CN111961197A - Amino acid modified silane terminated polyether and preparation method thereof - Google Patents
Amino acid modified silane terminated polyether and preparation method thereof Download PDFInfo
- Publication number
- CN111961197A CN111961197A CN202010861804.6A CN202010861804A CN111961197A CN 111961197 A CN111961197 A CN 111961197A CN 202010861804 A CN202010861804 A CN 202010861804A CN 111961197 A CN111961197 A CN 111961197A
- Authority
- CN
- China
- Prior art keywords
- amino acid
- polyether
- diisocyanate
- silane
- terminated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 110
- 229920000570 polyether Polymers 0.000 title claims abstract description 110
- -1 Amino acid modified silane Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001413 amino acids Chemical class 0.000 claims abstract description 50
- 229920005862 polyol Polymers 0.000 claims abstract description 43
- 150000003077 polyols Chemical class 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 21
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 14
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 125000003088 (fluoren-9-ylmethoxy)carbonyl group Chemical group 0.000 claims description 8
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 8
- 229960003104 ornithine Drugs 0.000 claims description 8
- MJHLGXKXOPOSNH-GFCCVEGCSA-N (2r)-6-[bis(ethylamino)methylideneamino]-2-[(2-methylpropan-2-yl)oxycarbonylamino]hexanoic acid Chemical compound CCNC(NCC)=NCCCC[C@H](C(O)=O)NC(=O)OC(C)(C)C MJHLGXKXOPOSNH-GFCCVEGCSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 4
- 238000012661 block copolymerization Methods 0.000 abstract description 3
- 239000003707 silyl modified polymer Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229940024606 amino acid Drugs 0.000 description 53
- 238000003756 stirring Methods 0.000 description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 description 16
- 239000000565 sealant Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 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 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VKSCZTWQDPUHIK-UHFFFAOYSA-N isocyanic acid;trimethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OC)(OC)OC VKSCZTWQDPUHIK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000004588 polyurethane sealant Substances 0.000 description 3
- 239000012812 sealant material Substances 0.000 description 3
- 239000004526 silane-modified polyether Substances 0.000 description 3
- 239000004590 silicone sealant Substances 0.000 description 3
- UAYLDTQWSNYJDA-MPUYUTEFSA-N (3S)-3-amino-4-[4-[[4-[(2S)-2-amino-3-carboxypropanoyl]oxycyclohexyl]methyl]cyclohexyl]oxy-4-oxobutanoic acid Chemical compound N[C@@H](CC(O)=O)C(OC1CCC(CC(CC2)CCC2OC([C@H](CC(O)=O)N)=O)CC1)=O UAYLDTQWSNYJDA-MPUYUTEFSA-N 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 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 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 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- 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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides amino acid modified silane terminated polyether and a preparation method thereof, belonging to the technical field of high polymer materials. The amino acid modified silane terminated polyether provided by the invention is prepared from polyether polyol, diisocyanate, amino acid, isocyanate silane and a catalyst, wherein the molar ratio of the polyether polyol to the diisocyanate to the amino acid to the isocyanate silane is 1: (1-2): (0.5-1): (0.2-2), wherein the catalyst accounts for 0.1-1% of the total mass of the preparation raw materials. The amino acid and the polyether polyol have good compatibility, the obtained amino acid modified silane terminated polyether is a novel silane modified polymer of polyether polyol and amino acid block copolymerization, and the product has good transparency and excellent weather resistance, mechanical strength and adhesion.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to amino acid modified silane terminated polyether and a preparation method thereof.
Background
The sealant is widely used for bonding metal, glass, wood, plastic, ceramic, natural and synthetic fibers and the like. There are many types of sealants, among which polyurethane sealants contain free isocyanate and are easily foamed when cured. The silicone sealant has poor coating property and is easy to pollute building materials. The silane modified polyether sealant (MS sealant) is a high-performance environment-friendly sealant prepared by taking silyl terminated polyether as a basic polymer, has the advantages of both polyurethane sealant and silicone sealant, overcomes the defects of the polyurethane sealant and the silicone sealant, has excellent mechanical strength, coating decoration property and stain resistance, is free from isocyanate in products, is environment-friendly, and is widely applied to the fields of buildings, automobiles, home decoration and the like. However, the MS sealant can generate different degrees of swelling and cracking after aging, the color of the sealant gradually turns yellow, and even the sealant is debonded from a base material.
