CN115246918A - Silane modified polyurethane resin and preparation method and application thereof - Google Patents
Silane modified polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN115246918A CN115246918A CN202111247773.6A CN202111247773A CN115246918A CN 115246918 A CN115246918 A CN 115246918A CN 202111247773 A CN202111247773 A CN 202111247773A CN 115246918 A CN115246918 A CN 115246918A
- Authority
- CN
- China
- Prior art keywords
- nco
- silane
- polyurethane resin
- polyol polymer
- modified polyurethane
- 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.)
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- 239000004432 silane-modified polyurethane Substances 0.000 title claims abstract description 65
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 229920005862 polyol Polymers 0.000 claims abstract description 80
- 150000003077 polyols Chemical class 0.000 claims abstract description 78
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 239000012948 isocyanate Substances 0.000 claims abstract description 34
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 33
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 50
- 229920000570 polyether Polymers 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000000565 sealant Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000178 monomer Substances 0.000 abstract description 41
- 229920005989 resin Polymers 0.000 abstract description 30
- 239000011347 resin Substances 0.000 abstract description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000077 silane Inorganic materials 0.000 abstract description 10
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 239000003292 glue Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 22
- 239000005058 Isophorone diisocyanate Substances 0.000 description 19
- 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 19
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000004814 polyurethane Substances 0.000 description 14
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 11
- 238000007599 discharging Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 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 7
- 238000001816 cooling Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- -1 aminosiloxane Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 4
- KGNDVXPHQJMHLX-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CCCNC1CCCCC1 KGNDVXPHQJMHLX-UHFFFAOYSA-N 0.000 description 3
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- GGZBCIDSFGUWRA-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n-methylpropan-1-amine Chemical compound CNCCC[Si](C)(OC)OC GGZBCIDSFGUWRA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000013466 adhesive and sealant Substances 0.000 description 2
- KRJRKEPWQOASJN-UHFFFAOYSA-N aniline;trimethoxy(methyl)silane Chemical compound NC1=CC=CC=C1.CO[Si](C)(OC)OC KRJRKEPWQOASJN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241001330498 Corsia Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YFBFAHMPVMWKIM-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)cyclohexanamine Chemical compound CCO[Si](OCC)(OCC)CCCNC1CCCCC1 YFBFAHMPVMWKIM-UHFFFAOYSA-N 0.000 description 1
- DTPZJXALAREFEY-UHFFFAOYSA-N n-methyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNC DTPZJXALAREFEY-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003707 silyl modified polymer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 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 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention belongs to the technical field of silane modified resin, and particularly relates to silane modified polyurethane resin and a preparation method and application thereof. The preparation method comprises the following technical steps of firstly, adopting a polyol polymer A to react with isocyanate to synthesize an NCO-terminated prepolymer, and adopting reduced pressure distillation to remove unreacted NCO monomer to obtain a polyurethane prepolymer with low free monomer; introducing a polyol polymer B and/or a polyol polymer C to continue the reaction to obtain an NCO-terminated prepolymer containing a block structure, and removing most of residual NCO monomers after the reaction in the first step, so that the polyurethane prepolymer containing the block structure obtained in the reaction in the second step has narrow molecular weight distribution, stronger structural controllability and improved structural stability; and thirdly, adding siloxane which can react with NCO groups and contains active hydrogen, wherein NCO/active hydrogen is 1:1.2 to 1.5, and excess siloxane is used for ensuring that NCO is completely or nearly completely reacted, so that the silane modified polyurethane resin with high stability is finally obtained.
Description
Technical Field
The invention belongs to the technical field of silane modified resin, and particularly relates to silane modified polyurethane resin and a preparation method and application thereof.
Background
The silane modified polyurethane is a new polyurethane material. Compared with the traditional polyurethane material, the polyurethane material also has the main chain structure of polyether and carbamate, has the characteristics of high strength, impact resistance, tear resistance and the like, and is different in that the end group functional group is hydrolyzable siloxane, so that the polyurethane material avoids the problem of bubbles caused by the reaction of isocyanate groups (NCO groups) and water while being moisture-curable; in addition, due to the introduction of the low-polarity high-bond-energy organic silicon chain segment, the silane modified polyurethane has excellent adhesive force to various base materials, and is very suitable for being applied to the field of single-component moisture-cured adhesives and sealants.
At present, the preparation methods of silane modified polyurethane resin reported by domestic and foreign documents mainly comprise two methods: one is to react polyether polyol with a certain amount of isocyanate monomer to prepare NCO-terminated prepolymer, and then carry out end-capping modification on the prepolymer by amino or mercaptosilane containing active hydrogen; the other method is to react polyether polyol with a certain amount of isocyanate to prepare an OH end-capping prepolymer, and then carry out end-capping modification on the OH end-capping prepolymer by using silane containing NCO, or directly carry out end-capping modification on NCO silane and large molecular weight polyether polyol.
For example, U.S. Pat. No. 4,925,925 discloses a method for preparing a silane-modified polyurethane resin by reacting an aminosiloxane with an NCO-terminated polyurethane prepolymer, but the silane-modified polyurethane prepared by this method is not suitable for practical use because of its broad molecular weight distribution, high viscosity, large amount of free isocyanate monomer, and poor storage stability due to the random copolymerization.
