CN101205285A - Moisture curable alkoxyl silicone terminated polymer and preparation thereof - Google Patents
Moisture curable alkoxyl silicone terminated polymer and preparation thereof Download PDFInfo
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- CN101205285A CN101205285A CNA2007101906278A CN200710190627A CN101205285A CN 101205285 A CN101205285 A CN 101205285A CN A2007101906278 A CNA2007101906278 A CN A2007101906278A CN 200710190627 A CN200710190627 A CN 200710190627A CN 101205285 A CN101205285 A CN 101205285A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000003545 alkoxy group Chemical group 0.000 title claims description 24
- 229920001296 polysiloxane Polymers 0.000 title claims description 18
- 239000000126 substance Substances 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 229920000570 polyether Polymers 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 abstract 1
- LCWWSQJYMQKLAM-UHFFFAOYSA-N silane sulfanylsilane Chemical compound [SiH4].S[SiH3] LCWWSQJYMQKLAM-UHFFFAOYSA-N 0.000 abstract 1
- -1 aminoalkoxy silane Chemical compound 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 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
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
A polymer terminated with silicon alkoxy for moisture curable has the following chemical structural formula: (OR)<3-n>Si(CH3)n (CH2)aS-[PU]-CONH-R<1>-NHCO-S-(CH2>)a-Si(CH3)n (OR)<3-n>; wherein, PU symbolizes -[CONHR<1>NHCO(OC2H4)b (OC3H6)cO] x-; a is equal to 1 or 3, R symbolizes -CH3 or -C2H5, n is equal to 0 or 1, b ranges from 0 to 10, c ranges from 10 to 100 and x ranges from 1 to 5. The invention has the advantages that the prepolymer containing NCO is terminated using th mercaptosilane silane, the generated polymer terminated with the silicon alkoxy has small viscosity, and the preparation process is easy to be controlled so as to drive the production operation to be simple and convenient and simultaneously the obtained polymers can be used conveniently. The invention discloses the preparation method for polymer terminated with silicon alkoxy for moisture curable.
Description
Technical field
What the present invention relates to is a kind of alkoxyl silicone terminated polymkeric substance of moisture-curable, and the preparation method of this polymkeric substance.More specifically, relate to the polymkeric substance and preparation method thereof that the lower end of a kind of viscosity contains the alkoxyl silicone group of hydrolyzable interlinkage.
Background technology
When containing the polymkeric substance chance moisture of alkoxyl silicone group, the alkoxyl group hydrolyzable, and then the polymkeric substance interlinkage is solidified, be widely used in the industries such as building, house ornamentation and automotive industry as coating, seal gum and tackiness agent etc.In these application scenarios, strict requirement has been proposed all elasticity, bonding strength and the solidification rate etc. that solidify the post polymerization thing.
In patent and the reported in literature many polymkeric substance and synthetic methods thereof about containing the alkoxyl silicone group have appearred both at home and abroad.In the patent abroad (as USP5296582), at present major part is to adopt the polymkeric substance of terminal hydroxy group to react with the silane that contains isocyanate groups to prepare this base polymer, but owing to contain the synthetic difficulty (USP3598852) relatively of the silane of isocyanate groups, market value is very expensive, and this has limited the development of the polymkeric substance that contains the alkoxyl silicone group to a certain extent; A kind of method in addition is: earlier with excessive tolylene diisocyanate, as TDI etc., prepare isocyanate-terminated prepolymer with hydroxy-end capped polymer reaction, then this prepolymer is reacted end-blocking with aminoalkoxy silane (as aminopropyl triethoxysilane) and obtain polymkeric substance, but amino reaction with isocyanic ester is difficult to control, easily produce gel, and the urea acid esters group-NHCONH-that generates can increase the viscosity of polymkeric substance greatly, the further processing and the use of polymkeric substance have been influenced, a certain amount of softening agent of need adding etc. could use [Shi Xiaomeng etc., thermosetting resin, 2003,18 (1), P10].Adopt the same hydrogen-containing siloxane of polymkeric substance (as Trimethoxy silane) of allyl capped also can obtain alkoxyl silicone terminated polymkeric substance though carry out addition reaction of silicon with hydrogen, side reaction is more, and operational difficulty has influenced polymer properties (USP4302751).