Disclosure of Invention
The invention aims to provide amino acid modified silane terminated polyether and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides amino acid modified silane terminated polyether, which is prepared from polyether polyol, diisocyanate, amino acid, isocyanate silane and a catalyst, wherein the molar ratio of the polyether polyol to the diisocyanate to the amino acid to the isocyanate silane is 1: (1-2): (0.5-1): (0.2-2), wherein the catalyst accounts for 0.1-1% of the total mass of the preparation raw materials.
Preferably, the polyether polyol comprises polyether diol and/or polyether triol, and the relative molecular weight of the polyether polyol is 1000-10000.
Preferably, the diisocyanate includes at least one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and m-xylylene diisocyanate.
Preferably, the amino acid comprises at least one of N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine, N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine, and tetraethyl N, N' - (methylenebis-4, 1-cyclohexanediyl) bisaspartate.
Preferably, the isocyanatosilane comprises alpha-isocyanatosilane or gamma-isocyanatosilane.
Preferably, the catalyst comprises a tertiary amine catalyst or an organotin catalyst.
The invention provides a preparation method of amino acid modified silane terminated polyether, which comprises the following steps:
mixing polyether polyol, diisocyanate and amino acid, and then carrying out I nucleophilic addition reaction to obtain an I nucleophilic addition reaction product system;
mixing the product system of the first nucleophilic addition reaction with a catalyst and then carrying out a second nucleophilic addition reaction to obtain hydroxyl-terminated amino acid modified polyether;
and mixing the hydroxyl-terminated amino acid modified polyether with isocyanate silane, and then carrying out III nucleophilic addition reaction to obtain the amino acid modified silane-terminated polyether.
Preferably, the I nucleophilic addition reaction comprises a first stage reaction and a second stage reaction which are carried out in sequence; the temperature of the first-stage reaction is 15-35 ℃, and the time is 1.5-2.5 h; the temperature of the second stage reaction is 55-65 ℃, and the time is 1.5-2.5 h.
Preferably, the temperature of the nucleophilic addition reaction of the II is 55-65 ℃ and the time is 3-5 h.
Preferably, the temperature of the nucleophilic addition reaction of the III is 60-80 ℃ and the time is 3-5 h.
The invention provides amino acid modified silane terminated polyether, which is prepared from polyether polyol, diisocyanate, amino acid, isocyanate silane and a catalyst, wherein the molar ratio of the polyether polyol to the diisocyanate to the amino acid to the isocyanate silane is 1: (1-2): (0.5-1): (0.2-2), wherein the catalyst accounts for 0.1-1% of the total mass of the preparation raw materials. The amino acid and the polyether polyol have good compatibility, the obtained amino acid modified silane terminated polyether is a novel silane modified polymer obtained by block copolymerization of the silane modified polyether polyol and the amino acid, the product has good transparency, and has excellent weather resistance, mechanical strength and adhesion, the problems of poor product transparency, low body strength, poor aging resistance and yellowing resistance of the product in the prior art are solved, and the adhesion strength of the product to a base material is enhanced.
Detailed Description
The invention provides amino acid modified silane terminated polyether, which is prepared from polyether polyol, diisocyanate, amino acid, isocyanate silane and a catalyst, wherein the molar ratio of the polyether polyol to the diisocyanate to the amino acid to the isocyanate silane is 1: (1-2): (0.5-1): (0.2-2), wherein the catalyst accounts for 0.1-1% of the total mass of the preparation raw materials.
The raw materials for preparing the amino acid modified silane terminated polyether comprise polyether polyol. In the invention, the polyether polyol preferably comprises polyether diol and/or polyether triol, and the molecular weight of the polyether polyol is preferably 1000-10000, more preferably 3000-9000; specifically, the type of the polyether polyol can be HSH-220, HSH-330 or HSH-280.