Patent document CN1229804A discloses another method for preparing silane-modified polyurethane resin by reacting NCO-containing silane with hydroxyl-terminated polyurethane prepolymer, but the silane-modified polyurethane resin prepared by this method has poor structure controllability, the control of molecular weight depends on the hydroxyl-terminated prepolymer obtained by chain extension reaction of polyether polyol with large molecular weight and isocyanate, the mechanical properties of the resin are limited, and it is difficult to obtain resin with high strength, high modulus and high elongation. In addition, the isocyanate monomer introduced in the first reaction step and the NCO-containing silane introduced in the second reaction step are hardly completely consumed, and the residual NCO-containing monomer has a great influence on the storage stability of the resin.
Patent document CN11214295A discloses a method for preparing high-stability silane-terminated polymer resin, which introduces small-molecule diol diamine to make the hydroxyl-terminated prepolymer react more thoroughly to improve the resin stability, but the second step reaction also generates free silane monomer containing NCO, which cannot really solve the problem of resin storage stability, and the introduction of small-molecule diol and diamine affects the mechanical properties of the resin.
Patent document CN102015811A discloses a method for preparing silanized polyether block polyurethane, which comprises synthesizing polyether polyol with ABA block structure, and reacting with NCO-containing siloxane to obtain silanized polyurethane with ABA block structure, but the silanized polyurethane prepared by the method has low hard segment content and low resin modulus, and is difficult to obtain high-strength and high-modulus resin.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of wide molecular weight distribution, high viscosity, poor structure controllability, poor storage stability, low resin modulus, poor mechanical property and the like of the silane-modified polyurethane resin in the prior art, thereby providing the silane-modified polyurethane resin and the preparation method and the application thereof.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of silane modified polyurethane resin, which comprises the following steps:
s1, reacting a polyol polymer A with isocyanate until the concentration of NCO groups is not reduced, and removing unreacted isocyanate monomers to obtain an NCO-terminated polyurethane prepolymer;
s2, reacting the obtained NCO-terminated polyurethane prepolymer with a polyol polymer B to obtain an NCO-terminated polyurethane prepolymer with an ABA-block structure;
optionally, reacting the obtained NCO-terminated polyurethane prepolymer with ABA-block structure with a polyol polymer C to obtain an NCO-terminated polyurethane prepolymer with ABACABA-block structure;
s3, reacting the obtained NCO-terminated polyurethane prepolymer with ABA-block structure or ABACABA-block structure with NCO-terminated polyurethane prepolymer with active hydrogen to obtain the silane modified polyurethane resin with ABA-block structure or ABACABA-block structure.
Optionally, in the step S1, unreacted isocyanate monomer is removed by reduced pressure distillation;
optionally, the reduced pressure distillation temperature is 150-200 ℃, and the pressure is 0.1-100Pa.
Optionally, the molar ratio of NCO groups in the isocyanate to OH groups in the polyol polymer in step S1 is 3.5 to 5:1;
optionally, the reaction temperature is 70-90 ℃, and the reaction time is 3-5h;
optionally, the catalyst also comprises 0.01-0.02% of catalyst by total mass of reactant raw materials, and the catalyst is an organic zinc metal catalyst.
Specifically, in the step S1, the polyol polymer A is dehydrated for 2 to 4 hours in vacuum at the temperature of between 105 and 120 ℃, and the water content is controlled within 200ppm for standby application; under the protection of nitrogen atmosphere, firstly adding an isocyanate monomer into a reaction container, stirring and preheating to a reaction temperature, and then slowly dropwise adding the dehydrated polyol polymer A into the reaction container for 1-2h; the NCO/OH molar ratio is preferably 3.5-5/1; the reaction temperature is preferably 70-90 ℃; the catalyst is preferably an organic zinc metal catalyst, and the using amount is preferably 0.01-0.02%; the reaction time is preferably 3 to 5 hours.
In the step (1), when NCO does not decrease any more, the obtained NCO-terminated prepolymer enters a film evaporation device at a feeding speed of 0.5-10 g/min, and the temperature is preferably 150-200 ℃; the pressure is preferably 0.1 to 100Pa; after reduced pressure distillation, the separated isocyanate monomer can be recycled, and the NCO-terminated polyurethane prepolymer containing low free monomer is finally prepared, wherein the content of the free isocyanate monomer is lower than 0.2 percent.
Optionally, in step S2, the NCO/OH molar ratio of the NCO-terminated polyurethane prepolymer to the polyol polymer B, in terms of the molar ratio of NCO groups to OH groups, is 2.2 to 2.5:1;
the molar ratio of NCO group to OH group is that NCO/OH molar ratio of NCO end capping polyurethane prepolymer with ABA-block structure to polyol polymer C is 2.2-2.5:1.
optionally, the reaction temperature is 70-90 ℃, and the reaction time is 3-5h;
optionally, the catalyst also comprises 0.01-0.02% of catalyst calculated by the total mass of the reactant raw materials, and the catalyst is an organic zinc metal catalyst.