Summary of the invention
The purpose of this invention is to provide a kind of moisture cured more low viscous alkoxyl silicone terminated polymkeric substance, and a kind of simple preparation method of this polymkeric substance, but this polymkeric substance interlinkage under contact moisture condition solidifies, thereby plays effect such as bonding, sealing.
A kind of alkoxyl silicone terminated polymkeric substance of moisture-curable, it has following chemical structural formula:
(OR)
3-nSi(CH
3)
n(CH
2)
aS-[PU]-CONH-R
1-NHCO-S-(CH
2)
a-Si(CH
3)
n(OR)
3-n
Wherein, PU representative :-[CONHR
1NHCO (OC
2H
4)
b(OC
3H
6)
cO]
x-; A=1 or 3; R representative-CH
3Or-C
2H
5N=0 or 1; B=0～10; C=10～100; X=1～5;
R
1=H
3 
Or
A kind of method for preparing above-mentioned polymkeric substance, it is made up of following steps:
Step 2. with (A) and (B) the NCO prepolymer that obtains of reaction again with hydrosulphonyl silane (C) reaction, generate the alkoxyl silicone terminated polymkeric substance of moisture-curable of the present invention, wherein:
A is that number-average molecular weight is 1000 to 5000 two hydroxy-end capped polyethers, its general formula following (I):
H-(-OC
2H
4)
b-(O-iso-C
3H
6)
c-OH (I)
In the formula, b=0～10, c=10～100;
B is the compound that contains two isocyanate group;
C is the silicon base compound that contains a sulfydryl and have the alkoxyl group of hydrolytic activity more than, its general formula following (II):
HS-(CH
2)
a-Si(CH
3)
n(OR)
3-n (II)
In the formula, a=1 or 3; R representative-CH
3, or-C
2H
5N=0 or 1.
Above-mentioned preparation method, in step 1 or the step 2, can add reaction that appropriate amount of catalysts quickens hydroxyl or sulfydryl and isocyanate group, reduce the temperature of reaction and reduce time of reaction, the catalyzer that catalyzer is adopted in the time of can be for synthesis of polyurethane commonly used.
In particular:
The present invention relates to a kind of alkoxyl silicone terminated polymkeric substance of moisture-curable, it is to get by two hydroxyl terminated polyether, isocyanic ester and the reaction of sulfydryl organoalkoxysilane, wherein:
Hydroxyl terminated polyether compound (A) is two hydroxy-end capped polyether glycols, as poly-(propylene oxide), poly-(oxyethane) etc., or their multipolymer.The size of the number-average molecular weight of A will be according to final polymer properties being required to determine the while is convenient in conjunction with production operation.Usually its molecular weight is big, and the polymer elasticity that obtains is big and intensity is low, and its suitable molecular weight ranges is 500～10000, and preferably 1000～5000.
The compound (B) that contains two isocyanate group is aromatic isocyanate commonly used, as: 2,4 toluene diisocyanate (2,4-TDI) or 2, the 6-tolylene diisocyanate (2,6-TDI) or these mixture of isomers, or 2,2 '-'-diphenylmethane diisocyanate (2,2 '-MDI), 2,4 '-'-diphenylmethane diisocyanate (2,4 '-MDI) or 4,4 '-'-diphenylmethane diisocyanate (4,4 '-MDI) or their mixture of different isomerization body.The isocyanate-based compound of certainly adding an amount of polyfunctionality is regulated or is improved final polymer properties, as triphenylmethane triisocyanate etc.
