CN111393657B - Preparation method of organic silicon modified polyurethane - Google Patents
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- CN111393657B CN111393657B CN201910834828.XA CN201910834828A CN111393657B CN 111393657 B CN111393657 B CN 111393657B CN 201910834828 A CN201910834828 A CN 201910834828A CN 111393657 B CN111393657 B CN 111393657B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 41
- 239000010703 silicon Substances 0.000 title claims abstract description 41
- 229920000570 polyether Polymers 0.000 claims abstract description 72
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 71
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 56
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 36
- 229920001400 block copolymer Polymers 0.000 claims abstract description 30
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 239000007810 chemical reaction solvent Substances 0.000 claims description 17
- -1 coatings Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical group 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 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 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 5
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- IXQYZUOOHQWOQL-UHFFFAOYSA-N potassium;methanol;methanolate Chemical compound [K+].OC.[O-]C IXQYZUOOHQWOQL-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000004754 hydrosilicons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052990 silicon hydride Inorganic materials 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of organic silicon, and aims to solve the problems existing in the existing synthesis of hyperbranched polyurethane, and provides a preparation method of organic silicon modified polyurethane, which takes hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer and hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer as raw materials to react with polytetrahydrofuran, 1, 4-butanediol and diisocyanate to prepare an isocyanate-terminated component A and a hydroxyl-terminated component B, and then uniformly mixes the component A and the component B according to the molar ratio of isocyanate groups to hydroxyl groups of 6: 1-1: 9 to obtain a cured product, wherein the cured product has excellent alkali resistance and salt resistance, good thermal stability and better mechanical property.
Description
Technical Field
The invention relates to the technical field of organic silicon, in particular to a preparation method of organic silicon modified polyurethane.
Technical Field
The polyurethane material is one of the fastest-developing high polymer materials, has the characteristics of wear resistance, tear resistance, good bending resistance and flexibility and the like, can be prepared into products with different properties, and has wide application. The structure of the polyurethane is that the soft segment and the hard segment are formed in a block, graft or interpenetrating network mode. The soft segments are usually polyethers or polyesters, giving the polyurethane flexibility and toughness, and the hard segments are usually condensates of diisocyanates with small molecule diols or diamines, giving the polyurethane strength and rigidity. Materials with different properties can be obtained by adjusting the proportion of soft and hard segments and the structures of different polyols. The hydrophilic group is introduced into the molecular chain of the waterborne polyurethane, so that the water resistance of the waterborne polyurethane product is poorer than the solvent resistance. The organic silicon has good high temperature resistance, thermal aging resistance and hydrophobicity, and the wet and dry adhesive property, adhesive strength, water resistance, durability and tensile strength of the polyurethane can be improved by using the organic silicon modified polyurethane.
The hyperbranched polyurethane has the characteristics of dendritic structure, low viscosity, multifunction, easy film forming property and the like. The hyperbranched polyurethane has the common advantages of polyurethane and hyperbranched polymer, and is widely applied to the fields of coating, adhesive, printing ink and the like. The preparation method of the hyperbranched polyurethane mainly comprises two methods, one is that the hyperbranched polymer with terminal hydroxyl is reacted with isocyanate groups in isocyanate, and the other is that difunctional isocyanate molecules A2 are reacted with trifunctional hydroxyl or amino compound molecules B3. The hyperbranched polyurethane prepared by the two methods has the defect of poor heat resistance, and the application of the hyperbranched polyurethane is limited. In order to overcome the defects, the Chinese patent CN201611040503.7 adopts polyfunctional alkoxy silane to react with polyurethane to obtain organosilicon modified hyperbranched polyurethane with better heat resistance, but in the organosilicon modified polyurethane prepared by the method, only isolated chain segments after alkoxy silane is hydrolyzed are dispersed in polymer molecules, and the organosilicon chain segments are short and low in content, so that the advantage of organosilicon is difficult to fully exert.
Disclosure of Invention
In order to solve the problems existing in the existing synthesis of hyperbranched polyurethane, the invention provides a preparation method of organosilicon modified polyurethane, and the prepared organosilicon modified polyurethane has excellent alkali resistance and salt resistance, good thermal stability and better mechanical property.
