hours, 4.5 hours, 5 littleTime, 5.5 hours, 6 hours, 6.5 hours, 7 hours or 7.5 hours.
As optimal technical scheme, of the present invention 1, the preparation method of the two trialkoxy silane crosslinking agents of 2-specifically wrapsDraw together following steps:
(1) by raw material (R1O)3SiH and CH2=CH(CH2)nSi(R2O)3Mix, stir 1~3 hour at 20-30 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 0.5~1 hour at 20-30 DEG C;
(3) be heated to 50~80 DEG C of reaction 3-8 hour, obtain described 1, the two trialkoxy silane crosslinking agents of 2-;
Wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer, for exampleN is 0,1,2 or 3.
On the other hand, the invention provides as described in first aspect 1, the two trialkoxy silane crosslinking agents of 2-are being prepared siliconApplication in rubber. The present invention prepare 1, the two trialkoxy silane crosslinking agents of 2-help as organosilicon in the preparation of silicon rubberAgent, can strengthen the compatibility of crosslinking agent and siloxanes, and deep layer quick solidifying can improve domestic dealcoholized type fluid sealant deep layer and solidify slowDeficiency.
With respect to prior art, the present invention has following beneficial effect:
The present invention prepare 1, the two trialkoxy silane crosslinking agents of 2-can strengthen the compatibility of crosslinking agent and siloxanes, deeplyLayer quick solidifying, within 24 hours, curing depth can reach 3-7mm, and can improve domestic dealcoholized type fluid sealant deep layer and solidify slow deficiency,Be with a wide range of applications.
Detailed description of the invention
Further illustrate technical scheme of the present invention below by detailed description of the invention. Those skilled in the art should be bright, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
In the present embodiment, prepare the two trialkoxy silane crosslinking agents of 1,2-by the raw material of following weight portion:
(CH3O)3SiH80 weight portion
CH2=CHSi(OCH2CH3)3100 weight portions
Chloroplatinic acid 0.3 weight portion;
Preparation method is as follows:
(1) by raw material (CH3O)3SiH and CH2=CHSi(OCH2CH3)3Mix, stir 1 hour at 25 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 0.5 hour at 25 DEG C;
(3) be heated to 65 DEG C of reactions 6 hours, vacuumize and remove low molecule, cooling discharge obtains (CH3O)3SiCH2CH2Si(OCH2CH3)3
Embodiment 2
In the present embodiment, prepare the two trialkoxy silane crosslinking agents of 1,2-by the raw material of following weight portion:
(CH3CH2O)3SiH100 weight portion
CH2=CHSi(OCH3)380 weight portions
Chloroplatinic acid 0.3 weight portion;
Preparation method is as follows:
(1) by raw material (CH3CH2O)3SiH and CH2=CHSi(OCH3)3Mix, stir 3 hours at 20 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 1 hour at 20 DEG C;
(3) be heated to 50 DEG C of reactions 8 hours, vacuumize and remove low molecule, cooling discharge obtains (CH3O)3SiCH2CH2Si(OCH2CH3)3
Embodiment 3
In the present embodiment, prepare the two trialkoxy silane crosslinking agents of 1,2-by the raw material of following weight portion:
(CH3CH2O)3SiH90 weight portion
CH2=CHCH2Si(OCH2CH3)390 weight portions
Chloroplatinic acid 0.01 weight portion;
Preparation method is as follows:
(1) by raw material (CH3CH2O)3SiH and CH2=CHCH2Si(OCH2CH3)3Mix, stir 2 hours at 25 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 0.8 hour at 30 DEG C;
(3) be heated to 80 DEG C of reactions 3 hours, vacuumize and remove low molecule, cooling discharge obtains (CH3CH2O)3SiCH2CH2CH2Si(OCH2CH3)3
Embodiment 4
In the present embodiment, prepare the two trialkoxy silane crosslinking agents of 1,2-by the raw material of following weight portion:
(CH3CH2CH2O)3SiH85 weight portion
CH2=CHSi(OCH2CH3)3100 weight portions
Chloroplatinic acid 0.2 weight portion;
Preparation method is as follows:
(1) by raw material (CH3CH2CH2O)3SiH and CH2=CHSi(OCH2CH3)3Mix, stir 1 hour at 25 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 1 hour at 20 DEG C;
(3) be heated to 70 DEG C of reactions 4 hours, vacuumize and remove low molecule, cooling discharge obtains (CH3CH2CH2O)3SiCH2CH2Si(OCH2CH3)3
Embodiment 5
In the present embodiment, prepare the two trialkoxy silane crosslinking agents of 1,2-by the raw material of following weight portion:
(CH3O)3SiH85 weight portion
CH2=CHSi(OCH3)3100 weight portions
Chloroplatinic acid 0.2 weight portion;
Preparation method is as follows:
(1) by raw material (CH3O)3SiH and CH2=CHSi(OCH3)3Mix, stir 1 hour at 25 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 1 hour at 20 DEG C;
(3) be heated to 70 DEG C of reactions 4 hours, vacuumize and remove low molecule, cooling discharge obtains (CH3O)3SiCH2CH2Si(OCH3)3
Prepared by embodiment 1-5 1, the two trialkoxy silane crosslinking agents of 2-prepare dealcoholized type room temperature vulcanized silicone rubber and withCommon methyl trimethoxy oxygen radical siloxane crosslinking agent (comparative example 1) and vinyl trimethoxy siloxane crosslinker on the marketThe dealcoholized type room temperature vulcanized silicone rubber that (comparative example 2) makes contrasts, and investigates the curing performance of 24 hours of dealcoholized silicone rubber.
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
Curing depth 5mm 6mm 7mm 5mm 3mm 2mm 1.8mm
As can be seen from Table 1, the present invention prepare 1, the dealcoholysis that the two trialkoxy silane crosslinking agents of 2-prepareType room temperature vulcanized silicone rubber curing depth in 24 hours can reach 3-7mm, and comparative example 1 and comparative example 2 on the marketIn dealcoholized type room temperature vulcanized silicone rubber that crosslinking agent prepares 24 hours, curing depth can only reach 1.8-2mm, therefore thisBright crosslinking agent can improve domestic dealcoholized type fluid sealant deep layer and solidify slow deficiency.
Applicant statement, the present invention illustrates of the present invention 1 by above-described embodiment, the two trialkoxy silane crosslinking agents of 2-And its preparation method and application, but the present invention is not limited to above-described embodiment, does not mean that the present invention must rely on above-mentionedEmbodiment could implement. Person of ordinary skill in the field should understand, any improvement in the present invention, to product of the present inventionThe selections of the equivalence replacement of each raw material and the interpolation of auxiliary element, concrete mode etc., all drop on protection scope of the present invention and public affairsWithin opening scope.