The silicon base compound (C) that contains a sulfydryl and have the alkoxyl group of hydrolytic activity more than one is meant the mercapto hydrocarbyl si lanes, wherein sulfydryl links to each other with Siliciumatom by carbochain, the length of carbochain is 1～3 carbon, simultaneously contain more than one hydrolyzable alkoxyl group in this silane, as methoxy or ethoxy etc.For example 3-sulfydryl propyl group-Trimethoxy silane, 3-sulfydryl propyl group-triethoxyl silane, 3-sulfydryl propyl group-methyl-dimethoxy silane or 3-sulfydryl propyl group-methyl-diethoxy silane or the like.
Above-mentioned preparation method in step 1 preparation performed polymer process, can add the carrying out that appropriate amount of catalysts is come accelerated reaction.The catalyzer that the catalysis isocyanic ester was used always with hydroxyl reaction when catalyzer was synthesis of polyurethane.Include but not limited to trimethylamine or organo-metallic soap catalyzer,, do not have special requirement as Tetramethyl Ethylene Diamine, Tributylamine, dibutyl tin laurate, dibutyltin diacetate, Dibutyltin oxide, stannous octoate etc.Its consumption is 2%～0.001% of a reactant gross weight, is generally about 0.1%.
Above-mentioned preparation method, in the process of step 1 preparation NCO prepolymer, the ratio of the amount of substance of NCO: OH determines the molecular weight of resulting performed polymer, and influences the physics and the chemical property of final product to a certain extent, be generally preferred 1.5: 1～1.8: 1 1.2: 1～2.0: 1.
Above-mentioned preparation method, in the process of step 1 preparation NCO prepolymer, according to reaction raw materials, activity of such catalysts and catalyst consumption, suitable temperature of reaction is 30～120 ℃, is preferably 60～90 ℃.Under these conditions, the suitable reaction times is 1～10 hour, is 1～4 hour in the reaction times of 60～90 ℃ of the bests usually.
Above-mentioned preparation method, after the NCO performed polymer was finished in step 1 preparation, step 2 added an amount of silane that contains sulfydryl and carries out end capping, obtains alkoxyl silicone terminated polymkeric substance, and the adding mode is for dripping or disposable adding.
Usually, the catalyzer that adds when preparation NCO performed polymer just can the catalysis sulfydryl and the reaction of NCO group, need not to add in addition catalyzer.Certainly, for fast reaction speed, also can add extra catalyzer again.The kind of the extra catalyzer that is added still is organic amine or organo-metallic soap, as Tetramethyl Ethylene Diamine, Tributylamine, dibutyl tin laurate, dibutyltin diacetate, Dibutyltin oxide and stannous octoate or the like.
On proportioning raw materials, making remaining NCO in the performed polymer is NCO: SH=1 with the ratio of the amount of substance of SH in the hydrosulphonyl silane: 0.9～1: 1.2, preferably 1: 0.95～1: 1.1, be retained in excessive N CO group in the system or hydrosulphonyl silane can play tackifier when interlinkage solidifies effect on a small quantity.
The optimal temperature scope of prepolymer and hydrosulphonyl silane reaction is at 30～120 ℃, preferably 60～90 ℃.
Under these conditions, the suitable reaction times is 1～10 hour, is 1～4 hour in the reaction times of 60～90 ℃ of the bests usually.
Owing to contain the raw material responsive to water, oxygen etc. in the reactant that the present invention relates to, therefore responding all needs to carry out under the exsiccant atmosphere of inert gases, as nitrogen and argon gas etc.
In addition, adopt other some raw materials, but also can produce the alkoxy end-capped polymkeric substance of moisture crosslinking curing according to method of the present invention.These raw materials include, but are not limited to:
Hydroxyl terminated polyether: contain two or more can be with the activity hydroxy or the sulfhydryl compound of-NCO radical reaction, as PTMG or multipolymer, lower molecular weight liquid polyoxymethylene or multipolymer or liquid polythioether; Perhaps terminal liquid polymeric amide, urethane or the polyester of activity hydroxy or sulfydryl or their multipolymer etc. of containing.
