CN107903863A - A kind of silane modified polyether base rubber and its sulfydryl free radical addition preparation method - Google Patents
A kind of silane modified polyether base rubber and its sulfydryl free radical addition preparation method Download PDFInfo
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- CN107903863A CN107903863A CN201711306052.1A CN201711306052A CN107903863A CN 107903863 A CN107903863 A CN 107903863A CN 201711306052 A CN201711306052 A CN 201711306052A CN 107903863 A CN107903863 A CN 107903863A
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- base rubber
- modified polyether
- silane modified
- polyether base
- free radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a kind of silane modified polyether base rubber and its preparation method of sulfydryl free radical addition, carries out Radical Addition using the terminal olefine of sulfydryl and polyethers to prepare silane modified polyether base rubber；During preparation：The polyethers of 1 molar part end-allyl group is sequentially added in the reactor, the mercaptoalkoxysilane of 2.1 ~ 3 molar parts, 0.1 ~ 2 molar part radical initiator, 0 ~ 100 molar part solvent, at 50 DEG C ~ 120 DEG C reaction 1 ~ 24 it is small when, then it is purified, be dried to obtain silane modified polyether base rubber.The preparation process heavy metal free catalyst of the present invention, cost is low, aftertreatment technology is simple, rapid reaction, high income, stability are good, and base rubber product viscosity is low, the features such as during curing without autocatalysis, there is good industrialization prospect.
Description
Technical field
The invention belongs to organic gel field, especially be related to a kind of silane modified polyether base rubber and its sulfydryl free radical adds
Into preparation method, a kind of polyethers of alkoxysilyl group end-blocking is specifically obtained.
Background technology
Fluid sealant is widely used in metal, glass, and timber, silicone resin plus sulphur silicon rubber, ceramics, natural and synthesis are fine
Dimension, and the bonding of many paint frostings.Polyurethane sealant cures containing free isocyanates and is also easy to produce bubble.
Silicone sealant tearing strength is low, covering with paint property is poor, easily pollutes building materials.Silane modified polyether seal glue (MS glue) be it is a kind of with
Silyl-terminated polyether is high-performance environment-friendly fluid sealant prepared by basic polymer.MS glue has polyurethane and silicone sealant concurrently
Advantage, overcomes shortcoming, has excellent mechanical strength, covering with paint property, resistance to soiling, and isocyanate-free and organic molten in product
Agent, is the main direction of development of domestic and international novel elastic fluid sealant.
The base rubber technology of preparing of MS glue is based on KANEKA and the technology of two companies of WACKER exploitation.KANEKA is used
Allyl polyether carries out hydrosilylation addition reaction to block after chain extension, allyl halide end-blocking, then with hydrogen siloxane.
As click chemistry research is goed deep into by academia, more and more click chemistry technologies are used for actual production.
Mercapto-olefin free radical addition is a kind of typical click chemistry reaction.Under radical initiator effect, sulfydryl switchs to sulphur
Free radical, efficiently and rapidly can carry out addition reaction with unsaturated olefin.
This case will be reacted using mercaptoalkoxysilane with allyl-terminated polyether, to substitute hydrosilylation addition reaction,
Avoid simple using being difficult to remove and heavy metal catalyst costly, technique.
The content of the invention
The object of the present invention is to provide a kind of silane modified polyether base rubber, and its preparation method of sulfydryl free radical addition.
To achieve the above object, there is provided following technical scheme：
A kind of silane modified polyether base rubber, it is characterised in that：The construction unit such as following formula I is included in polyethers end group：
In formula, R1、R2、R3For alkyl or alkoxy, n 1-10.
Represent by being connected to here on strand.
The preparation method of the sulfydryl free radical addition of the corresponding silane modified polyether base rubber for preparing said structure, including
Following steps：
The polyethers of 1 molar part end-allyl group, the sulfydryl alkoxyl silicone of 2.1~3 molar parts are sequentially added in the reactor
Alkane, 0.1~2 molar part radical initiator, 0~100 molar part solvent, when reaction 1~24 is small at 50 DEG C~120 DEG C, then
It is purified, be dried to obtain silane modified polyether base rubber.
The polyethers of so-called end-allyl group, refers to that the both ends of the polyethers are respectively provided with pi-allyl.
Preferably, the polyethers is selected from polyethylene glycol, polypropylene glycol, polypropylene oxide, polyethylene oxide, poly- tetrahydrochysene
One or more in furans, polybutylene oxide, copolymerization ethylene oxide propylene oxide, copolymerization ethylene oxide tetrahydrofuran.