The raw materials for preparing the amino acid modified silane terminated polyether comprise diisocyanate. In the present invention, the diisocyanate includes at least one of Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), diphenylmethylene diisocyanate (MDI) and m-Xylylene Diisocyanate (XDI), and is more preferably TDI, HDI, MDI or XDI.
The raw materials for preparing the amino acid modified silane terminated polyether comprise amino acid. In the present invention, the amino acid preferably includes at least one of N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine, N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine and tetraethyl N, N' - (methylenebis-4, 1-cyclohexanediyl) di-aspartate, more preferably N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine, N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine or N, n' - (methylenebis-4, 1-cyclohexanediyl) tetraacetate.
The raw material for preparing the amino acid modified silane terminated polyether comprises isocyanate silane. In the present invention, the isocyanatosilane preferably comprises alpha-isocyanatosilane or gamma-isocyanatosilane, more preferably alpha-isocyanatomethyltrimethoxysilane or gamma-isocyanatopropyltrimethoxysilane.
The raw materials for preparing the amino acid modified silane terminated polyether comprise a catalyst. In the present invention, the catalyst preferably includes a tertiary amine-based catalyst or an organotin catalyst, and in the present invention, the tertiary amine-based catalyst preferably includes triethylamine, triethylenediamine, N-alkyl morpholine, which is preferably N-methyl morpholine or N-ethyl morpholine, or bis (dimethylaminoethyl) ether. In the present invention, the organotin catalyst preferably includes dibutyltin dilaurate, stannous octoate or dibutyltin diacetate; in the examples of the present invention, dibutyltin dilaurate (DBTDL) is specifically used.
In the invention, the molar ratio of the polyether polyol, the diisocyanate, the amino acid and the isocyanatosilane is 1: (1-2): (0.5-1): (0.2-2), preferably 1: (1-1.2): (0.5-0.6): (1-2), wherein the catalyst accounts for 0.1-1% of the total mass of the preparation raw materials, and preferably accounts for 0.1-0.5%. In the invention, the amino acid and the polyether polyol have better compatibility, the obtained amino acid modified silane terminated polyether is a novel silane modified polymer of polyether polyol and amino acid block copolymerization, and the product has good transparency and excellent weather resistance, mechanical strength and adhesion. Specifically, the amino acid modified silane terminated polyether is colorless transparent liquid, the hardness after curing can reach 50(shore A), and the mechanical strength can reach 2.1 Mpa.
The invention provides a preparation method of amino acid modified silane terminated polyether, which comprises the following steps:
mixing polyether polyol, diisocyanate and amino acid, and then carrying out I nucleophilic addition reaction to obtain an I nucleophilic addition reaction product system;
mixing the product system of the first nucleophilic addition reaction with a catalyst and then carrying out a second nucleophilic addition reaction to obtain hydroxyl-terminated amino acid modified polyether;
and mixing the hydroxyl-terminated amino acid modified polyether with isocyanate silane, and then carrying out III nucleophilic addition reaction to obtain the amino acid modified silane-terminated polyether.
According to the invention, polyether polyol, diisocyanate and amino acid are mixed and then subjected to I nucleophilic addition reaction to obtain an I nucleophilic addition reaction product system. In the present invention, the polyether polyol is preferably dried before use to remove moisture therefrom, and thereafter the resultant dried polyether polyol, diisocyanate and amino acid are mixed to conduct the I-th nucleophilic addition reaction. The present invention is not particularly limited to the drying, and a method well known to those skilled in the art may be used; in the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 85-95 ℃, and more preferably 90 ℃; the time is preferably 50-70 min, and more preferably 60 min.
In the present invention, the I nucleophilic addition reaction includes a first-stage reaction and a second-stage reaction which are sequentially performed. In the invention, the temperature of the first-stage reaction is preferably 15-35 ℃, and more preferably 20-30 ℃; the time of the first-stage reaction is preferably 1.5-2.5 h, and more preferably 2 h.