The invention is realized by the following technical scheme: the preparation method of the organic silicon modified polyurethane comprises the following steps:
(1) preparing an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound as a component A;
(2) preparing a hydroxyl-terminated hyperbranched organic silicon modified polyurethane compound as a component B;
(3) and then uniformly mixing the component A and the component B according to the molar ratio of isocyanate group to hydroxyl group of 6: 1-1: 9, removing bubbles in vacuum for 15-40 min, and curing at 30-80 ℃ for 1-12 h to obtain a cured substance, namely the organosilicon modified polyurethane.
The organosilicon chain segment in the polyurethane modified by organosilicon is longer and high in content, and the advantages of the organosilicon such as temperature resistance, weather resistance, aging resistance, hydrophobicity and the like can be fully exerted.
The preparation method of the isocyanate group-terminated hyperbranched organic silicon modified polyurethane compound comprises the following steps: hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, polytetrahydrofuran, 1, 4-butanediol and diisocyanate are used as raw materials, and are reacted in a reaction solvent under the action of a catalyst, and then the solvent is removed to obtain an isocyanate-terminated hyperbranched organosilicon modified polyurethane compound;
wherein the mole ratio of the isocyanate group in the diisocyanate to all the hydroxyl groups in the hydroxyl-terminated hyperbranched aliphatic polyether block copolymer, the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol is 1.05: 1-4: 1, and preferably 1.5: 1-3: 1. .
A preparation method of the hydroxyl-terminated hyperbranched organic silicon modified polyurethane compound in the step (2); reacting hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer, polytetrahydrofuran, 1, 4-butanediol and diisocyanate serving as raw materials in a reaction solvent under the action of a catalyst, and then removing the solvent to obtain a hydroxyl-terminated hyperbranched organic silicon modified polyurethane compound;
wherein the mole ratio of all hydroxyl groups in the hydroxyl-terminated hyperbranched aliphatic polyether block copolymer, the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol to the isocyanate groups in the diisocyanate is 1.1: 1-3: 1, and the preferred ratio is 1.5: 1-2: 1.
In the preparation of A and B, although the raw materials are substantially the same, the isocyanate is excessive in the preparation of A, so that the product ends up as an isocyanate group; in the preparation of B, the hydroxyl group is excessive, so that the product ends up as a hydroxyl group. When the isocyanate group A and the hydroxyl group B are mixed at a certain molar ratio, they can be cured by the reaction between the isocyanate group and the hydroxyl group.
The hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer in the steps (1) and (2) accounts for 1-15% of the total mass; the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer accounts for 5-30% of the total mass, the 1, 4-butanediol accounts for 1-8% of the total mass, and the polytetrahydrofuran accounts for the rest mass; preferably, the hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer accounts for 3-10% of the total mass; the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer accounts for 5-20% of the total mass, the 1, 4-butanediol accounts for 3-8% of the total mass, and the polytetrahydrofuran accounts for the rest mass.
The total mass of the hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol is the sum of the mass.
The reaction solvent in the step (1) and the step (2) is one or more selected from tetrahydrofuran, acetone and N-methyl pyrrolidone, preferably, the reaction solvent is one or two selected from tetrahydrofuran and acetone. The solvent consumption in the preparation of the component A and the component B is 20-200%, preferably 50-100% of the total mass of the raw materials of diisocyanate, hydroxyl-terminated hyperbranched aliphatic polyether block copolymer, hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, polytetrahydrofuran and 1, 4-butanediol.
The catalyst in the step (1) and the step (2) is dibutyl tin dilaurate. The usage amount of the catalyst is 0.08-0.5 percent of the total mass of the diisocyanate, the hydroxyl-terminated hyperbranched aliphatic polyether block copolymer, the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol raw materials in the preparation of the component A and the preparation of the component B respectively.
The diisocyanate in the steps (1) and (2) is selected from one or more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate isomer mixture (TDI), diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI), and preferably, the diisocyanate is one or more of TDI, HDI and IPDI.
The reaction conditions in the step (1) and the step (2) are 30-95 ℃ for 1-6 h, preferably, the synthesis reaction temperature is 40-70 ℃, and the reaction time is 2-5 h.
And (3) decompressing to 60-120 ℃/130mmHg in the step (1) and the step (2) to remove the solvent.
Preferably, the preparation method of the hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer comprises the following steps: hydroxyl-terminated hyperbranched aliphatic polyether and n-butyllithium are added according to the molar ratio of hydroxyl to lithium atoms of 1:1, reacting in DMF solution to generate a macroinitiator, then initiating the ring-opening polymerization of hexamethylcyclotrisiloxane, and terminating the reaction by water.
