CN114015036A - Low-viscosity silane modified polyether resin and preparation method thereof - Google Patents
Low-viscosity silane modified polyether resin and preparation method thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 84
- 239000011347 resin Substances 0.000 title claims abstract description 84
- 239000004526 silane-modified polyether Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 78
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 229920005862 polyol Polymers 0.000 claims abstract description 29
- 150000003077 polyols Chemical class 0.000 claims abstract description 29
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 abstract description 15
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 8
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 29
- 239000000565 sealant Substances 0.000 description 16
- 150000004756 silanes Chemical class 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 239000002994 raw material Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 241000276489 Merlangius merlangus Species 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polythio Polymers 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- LFKYBJLFJOOKAE-UHFFFAOYSA-N imidazol-2-ylidenemethanone Chemical compound O=C=C1N=CC=N1 LFKYBJLFJOOKAE-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 239000004588 polyurethane sealant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004590 silicone sealant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- DCVOWNNIQFCMDW-UHFFFAOYSA-N methoxysilicon Chemical compound CO[Si] DCVOWNNIQFCMDW-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
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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
-
- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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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
-
- 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
- C08G2170/00—Compositions for adhesives
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a low-viscosity silane modified polyether resin and a preparation method thereof, wherein the low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the molecular weight of the polyether polyol is 4000-8000 g/mol. The invention overcomes the defects that the viscosity of the resin is higher due to the chain extension reaction by applying diisocyanate and short-chain polypropylene glycol in the prior method for preparing the low-viscosity silane modified polyether resin by adopting a polyurethane prepolymer method, and the MS glue prepared by the resin has high modulus and toxicity, introduces N' N-Carbonyl Diimidazole (CDI) to carry out the chain extension reaction of the polyether, does not need to use a toxic isocyanate silane coupling agent, and has low viscosity, low modulus and no toxicityThe advantages of (1).
Description
Technical Field
The invention relates to a low-viscosity silane modified polyether resin and a preparation method thereof, which are applied to the field of sealant production.
Background
The early three types of high-grade elastic sealants (polythio type, polyurethane and silicone type sealants) play an important role in promoting the development of various fields, but due to certain weaknesses of the three types of high-grade elastic sealants, the development and development of novel elastic sealants are accelerated.
Silane-modified polyether is abbreviated as MS-Polymer, which was successfully and rapidly developed and rapidly popularized in the Japanese market by the Nippon Kao chemical company in the 80 s of the last century. The silane modified polyether polymer consists of a polypropylene oxide chain segment of a main chain and siloxane of a terminal group, the main chain structure of the polyether provides good flexibility and ductility, the terminal silicon alkoxy group of the polyether can generate hydrolysis condensation reaction under the action of moisture and a catalyst to form a-Si-O-Si-network structure, an MS sealant (modified silane polyether adhesive) prepared from the silane modified polyether resin has the advantages of a silicone sealant and a polyurethane sealant, has excellent weather resistance, mechanical property and wide adhesion to a base material, simultaneously overcomes the defects that the silicone sealant is easy to cause base material pollution, is difficult to coat, easily generates bubbles during curing of the polyurethane sealant and the like, and obtains wide attention of domestic and foreign chemical researchers.
At present, domestic research on the synthesis of silane modified polyether resin mainly focuses on two methods, namely an allyl-hydrosilylation method and a polyurethane prepolymer method, wherein the allyl-hydrosilylation method route is generally completed by a two-step method, which is also called as a methylene dichloride chain extension method: the first step is to prepare allyl terminated polyether intermediate by taking allyl polyether alcohol, hydroxyl terminated polyether and the like as raw materials, caustic alkali as catalyst and methylene dihalide as chain extender; the second step is that the refined polyether intermediate is subjected to hydrosilylation reaction with methyl dimethylsilane in the presence of a platinum catalyst to generate a high molecular polymer which takes methoxy silicon-based terminated polyether as a main chain, and the specific synthetic route is shown in figure 1. It can be seen that the synthesis steps and treatment engineering are complicated, and the process difficulties of industrial production such as desalination, refining and the like are involved, so that the silane modified polyether resin is prepared by adopting a polyurethane prepolymer method at home more.