Specifically, in the step S2, the polyol polymer B is dehydrated for 2 to 4 hours in vacuum at the temperature of between 105 and 120 ℃, and the water content is controlled within 200ppm for standby application; under the protection of nitrogen atmosphere, firstly adding the NCO-terminated polyurethane prepolymer of the low free monomer obtained in the step S1 into a reaction container, stirring and preheating to a reaction temperature, and then slowly dropwise adding the dehydrated polyol polymer B into the reaction container for 1-2 hours; the NCO/OH molar ratio is preferably 2.2-2.5/1; the reaction temperature is preferably 70-90 ℃; the catalyst is preferably an organic zinc metal catalyst, and the using amount is preferably 0.01-0.02%; the reaction time is preferably 3 to 4 hours; after the reaction is finished, NCO end-capped polyurethane prepolymer with different soft segment ABA-block structures is obtained.
In the step S2, the polyol polymer C is dehydrated for 2 to 4 hours in vacuum at the temperature of between 105 and 120 ℃, and the water content is controlled within 200ppm for standby; under the protection of nitrogen atmosphere, firstly adding the NCO end-capped polyurethane prepolymer with different soft segment-ABA-block structures obtained in the step (2) into a reaction container, stirring and preheating to a reaction temperature, and then slowly dropwise adding the dehydrated polyol polymer C into the reaction container for 1-2 hours; the NCO/OH molar ratio is preferably 2.2-2.5/1; the reaction temperature is preferably 70-90 ℃; the catalyst is preferably an organic zinc metal catalyst, and the using amount is preferably 0.01-0.02%; the reaction time is preferably 3 to 4 hours; after the reaction is finished, NCO end-capped polyurethane prepolymer with different soft segment-ABACABA-block structures is obtained.
Optionally, in step S3, in terms of a molar ratio of an NCO group to active hydrogen of siloxane, the ratio of the NCO-terminated polyurethane prepolymer having an ABA-block structure or the NCO-terminated polyurethane prepolymer having an abaacaba-block structure to the siloxane having active hydrogen is 1:1.2-1.5;
optionally, the reaction temperature is 70-90 ℃, and the reaction time is 1-2h;
optionally, the catalyst also comprises 0.1-0.2% of catalyst by total mass of reactant raw materials, and the catalyst is an organic zinc metal catalyst.
Specifically, in the step (3), the NCO-terminated polyurethane prepolymer with different soft segment-ABA-or-ABACABA-block structures obtained in the step (2) reacts with siloxane containing active hydrogen, and the preferable dosage of silane is that the NCO/siloxane molar ratio is 1/1.2-1.5; the reaction temperature is preferably 70-90 ℃; the reaction time is preferably 1 to 2 hours; finally obtaining the silane terminated polyurethane resin with ABA-or ABACABA-block structure.
Optionally, the polyol polymer a, the polyol polymer B and the polyol polymer C are independently at least one selected from polyether polyol, polyester polyol, polycarbonate polyol and polytetrahydrofuran polyol;
optionally, the molecular weight of the polyol polymer A, the polyol polymer B and the polyol polymer C is 1000-30000g/mol; further alternatively, the molecular weight is 4000-20000g/mol;
optionally, the polyol polymer A, the polyol polymer B and the polyol polymer C are dehydrated before use, and the water content is controlled to be below 200 ppm;
optionally, vacuum dehydration is carried out at 105-120 deg.C for 2-4h.
Optionally, the isocyanate has a functionality of 2 and above;
optionally, the isocyanate is one or more selected from aliphatic polyisocyanate and derivatives thereof, alicyclic polyisocyanate and derivatives thereof, aromatic polyisocyanate and derivatives thereof, and araliphatic polyisocyanate and derivatives thereof.
Preferably, the isocyanate is one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 1, 5-naphthyl diisocyanate and diisocyanate derivatives containing urethane thereof; more preferred is one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.
The siloxane containing active hydrogen is selected from one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N-methyl-gamma-aminopropyltrimethoxysilane, N-methyl-gamma-aminopropylmethyldimethoxysilane, N-methyl-gamma-aminopropyltriethoxysilane, N- (N-butyl) -gamma-aminopropyltrimethoxysilane, N- (N-butyl) -gamma-aminopropylmethyldimethoxysilane, N- (N-butyl) -gamma-aminopropyltriethoxysilane, N- (cyclohexyl) -gamma-aminopropyltrimethoxysilane, N- (cyclohexyl) -gamma-aminopropylmethyldimethoxysilane, N- (cyclohexyl) -gamma-aminopropyltriethoxysilane, aniline methyltrimethoxysilane and aniline methyltrimethoxysilane, more preferably from one or more of N-methyl-gamma-aminopropyltrimethoxysilane, N- (N-butyl) -gamma-aminopropyltrimethoxysilane and N- (cyclohexyl) -gamma-aminopropyltrimethoxysilane. More preferably gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, N-methyl-gamma-aminopropyltrimethoxysilane, N-methyl-gamma-aminopropylmethyldimethoxysilane, N- (N-butyl) -gamma-aminopropyltrimethoxysilane, N- (N-butyl) -gamma-aminopropylmethyldimethoxysilane, N- (cyclohexyl) -gamma-aminopropyltrimethoxysilane, N- (cyclohexyl) -gamma-aminopropylmethyldimethoxysilane or more.