The preparation method of the hydroxyl-terminated hyperbranched aliphatic polyether comprises the following steps: a clean and dry three-neck flask was taken, 134.2g (1.0mol) of trimethylolpropane and 73.5mL of potassium methoxide-methanol solution (1.36mol/L) were added under nitrogen protection, and after 1 hour of reaction at 80 ℃, 1555.7g of glycidol (21.0mol) was added dropwise, and after about 6 hours of addition, the reaction was continued for 6 hours. After the reaction is finished, methanol is added to dissolve the product, 36.5% hydrochloric acid is added dropwise to neutralize the product, and acetone is poured into the product for precipitation. After the purification is repeated for two times, the transparent viscous liquid is obtained after vacuum drying for 24 hours at the temperature of 70 ℃, and the transparent viscous liquid is the hydroxyl-terminated hyperbranched aliphatic polyether. The reaction formula is shown as (I):
preferably, the synthesis method of the hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane comprises the following steps: under the protection of nitrogen, 3.52g of hydroxyl-terminated hyperbranched aliphatic polyether (0.001mol) is placed into a three-neck flask, 5-50 mL of DMSO and 10mL (2.5mol/L of hexane solution) of n-BuLi are stirred at normal temperature for 30-120 min, 1-100 times of hexamethylcyclotrisiloxane in the molar number of hydroxyl (0.024mol) in 3.52g of hydroxyl-terminated hyperbranched aliphatic polyether is added, the mixture is reacted at 90-150 ℃ for 1-8 h, then the temperature is reduced to 30-60 ℃, 0.432g of water is added, the mixture is stirred for 1-2 h and then filtered, the filtrate is decompressed to 150-170 ℃/130mmHg to remove low molecules and residual solvent, and the hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane is obtained. The reaction structural formula is shown as (II):
preferably, the preparation method of the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer comprises the following steps: the hydrogen-containing silicone oil with two ends of silicon hydride and the copolymer of ethylene oxide and propylene oxide with one end of hydroxyl and the other end of allyl are processed byCarrying out hydrosilylation reaction catalyzed by a platinum catalyst for 2-3 h at 80-100 ℃. Wherein the molecular structural formula of the hydrogen-containing silicone oil with silicon hydride at two ends is HMe2SiO(Me2SiO)m(MePhSiO)nSiMe2H, wherein m is an integer of 10-100, n is an integer of 0-50, and n/m is more than or equal to 0 and less than or equal to 0.6. The molecular structural formula of the ethylene oxide and propylene oxide copolymer with one end of hydroxyl and the other end of allyl is CH2＝CHCH2O(CH2CH2O)x(CH2CH3CHO)yH, wherein x is a positive integer of 4-40, y is a positive integer of 0-20, and y/x is more than or equal to 0 and less than or equal to 0.5.
Wherein the platinum catalyst is H2PtCl6Solution of isopropanol of (1), H2PtCl6The platinum concentration of the tetrahydrofuran solution, the platinum complex coordinated by methyl vinyl siloxane and the platinum complex coordinated by diethyl phthalate is 2000-8000 ppm, and the dosage of the platinum complex is 3-50 ppm of the total amount of the hydrogen-containing silicone oil with hydrosilation at two ends and the ethylene oxide and propylene oxide copolymer with hydroxyl at one end and allyl at the other end.
An application of organosilicon modified polyurethane prepared by the preparation method of organosilicon modified polyurethane in solvent-free paint, coating and sealant. According to the invention, hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer and hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer are used as raw materials to react with polytetrahydrofuran, 1, 4-butanediol and diisocyanate to prepare an isocyanate-terminated component A and a hydroxyl-terminated component B, then the component A and the component B are uniformly mixed according to the molar ratio of isocyanate group to hydroxyl group of 6: 1-1: 9, bubbles are removed in vacuum for 15-40 min, and the mixture is cured for 1-12 h at 30-80 ℃ to obtain a cured product. The organic silicon modified polyurethane has longer organic silicon chain segment and high content, can fully exert the advantages of temperature resistance, weather resistance, aging resistance, hydrophobicity and the like of the organic silicon, and a cured product has excellent alkali resistance and salt resistance, good thermal stability and better mechanical property.