The polyurethane prepolymer method generally uses polypropylene glycol having a low molecular weight as a starting material, but in order to obtain high elasticity and high elastic recovery of an MS sealant, it is necessary to further increase the molecular weight of the resin by a chain extension reaction. The currently mainstream domestic mode of the polyurethane prepolymer method is to apply diisocyanate and short-chain polypropylene glycol to carry out chain extension reaction, wherein diisocyanate is used as a coupling group, polyether with lower molecular weight is coupled into hydroxyl-terminated polyether with high molecular weight, and then the terminal hydroxyl and a silane coupling agent with isocyanate groups are subjected to further end-capping reaction to obtain silane-terminated polyether resin, but the resin prepared by the method contains a large amount of carbamate groups, as shown in fig. 2 (II), a physical cross-linking network can be formed between the carbamate groups in a polymer chain due to strong hydrogen bond action, so that the viscosity of the resin is higher, the realization of the low modulus of the MS sealant is not facilitated, and in addition, the isocyanate groups possibly remaining in the system also have certain toxicity.
Therefore, it is desirable to provide a low viscosity silane modified polyether resin with low viscosity, low modulus, and no toxicity, and a preparation method thereof.
Disclosure of Invention
In order to overcome the defects that the viscosity of the resin is higher (the viscosity is about 30000-80000cp) due to the fact that diisocyanate and short-chain polypropylene glycol are used for chain extension reaction in the conventional method for preparing the silane modified polyether resin by adopting a polyurethane prepolymer method, and the low modulus and toxicity are not easily realized by using the resin, the invention provides the low-viscosity silane modified polyether resin (the viscosity is lower than 30000cp) and the preparation method thereof, introduces N' N-Carbonyl Diimidazole (CDI) for polyether chain extension reaction, does not need to use a toxic isocyanate silane coupling agent, and has the advantages of low viscosity, low modulus and no toxicity.
The technical scheme of the invention is as follows:
the low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the molecular weight of the polyether polyol is 4000-8000 g/mol.
In the prior art, polyether or polyester polyol with small molecular terminal hydroxyl groups and diisocyanate are adopted to carry out chain extension reaction in the preparation of silane modified polyether resin by adopting a polyurethane prepolymer method, and if the diisocyanate in a reactant is excessive, an NCO-terminated prepolymer is obtained and then reacts with amino alkoxy silane with active hydrogen to obtain a silane-terminated polyurethane prepolymer; if the reactant is polyether or polyester polyol in excess, hydroxyl-terminated prepolymer is obtained, and then the hydroxyl-terminated prepolymer is reacted with alkoxy silane with NCO to obtain silane-terminated polyurethane prepolymer. It has the disadvantages of high resin viscosity, high MS glue modulus and toxicity. The low-viscosity silane modified polyether resin is prepared by taking polypropylene glycol as a raw material, N' -carbonyldiimidazole as a coupling agent and trace amount of alkali catalyst as a catalyst, performing polyether chain extension reaction through esterification reaction, and then performing end capping on the polyether chain extension reaction by using an aminosilane coupling agent (as shown in figure 3). N' N-Carbonyl Diimidazole (CDI) is introduced, so that polyether chain segments are connected through ester groups, although silane end groups and a polyether main chain are connected through carbamate bonds, no carbamate groups exist on the main chain, and a hydrogen bond network cannot be formed among polymer main chains (as shown in figure 2 (I)), so that the viscosity of a system is low (the viscosity is about 30-50%), the MS sealant with low modulus can be prepared when the MS sealant is used alone, and the low modulus can be realized without resin compounding or adding excessive plasticizer, but the silane modified polyether resin prepared by the existing method can be realized by compounding other resins.