Isocyanic ester: aliphatics or the alicyclic compound that contains two or more isocyanate groups, as: 1,6-hexyl diisocyanate (HDI) or isophorone diisocyanate (IPDI) etc., or their mixtures; Also can be low-molecular-weight diisocyanate based end capped urethane or polyester.
But the present invention and not requiring protects these scopes.
Advantage of the present invention is: carry out end-blocking with hydrosulphonyl silane to containing the NCO performed polymer, the viscosity of the alkoxyl silicone terminated polymkeric substance of generation is less, and preparation process be easy to control, make production operation simple and convenient, the polymkeric substance that obtains simultaneously is easy to use.
Description of drawings
The IR figure of the NCO performed polymer that Fig. 1 obtains for embodiment 1.
The IR figure of the alkoxyl silicone terminated polymkeric substance that Fig. 2 obtains for embodiment 1.
The H of the alkoxyl silicone terminated polymkeric substance that Fig. 3 obtains for embodiment 1
1-NMR figure
Come further content of the present invention to be described below by some embodiment, still do not constitute restriction other protection domain of patent of the present invention.
Embodiment
Under nitrogen protection; polyether glycol PPO240 (two hydroxy-end capped poly(propylene oxide)s with 509.08g vacuum hydro-extraction; number-average molecular weight is 4000) and 33.30g tolylene diisocyanate isomer mixture (80%2; 4-TDI and 20%2; 6-TDI; down with) in the four neck flasks of the 1000ml that is equipped with agitator, thermometer and reflux condensing tube of packing into; stir; add the 0.45g dibutyltin diacetate again; keep thermotonus 2.5h after slowly being heated to 80 ℃ under stirring; Infrared spectroscopy (seeing accompanying drawing 1), 2274cm are carried out in sampling
-1The absorption peak proof at place also has excessive N CO group to exist.Cool to 50 ℃, add 22.57g 3-sulfydryl propyl group-Trimethoxy silane again, continue reaction 1h down at 50 ℃ earlier, be heated to 80 ℃ then and continue reaction 3h, finish reaction.Through Infrared spectroscopy, in the product that obtains, do not detected the NCO group at 2274cm
-1Charateristic avsorption band (seeing accompanying drawing 2).The viscosity that records polymkeric substance is 65.0Pas, and its proton nmr spectra is seen accompanying drawing 3.
Comparative example 1
Replace 22.57g 3-sulfydryl propyl group-Trimethoxy silane with 25.45 g 3-aminopropyls-triethoxyl silane, repeat embodiment 1.Discovery is in the process that drips 3-aminopropyl-triethoxyl silane, and system viscosity increases fast, the polymkeric substance pole-climbing, and gel appears, reaction can't be proceeded.
Embodiment 2
Under nitrogen protection; with 222.75g polyether glycol PPO220 (two hydroxy-end capped poly(propylene oxide)s; number-average molecular weight is 2000) pack in the four neck flasks of the 500ml that is equipped with agitator, thermometer and reflux condensing tube with 38.76g tolylene diisocyanate isomer mixture; add the 1.0g dibutyl tin laurate; after being heated to 75 ℃ then, keep thermotonus 3.5h.Add 21.83g 3-sulfydryl propyl group-Trimethoxy silane again, 90 ℃ are continued reaction 2h down, and reaction remains in the nitrogen atmosphere always to be carried out.Through Infrared spectroscopy, in product, there be not the charateristic avsorption band of NCO group at 2270cm-1.The viscosity that records polymkeric substance is 31.5Pas.
Under nitrogen protection; polyether glycol PPO240 (two hydroxy-end capped poly(propylene oxide)s with 515.29g vacuum hydro-extraction; number-average molecular weight is 4000) pack in the four neck flasks of the 1000ml that is equipped with agitator, thermometer and reflux condensing tube with 33.63g tolylene diisocyanate isomer mixture; add the 0.50g dibutyltin diacetate, be heated to 60 ℃ and keep thermotonus 5h.Add 21.03g 3-sulfydryl propyl group-methyl-diethoxy silane again, 80 ℃ are continued reaction 3h down, finish reaction.Do not detect the NCO group in the product that obtains.