Compared with the prior art, the invention has the beneficial effects that:
(1) the organic silicon modified polyurethane has longer organic silicon chain segment and high content, and can fully exert the advantages of temperature resistance, weather resistance, aging resistance, hydrophobicity and the like of the organic silicon;
(2) the condensate has excellent alkali resistance and salt resistance, good thermal stability and better mechanical property.
Drawings
FIG. 1 is a FT-IR spectrum of a hydroxyl terminated hyperbranched aliphatic polyether;
FIG. 2 is the preparation of hydroxyl terminated hyperbranched aliphatic polyether1H NMR spectrum.
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings, in which the starting materials are commercially available or can be prepared by conventional methods.
Test of tensile strength and elongation at break: testing the mechanical property of the composite material by using a universal drawing machine, and testing the tensile property of a sample strip according to the ASTM D-638 standard: standard dumbbell-shaped samples (80.0 mm in length by 12.5mm in width by 4.0mm in thickness) were prepared, subjected to a tensile test at a rate of 1.0mm/min and averaged after measuring at least 5 samples.
And (3) testing thermal stability: the temperature at which 5% of its weight loss on heating was determined by thermogravimetric analysis as the initial decomposition temperature for comparison of the thermal stability of the materials. And (3) testing conditions are as follows: under the protection of nitrogen, the temperature is increased from room temperature to 800 ℃, and the temperature increasing rate is 10 ℃/min.
Acid, alkali and salt resistance test: the specimen 20.0mm in length, 10mm in width and 4.0mm in thickness was immersed in 10 wt% hydrochloric acid, 10 wt% NaOH and 10 wt% NaCl solutions, respectively, for 7 days, and the mass loss was measured.
Preparation example 1:
1. preparation of hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane
(1) Preparation of hydroxyl-terminated hyperbranched aliphatic polyether
A clean dry three-neck flask was taken, 134.2g (1.0mol) of trimethylolpropane and 73.5mL of potassium methoxide-methanol solution (1.36mol/L) were added under nitrogen protection, and after 1 hour of reaction at 80 ℃, 1555.7g of glycidol (21.0mol) was added dropwise, and after about 6 hours of dropwise addition, the reaction was continued for 6 hours. After the reaction is finished, methanol is added to dissolve the product, 36.5% hydrochloric acid is added dropwise to neutralize the product, and acetone is poured into the product for precipitation. After the purification is repeated for two times, the transparent viscous liquid is obtained after vacuum drying for 24 hours at the temperature of 70 ℃, and the transparent viscous liquid is the hydroxyl-terminated hyperbranched aliphatic polyether.
The FT-IR spectrum of the hydroxyl-terminated hyperbranched aliphatic polyether is shown in figure 1, and the 1HNMR spectrum of the hydroxyl-terminated hyperbranched aliphatic polyether is shown in figure 2.
(2) Under the protection of nitrogen, 3.52g of hydroxyl-terminated hyperbranched aliphatic polyether (0.001mol) is put into a three-neck flask, 20ml of DMSO and 10ml (2.5mol/L of hexane solution) n-BuLi are stirred for 30min at normal temperature, 266.4g of hexamethylcyclotrisiloxane (1.20mol) calculated according to the charge ratio is added, after the reaction is carried out for 4h at 120 ℃, the temperature is reduced to 60 ℃, 0.432g of water is added, the stirring is carried out for 2h, then the filtration is carried out, the filtrate is decompressed to 170 ℃/130mmHg, the low molecules and the residual solvent are removed, and 245g of hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane is obtained.
2. Preparation of hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer
Taking 102.2g of hydrogen-containing silicone oil HMe with hydrosilicon at two ends2SiO(Me2SiO)12SiMe2H, 82.0g of a copolymer CH of ethylene oxide and propylene oxide having a hydroxyl group at one end and an allyl group at the other end2＝CHCH2O(CH2CH2O)8H0.30 g8000ppm of H2PtCl6The isopropanol solution of (A) catalyzes hydrosilylation reaction, and 184.2g of hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer is obtained after reaction for 3 hours at 80.