The alkali catalyst is KOH or triethylamine.
Preferably, the alkali catalyst is common chemical in laboratories, and is common and easily available.
The molecular weight of the polyether polyol is 8000 g/mol.
The preferred polyether polyol raw material is easy to obtain, and has stable suppliers in China.
The weight ratio of N' N-carbonyldiimidazole to polyether polyol was 1.2: 1.
The polyether glycol PPG and the N' N-carbonyl diimidazole CDI belong to difunctional monomers, and the chain extension reaction belongs to condensation polymerization reaction. Theoretically, when the ratio of the two is closer to 1:1, the molecular weight of the polymer chain obtained by the chain extension reaction is higher. In order to realize better elasticity and mechanical property of the sealant, the relationship between molecular weight and viscosity needs to be considered, and high molecular weight polyether is synthesized as much as possible on the premise that the viscosity is acceptable. In order to examine the relationship between the feeding ratio and the molecular weight of the obtained polymer, the experiment takes 90 ℃ as the reaction temperature and takes KOH with the mass fraction of 0.1 percent as the catalyst, and the influence of different CDI/PPG feeding ratios on the molecular weight of the chain-extended macromolecular polyether is researched. Chain extension reactions are carried out according to three feeding ratios of 1.2, 1.3 and 1.5 of CDI/PPG equivalent ratio respectively, after the chain extension reaction is finished, a small amount of reaction liquid is taken to be dissolved in Tetrahydrofuran (THF), and THF phase GPC is used for testing, and the result shows that (the influence of the CDI/PPG feeding ratio on the chain extension reaction is shown in table 1 in detail), when n (CDI) and n (PPG) are 1.2:1, the molecular weight of the obtained polymer after chain extension is the highest and is about 28000g/mol, the molecular weight distribution (PDI) is also narrow and is 1.84, but the higher molecular weight also enables the polymer chain to be entangled seriously, so that the viscosity of a polyether system is higher and reaches 24000 CP; at a higher charge ratio, the molecular weight of the obtained polymer is reduced, and at an equivalent ratio of 1.3, the molecular weight of the obtained polymer is about 24000g/mol, and the PDI is 1.87; when the equivalent ratio is 1.5, the molecular weight of the obtained polymer is only 14500, the PDI is wider and reaches 2.20, and the viscosity of the polymer are 22500CP and 11000CP respectively due to the lower molecular weight. The viscosity of the resin synthesized by the existing polyurethane prepolymer method is usually higher than 30000CP, so that the relationship between molecular weight and viscosity is considered, and high molecular weight polyether is synthesized as much as possible on the premise that the viscosity can be accepted.
TABLE 1 influence of CDI/PPG feed ratio on chain extension reaction
The polyether polyol is polypropylene glycol.
The preferable polyether polyol has cheap and easily obtained reaction raw materials, and has excellent weather resistance, water resistance, aging resistance and durability.
The amino silane coupling agent is an amino silane coupling agent with one or two amino groups.
The reaction activity of the amino group and the carbonyl imidazole intermediate is higher by adopting the preferable amino silane coupling agent.
The aminosilane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-N-cyclohexylaminopropyltrimethoxysilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, N-phenylmethyldiethoxysilane, N-phenylsilane, N-cyclohexyltrimethoxysilane, N-phenylsilane, N-isopropyltrimethoxysilane, N-allyltrimethoxysilane, N-3-allyltrimethoxysilane, N-allyltrimethoxysilane, or a mixture of, One or any combination of more than two of N-N-butyl-3-aminopropyltriethoxysilane and N-N-butyl-3-aminopropyltrimethoxysilane.
The preferable aminosilane coupling agent is a commercial aminosilane coupling agent which is common in the market, and the raw materials are cheap and easy to obtain.