Embodiment 4
Under nitrogen protection; polyether glycol PPO210 (two hydroxyl terminated polyether multipolymers with 120.5g vacuum hydro-extraction; contain 90% poly(propylene oxide) and 10% polyethylene oxide; number-average molecular weight is 1000) pack in the four neck flasks of the 500ml that is equipped with agitator, thermometer and reflux condensing tube with 48.5g '-diphenylmethane diisocyanate (MDI) isomer; add the 2g Tributylamine, be heated to 80 ℃ and keep thermotonus 5h.Add 20.20g 3-sulfydryl propyl group-triethoxyl silane again, 80 ℃ are continued reaction 3h down, finish reaction.Do not detect the NCO group in the product that obtains.
Application examples 1
Polymkeric substance 100g, 3-aminopropyl-triethoxyl silane 0.5g and dibutyltin diacetate 0.50g that embodiment 1 is obtained stir under air-tight state, are packaged in the aluminum pipe.Carried out bonding experiment respectively to aluminium flake and stainless steel substrates, the glue sample is coated in an end of two test pieces respectively, about 1.5cm * the 2cm of coated face area, again coated face being aimed in two test pieces closes up, clamping the back with iron clamp solidified 7 days under room temperature environment, with American I NSTRON company 4466 type universal material test machines tests (draw speed 10mm/min), shearing resistance is respectively: aluminium flake/aluminium flake, 0.82MP; Stainless steel/stainless steel, 0.74MP.
Application examples 2
The polymkeric substance that the polymkeric substance 100g that obtains with embodiment 3 replaces embodiment 1 to obtain, the experiment in the repeated application example 1, the glue sample stirs under air-tight state, is packaged in the aluminum pipe.Carry out the bonding experiment to aluminium flake and stainless steel substrates respectively, the agglutinating sample solidifies after 7 days under room temperature environment, and shearing resistance is respectively: aluminium flake/aluminium flake, 1.48MP; Stainless steel/stainless steel, 1.18MP.
Claims (4)
1. the alkoxyl silicone terminated polymkeric substance of a moisture-curable is characterized in that having following structural formula:
(OR)
3-nSi (CH
3)
n(CH
2)
aS-[PU]-CONH-R
1-NHCO-S-(CH
2)
a-Si (CH
3)
n(OR)
3-nWherein, PU representative :-[CONHR
1NHCO (OC
2H
4)
b(OC
3H
6)
cO]
x-; A=1 or 3; R representative-CH
3Or-C
2H
5N=0 or 1; B=0～10; C=10～100; X=1～5;
R
1=H
3 
Or
2. method for preparing the described polymkeric substance of claim 1 is characterized in that it is made up of following steps:
Step 1. is under the inert gasses protection, and with two hydroxy-end capped polyethers and isocyanate reaction, the ratio of the amount of substance of NCO: OH is 1.2: 1～2.0: 1; temperature of reaction is 30～120 ℃; reaction times is 1～10 hour, generates the performed polymer of NCO group end capping
Step 2. is under the inert gasses protection; the prepolymer of the NCO group end capping that step 1 is obtained reacts with hydrosulphonyl silane again; the amount that hydrosulphonyl silane adds is: remaining NCO is NCO: SH=1 with the ratio of the amount of substance of SH in the hydrosulphonyl silane in the performed polymer: 0.9～1: 1.2; temperature of reaction is 30～120 ℃; reaction times is 1～10 hour; promptly generate the alkoxyl silicone terminated polymkeric substance of moisture-curable of the present invention
Wherein: described two hydroxy-end capped polyethers are that number-average molecular weight is 1000 to 5000 two hydroxy-end capped polyethers, and its general formula is as follows:
H-(-OC
2H
4)
b-(O-iso-C
3H
6)
c-OH
In the formula, b=0～10, c=10～100;
Described isocyanic ester is the compound that contains two isocyanate group,
Described hydrosulphonyl silane is the silicon base compound that contains a sulfydryl and have the alkoxyl group of hydrolytic activity more than, and its general formula is as follows:
HS-(CH
2)
a-Si(CH
3)
n(OR)
3-n)
In the formula, a=1 or 3; R representative-CH
3, or-C
2H
5N=0 or 1.