The invention also provides the silane modified polyurethane resin prepared by the preparation method.
The invention also provides application of the silane modified polyurethane resin in adhesives, sealants and coatings.
The silane modified polyurethane resin is applied to a coating, and can improve the adhesion and the resistance of the coating.
The technical scheme of the invention has the following advantages:
the preparation method of the silane modified polyurethane resin provided by the invention comprises the following steps of firstly, adopting a polyol polymer A to react with isocyanate to synthesize an NCO end-capping prepolymer, and adopting reduced pressure distillation to remove unreacted NCO monomers to obtain a polyurethane prepolymer with low free monomers; introducing a polyol polymer B and/or a polyol polymer C to continue reacting to obtain an NCO-terminated prepolymer containing a block structure, and removing most of residual NCO monomers after the first-step reaction, so that the block-structure polyurethane prepolymer obtained in the second-step reaction has narrow molecular weight distribution, stronger structural controllability and improved structural stability; and step three, adding siloxane containing active hydrogen and capable of reacting with NCO groups, wherein NCO/active hydrogen is 1:1.2 to 1.5, and excess siloxane is used for ensuring that NCO is completely or nearly completely reacted, so that the silane modified polyurethane resin with high stability is finally obtained. The invention adopts chain extension step by step to prepare the silane modified polyurethane prepolymer with ABA-or ABACABA-block structure, the molecular weight distribution is narrowed, the structure controllability is enhanced, and more excellent mechanical properties can be obtained.
The silane modified polyurethane resin prepared by the method provided by the invention contains extremely low free isocyanate monomer, reduces the viscosity increase caused by the reaction of the free isocyanate monomer and water to form a large number of urea bonds and hydrogen bonds in the storage process, and improves the storage stability of the resin.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
To facilitate comparison between the data, the sources of the starting materials used in the following examples and comparative examples of the invention are as follows:
1. polyether polyol having a molecular weight of 4000 and a functionality of 2, available from Corsia under the designation
4200；
2. Polyether polyol, molecular weight 8000, functionality 2, available from Corsai, under the designation
8200N；
3. Polyether polyol having a molecular weight of 12000 and a functionality of 2, available from Corcission under the designation
12200N；
4. Polyester polyol, molecular weight 40000, functionality 2, available from watson chemical, under the designation CMA-4044;
5. polycarbonate polyol, molecular weight 4000, functionality 2, available from Tosoh, japan under the designation N-963;
6. isocyanate MDI, IPDI, HDI, available from Vanhua Chemicals, product designations respectively
MDI-100，
IPDI，
HDI；
7. Gamma-aminopropyltrimethoxysilane, available from mai-gao-nova materials group ltd;
8. gamma-aminopropylmethyldimethoxysilane, available from advanced materials group of michael, incorporated by reference;
9. gamma-aminopropyltriethoxysilane available from mai-shoji high and new materials group ltd;
10. gamma-isocyanatopropyltrimethoxysilane, available from mai shoji advanced materials group ltd, under the designation a-link35;
11. an organozinc metal catalyst available from advanced chemicals in the United states under the designation Bicat 3228.
Example 1
The embodiment provides a silane modified polyurethane resin, which is prepared by the following steps:
polyether polyols
4200 Vacuum dehydrating at 105 deg.C for 3h, and measuring water content of polyether polyol with moisture meter to 170 ppm; 177.6g of IPDI are added into a reaction flask, nitrogen is introduced for protection, the mixture is preheated to 80 ℃ while stirring, 800g of dehydrated IPDI is taken
4200, slowly dropping into a reaction bottle containing IPDI for 1.5h, adding 0.15g of catalyst Bicat3228 after dropping, reacting for 4h at 80 ℃, cooling to room temperature when determining that the NCO content is not reduced, and obtaining the NCO-terminated prepolymer. And (3) allowing the obtained prepolymer to pass through a film evaporation device at a feeding speed of 5g/min, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO end-capped polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.12%.
Polyether polyols
8200N,105 deg.C, vacuum dehydrating for 3 hr, and measuring water content of polyether polyol to 150ppm with moisture analyzer; 500g of NCO end-capping polyurethane prepolymer with low free monomer obtained in the step is added into the mixtureIntroducing nitrogen into a bottle, stirring while preheating to 80 deg.C, and collecting 391.3g of dehydrated product
8200N, slowly dropping into a reaction bottle for 1h, adding 0.09g of catalyst Bicat3228 after the dropping is finished, reacting for 4h at 80 ℃, adding 29.6g of gamma-aminopropyl trimethoxy silane when the NCO content is not reduced, continuously reacting for 1.5h at 80 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was measured to be 29800cps, and the molecular weight distribution was 1.31 as determined by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Example 2
The embodiment provides a silane modified polyurethane resin, which is prepared by the following steps:
polyether polyols
4200 Dehydrating at 105 ℃ for 3 hours in vacuum, and measuring the water content of the polyether polyol by a moisture meter to be 180ppm for later use; adding 155.4g of IPDI into a reaction bottle, introducing nitrogen for protection, preheating to 90 ℃ while stirring, and taking 800g of dehydrated IPDI
4200, slowly dropping into a reaction bottle containing IPDI for 1.5h, adding 0.12g of catalyst Bicat3228 after dropping, reacting for 3h at 90 ℃, cooling to room temperature when determining that the NCO content is not reduced, and obtaining the NCO-terminated prepolymer. And (3) passing the obtained prepolymer through a film evaporation device at a feeding speed of 5g/min, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO-terminated polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.11%.