The preparation method of the low-viscosity silane modified polyether resin mainly comprises the following steps of:
(1) taking polyether polyol, vacuum dehydrating at 100-120 ℃ for at least 2h, and cooling to 65-75 ℃;
(2) mixing N' N-carbonyldiimidazole and an alkali catalyst with the polyether polyol obtained in the step (1), introducing nitrogen for protection, and heating to 85-95 ℃ for reaction for at least 2 hours to obtain a reactant A;
(3) cooling the reactant A obtained in the step (2) to 75-85 ℃, adding an aminosilane coupling agent to mix with the reactant A, and reacting for at least 1.5h to obtain a reactant B;
(4) cooling the reactant B obtained in the step (3) to 45-55 ℃, adding vinyl trimethoxy silane to mix with the reactant B, and continuously stirring for at least 0.5 h;
(5) cooling the reactant obtained in the step (4) to 23-27 ℃ and keeping for at least 2h to obtain resin;
(6) and (3) filtering the resin obtained in the step (5) by using a 180-220-mesh filter mesh bag to obtain the low-viscosity silane modified polyether resin.
The preparation method of the low-viscosity silane modified polyether resin is simple and convenient in steps and convenient to operate.
The reaction temperature in step (2) was 90 ℃.
Polypropylene Glycol (PPG) and CDI with molecular weight of about 8000 are taken as raw materials, KOH with mass fraction of 0.1% is taken as a catalyst, the feeding ratio of n (CDI) to n (PPG) is 1.3:1, polyether chain extension reaction is respectively carried out at different temperatures, and the influence of the reaction temperature on the chain extension reaction is examined. As shown in Table 2, the results show that at 70 ℃ and 80 ℃, as the reaction begins, the terminal hydroxyl groups of the polyether and carbonyldiimidazole have a first step of alcoholysis reaction to generate imidazolecarbonylpolypropylene glycol ester and one molecule of imidazole monomer, and the melting point of imidazole is about 89 ℃, so that at the reaction temperature, the imidazole accumulates in the reaction system in the form of pale yellow imidazole crystals; with the further progress of the reaction, the imidazole carbonyl polypropylene glycol ester generated in the first step and another molecular hydroxyl group undergo a second esterification reaction, so that crystals in the system gradually increase, and when the crystals do not increase any more (the reaction end point can be determined by detecting and tracking the reaction through an infrared spectrometer and determining the reaction end point by the disappearance of a carbonyl imidazole characteristic peak, or roughly judged by visual observation), the chain extension reaction end point can be regarded as the step. When the reaction temperature is raised to be higher than the melting point of imidazole, the chain extension reaction rate is obviously accelerated, the imidazole in the system is melted, and when the reaction temperature is 90 ℃, the reaction system is faint yellow and turbid, and the reaction can be completed within about 2.5 hours; the temperature is further increased to 100 ℃, the reaction system is in a light yellow homogeneous phase state, the reaction can reach the end point in only 1.5 hours, but the stability and other side reactions of the polyether raw material can be caused by excessively high reaction temperature. Further, it is considered that the system is cooled after the completion of the reaction, and imidazole crystals are precipitated (imidazole melting point: 89 ℃ C.) and filtered out of the system. Therefore, the energy consumption is increased due to the excessively high reaction temperature, and other side reactions are caused, so that the reaction temperature is easily controlled to be 90 ℃ (just higher than the boiling point of the imidazole crystal) optimally by comprehensively considering the reaction time and the reaction system state.