In the invention, the temperature of the second-stage reaction is preferably 55-65 ℃, and more preferably 60 ℃; the time is preferably 1.5 to 2.5 hours, and more preferably 2 hours. In the present invention, after the first-stage reaction is finished, the temperature of the first-stage reaction is preferably raised to the temperature of the second-stage reaction for reaction; the heating rate is preferably 1-2 ℃/min, the reaction temperature is preferably controlled to be slowly increased, and the increase of material viscosity or polymerization caused by uncontrollable overhigh temperature is prevented. In the invention, the secondary amino group of the amino acid and the diisocyanate react in the two stages of the nucleophilic addition reaction of the I stage to generate the amino acid containing two isocyanate groups, specifically, the reaction temperature of the first stage is lower, which is beneficial to controlling the reaction rate and avoiding viscosity increase or polymerization, and the reaction temperature of the second stage is higher, which is beneficial to ensuring the complete reaction of the amino group. The nucleophilic addition reaction of the I th amine group is carried out in two stages, so that the reaction can be optimized on the basis of ensuring the complete reaction of the secondary amine group, and the invention is favorable for ensuring lower viscosity and narrower molecular weight distribution of materials.
After the first nucleophilic addition reaction product system is obtained, the second nucleophilic addition reaction is carried out after the first nucleophilic addition reaction product system is mixed with a catalyst, and the hydroxyl-terminated amino acid modified polyether is obtained. In the invention, the temperature of the II nucleophilic addition reaction is preferably 55-65 ℃, and more preferably 60 ℃; the time is preferably 3 to 5 hours, and more preferably 4 hours. In the invention, hydroxyl of polyether polyol and isocyanate group react in the nucleophilic addition reaction process of II to obtain hydroxyl-terminated amino acid modified polyether.
After the hydroxyl-terminated amino acid modified polyether is obtained, the hydroxyl-terminated amino acid modified polyether and isocyanate silane are mixed and then subjected to III nucleophilic addition reaction to obtain the amino acid modified silane-terminated polyether. In the invention, the temperature of the nucleophilic addition reaction of the III is preferably 60-80 ℃, and more preferably 60-70 ℃; the time is preferably 3 to 5 hours, and more preferably 4 hours. In the invention, in the process of the III nucleophilic addition reaction, an isocyanate group in isocyanate silane and a hydroxyl group in the amino acid modified polyether with a hydroxyl terminated end react to obtain the silane terminated polyether with the modified amino acid block.
In the present invention, the first nucleophilic addition reaction, the second nucleophilic addition reaction and the third nucleophilic addition reaction are preferably performed under stirring conditions, and the stirring rate is not particularly limited in the present invention, and may be a stirring rate well known to those skilled in the art. In the invention, after the first nucleophilic addition reaction and the second nucleophilic addition reaction, any post-treatment is not needed, and the next reaction is directly carried out; and after the nucleophilic addition reaction of the III, any post-treatment is not needed, and the target product amino acid modified silane terminated polyether is obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Vacuum drying polyether polyol (HSH-280, molecular weight of 8000) at 90 deg.C for 60 min;
placing 1000g of dry polyether polyol HSH-280, 21.75g of Toluene Diisocyanate (TDI) and 26.41g of N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine into a reaction kettle, stirring and reacting for 2H at room temperature (25 ℃), then heating to 60 ℃ at the speed of 1 ℃/min, and stirring and reacting for 2H;
adding 1g of catalyst (dibutyltin dilaurate, DBTDL) into the obtained system, and stirring and reacting for 4H at the temperature of 60 ℃ to obtain hydroxyl-terminated N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine modified polyether;
adding 25.66g of isocyanate propyl trimethoxy silane into the hydroxyl terminated N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine modified polyether, stirring and reacting for 4H at the temperature of 60 ℃, and then cooling to room temperature to obtain N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine modified trimethoxy silane terminated polyether.
