CN111154062B - Isocyanate prepolymer for polyurethane-fiber composite material and preparation method and application thereof - Google Patents
Isocyanate prepolymer for polyurethane-fiber composite material and preparation method and application thereof Download PDFInfo
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- CN111154062B CN111154062B CN202010011218.2A CN202010011218A CN111154062B CN 111154062 B CN111154062 B CN 111154062B CN 202010011218 A CN202010011218 A CN 202010011218A CN 111154062 B CN111154062 B CN 111154062B
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- isocyanate prepolymer
- polyether polyol
- polyurethane
- diisocyanate
- fiber composite
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 85
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229920006306 polyurethane fiber Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920005862 polyol Polymers 0.000 claims abstract description 56
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 51
- 229920000570 polyether Polymers 0.000 claims abstract description 51
- 150000003077 polyols Chemical class 0.000 claims abstract description 51
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 25
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 25
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229920005749 polyurethane resin Polymers 0.000 claims description 26
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000003636 chemical group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 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 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- BWLKKFSDKDJGDZ-UHFFFAOYSA-N [isocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)C1=CC=CC=C1 BWLKKFSDKDJGDZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- 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 provides an isocyanate prepolymer for a polyurethane-fiber composite material, and a preparation method and application thereof. The isocyanate prepolymer is prepared from the following raw material components: an aliphatic polyisocyanate; a polyether polyol having a molecular weight of 200-; an alicyclic diisocyanate. According to the invention, the polyether polyol with a specific structure is introduced to carry out prepolymerization on the aliphatic polyisocyanate component, and the alicyclic diisocyanate with a specific content is introduced to carry out blending modification, so that the prepared isocyanate prepolymer has the characteristics of low viscosity and good mechanical property, and is particularly suitable for preparing the polyurethane-fiber composite material.
Description
Technical Field
The invention belongs to the field of macromolecules, and particularly relates to an isocyanate prepolymer for a polyurethane-fiber composite material, and a preparation method and application thereof.
Background
Polyurethanes are a generic term for macromolecular compounds containing repeating urethane groups in their main chains, are generally formed by reacting a polyisocyanate component and a polyol component under certain conditions, and are widely used in the fields of polyurethane coatings, adhesives, elastomers, foams, fiber composites, and the like. Because the volatility of the isocyanate monomer is strong and the forming and curing time is long, downstream products are mostly applied in the form of isocyanate self-polymerization or isocyanate prepolymer. Therefore, the research on the isocyanate prepolymer is of great significance to the research and development of polyurethane products.
At present, most of polyurethane-fiber composite materials are based on aromatic polyisocyanate prepolymers, such as Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), and these composite material products have good mechanical properties, but because aromatic isocyanate systems are easy to yellow and age under the irradiation of sunlight, the aromatic isocyanate systems degrade and expose internal reinforcing fibers, so that the mechanical properties of the aromatic isocyanate systems are seriously reduced. Composites based on aliphatic isocyanates, however, have good weathering resistance, but their mechanical strength is weak, which limits their use. The polyurethane-fiber composite material field relates to the impregnation and infiltration of reinforced fibers, and properly reducing the viscosity of isocyanate prepolymer resin is beneficial to improving the fiber impregnation efficiency and the impregnation effect, thereby improving the product quality and reducing the cost. At present, most of isocyanate prepolymers on the market have the defects of deep modification degree, high viscosity, insufficient strength and the like, and are difficult to meet the use requirements.
In order to solve the above problems, U.S. patent document US-a4443563A discloses: the polyurethane prepolymer is prepared by reacting 1,4-3, 6-dianhydrohexitol, polyisocyanate and polyol, and can be used in the fields of paint films, composite material members, foams and the like, but in the preparation process of the polymer, an organic solvent is needed to reduce the viscosity of the system, otherwise, the viscosity of the system is too high. Chinese patent document CN102643407A discloses: sequentially adopting polyalcohol and trimethylolpropane to modify isophorone diisocyanate, and then carrying out trimerization reaction to prepare an isocyanate prepolymer which has good compatibility with hydroxyl resin and good mechanical property; however, the method has complicated steps and high system viscosity, an organic solvent is required to be used in the preparation process to reduce the system viscosity, and a large amount of VOC volatilization during final processing is unfavorable for construction environment. Chinese patent document CN104045806A discloses: the diphenylmethane isocyanate is modified by adopting the polyalcohol. This patent document requires that the isomer content of diphenylmethane diisocyanate must be in a certain range, that the isomerization ratio of diphenylmethane isocyanate should be formulated in advance, and that the raw material is based on aromatic isocyanate and therefore far less excellent in weather resistance than aliphatic isocyanate.
In summary, there is a need for an isocyanate prepolymer for polyurethane-fiber composites that has low viscosity and excellent mechanical properties.
Disclosure of Invention
Therefore, the invention aims to provide an isocyanate prepolymer with low viscosity and excellent mechanical properties, and further provides a preparation method and application thereof, and further provides a polyurethane-fiber composite material prepared from the isocyanate prepolymer.