TABLE 2 Effect of reaction temperature on the CDI and PPG chain extension reaction
The modified silane polyether adhesive prepared from the low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the modified silane polyether adhesive end group is a trimethoxy end group, the reactivity is high, the surface drying time is about 23 minutes under the action of dibutyltin dilaurate, the Shore A hardness is about 26.8 after vulcanization, the mass loss rate is about 1.9%, cohesive failure is achieved before and after soaking when the modified silane polyether adhesive end group is coated on substrates such as glass, aluminum, stainless steel, ceramic and the like, and the indexes show that the modified silane polyether adhesive end group is good in comprehensive performance and has excellent bonding performance and environmental protection performance. In the aspect of mechanical property, the tensile strength is about 0.83MPa, the tensile modulus is about 0.35MPa, the elastic recovery rate is 78%, and the elongation rate also reaches 460%. The composite material has the advantages of good comprehensiveness, excellent elastic property and mechanical strength, lower modulus and excellent waterproof property, and is suitable for industries such as assembly type building industry, home decoration waterproofing, ceramic tile joint filling and the like.
The preparation method of the modified silane polyether adhesive mainly comprises the following steps of:
adding the low-viscosity silane modified polyether resin, a plasticizer, coarse whiting, nano calcium and a thixotropic agent into a double-planetary power mixing reaction kettle for mixing, and then dehydrating in vacuum at the temperature of 100-120 ℃ (less than or equal to 0.002mbar) for 110-130 minutes; keeping the vacuum state, cooling to below 60 ℃, adding a dehydrating agent into the mixture, and stirring for about 8-12 minutes; then adding the coupling agent, the catalyst, the light stabilizer and the ultraviolet absorbent into the mixture in sequence, and stirring uniformly; and then the vacuum state is released, and the sealant is prepared.
The preparation method of the modified silane polyether adhesive is simple and convenient in steps and convenient to operate.
Compared with the prior art, the method has the following advantages:
1) the low-viscosity silane modified polyether resin introduces N' N-Carbonyl Diimidazole (CDI) to carry out the chain extension reaction of polyether, so that the viscosity of the high-molecular-weight polyether obtained after chain extension can be obviously reduced, and the effect is obviously superior to that of the chain extension reaction carried out by using isocyanate; the use of a toxic isocyanate silane coupling agent is not needed, the cost is reduced, and the product is non-toxic;
2) the modified silane polyether adhesive prepared by the low-viscosity silane modified polyether resin has low modulus;
3) by regulating the charge ratio of CDI to PPG, the chain extension effect can be effectively controlled, and the polyether with higher molecular weight is beneficial to the low-viscosity silane modified polyether resin to have better elasticity;
4) the preparation method of the low-viscosity silane modified polyether resin and the modified silane polyether adhesive is simple and convenient in steps and convenient to operate.
Drawings
FIG. 1 is a schematic diagram of a route for the allyl-hydrosilylation synthesis of silane-modified polyether resins;
FIG. 2 is a schematic structural diagram of a polymer obtained by a chain extension reaction using diisocyanate and N' N-carbonyldiimidazole as coupling groups, respectively;
FIG. 3 is a schematic diagram of the synthetic route of the low-viscosity silane-modified polyether resin and the preparation method thereof.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the embodiments of the specification.
Example 1
The low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the molecular weight of the polyether polyol is 8000 g/mol.
The base catalyst is KOH.
The weight ratio of N' N-carbonyldiimidazole to polyether polyol was 1.2: 1.
The polyether polyol is polypropylene glycol; the amino silane coupling agent is 3-aminopropyl trimethoxy silane.
The preparation method of the low-viscosity silane modified polyether resin mainly comprises the following steps of:
(1) taking polyether polyol, removing water at 110 ℃ in vacuum for 2h, and cooling to 70 ℃;
(2) mixing N' N-carbonyldiimidazole and an alkali catalyst with the polyether polyol obtained in the step (1), introducing nitrogen for protection, and heating to 90 ℃ for reaction for 2 hours to obtain a reactant A;
(3) cooling the reactant A obtained in the step (2) to 80 ℃, adding an aminosilane coupling agent to mix with the reactant A, and reacting for 1.5h to obtain a reactant B;
(4) cooling the reactant B obtained in the step (3) to 50 ℃, adding vinyl trimethoxy silane to mix with the reactant B, and continuously stirring for 0.5 h;
(5) cooling the reactant obtained in the step (4) to 25 ℃, and keeping for 2h to obtain resin;
(6) and (3) filtering the resin obtained in the step (5) by using a 200-mesh filter mesh bag to obtain the low-viscosity silane modified polyether resin.