Example 2
Vacuum drying polyether polyol (HSH-240, molecular weight 4000) at 90 deg.C for 60 min;
1000g of dry polyether polyol, 28.03g of Hexamethylene Diisocyanate (HDI) and 18.94g of N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine were placed in a reaction vessel, stirred and reacted at room temperature (25 ℃) for 2 hours, then heated to 60 ℃ at a rate of 1 ℃/min, and stirred and reacted for 2 hours;
adding 0.5g of catalyst (dibutyltin dilaurate, DBTDL) into the obtained system, and stirring and reacting for 4h at the temperature of 60 ℃ to obtain hydroxyl-terminated N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine modified polyether;
17.1g of isocyanatopropyl trimethoxy silane is added into the hydroxyl-terminated N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine modified polyether, the mixture is stirred and reacted for 4 hours at the temperature of 60 ℃, and then the temperature is reduced to room temperature, so that N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine modified trimethoxy silane terminated polyether is obtained.
Example 3
Vacuum drying polyether polyol (HSH-280, molecular weight of 8000) at 90 deg.C for 60 min;
placing 1000g of dry polyether polyol HSH-280, 31.28g of 4,4 '-diphenylmethane diisocyanate (MDI) and 34.67g of N, N' - (methylenebis-4, 1-cyclohexanediyl) tetraaspartic acid tetraethyl ester into a reaction kettle, stirring and reacting for 2 hours at room temperature (25 ℃), then heating to 60 ℃ at the speed of 1 ℃/min, and stirring and reacting for 2 hours;
adding 1g of catalyst (dibutyltin dilaurate, DBTDL) into the obtained system, and stirring and reacting for 4h at the temperature of 60 ℃ to obtain hydroxyl-terminated N, N' - (methylenedi-4, 1-cyclohexanediyl) tetraaspartic acid tetraethyl ester modified polyether;
adding 25.66g of isocyanate propyl trimethoxy silane into the hydroxyl terminated N, N '- (methylene di-4, 1-cyclohexanediyl) tetraaspartic acid tetraethyl ester modified polyether, stirring and reacting for 4 hours at the temperature of 60 ℃, and then cooling to room temperature to obtain the N, N' - (methylene di-4, 1-cyclohexanediyl) tetraaspartic acid tetraethyl ester modified trimethoxy silane terminated polyether.
Comparative example 1
Vacuum drying polyether polyol (HSH-280, molecular weight of 8000) at 90 deg.C for 60 min;
placing 1000g of dry polyether polyol HSH-280, 10.875g of TDI and 1g of DBTDL in a reaction kettle, and stirring and reacting for 4 hours at 70 ℃ to obtain hydroxyl terminated polyether;
adding 25.66g of isocyanate propyl trimethoxy silane into the hydroxyl terminated polyether, stirring and reacting for 4h at 70 ℃, and then cooling to room temperature to obtain the trimethoxy silane terminated polyether.
Comparative example 2
Respectively vacuum drying polyether polyol (HSH-280, molecular weight of 8000) and hydroxyl-terminated polydimethylsiloxane (hydroxyl content of 3%, Shandong Dayi DY-OH502 hydroxyl silicone oil) at 90 deg.C for 60 min;
taking 70.8g of the dried hydroxyl-terminated polydimethylsiloxane, 21.75g of Toluene Diisocyanate (TDI) and 1g of catalyst (dibutyltin dilaurate, DBTDL) into a reaction kettle, heating from room temperature for 1h to 60 ℃, and stirring at 60 ℃ for reaction for 4h to obtain isocyanate-terminated polydimethylsiloxane;
adding 1000g of the dried polyether polyol (HSH-280, molecular weight of 8000) into the obtained system, and continuously stirring and reacting for 4h at 60 ℃ to obtain hydroxyl-terminated polydimethylsiloxane modified polyether;
adding 25.66g of isocyanate propyl trimethoxy silane into the polydimethylsiloxane modified polyether, stirring and reacting for 4h at the temperature of 60 ℃, and then cooling to room temperature to obtain the polydimethylsiloxane modified trimethoxy silane terminated polyether.
The products prepared in examples 1-3 and comparative examples 1-2 were tested for performance, as follows:
preparing a performance detection sample:
preparation of an aged sample: each of the examples and comparative examples was placed in a sealed glass bottle and aged at 80 ℃ for 7 days.