Polyether polyols
12200N,105 deg.C, vacuum dewatering for 3 hr, and measuring the water content of polyether polyol with moisture meter to 140 ppm. Adding 500g of NCO end-capped polyurethane prepolymer of the low free monomer obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 90 ℃ while stirring, and taking 613.7g of dehydrated polyurethane prepolymer
12200N, slowly adding into a reaction bottle in a dropwise manner for 1.5h, adding 0.11g of catalyst Bicat3228 after the dropwise addition is finished, reacting for 3h at 90 ℃, adding 26.4g of gamma-aminopropyl trimethoxy silane when determining that the NCO content is not reduced, continuing to react for 1h at 90 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was measured to be 33200cps and the molecular weight distribution was 1.29 by GPC.
The silane modified polyurethane prepared above is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of 23 ℃ and 50% humidity under the standard curing condition, and the mechanical property of the glue film is tested.
Example 3
The embodiment provides a silane-modified polyurethane resin, which is prepared by the following steps:
polyether polyols
8200N,105 ℃, vacuum dehydration for 3 hours, and measuring the water content of the polyether polyol to be 160ppm by a moisture meter for later use; adding 84g of HDI into a reaction bottle, introducing nitrogen for protection, preheating to 70 ℃ while stirring, and taking 800g of dehydrated HDI
8200N, slowly adding the mixture into a reaction bottle containing HDI in a dropwise manner for 1.5h, adding 0.16g of a catalyst Bicat3228 after the dropwise addition is finished, reacting for 5h at 70 ℃, and cooling to room temperature when the NCO content is not reduced during determination to obtain an NCO end-capping prepolymer. The obtained prepolymer is fed at a feeding speed of 5g/minAnd (3) passing through a film evaporation device, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO end-capped polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.12%.
Polyether polyols
12200N,105 deg.C, vacuum dewatering for 3 hr, and measuring water content of polyether polyol with moisture meter to 150 ppm. Adding 500g of NCO end-capped polyurethane prepolymer of the low free monomer obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 70 ℃ while stirring, and taking 287.9g of dehydrated polyurethane prepolymer
12200N, slowly adding into a reaction bottle, wherein the adding time is 1.5h, adding 0.08g of catalyst Bicat3228 after adding, reacting for 5h at 70 ℃, adding 17.6g of gamma-aminopropyl methyl dimethoxysilane when determining that the NCO content is not reduced, continuing to react for 2h at 70 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was measured to be 39200cps and the molecular weight distribution was 1.27 by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Example 4
The embodiment provides a silane modified polyurethane resin, which is prepared by the following steps:
carrying out vacuum dehydration on polycarbonate polyol N-963 at 105 ℃ for 3h, and measuring the water content of polyether polyol to be 170ppm by using a moisture analyzer for later use; 177.6g of IPDI is added into a reaction bottle, nitrogen is introduced for protection, the reaction bottle is preheated to 80 ℃ while stirring, 800g of dehydrated polycarbonate polyol PCDL is slowly dripped into the reaction bottle containing IPDI, the dripping time is 1.5h, 0.15g of catalyst Bicat3228 is added after the dripping is finished, the reaction is carried out for 4h at the temperature of 80 ℃, and when the NCO content is determined not to be reduced, the temperature is reduced and cooled to the room temperature, so that the NCO-terminated prepolymer is obtained. And (3) passing the obtained prepolymer through a film evaporation device at a feeding speed of 5g/min, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO-terminated polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.13%.
Polyether polyols
8200N,105 deg.C, vacuum dehydrating for 3 hr, and measuring water content of polyether polyol to 150ppm with moisture analyzer; adding 500g of NCO end-capped polyurethane prepolymer of the low free monomer obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 80 ℃ while stirring, and taking 391.3g of dehydrated polyurethane prepolymer
8200N, slowly dropping into a reaction bottle for 1.5h, adding 0.09g of catalyst Bicat3228 after the dropping is finished, reacting for 4h at 80 ℃, adding 29.6g of gamma-aminopropyl trimethoxy silane when determining that the NCO content is not reduced, continuously reacting for 1.5h at 80 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was found to be 31400cps and the molecular weight distribution was found to be 1.37 by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Example 5
The embodiment provides a silane modified polyurethane resin, which is prepared by the following steps:
dehydrating the polyester polyol CMA-4044 at 105 ℃ for 3h in vacuum, and measuring the water content of the polyester polyol to be 170ppm by using a moisture meter for later use; adding 200g of MDI into a reaction bottle, introducing nitrogen for protection, preheating to 80 ℃ while stirring, slowly dropwise adding 800g of dehydrated CMA-4044 into the reaction bottle containing the MDI for 1.5h, adding 0.12g of catalyst Bicat3228 after dropwise adding, reacting for 4h at 80 ℃, and cooling to room temperature when determining that the NCO content is not reduced to obtain the NCO end-capped prepolymer. And (3) passing the obtained prepolymer through a film evaporation device at a feeding speed of 5g/min, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO-terminated polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.12%.