The modified silane polyether adhesive prepared from the low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the preparation method of the modified silane polyether adhesive mainly comprises the following steps of:
adding the low-viscosity silane modified polyether resin, a plasticizer, coarse whiting, nano calcium and a thixotropic agent into a double-planetary power mixing reaction kettle together for mixing, and then carrying out vacuum dehydration (with the pressure of 0.002mbar) at 110 ℃ for 120 minutes; keeping the vacuum state, cooling to 55 ℃, adding a dehydrating agent into the mixture, and stirring for about 10 minutes; then adding the coupling agent, the catalyst, the light stabilizer and the ultraviolet absorbent into the mixture in sequence, and stirring uniformly; and then the vacuum state is released, and the sealant is prepared.
Example 2
The low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the polyether polyol has a molecular weight of 4000 g/mol.
The base catalyst is triethylamine.
The polyether polyol is polypropylene glycol; the aminosilane coupling agent is any combination of 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane.
The preparation method of the low-viscosity silane modified polyether resin mainly comprises the following steps of:
(1) taking polyether polyol, removing water at 100 ℃ in vacuum for 2.5h, and cooling to 65 ℃;
(2) mixing N' N-carbonyldiimidazole and an alkali catalyst with the polyether polyol obtained in the step (1), introducing nitrogen for protection, and heating to 85 ℃ for reaction for 3 hours to obtain a reactant A;
(3) cooling the reactant A obtained in the step (2) to 75 ℃, adding an aminosilane coupling agent to mix with the reactant A, and reacting for 2h to obtain a reactant B;
(4) cooling the reactant B obtained in the step (3) to 45 ℃, adding vinyl trimethoxy silane to mix with the reactant B, and continuing stirring for 1 h;
(5) cooling the reactant obtained in the step (4) to 27 ℃, and keeping for 2.5 hours to obtain resin;
(6) and (3) filtering the resin obtained in the step (5) by using a 180-mesh filter mesh bag to obtain the low-viscosity silane modified polyether resin.
The modified silane polyether adhesive prepared from the low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the preparation method of the modified silane polyether adhesive mainly comprises the following steps of:
adding the low-viscosity silane modified polyether resin, a plasticizer, coarse whiting, nano calcium and a thixotropic agent into a double-planetary power mixing reaction kettle together for mixing, and then carrying out vacuum dehydration (with the pressure of 0.0015mbar) at 100 ℃ for 130 minutes; keeping the vacuum state, cooling to 60 ℃, adding a dehydrating agent into the mixture, and stirring for about 8 minutes; then adding the coupling agent, the catalyst, the light stabilizer and the ultraviolet absorbent into the mixture in sequence, and stirring uniformly; and then the vacuum state is released, and the sealant is prepared.
Example 3
The low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the molecular weight of the polyether polyol is 6000 g/mol.
The base catalyst is triethylamine.
The polyether polyol is polypropylene glycol; the aminosilane coupling agent is any combination of 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane and N-2-aminoethyl-3-aminopropylmethyldimethoxysilane.