Preparing a surface drying and curing hardness detection sample: according to the parts by weight, 50 parts of modified silane terminated polyether, 0.5 part of dibutyltin dilaurate (DBTDL) serving as a catalyst and 1 part of aminopropyltrimethoxysilane serving as an adhesion promoter in each example and comparative example are vacuumized to be below-0.09 MPa and stirred for 5 min. 5 parts of surface dry and cured hardness test samples of the examples 1, 2, 3, 1 and 2 are obtained.
Preparing a sealant detection sample:
respectively taking 50 parts of modified silane end-capped polyether, 35 parts of plasticizer diisononyl phthalate, 2921 parts of light stabilizer and 1.5 parts of water removing agent vinyl trimethoxy silane in each example and comparative example according to the mass parts, adding into a high-speed dispersion machine, stirring for 10min at 400rpm, adding 10 parts of thixotropic agent fumed silica, completely melting the thixotropic agent into the cement, vacuumizing to below-0.09 MPa, and stirring for 15min at 1000 rpm; 0.5 part of catalyst dibutyltin dilaurate (DBTDL) and 2.5 parts of adhesion promoter aminopropyltrimethoxysilane are added, the vacuum pumping is carried out until the pressure is lower than-0.09 MPa, and the stirring is carried out for 5min under the condition of 1000rpm, thus obtaining 5 parts of the sealant strength and adhesion performance samples of the example 1, the example 2, the example 3, the comparative example 1 and the comparative example 2.
The detection method for the surface dryness of the product comprises the following steps: reference GB/T13477.5 test method for construction sealant Material part 5: measuring the surface dry time;
the method for detecting the hardness of the cured product comprises the following steps: reference is made to GB/T531-2008 vulcanized rubber or thermoplastic rubber press-in hardness test method part 1: shore durometer (shore hardness);
the sealant strength detection method comprises the following steps: reference is made to GB/T13477.8-2002 test method for building sealant materials part 8: measuring the tensile adhesion;
the method for detecting the adhesive property of the sealant comprises the following steps: reference is made to GB/T13477.18-2002 test method for building sealant materials for determination of peel adhesion at part 18.
The results of the performance tests are shown in table 1.
Table 1 test results of product performances in examples 1 to 3 and comparative examples 1 to 2
The results show that the prepared modified polyether is colorless and transparent, which indicates that the amino acid and the polyether polyol have better compatibility; particularly, the performance test results show that the resin modified by the amino acid has greatly improved hardness, strength and bonding performance, and can still maintain better performance after aging, which indicates that the weather resistance of the resin modified by the amino acid is also improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The amino acid modified silane-terminated polyether is prepared from polyether polyol, diisocyanate, amino acid, isocyanate silane and a catalyst, wherein the molar ratio of the polyether polyol to the diisocyanate to the amino acid to the isocyanate silane is 1: (1-2): (0.5-1): (0.2-2), wherein the catalyst accounts for 0.1-1% of the total mass of the preparation raw materials.
2. The amino acid modified silane-terminated polyether of claim 1, wherein the polyether polyol comprises polyether diol and/or polyether triol, and the polyether polyol has a relative molecular weight of 1000-10000.
3. The amino acid-modified silane-terminated polyether of claim 1, wherein the diisocyanate comprises at least one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and m-xylylene diisocyanate.
4. The amino acid-modified silane-terminated polyether of claim 1, wherein the amino acid comprises at least one of N5- [ bis (methylamino) methylene ] -N2- [ (9H-fluoren-9-ylmethoxy) carbonyl ] -L-ornithine, N6- [ bis (ethylamino) methylene ] -N2- [ (1, 1-dimethylethoxy) carbonyl ] -D-lysine, and N, N' - (methylenebis-4, 1-cyclohexanediyl) tetraaspartic acid tetraethyl ester.
5. The amino acid-modified silane-terminated polyether of claim 1, wherein the isocyanatosilane comprises alpha-isocyanatosilane or gamma-isocyanatosilane.
6. The amino acid-modified silane-terminated polyether of claim 1, wherein the catalyst comprises a tertiary amine catalyst or an organotin catalyst.