Polyether polyols
8200N,105 ℃, vacuum dehydration for 3 hours, and measuring the water content of the polyether polyol to be 150ppm by a moisture meter for later use; adding 500g of the NCO end-capped polyurethane prepolymer with low free monomer obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 80 ℃ while stirring, and taking 386.5g of dehydrated polyurethane prepolymer
8200N, slowly dropping into a reaction bottle for 1.5h, adding 0.10g of catalyst Bicat3228 after the dropping is finished, reacting for 4h at 80 ℃, adding 29.2g of gamma-aminopropyl trimethoxy silane when determining that the NCO content is not reduced, continuously reacting for 1.5h at 80 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was found to be 30500cps, and the molecular weight distribution was found to be 1.26 by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Example 6
The embodiment provides a silane-modified polyurethane resin, which is prepared by the following steps:
carrying out vacuum dehydration on polyether carbonate polyol N-963 at 105 ℃ for 3h, and measuring the water content of the polyether polyol to be 150ppm by using a moisture analyzer for later use; adding 200g of MDI into a reaction bottle, introducing nitrogen for protection, preheating to 90 ℃ while stirring, taking 400g of dehydrated polyether carbonate polyol PCDL, slowly dripping into the reaction bottle containing the MDI for 1.5h, adding 0.06g of catalyst Bicat3228 after dripping is finished, reacting for 4h at 90 ℃, and cooling to room temperature when the NCO content is not reduced, thus obtaining the NCO end capping prepolymer. And (3) passing the obtained prepolymer through a film evaporation device at a feeding speed of 5g/min, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO-terminated polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.13%.
Polyether polyols
4200 Vacuum dehydrating at 105 deg.C for 3h, and measuring water content of polyether polyol with moisture meter to 160 ppm; adding 500g of NCO end-capped polyurethane prepolymer of the low free monomer obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 90 ℃ while stirring, and taking 347.8g of dehydrated polyurethane prepolymer
4200, slowly dripping into a reaction bottle for 1.5h, adding 0.09g of catalyst Bicat3228 after dripping, reacting for 4h at 90 ℃, and obtaining the NCO-terminated polyurethane prepolymer containing ABA-block structure without NCO content reduction.
Polyether polyols
8200N,105 deg.C, vacuum dehydrating for 3 hr, and measuring water content of polyether polyol to 150ppm with moisture analyzer; adding 500g of NCO end-capped polyurethane prepolymer containing ABA-block structure obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 90 ℃ while stirring, and taking 96.6g of dehydrated polyurethane prepolymer
8200N, slowly dripping into a reaction bottle for 1.5h, adding 0.06g of Bicat3228 as a catalyst after dripping is finished, reacting for 4h at 90 ℃ when the NCO content is not reduced, adding 7.31g of gamma-aminopropyl trimethoxysilane, continuously reacting for 1.5h at 90 ℃, discharging after the reaction is finished, and obtaining the silane modified product containing ABACAB-block structureA polyurethane resin.
The resin viscosity was measured to be 41500cps and the molecular weight distribution was 1.36 as determined by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Comparative example 1
The comparative example provides a silane-modified polyurethane resin, which is prepared by the following steps:
polyether polyols
4200 Vacuum dehydrating at 105 deg.C for 3h, and measuring water content of polyether polyol with moisture meter to 170 ppm; polyether polyols
8200N,105 ℃, vacuum dehydration for 3 hours, and measuring the water content of the polyether polyol to be 160ppm by a moisture meter for later use; adding 89.1g of IPDI into a reaction bottle, introducing nitrogen for protection, preheating to 80 ℃ while stirring, and taking 400g of dehydrated IPDI
4200 and 400g dewatered
8200N, stirring uniformly, adding 0.08g of catalyst Bicat3228, reacting at 80 ℃ for 4 hours, when the NCO content is not reduced, adding 69.81g of gamma-aminopropyl trimethoxy silane, continuing to react at 80 ℃ for 1.5 hours, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was measured to be 61400cps, and the molecular weight distribution was 2.55 by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Comparative example 2
The comparative example provides a silane-modified polyurethane resin, which is prepared by the following steps:
polyether polyols
8200N,105 deg.C, vacuum dehydrating for 3 hr, and measuring water content of polyether polyol to 180ppm with moisture analyzer; adding 11.1g IPDI into a reaction bottle, introducing nitrogen gas for protection, preheating to 80 deg.C while stirring, and collecting 400g dehydrated IPDI
8200N is added into a reaction bottle, after the mixture is uniformly stirred, 0.08g of Bicat3228 catalyst is added, the mixture reacts for 4 hours at 80 ℃, when the NCO content is determined not to be reduced, 13.3g of gamma-isocyanate propyl trimethoxy silane is added, the reaction continues for 1.5 hours at 80 ℃, and after the reaction is finished, the mixture is discharged, so that the silane modified polyurethane resin is obtained. The viscosity of the test resin was 48500cps and the molecular weight distribution was 1.97 by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Comparative example 3
The comparative example provides a silane-modified polyurethane resin, which is prepared by the following steps:
polyether polyols
4200 Vacuum dehydrating at 105 deg.C for 3h, and measuring water content of polyether polyol with moisture meter to 170 ppm; 177.6g of IPDI are added into a reaction flask, nitrogen is introduced into the reaction flask, the reaction flask is preheated to 80 ℃ while stirring, and 800g of dehydrated IPDI is taken
4200, slowly dripping into a reaction bottle containing IPDI for 1.5h, adding 0.15g of Bicat3228 catalyst after finishing dripping, reacting for 4h at 80 ℃, cooling to room temperature when determining that NCO content is not reduced, and obtaining NCO end capping prepolymer.