3. preparation method according to claim 2 is characterized in that: in step 1 preparation performed polymer process, add the carrying out that catalyzer comes accelerated reaction, the catalyzer that the catalysis isocyanic ester was used always with hydroxyl reaction when described catalyzer was synthesis of polyurethane.
4. preparation method according to claim 2 is characterized in that: in step 2 reaction process, add the carrying out that catalyzer comes accelerated reaction, described catalyzer is organic amine or organo-metallic soap.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101906278A CN101205285A (en) | 2007-11-27 | 2007-11-27 | Moisture curable alkoxyl silicone terminated polymer and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101906278A CN101205285A (en) | 2007-11-27 | 2007-11-27 | Moisture curable alkoxyl silicone terminated polymer and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101205285A true CN101205285A (en) | 2008-06-25 |
Family
ID=39565780
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101906278A Pending CN101205285A (en) | 2007-11-27 | 2007-11-27 | Moisture curable alkoxyl silicone terminated polymer and preparation thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781539A (en) * | 2010-03-15 | 2010-07-21 | 日邦树脂(无锡)有限公司 | Method for preparing moisture-cured multi-grafted solvent type adhesive |
| CN103602304A (en) * | 2013-11-11 | 2014-02-26 | 苏州毫邦新材料有限公司 | Fast moisture-cured composition |
| CN103946259A (en) * | 2011-09-29 | 2014-07-23 | 拜耳知识产权有限责任公司 | Alpha-alkoxysilane-terminated prepolymer for fast-curing spray foams with improved propellant gas solubility |
| CN106232668A (en) * | 2014-03-11 | 2016-12-14 | Sika技术股份公司 | There is low monomeric diisocyanate content and the polyurethane-hot melt adhesive of good crosslinking rate |
| US9957415B2 (en) | 2008-12-19 | 2018-05-01 | Sika Technology Ag | Liquid film based on silane-terminated polymers |
| JP2018532831A (en) * | 2015-09-09 | 2018-11-08 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Scratch-resistant two-component polyurethane coating |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9957415B2 (en) | 2008-12-19 | 2018-05-01 | Sika Technology Ag | Liquid film based on silane-terminated polymers |
| CN105694693B (en) * | 2008-12-19 | 2019-08-16 | Sika技术股份公司 | Fluid film based on silicone terminated polymer |
| CN101781539A (en) * | 2010-03-15 | 2010-07-21 | 日邦树脂(无锡)有限公司 | Method for preparing moisture-cured multi-grafted solvent type adhesive |
| CN101781539B (en) * | 2010-03-15 | 2012-11-21 | 日邦树脂(无锡)有限公司 | Method for preparing moisture-cured multi-grafted solvent type adhesive |
| CN103946259A (en) * | 2011-09-29 | 2014-07-23 | 拜耳知识产权有限责任公司 | Alpha-alkoxysilane-terminated prepolymer for fast-curing spray foams with improved propellant gas solubility |
| CN103602304A (en) * | 2013-11-11 | 2014-02-26 | 苏州毫邦新材料有限公司 | Fast moisture-cured composition |
| CN106232668A (en) * | 2014-03-11 | 2016-12-14 | Sika技术股份公司 | There is low monomeric diisocyanate content and the polyurethane-hot melt adhesive of good crosslinking rate |
| CN106232668B (en) * | 2014-03-11 | 2019-08-23 | Sika技术股份公司 | Polyurethane-hot melt adhesive with low monomeric diisocyanate content and good crosslinking rate |
| JP2018532831A (en) * | 2015-09-09 | 2018-11-08 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Scratch-resistant two-component polyurethane coating |
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