Claims (10)

1. one kind 1, the two trialkoxy silane crosslinking agents of 2-, is characterized in that, described crosslinking agent has following structure: (R1O)3SiCH2CH2(CH2)nSi(R2O)3, wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer.
2. according to claim 11, the two trialkoxy silane crosslinking agents of 2-, is characterized in that, described crosslinking agent is for havingThe combination of a kind of in the compound of following structure or at least two kinds: (CH3O)3SiCH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2Si(OCH2CH3)3、(CH3CH2O)3SiCH2CH2CH2Si(OCH3)3、(CH3CH2O)3SiCH2CH2CH2Si(OCH2CH3)3、(CH3CH2O)3SiCH2CH2CH2Si(OCH3)3、(CH3O)3SiCH2CH2CH2CH2CH2Si(OCH3)3、(CH3CH2O)3SiCH2CH2CH2CH2Si(OCH2CH3)3、(CH3CH2CH2O)3SiCH2CH2Si(OCH2CH3)3Or (CH3CH2CH2O)3SiCH2CH2Si(OCH2CH2CH3)3
3. according to claim 1 and 21, the two trialkoxy silane crosslinking agents of 2-, is characterized in that, described crosslinking agent byThe raw material of following weight portion prepares:
(R1O)3SiH80~100 weight portion
CH2=CH(CH2)nSi(R2O)380~100 weight portions
Catalyst 0.01~0.3 weight portion;
Wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer.
4. according to claim 31, the two trialkoxy silane crosslinking agents of 2-, is characterized in that, described catalyst is chlorine platinumAcid, Pt/C or Pt/Al2O3In the combination of any one or at least two kinds, preferably chloroplatinic acid.
5. according to 1 described in any one in claim 1-4, the preparation method of the two trialkoxy silane crosslinking agents of 2-, its featureBe, described method is:
(1) by raw material (R1O)3SiH and CH2=CH(CH2)nSi(R2O)3Mixing and stirring;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid to stir;
(3) be heated to 50~80 DEG C of reactions obtain described 1, the two trialkoxy silane crosslinking agents of 2-;
Wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer.
6. preparation method according to claim 5, is characterized in that, is stirred in 20-30 described in step (1) and step (2)At DEG C, carry out.
7. according to the preparation method described in claim 5 or 6, it is characterized in that, the time of the described stirring of step (1) is 1~3 littleTime;
Preferably, the time of the described stirring of step (2) is 0.5~1 hour.
8. according to the preparation method described in any one in claim 5-7, it is characterized in that the time of the described reaction of step (3)For 3-8 hour.
9. according to the preparation method described in any one in claim 5-8, it is characterized in that, said method comprising the steps of:
(1) by raw material (R1O)3SiH and CH2=CH(CH2)nSi(R2O)3Mix, stir 1~3 hour at 20-30 DEG C;
(2) in the mixed liquor obtaining to step (1), add chloroplatinic acid, stir 0.5~1 hour at 20-30 DEG C;
(3) be heated to 50~80 DEG C of reaction 3-8 hour, obtain described 1, the two trialkoxy silane crosslinking agents of 2-;
Wherein R1、R2Be independently-CH3、-CH2CH3Or-CH2CH2CH3In any one; N is 0~3 integer.
10. according to 1 described in any one in claim 1-4, the two trialkoxy silane crosslinking agents of 2-are preparing in silicon rubberApplication.
CN201510946502.8A 2015-12-16 2015-12-16 1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof Pending CN105585734A (en)

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CN109384958A (en) * 2018-10-19 2019-02-26 山东大学 A kind of room temperature vulcanized silicone rubber crosslinking agent preparation method and applications

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CN109384958A (en) * 2018-10-19 2019-02-26 山东大学 A kind of room temperature vulcanized silicone rubber crosslinking agent preparation method and applications

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Application publication date: 20160518