Polyether polyols
8200N,105 ℃, vacuum dehydration for 3 hours, and measuring the water content of the polyether polyol to be 150ppm by a moisture meter for later use; adding 500g of NCO-terminated polyurethane prepolymer obtained in the step into a reaction bottle, introducing nitrogen for protection, preheating to 80 ℃ while stirring, and taking 391.3g of dehydrated polyurethane prepolymer
8200N, slowly dropping into a reaction bottle for 1.5h, adding 0.09g of catalyst Bicat3228 after the dropping is finished, reacting for 4h at 80 ℃, adding 29.6g of gamma-aminopropyl trimethoxy silane when determining that the NCO content is not reduced, continuously reacting for 1.5h at 80 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was found to be 48300cps, with a molecular weight distribution of 2.21 as determined by GPC.
The prepared silane modified polyurethane is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of the standard curing condition of 23 ℃ and the humidity of 50 percent, and the mechanical property of the glue film is tested.
Comparative example 4
The comparative example provides a silane-modified polyurethane resin, which is prepared by the following steps:
polyether polyols
4200 Vacuum dehydrating at 105 deg.C for 3h, and measuring water content of polyether polyol with moisture meter to 170 ppm; polyether polyols
8200N,105 ℃, vacuum dehydration for 3 hours, and measuring the water content of the polyether polyol to be 150ppm by a moisture meter for later use; 177.6g of IPDI are added into a reaction flask, nitrogen is introduced for protection, the mixture is preheated to 80 ℃ while stirring, 800g of dehydrated IPDI is taken
4200 391.3g for removingAfter water treatment
8200N, slowly adding the solution dropwise into a reaction bottle containing IPDI for 1.5h, adding 0.1g of a catalyst Bicat3228 after the dropwise adding is finished, reacting for 4h at 80 ℃, and cooling to room temperature when the NCO content is not reduced, thereby obtaining the NCO end-capping prepolymer. And (3) passing the obtained prepolymer through a film evaporation device at a feeding speed of 5g/min, setting the distillation temperature to be 180 ℃ and the pressure to be 100Pa, separating the NCO-terminated polyurethane prepolymer with low free monomer after the prepolymer completely passes through, and measuring the content of the free isocyanate monomer to be 0.14%. Adding 29.6g of gamma-aminopropyl trimethoxy silane, continuing to react for 1.5h at 80 ℃, and discharging after the reaction is finished to obtain the silane modified polyurethane resin.
The resin viscosity was found to be 49700cps, molecular weight distribution was found to be 2.78 by GPC.
The silane modified polyurethane prepared above is cast into a glue film with the thickness of 2mm, the glue film is cured for 14 days under the conditions of 23 ℃ and 50% humidity under the standard curing condition, and the mechanical property of the glue film is tested.
Performance testing
1. And (3) viscosity testing: measured at 25 ℃ using a Brookfield model DT-RV rotary viscometer according to DN 53019.
2. GPC measurement: shimadzu LC-20AD gel chromatograph GPC, refractive index detector, column temperature 30 deg.C, mobile phase is tetrahydrofuran (1 mL/min), and polystyrene is used as standard sample.
3. NCO test: the percentage NCO is determined by titration with 0.5mol/L hydrochloric acid after reaction with di-n-butylamine, according to the industry standard.
4. And (3) testing mechanical properties: reference is made to GB/T528-2009.
5. And (3) weather resistance test: the cured sealant sample was placed in an 85% RH humidity environment at 85 ℃ for 168 hours, and the mechanical property change was tested.