Preferably, the mercaptoalkoxysilane includes mercaptopropyl trimethoxysilane, mercapto dimethylamine epoxide methyl
One in silane, thiopurine methyltransferase trimethoxy silane, thiopurine methyltransferase dimethoxymethylsilane, mercapto ethyl dimethoxymethylsilane
Kind is several.
Preferably, the radical initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, azo dicyano penta
Acid, azo-bis-iso-dimethyl, 2,2 '-azo double (4- methoxy -2,4- methyl pentane nitriles), benzoyl peroxide, persulfuric acid
One or more in potassium, ammonium persulfate, dicetyl peroxydicarbonate two (2- ethylhexyls) ester, di-isopropyl peroxydicarbonate,
But not limited to this.
Preferably, the solvent is selected from methanol, ethanol, isopropanol, toluene, benzene, chloroform, dichloromethane, tetrahydrochysene furan
Mutter, dioxanes, hexane, ether, ethyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- crassitudes
One or several kinds of mixtures in ketone, but not limited to this.
The beneficial effects of the invention are as follows preparation process heavy metal free catalyst, cost is low, aftertreatment technology is simple, reaction
Quickly, high income, stability are good, and product viscosity is low, the features such as during curing without autocatalysis, before having good industrialization
Scape.
Embodiment
The principle of the present invention is using the click chemistry reaction of this high-efficient simple of mercapto-olefin free radical addition, in alkene
Alkoxy silane is accessed on the polyethers of alkyl end-blocking.
The present invention is further illustrated below according to embodiment, and the objects and effects of the present invention will be more apparent.
Embodiment 1：
The polyethylene oxide of 1 molar part end-allyl group, the mercapto propyl group trimethoxy of 3 molar parts are sequentially added in the reactor
Base silane, 2 molar part dicetyl peroxydicarbonate two (2- ethylhexyls) esters, 0 molar part solvent, when reaction 24 is small at 50 DEG C, then
It is purified, be dried to obtain silane modified polyether base rubber.
Embodiment 2：
The polyethylene oxide of 1 molar part end-allyl group, the mercapto propyl group front three of 2.1 molar parts are sequentially added in the reactor
Oxysilane, 0.1 molar part benzoyl peroxide, 100 molar part ethylbenzene, when reaction 1 is small at 120 DEG C, then it is purified, dry
It is dry to obtain silane modified polyether base rubber.
Embodiment 3：
The polyethylene oxide (number-average molecular weight 10000) of 1 molar part end-allyl group is sequentially added in the reactor, and 2.2 rub
The mercaptopropyl trimethoxysilane of your part, 0.2 molar part dicetyl peroxydicarbonate two (2- ethylhexyls) ester, 1 molar part methanol,
At 60 DEG C reaction 10 it is small when, then it is purified, be dried to obtain silane modified polyether base rubber.
Spectral analysis of the nuclear magnetic resonance is carried out to product, obtains following result：0.73(m,2H, CH2Si),1.70-1.85
(4H,CH2CH2SCH2CH2CH2Si),2.50-2.70(4H, CH2SCH2CH2CH2Si),3.59(s,9H,OCH3), 3.6 (polycyclics
Oxidative ethane backbone protons).
Base rubber product physical property：Water white transparency, base rubber viscosity 7000mPa.s or so at 25 DEG C.
Embodiment 4：
The polypropylene oxide of 1 molar part end-allyl group, the mercapto hydroxypropyl methyl of 2.3 molar parts are sequentially added in the reactor
Dimethoxysilane, 0.2 molar part di-isopropyl peroxydicarbonate, 0.5 molar part ethyl acetate, reacts 12 at 70 DEG C
Hour, then it is purified, be dried to obtain silane modified polyether base rubber.
Embodiment 5：
The copolymerization tetrahydrofuran propylene oxide of 1 molar part end-allyl group is sequentially added in the reactor, 2.5 molar parts
Mercapto hydroxypropyl methyl dimethoxysilane, 0.3 molar part azodiisobutyronitrile, 0.5 molar part methanol, it is small to react 20 at 65 DEG C
When, then it is purified, be dried to obtain silane modified polyether base rubber.
Embodiment 6：
The copolymerization ethylene oxide propylene oxide of 1 molar part end-allyl group is sequentially added in the reactor, 2.2 molar parts
Thiopurine methyltransferase methyldiethoxysilane, 0.2 molar part azobisisoheptonitrile, 1 molar part ethyl acetate, reacts 20 at 70 DEG C
Hour, then it is purified, be dried to obtain silane modified polyether base rubber.