Example 1
(1) Taking 5g of the hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, 10g of the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, 38.0g of polytetrahydrofuran with molecular weight of 2000, 0.530g of 1, 4-butanediol and 11.0g of HDI (hexamethylene diisocyanate), reacting for 4h at 40 ℃ in 76.2g of reaction solvent acetone under the catalysis of 0.0482g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 60 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organosilicon modified polyurethane compound serving as a component A;
(2) taking 3g of the hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, 20g of the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, 72g of polytetrahydrofuran with molecular weight of 2000, 1.778g of 1, 4-butanediol and 4.0g of HDI (hexamethylene diisocyanate), reacting for 4 hours at 40 ℃ in 73.2g of reaction solvent acetone under the catalysis of 0.508g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 60 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organosilicon modified polyurethane compound serving as a component B;
(3) uniformly mixing 20gA and 10gB components, removing bubbles in vacuum for 30min, and curing at 60 ℃ for 6h to obtain the organosilicon modified polyurethane cured product.
The tensile strength of the obtained cured product is 1.3MPa, the breaking tensile strength is 97.0 percent, the initial thermal decomposition temperature is 285 ℃, the mass loss of the cured product after the cured product is soaked in 10 weight percent of NaOH aqueous solution for 7 days is 2.1 percent, and the mass loss of the cured product after the cured product is soaked in 10 weight percent of NaCl aqueous solution for 7 days is 3.9 percent.
Example 2
(1) Taking 6g of the hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, 20g of the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer, 55g of polytetrahydrofuran with molecular weight of 2000, 1.5g of 1, 4-butanediol and 25.0g of TDI obtained in preparation example 1, reacting at 90 ℃ for 1h in 37.2g of reaction solvent N-methylpyrrolidone under the catalysis of 0.93g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 120 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound serving as a component A;
(2) taking 5g of hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, 20g of hydroxyl-terminated hyperbranched polyether-organic silicon-polyether triblock copolymer, 43.6g of polytetrahydrofuran with molecular weight of 2000, 1.778g of 1, 4-butanediol and 6.0g of TDI obtained in preparation example 1, reacting for 1 hour at 90 ℃ in 74.2g of reaction solvent N-methylpyrrolidone under the catalysis of 0.0764g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 120 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound serving as a component B;
(3) uniformly mixing 15gA and 10gB components, removing bubbles in vacuum for 30min, and curing at 80 ℃ for 4h to obtain the organosilicon modified polyurethane cured product.
The tensile strength of the obtained cured product is 1.8MPa, the breaking tensile strength is 419.0 percent, the initial thermal decomposition temperature is 295 ℃, the mass loss of the cured product after the cured product is soaked in 10 weight percent of NaOH aqueous solution for 7 days is 1.5 percent, and the mass loss of the cured product after the cured product is soaked in 10 weight percent of NaCl aqueous solution for 7 days is 0.78 percent.
Example 3
(1) Taking 8g of the hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, 15g of the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer, 50g of polytetrahydrofuran with molecular weight of 2000, 1.5g of 1, 4-butanediol and 36.0g of IPDI (isophorone diisocyanate) obtained in preparation example 1, reacting for 6 hours at 30 ℃ in 80g of reaction solvent N-methyl pyrrolidone under the catalysis of 0.93g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 120 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound serving as a component A;
(2) taking 8g of hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, 10g of hydroxyl-terminated hyperbranched polyether-organic silicon-polyether triblock copolymer, 100g of polytetrahydrofuran with molecular weight of 2000, 1.778g of 1, 4-butanediol and 7.0g of IPDI (isophorone diisocyanate) obtained in preparation example 1, reacting for 6 hours at 30 ℃ in 120g of reaction solvent N-methyl pyrrolidone under the catalysis of 0.383g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 120 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound serving as a component B;
(3) uniformly mixing 20gA and 8gB components, removing bubbles in vacuum for 30min, and curing at 80 ℃ for 4h to obtain the organosilicon modified polyurethane cured product.
The tensile strength of the obtained condensate is 1.5MPa, the breaking tensile strength is 363.0 percent, the initial thermal decomposition temperature is 281.5 ℃, the mass loss of the condensate after the condensate is soaked in 10 weight percent of NaOH aqueous solution for 7 days is 2.3 percent, and the mass loss of the condensate after the condensate is soaked in 10 weight percent of NaCl aqueous solution for 7 days is 0.55 percent.