The specific test results are shown in the following table:
TABLE 1
Compared with the comparative examples 1 and 2, the molecular weight distribution of the resin is narrowed, the viscosity is relatively low, and the storage stability of the resin viscosity is obviously improved; compared with the comparative example 1, the silane modified polyurethane resin in the embodiment 1 adopts the same raw materials, but has higher elongation at break, better elasticity and more excellent mechanical property, and the ABA-block structure is-ABA-block structure; compared with the comparative example 3, the polymer obtained by adopting the same raw materials in the example 1 has wider molecular weight distribution and obviously poor viscosity storage stability, but the residual NCO monomer is not removed in the comparative example 3, and the mechanical property, the strength and the elongation at break of the resin are reduced; compared with the comparative example 4, the raw materials of the example 1 are the same, but the comparative example 4 adopts a one-step chain extension method, so that the molecular weight distribution is wide, the viscosity storage stability of the resin is reduced, and the strength and the elongation at break of the resin are also reduced. Compared with the comparative examples 1 and 2, the ABACABA-block structure introduces the polycarbonate functional chain segment, so that the resin has ultrahigh strength, and meanwhile, the weather resistance is greatly improved, and the resin can be applied to adhesives with high strength and high weather resistance requirements. The silane modified polyurethane resin prepared by the method disclosed by the invention not only has excellent viscosity storage stability, but also has strong structure controllability and excellent resin mechanical properties, and can be widely applied to the fields of adhesives and sealants or coatings.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of silane modified polyurethane resin is characterized by comprising the following steps:
s1, reacting a polyol polymer A with isocyanate until the concentration of NCO groups is not reduced, and removing unreacted isocyanate to obtain an NCO-terminated polyurethane prepolymer;
s2, reacting the obtained NCO-terminated polyurethane prepolymer with a polyol polymer B to obtain an NCO-terminated polyurethane prepolymer with an ABA-block structure;
optionally, reacting the obtained NCO-terminated polyurethane prepolymer with ABA-block structure with a polyol polymer C to obtain an NCO-terminated polyurethane prepolymer with ABACABA-block structure;
s3, reacting the obtained NCO-terminated polyurethane prepolymer with ABA-block structure or ABACABA-block structure with NCO-terminated polyurethane prepolymer with active hydrogen to obtain the silane modified polyurethane resin with ABA-block structure or ABACABA-block structure.
2. The method for preparing the silane-modified polyurethane resin according to claim 1, wherein in the step S1, unreacted isocyanate is removed by reduced pressure distillation;
optionally, the reduced pressure distillation temperature is 150-200 ℃, and the pressure is 0.1-100Pa.
3. The method for producing the silane-modified polyurethane resin according to claim 1, wherein the molar ratio of NCO groups in the isocyanate to OH groups in the polyol polymer in step S1 is 3.5 to 5:1;
optionally, the reaction temperature is 70-90 ℃, and the reaction time is 3-5h;
optionally, the catalyst also comprises 0.01-0.02% of catalyst calculated by the total mass of the reactant raw materials, and the catalyst is an organic zinc metal catalyst.
4. The method for preparing the silane-modified polyurethane resin according to claim 1, wherein in the step S2, the molar ratio of NCO groups to OH groups between the NCO-terminated polyurethane prepolymer and the polyol polymer B is 2.2 to 2.5:1;
the molar ratio of NCO group to OH group is 2.2-2.5, wherein the NCO/OH molar ratio of NCO-terminated polyurethane prepolymer with ABA-block structure to polyol polymer C is: 1.
5. the method for preparing the silane-modified polyurethane resin according to claim 4, wherein the reaction temperature is 70 to 90 ℃ and the reaction time is 3 to 5 hours;
optionally, the catalyst also comprises 0.01-0.02% of catalyst calculated by the total mass of the reactant raw materials, and the catalyst is an organic zinc metal catalyst.
6. The method for preparing the silane-modified polyurethane resin according to claim 1, wherein in the step S3, the molar ratio of NCO content in the NCO-terminated polyurethane prepolymer having an ABA-block structure or the NCO-terminated polyurethane prepolymer having an abaacaba-block structure to the amount of the active hydrogen-containing siloxane is 1:1.2-1.5;
optionally, the reaction temperature is 70-90 ℃, and the reaction time is 1-2h;
optionally, the catalyst also comprises 0.01-0.02% of catalyst calculated by the total mass of the reactant raw materials, and the catalyst is an organic zinc metal catalyst.
7. The method for producing the silane-modified polyurethane resin according to any one of claims 1 to 6, wherein the polyol polymer A, the polyol polymer B and the polyol polymer C are independently at least one selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol and polytetrahydrofuran polyol;
optionally, the molecular weight of the polyol polymer A, the polyol polymer B and the polyol polymer C is 1000-30000g/mol; further alternatively, the molecular weight is 4000-20000g/mol;
optionally, the polyol polymer A, the polyol polymer B and the polyol polymer C are dehydrated before use, and the water content is controlled to be below 200 ppm;
optionally, vacuum dehydration is carried out at 105-120 deg.C for 2-4h.
8. The method for producing the silane-modified polyurethane resin according to claim 7, wherein the isocyanate has a functionality of 2 or more;
optionally, the isocyanate is one or more selected from aliphatic polyisocyanate and derivatives thereof, alicyclic polyisocyanate and derivatives thereof, aromatic polyisocyanate and derivatives thereof, and araliphatic polyisocyanate and derivatives thereof.
9. A silane-modified polyurethane resin prepared by the preparation method of any one of claims 1 to 8.
10. Use of the silane-modified polyurethane resin of claim 9 in adhesives, sealants and coatings.
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