7. A method for preparing the amino acid modified silane-terminated polyether of any one of claims 1 to 6, comprising the steps of:
mixing polyether polyol, diisocyanate and amino acid, and then carrying out I nucleophilic addition reaction to obtain an I nucleophilic addition reaction product system;
mixing the product system of the first nucleophilic addition reaction with a catalyst and then carrying out a second nucleophilic addition reaction to obtain hydroxyl-terminated amino acid modified polyether;
and mixing the hydroxyl-terminated amino acid modified polyether with isocyanate silane, and then carrying out III nucleophilic addition reaction to obtain the amino acid modified silane-terminated polyether.
8. The method according to claim 7, wherein the I nucleophilic addition reaction comprises a first-stage reaction and a second-stage reaction which are carried out in this order; the temperature of the first-stage reaction is 15-35 ℃, and the time is 1.5-2.5 h; the temperature of the second stage reaction is 55-65 ℃, and the time is 1.5-2.5 h.
9. The preparation method according to claim 7, wherein the temperature of the nucleophilic addition reaction of the II is 55-65 ℃ and the time is 3-5 h.
10. The preparation method according to claim 7, wherein the temperature of the nucleophilic addition reaction of the III is 60-80 ℃ and the time is 3-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010861804.6A CN111961197B (en) | 2020-08-25 | 2020-08-25 | Amino acid modified silane terminated polyether and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010861804.6A CN111961197B (en) | 2020-08-25 | 2020-08-25 | Amino acid modified silane terminated polyether and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111961197A true CN111961197A (en) | 2020-11-20 |
| CN111961197B CN111961197B (en) | 2021-05-14 |
Family
ID=73390250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010861804.6A Active CN111961197B (en) | 2020-08-25 | 2020-08-25 | Amino acid modified silane terminated polyether and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111961197B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6046295A (en) * | 1993-08-20 | 2000-04-04 | 3M Innovative Properties Company | Room temperature curable silane-terminated polyurethane dispersions |
| US6626988B1 (en) * | 1999-05-21 | 2003-09-30 | Bayer Aktiengesellschaft | Phosphate-stabilized polyurethane materials, cross-linked by condensation, method for their production and use thereof |
| CN1871270A (en) * | 2003-10-22 | 2006-11-29 | 拜尔材料科学有限公司 | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
| US20110301639A1 (en) * | 2010-05-28 | 2011-12-08 | Beckman Eric J | One-Part Moisture-Curable Tissue Sealant |
| CN104277227A (en) * | 2013-07-01 | 2015-01-14 | 赢创工业集团股份有限公司 | Siloxane polymer with a central polysiloxane polymer block with terminal organofunctional radicals comprising urea and/or carbamate groups and amino acid radicals |
| CN104387547A (en) * | 2014-11-19 | 2015-03-04 | 上海华峰新材料研发科技有限公司 | Waterborne polyurethane resin as well as preparation method and application thereof |
| CN107001556A (en) * | 2014-11-24 | 2017-08-01 | Sika技术股份公司 | Fast curing compositions containing silane group |
| CN107001568A (en) * | 2014-11-24 | 2017-08-01 | Sika技术股份公司 | The fast curing compositions of containing silane groups |
| CN111479846A (en) * | 2017-12-19 | 2020-07-31 | 科思创德国股份有限公司 | Method for producing polyetherester polyols |
-
2020
- 2020-08-25 CN CN202010861804.6A patent/CN111961197B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6046295A (en) * | 1993-08-20 | 2000-04-04 | 3M Innovative Properties Company | Room temperature curable silane-terminated polyurethane dispersions |
| US6626988B1 (en) * | 1999-05-21 | 2003-09-30 | Bayer Aktiengesellschaft | Phosphate-stabilized polyurethane materials, cross-linked by condensation, method for their production and use thereof |
| CN1871270A (en) * | 2003-10-22 | 2006-11-29 | 拜尔材料科学有限公司 | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
| US20110301639A1 (en) * | 2010-05-28 | 2011-12-08 | Beckman Eric J | One-Part Moisture-Curable Tissue Sealant |