Preparation example 2
1. Preparation of hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane
(1) Preparation of hydroxyl-terminated hyperbranched aliphatic polyether
A clean and dry three-neck flask was taken, 134.2g (1.0mol) of trimethylolpropane and 73.5mL of potassium methoxide-methanol solution (1.36mol/L) were added under nitrogen protection, and after 1 hour of reaction at 80 ℃, 1555.7g of glycidol (21.0mol) was added dropwise, and after about 6 hours of addition, the reaction was continued for 6 hours. After the reaction is finished, methanol is added to dissolve the product, 36.5% hydrochloric acid is added dropwise to neutralize the product, and acetone is poured into the product for precipitation. After the purification is repeated for two times, the transparent viscous liquid is obtained after vacuum drying for 24 hours at the temperature of 70 ℃, and the transparent viscous liquid is the hydroxyl-terminated hyperbranched aliphatic polyether.
(2) Under the protection of nitrogen, 3.52g of hydroxyl-terminated hyperbranched aliphatic polyether (0.001mol) is put into a three-neck flask, 50ml of DMSO and 10ml (2.5mol/L hexane solution) of n-BuLi are stirred for 30min at normal temperature, 532.8g of hexamethylcyclotrisiloxane (2.40mol) calculated according to the charge ratio is added, after reaction is carried out for 4h at 140 ℃, the temperature is reduced to 60 ℃, 0.432g of water is added, the mixture is stirred for 2h and then filtered, the filtrate is decompressed to 170 ℃/130mmHg to remove low molecules and residual solvent, and 524g of hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane is obtained.
2. Preparation of hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer
Taking 309.4g of hydrogen-containing silicone oil HMe with hydrosilicon at two ends2SiO(Me2SiO)40SiMe2H, 187.6g of a copolymer CH of ethylene oxide and propylene oxide having a hydroxyl group at one end and an allyl group at the other end2＝CHCH2O(CH2CH2O)20And carrying out hydrosilylation reaction on 1.2g of 5000ppm methyl vinyl siloxane coordinated platinum complex catalyst, and reacting for 2H at 90 ℃ to obtain 497g of hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer.
Example 4
(1) Taking 5g of hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, 10g of hydroxyl-terminated hyperbranched polyether-organic silicon-polyether triblock copolymer, 38.0g of polytetrahydrofuran with molecular weight of 2000, 0.530g of 1, 4-butanediol and 14.5g of TDI, reacting for 3h at 50 ℃ in 78.2g of reaction solvent tetrahydrofuran under the catalysis of 0.303g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 60 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound serving as a component A;
(2) taking 3g of hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, 20g of hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer, 72g of polytetrahydrofuran with molecular weight of 2000, 1.778g of 1, 4-butanediol and 5.0g of TDI obtained in preparation example 2, reacting for 3h at 50 ℃ in 74.2g of reaction solvent tetrahydrofuran under the catalysis of 0.102g of dibutyltin dilaurate, and removing the solvent by reducing the pressure to 60 ℃/130mmHg to obtain an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound serving as a component B;
(3) uniformly mixing 20gA and 10gB components, removing bubbles in vacuum for 30min, and curing at 60 ℃ for 6h to obtain the organosilicon modified polyurethane cured product.
The tensile strength of the obtained cured product is 1.0MPa, the breaking tensile strength is 285.0 percent, the initial thermal decomposition temperature is 295 ℃, the mass loss of the cured product after the cured product is soaked in 10 weight percent of NaOH aqueous solution for 7 days is 2.8 percent, and the mass loss of the cured product after the cured product is soaked in 10 weight percent of NaCl aqueous solution for 7 days is 1.4 percent.
Example 5
Respectively taking 30gA and 10gB components in example 4, uniformly mixing, removing bubbles in vacuum for 30min, and curing at 60 ℃ for 6h to obtain the cured organosilicon modified polyurethane.
The tensile strength of the obtained condensate is 1.8MPa, the breaking tensile strength is 324.0 percent, the initial thermal decomposition temperature is 292.0 ℃, the mass loss of the condensate is 1.6 percent after the condensate is soaked in 10 weight percent of NaOH aqueous solution for 7 days, and the mass loss of the condensate is 0.85 percent after the condensate is soaked in 10 weight percent of NaCl aqueous solution for 7 days.
Example 6
The components of 40gA and 10gB in example 4 were uniformly mixed, and after removing bubbles in vacuum for 40min, the mixture was cured at 60 ℃ for 5 hours to obtain an organosilicon modified polyurethane cured product.