The preparation method of the low-viscosity silane modified polyether resin mainly comprises the following steps of:
(1) taking polyether polyol, vacuum dehydrating at 120 ℃ for 3h, and cooling to 75 ℃;
(2) mixing N' N-carbonyldiimidazole and an alkali catalyst with the polyether polyol obtained in the step (1), introducing nitrogen for protection, and heating to 95 ℃ for reaction for 4 hours to obtain a reactant A;
(3) cooling the reactant A obtained in the step (2) to 85 ℃, adding an aminosilane coupling agent to mix with the reactant A, and reacting for 2.5 hours to obtain a reactant B;
(4) cooling the reactant B obtained in the step (3) to 55 ℃, adding vinyl trimethoxy silane to mix with the reactant B, and continuing stirring for 1.5 h;
(5) cooling the reactant obtained in the step (4) to 23 ℃ and keeping for 4h to obtain resin;
(6) and (3) filtering the resin obtained in the step (5) by using a 220-mesh filter mesh bag to obtain the low-viscosity silane modified polyether resin.
The modified silane polyether adhesive prepared from the low-viscosity silane modified polyether resin is mainly prepared from the following components in parts by weight:
the preparation method of the modified silane polyether adhesive mainly comprises the following steps of:
adding the low-viscosity silane modified polyether resin, a plasticizer, coarse whiting, nano calcium and a thixotropic agent into a double-planetary power mixing reaction kettle together for mixing, and then carrying out vacuum dehydration (0.001mbar) at 120 ℃ for 110 minutes; keeping the vacuum state, then cooling to below 50 ℃, adding a dehydrating agent into the mixture, and stirring for about 12 minutes; then adding the coupling agent, the catalyst, the light stabilizer and the ultraviolet absorbent into the mixture in sequence, and stirring uniformly; and then the vacuum state is released, and the sealant is prepared.
Raw material information related to each example:
vinyl trimethoxy silane: nanjing Nentede New Material technology, Inc.;
nano calcium: jiangxi Huaming nano calcium carbonate Co., Ltd;
heavy calcium: guangxi Kelong powder Co., Ltd;
ultraviolet absorber: tinuvin 326, basf china ltd;
light stabilizer: tinuvin 770DF, basf china ltd;
dibutyltin dilaurate (DBTDL), new chemical materials (shanghai) ltd;
polypropylene glycol: Shandong-Nowei New materials Co., Ltd;
n' N-carbonyldiimidazole: shanghai koji chemical Co., Ltd;
other conventional chemical reagents are purchased from the national drug platform.
Experimental data:
comparative example 1:
preparing silane modified polyether resin by a polyurethane prepolymer method: adding 1000 g of 8000cp polyether into a reaction kettle, carrying out vacuum dehydration for 2 hours at 120 ℃, then reducing the temperature to 90 ℃, adding 37.5g of diphenylmethane diisocyanate (MDI) according to the equivalent ratio of 1.3:1(NCO: OH) to carry out chain extension reaction, stirring for about 3 hours, detecting the reaction by an infrared spectrometer, adding 8.95g of gamma-aminopropyltrimethoxysilane to carry out end capping reaction when the infrared absorption peak of NCO is not changed any more, and stirring for 2 hours to obtain the silane end-capped polyether resin.
The resin had a viscosity of about 59000cp and a pale yellow appearance.
Comparative example 2:
preparing silane modified polyether resin by a hydroxyl-terminated polyurethane prepolymer method: adding 1000 g of 8000cp polyether into a reaction kettle, carrying out vacuum dehydration at 120 ℃ for 2 hours, then reducing the temperature to 90 ℃, adding 33.4g of 4,4' -dicyclohexylmethane diisocyanate (HMDI) according to the equivalent ratio of 1.2:1(OH: NCO) to carry out chain extension reaction, stirring for about 3 hours, detecting the reaction progress by an infrared spectrometer, adding 8.54g of gamma-isocyanatopropyl trimethoxy silane to carry out end capping reaction after the infrared absorption peak of NCO in the system is completely reacted, and stirring for 2 hours to obtain the silane end capped polyether resin.
The resin had a viscosity of about 36000cp and a pale yellow appearance.
The detection method of the viscosity comprises the following steps: and (3) detecting according to a measuring method of part 7 viscosity of GB/T12008.7-2010 plastic polyether polyol.