| CN104277227A (en) * | 2013-07-01 | 2015-01-14 | 赢创工业集团股份有限公司 | Siloxane polymer with a central polysiloxane polymer block with terminal organofunctional radicals comprising urea and/or carbamate groups and amino acid radicals |
| CN104387547A (en) * | 2014-11-19 | 2015-03-04 | 上海华峰新材料研发科技有限公司 | Waterborne polyurethane resin as well as preparation method and application thereof |
| CN107001556A (en) * | 2014-11-24 | 2017-08-01 | Sika技术股份公司 | Fast curing compositions containing silane group |
| CN107001568A (en) * | 2014-11-24 | 2017-08-01 | Sika技术股份公司 | The fast curing compositions of containing silane groups |
| CN111479846A (en) * | 2017-12-19 | 2020-07-31 | 科思创德国股份有限公司 | Method for producing polyetherester polyols |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111961197B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216845B (en) | Siloxane-terminated polyurethane sealant and preparation method thereof | |
| CN101910311B (en) | Two-part moisture-curable resin composition and adhesive, sealant and coating compositions based thereon | |
| JP4221301B2 (en) | Crosslinkable polymer blends containing alkoxysilane-terminated polymers | |
| CN110157376B (en) | Transparent two-component silane modified polyether sealant and preparation method thereof | |
| CN101679583B (en) | Moisture-curable silylated polymer resin composition | |
| CN106634769B (en) | High-strength transparent adhesive and preparation method thereof | |
| CN106833481B (en) | Environment-friendly organic silicon modified polyether sealant and preparation method thereof | |
| CN109575870B (en) | Modified siloxane-terminated polyurethane sealant and preparation method thereof | |
| CN110862797A (en) | Silane-terminated polyether sealant and preparation method thereof | |
| CN109400870B (en) | Modified polyether resin and preparation method and application thereof | |
| CN112608444B (en) | Polyurethane resin, MS sealant and preparation method | |
| CN113444439B (en) | Organic silicon-fluorine modified single-component polyurethane waterproof coating and preparation method thereof | |
| CN109535362A (en) | A kind of fluorinated silicone modified polyether polymer and preparation method thereof | |
| CN109535366B (en) | Secondary amino silane modified polyether polymer and preparation method thereof | |
| CN111378413A (en) | Primer-free single-component polyurethane sealant and preparation method thereof | |
| CN112358843A (en) | Waterproof polyurethane resin adhesive and preparation method thereof | |
| EP3619254A1 (en) | Silane modified polymers with improved characteristics for adhesive compositions | |
| KR20040010546A (en) | High performance sealant formulations based on mdi prepolymers | |
| CN114015036A (en) | Low-viscosity silane modified polyether resin and preparation method thereof | |
| CN114031767A (en) | Cyclic carbonate prepolymer, silane modified non-isocyanate polyurethane resin, and preparation methods and applications thereof | |
| CN111978905A (en) | Rapid curing silane modified polyether sealant for buildings and preparation method thereof | |
| CN111961197B (en) | Amino acid modified silane terminated polyether and preparation method thereof | |
| CN113755126A (en) | Adhesive and preparation method and application thereof | |
| KR20110024499A (en) | Siloxane modified isocyanate alkoxy silane compound, preparation method thereof, and the use thereof | |
| CN116606415A (en) | Comb-type silane end-capped polyurethane polymer resin, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211213 Address after: Room 1122, building 3, No. 215, Lianhe North Road, Fengxian District, Shanghai 201400 Patentee after: Shanghai Xinda Chemical Co.,Ltd. Address before: Hua Cun Zhen Nan Chong Yi Cun, Sishui County, Jining City, Shandong Province 273211 Patentee before: SHANDONG WANDA SILICONE NEW MATERIAL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231221 Address after: Room 710, No. 2, Lane 58, Xinjian East Road, Minhang District, Shanghai, 201199 Patentee after: Yuxuan Investment (Hainan) Co.,Ltd. Address before: Room 1122, building 3, No. 215, Lianhe North Road, Fengxian District, Shanghai 201400 Patentee before: Shanghai Xinda Chemical Co.,Ltd. |