The tensile strength of the obtained condensate is 1.4MPa, the breaking tensile strength is 382.0 percent, the initial thermal decomposition temperature is 283.0 ℃, the mass loss of the condensate after the condensate is soaked in 10 weight percent of NaOH aqueous solution for 7 days is 1.9 percent, and the mass loss of the condensate after the condensate is soaked in 10 weight percent of NaCl aqueous solution for 7 days is 1.2 percent.
Preparation example 3
1. Preparation of hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane
(1) Preparation of hydroxyl-terminated hyperbranched aliphatic polyether
A clean and dry three-neck flask was taken, 134.2g (1.0mol) of trimethylolpropane and 73.5mL of potassium methoxide-methanol solution (1.36mol/L) were added under nitrogen protection, and after 1 hour of reaction at 80 ℃, 1555.7g of glycidol (21.0mol) was added dropwise, and after about 6 hours of addition, the reaction was continued for 6 hours. After the reaction is finished, methanol is added to dissolve the product, 36.5% hydrochloric acid is added dropwise to neutralize the product, and acetone is poured into the product for precipitation. After the purification is repeated for two times, the transparent viscous liquid is obtained after vacuum drying for 24 hours at the temperature of 70 ℃, and the transparent viscous liquid is the hydroxyl-terminated hyperbranched aliphatic polyether.
(2) Under the protection of nitrogen, 3.52g of hydroxyl-terminated hyperbranched aliphatic polyether (0.001mol) is put into a three-neck flask, 50ml of DMSO and 10ml (2.5mol/L hexane solution) of n-BuLi are stirred for 30min at normal temperature, 1065.6g of hexamethylcyclotrisiloxane (4.80mol) calculated according to the charge ratio is added, after reaction is carried out for 4h at 140 ℃, the temperature is reduced to 60 ℃, 0.432g of water is added, the mixture is stirred for 2h and then filtered, the filtrate is decompressed to 170 ℃/130mmHg to remove low molecules and residual solvent, and 1045g of hydroxyl-terminated hyperbranched aliphatic polyether block polydimethylsiloxane is obtained.
2. Preparation of hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer
143.34g of hydrogen-containing silicone oil HMe with hydrosilicon at two ends2SiO(Me2SiO)100(MePhSiO)50SiMe2H, 30.36g of a copolymer CH of ethylene oxide and propylene oxide having a hydroxyl group at one end and an allyl group at the other end2＝CHCH2O(CH2CH2O)20(CH2CH3CHO)10And carrying out hydrosilylation reaction on the H by using 0.6g of platinum complex coordinated by 3000ppm diethyl phthalate, and reacting for 2H at 90 ℃ to obtain 497g of hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer.
Example 7
(1) Taking 5g of hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, 10g of hydroxyl-terminated hyperbranched polyether-organosilicon-polyether triblock copolymer, 38.0g of polytetrahydrofuran with molecular weight of 2000, 4.24g of 1, 4-butanediol, 4.5g of HDI and 15.4g of IPDI (isophorone diisocyanate), reacting for 3h at 60 ℃ in 74.2g of reaction solvent acetone under the catalysis of 0.154g of dibutyltin dilaurate, and decompressing to 60 ℃/130mmHg to remove the solvent to obtain an isocyanate-terminated hyperbranched organosilicon modified polyurethane compound serving as a component A;
(2) taking 3g of hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, 20g of hydroxyl-terminated hyperbranched polyether-organosilicon-polyether triblock copolymer, 72g of polytetrahydrofuran with molecular weight of 2000, 1.778g of 1, 4-butanediol, 2.0g of HDI and 4.0g of IPDI, reacting for 3h at 60 ℃ in 71.2g of reaction solvent acetone under the catalysis of 0.317g of dibutyl tin dilaurate, and removing the solvent by reducing the pressure to 60 ℃/130mmHg to obtain isocyanate-terminated hyperbranched organosilicon modified polyurethane compound as a component B;
(3) uniformly mixing 20gA and 10gB components, removing bubbles in vacuum for 30min, and curing at 60 ℃ for 6h.
The tensile strength of the obtained condensate is 2.0MPa, the breaking tensile strength is 380.0 percent, the initial thermal decomposition temperature is 308.5 ℃, the mass loss of the condensate after the condensate is soaked in 10 weight percent of NaOH aqueous solution for 7 days is 1.0 percent, and the mass loss of the condensate after the condensate is soaked in 10 weight percent of NaCl aqueous solution for 7 days is 0.45 percent, thus obtaining the organosilicon modified polyurethane condensate.