Table 3 results of performance test of each example
Comparative example 1 is a basic model of conventional production by the current process, i.e. diisocyanate is used for chain extension reaction, and the obtained resin has high viscosity and requires to be compounded or added with excessive plasticizer in the later rubber making process. As can be seen from the above table, the viscosity of the low-viscosity silane modified polyether resin of each example is significantly lower than that of the comparative examples 1 and 2, and the MS sealant can be prepared by using the low-viscosity silane modified polyether resin alone at the later stage.
The low viscosity silane modified polyether resin and the preparation method thereof according to the present invention are not limited to the above-mentioned examples, and any modification or replacement according to the principle of the present invention should be within the scope of the present invention.
Claims (9)
1. A low-viscosity silane modified polyether resin is characterized in that: the adhesive is mainly prepared from the following components in parts by weight:
the molecular weight of the polyether polyol is 4000-8000 g/mol.
2. The low viscosity silane-modified polyether resin of claim 1, wherein: the alkali catalyst is KOH or triethylamine.
3. The low viscosity silane-modified polyether resin of claim 1, wherein: the molecular weight of the polyether polyol is 8000 g/mol.
4. The low viscosity silane-modified polyether resin of claim 1, wherein: the weight ratio of N' N-carbonyldiimidazole to polyether polyol was 1.2: 1.
5. The low viscosity silane-modified polyether resin of claim 1, wherein: the polyether polyol is polypropylene glycol.
6. The low viscosity silane-modified polyether resin of claim 1, wherein: the amino silane coupling agent is an amino silane coupling agent with one or two amino groups.
7. The low viscosity silane-modified polyether resin of claim 6, wherein: the aminosilane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-N-cyclohexylaminopropyltrimethoxysilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, N-phenylmethyldiethoxysilane, N-phenylsilane, N-cyclohexyltrimethoxysilane, N-phenylsilane, N-isopropyltrimethoxysilane, N-allyltrimethoxysilane, N-3-allyltrimethoxysilane, N-allyltrimethoxysilane, or a mixture of, One or any combination of more than two of N-N-butyl-3-aminopropyltriethoxysilane and N-N-butyl-3-aminopropyltrimethoxysilane.
8. The method for producing a low-viscosity silane-modified polyether resin according to any one of claims 1 to 7, wherein: mainly comprises the following steps which are carried out in sequence:
(1) taking polyether polyol, vacuum dehydrating at 100-120 ℃ for at least 2h, and cooling to 65-75 ℃;
(2) mixing N' N-carbonyldiimidazole and an alkali catalyst with the polyether polyol obtained in the step (1), introducing nitrogen for protection, and heating to 85-95 ℃ for reaction for at least 2 hours to obtain a reactant A;
(3) cooling the reactant A obtained in the step (2) to 75-85 ℃, adding an aminosilane coupling agent to mix with the reactant A, and reacting for at least 1.5h to obtain a reactant B;
(4) cooling the reactant B obtained in the step (3) to 45-55 ℃, adding vinyl trimethoxy silane to mix with the reactant B, and continuously stirring for at least 0.5 h;
(5) cooling the reactant obtained in the step (4) to 23-27 ℃ and keeping for at least 2h to obtain resin;
(6) and (3) filtering the resin obtained in the step (5) by using a 180-220-mesh filter mesh bag to obtain the low-viscosity silane modified polyether resin.
9. The method for producing a low-viscosity silane-modified polyether resin according to claim 8, wherein: the reaction temperature in step (2) was 90 ℃.
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| CN116535636A (en) * | 2023-05-17 | 2023-08-04 | 浙江皇马科技股份有限公司 | Silane end-capped resin for low-viscosity sealant and preparation method thereof |
| CN116535636B (en) * | 2023-05-17 | 2024-04-16 | 浙江皇马科技股份有限公司 | Silane end-capped resin for low-viscosity sealant and preparation method thereof |
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