Embodiment 7：
The copolymerization ethylene oxide propylene oxide of 1 molar part end-allyl group is sequentially added in the reactor, 2.2 molar parts
Mercapto hydroxypropyl methyl diethoxy silane, 0.2 molar part dicetyl peroxydicarbonate two (2- ethylhexyls) ester, 0.3 molar part ethanol,
At 60 DEG C reaction 20 it is small when, then it is purified, be dried to obtain silane modified polyether base rubber.
Claims (6)
- A kind of 1. silane modified polyether base rubber, it is characterised in that：The construction unit such as following formula I is included in polyethers end group：In formula, R1、R2、R3For alkyl or alkoxy, n 1-10.
- A kind of 2. sulfydryl free radical addition preparation method of the silane modified polyether base rubber described in claim 1, it is characterised in that： Comprise the following steps：Sequentially add the polyethers of 1 molar part end-allyl group in the reactor, the mercaptoalkoxysilane of 2.1~3 molar parts, 0.1 ~2 molar part radical initiators, 0~100 molar part solvent, when reaction 1~24 is small at 50 DEG C~120 DEG C, then purified, It is dried to obtain silane modified polyether base rubber.
- 3. the sulfydryl free radical addition preparation method of silane modified polyether base rubber according to claim 2, it is characterised in that： The polyethers be selected from polyethylene glycol, polypropylene glycol, polypropylene oxide, polyethylene oxide, PolyTHF, polybutylene oxide, The one or more being copolymerized in ethylene oxide propylene oxide, copolymerization ethylene oxide tetrahydrofuran.
- 4. the sulfydryl free radical addition preparation method of silane modified polyether base rubber according to claim 2, it is characterised in that： The mercaptoalkoxysilane includes mercaptopropyl trimethoxysilane, mercapto dimethylamine epoxide methyl-monosilane, thiopurine methyltransferase front three One or more in oxysilane, thiopurine methyltransferase dimethoxymethylsilane, mercapto ethyl dimethoxymethylsilane.
- 5. the sulfydryl free radical addition preparation method of silane modified polyether base rubber according to claim 2, it is characterised in that： The radical initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, azo dicyano valeric acid, two isobutyric acid two of azo Methyl esters, 2,2 '-azo double (4- methoxy -2,4- methyl pentane nitriles), benzoyl peroxide, potassium peroxydisulfate or ammonium persulfate, peroxide Change the one or more in two carbonic acid two (2- ethylhexyls) esters, di-isopropyl peroxydicarbonate.
- 6. the sulfydryl free radical addition preparation method of silane modified polyether base rubber according to claim 2, it is characterised in that： The solvent is selected from methanol, ethanol, isopropanol, toluene, benzene, chloroform, dichloromethane, tetrahydrofuran, dioxanes, hexane, second One or several kinds in ether, ethyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-methyl-2-pyrrolidinone Mixture.
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| CN201711306052.1A CN107903863A (en) | 2017-12-11 | 2017-12-11 | A kind of silane modified polyether base rubber and its sulfydryl free radical addition preparation method |
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| CN201711306052.1A CN107903863A (en) | 2017-12-11 | 2017-12-11 | A kind of silane modified polyether base rubber and its sulfydryl free radical addition preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021182118A1 (en) * | 2020-03-09 | 2021-09-16 | 株式会社カネカ | Organic polymer, curable composition, and cured product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03195768A (en) * | 1989-12-22 | 1991-08-27 | Dainippon Ink & Chem Inc | Moisture-curable composition |
| EP2399743A2 (en) * | 2010-06-28 | 2011-12-28 | Fujifilm Corporation | Resin composition for laser engraving, relief printing plate precursor for laser engraving and process for producing same, and process for making relief printing plate |
-
2017
- 2017-12-11 CN CN201711306052.1A patent/CN107903863A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03195768A (en) * | 1989-12-22 | 1991-08-27 | Dainippon Ink & Chem Inc | Moisture-curable composition |
| EP2399743A2 (en) * | 2010-06-28 | 2011-12-28 | Fujifilm Corporation | Resin composition for laser engraving, relief printing plate precursor for laser engraving and process for producing same, and process for making relief printing plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021182118A1 (en) * | 2020-03-09 | 2021-09-16 | 株式会社カネカ | Organic polymer, curable composition, and cured product |
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Application publication date: 20180413 |