Claims (10)
1. The preparation method of the organic silicon modified polyurethane is characterized by comprising the following steps:
(1) preparing an isocyanate-terminated hyperbranched organic silicon modified polyurethane compound as a component A;
the preparation method of the isocyanate group-terminated hyperbranched organic silicon modified polyurethane compound comprises the following steps: hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, polytetrahydrofuran, 1, 4-butanediol and diisocyanate are used as raw materials, and are reacted in a reaction solvent under the action of a catalyst, and then the solvent is removed to obtain an isocyanate-terminated hyperbranched organosilicon modified polyurethane compound;
(2) preparing a hydroxyl-terminated hyperbranched organic silicon modified polyurethane compound as a component B;
a preparation method of hydroxyl-terminated hyperbranched organic silicon modified polyurethane compound; reacting hydroxyl-terminated hyperbranched aliphatic polyether-organosilicon block copolymer, hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, polytetrahydrofuran, 1, 4-butanediol and diisocyanate as raw materials in a reaction solvent under the action of a catalyst, and then removing the solvent to obtain a hydroxyl-terminated hyperbranched organosilicon modified polyurethane compound;
(3) and then uniformly mixing the component A and the component B according to the molar ratio of isocyanate group to hydroxyl group of 6: 1-1: 9, removing bubbles in vacuum for 15-40 min, and curing at 30-80 ℃ for 1-12 h to obtain a cured substance, namely the organosilicon modified polyurethane.
2. The method for preparing the organosilicon modified polyurethane according to claim 1, wherein in the step (1), the molar ratio of the isocyanate groups in the diisocyanate to all the hydroxyl groups in the hydroxyl-terminated hyperbranched aliphatic polyether block copolymer, the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol is 1.05: 1-4: 1.
3. The method for preparing the organosilicon modified polyurethane according to claim 1, wherein the organosilicon modified polyurethane comprises the following steps: in the step (2), the mole ratio of all hydroxyl groups in the hydroxyl-terminated hyperbranched aliphatic polyether block copolymer, the hydroxyl-terminated polyether-organosilicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol to the isocyanate groups in the diisocyanate is 1.1: 1-3: 1.
4. The method for preparing the organosilicon-modified polyurethane according to claim 2 or 3, wherein the steps (1) and (2) are carried out in the step (1)
The hydroxyl-terminated hyperbranched aliphatic polyether block copolymer accounts for 1-15% of the total mass;
the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer accounts for 5-30% of the total mass of the raw materials, and the 1, 4-butanediol accounts for 1-8% of the total mass;
polytetrahydrofuran is the residual mass;
the total mass of the hydroxyl-terminated hyperbranched aliphatic polyether-organic silicon block copolymer, the hydroxyl-terminated polyether-organic silicon-polyether triblock copolymer, the polytetrahydrofuran and the 1, 4-butanediol is the sum of the mass.
5. The method for preparing the organosilicon modified polyurethane according to claim 2 or 3, wherein the reaction solvent is one or more selected from tetrahydrofuran, acetone, and N-methylpyrrolidone.
6. The preparation method of the organosilicon modified polyurethane according to claim 5, wherein the amount of the solvent used in the preparation of the component A and the component B is 20-200% of the total mass of the raw materials of diisocyanate, hydroxyl terminated hyperbranched aliphatic polyether block copolymer, hydroxyl terminated polyether-organosilicon-polyether triblock copolymer, polytetrahydrofuran and 1, 4-butanediol.
7. The method of claim 2 or 3, wherein the catalyst is dibutyl tin dilaurate.
8. The preparation method of the organosilicon modified polyurethane of claim 7, wherein the amount of the catalyst used is 0.08% -0.5% of the total mass of the raw materials of diisocyanate, hydroxyl terminated hyperbranched aliphatic polyether block copolymer, hydroxyl terminated polyether-organosilicon-polyether triblock copolymer, polytetrahydrofuran and 1, 4-butanediol in the preparation of the component A and the preparation of the component B respectively.
9. The preparation method of the organosilicon modified polyurethane according to claim 2 or 3, wherein the reaction conditions in step (1) and step (2) are 30 ℃ to 95 ℃ for 1 to 6 hours.
10. Use of the silicone-modified polyurethane prepared by the method of any one of claims 1 to 9 in paints, coatings, and sealants.
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