The invention is realized by the following technical scheme:
in a first aspect, the invention provides an isocyanate prepolymer for a polyurethane-fiber composite material, which is prepared from the following raw material components: (1) an aliphatic polyisocyanate; (2) polyether polyols having a molecular weight of 200-; (3) an alicyclic diisocyanate; in the isocyanate prepolymer, the weight percentage of the alicyclic diisocyanate is 40-85%, preferably 44-70%.
By carrying out prepolymerization modification on the polyether polyol with small molecular weight, the relative content of hard segments in the material can be properly improved, more chemical crosslinking points and corresponding crosslinking networks are formed, and the branching structure of functional groups of the prepolymer is improved.
Preferably, the aliphatic polyisocyanate of the present invention is an aliphatic polyisocyanate having a viscosity of not more than 250 cps at 25 ℃; preferably, the viscosity is from 5 to 50 centipoise at 25 ℃.
The aliphatic isocyanate has good weather resistance, and the carbon-carbon long chain in the structure can be used as an intramolecular rotation node, so that the toughness of the prepolymer or the final composite material is greatly enhanced.
The alicyclic diisocyanate has a mass percentage content within the above range, so that on one hand, the final prepolymer product can be ensured to have lower viscosity, and on the other hand, the alicyclic structure belongs to a weak rigid structure, the reaction activity is mild, and the prepolymer can be ensured to have enough time to be fully infiltrated with the reinforcing fibers due to the mass percentage content within the above range. After reaction, a large amount of alicyclic molecules are coalesced into a honeycomb structure due to microphase separation, so that the structural rigidity of the prepolymer or the final composite material can be effectively enhanced.
Preferably, in the isocyanate prepolymer of the polyurethane-fiber composite material of the present invention, the amount of the aliphatic polyisocyanate added is 10 to 40%, preferably 19 to 31%, based on 100% of the sum of the mass of the aliphatic polyisocyanate, the mass of the polyether polyol and the mass of the alicyclic diisocyanate; and/or, the addition amount of the polyether glycol is 5-25%, preferably 10-25%; and/or the alicyclic diisocyanate is added in an amount of 40-85%, preferably 44-70%.
The alicyclic diisocyanate with specific content is introduced, so that the material has excellent mechanical indexes such as rigidity, toughness, hardness and the like which are balanced by virtue of the synergistic effect of the rigid structure close to the aromatic isocyanate and the flexible structure in the prepolymer. Meanwhile, the introduction of the alicyclic diisocyanate greatly reduces the viscosity of the prepolymer, thereby facilitating the subsequent further dipping processing.
Preferably, in the above isocyanate prepolymer for polyurethane-fiber composite of the present invention, the polyether polyol is at least one selected from the group consisting of polypropylene oxide polyether polyol, polyethylene oxide polyether polyol and polypropylene oxide-ethylene oxide polyether polyol, preferably selected from the group consisting of polypropylene oxide polyether polyol and/or polypropylene oxide-ethylene oxide polyether polyol, and more preferably selected from the group consisting of polypropylene oxide polyether polyol; and/or the alicyclic diisocyanate is selected from at least one of isophorone diisocyanate, dicyclohexyl methane diisocyanate and methyl cyclohexyl diisocyanate, preferably selected from isophorone diisocyanate and/or dicyclohexyl methane diisocyanate; and/or the aliphatic polyisocyanate is selected from at least one of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate and corresponding oligomers thereof, preferably at least one of isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate.
The aliphatic polyisocyanate oligomer may be selected from aliphatic polyisocyanates, for exampleIsocyanurates, uretdiones, biurets, urethanes, allophanates, iminoureas formed by polymerization of estersOne or more of diazinedione, carbodiimide and the like.
The initiator of the polyether polyol can be dihydric alcohol, trihydric alcohol or tetrahydric alcohol. The diol may be, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, 1, 5-pentanediol or 1, 6-hexanediol. The triol may be trimethylolpropane, glycerol or castor oil, for example. The tetrahydric alcohol may be, for example, pentaerythritol.
Preferably, in the isocyanate prepolymer for polyurethane-fiber composite material of the present invention, the raw material composition further includes, based on 100% by mass of the total of the aliphatic polyisocyanate and the polyether polyol: the addition amount of the catalyst is 0.01-0.06%, and the preferable addition amount is 0.02-0.04%; and/or the catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, iron acetylacetonate, zinc octoate, lead octoate and potassium oleate, preferably from dibutyltin dilaurate and/or stannous octoate.
In a second aspect, the present invention provides a preparation method of the isocyanate prepolymer for the polyurethane-fiber composite material, including the following steps: adding aliphatic polyisocyanate with a selected weight into a reaction container under an inert atmosphere, heating to 45-120 ℃ under stirring, slowly dropwise adding polyether polyol with the selected weight into the reaction container, adding a catalyst with the selected weight after dropwise adding, continuously reacting for 0.5-4h at 45-120 ℃ under stirring, adding alicyclic diisocyanate with the selected weight, and uniformly stirring to obtain the isocyanate prepolymer.
In the above preparation method, the inert atmosphere is preferably nitrogen; the slow dripping is completed within 30-120 min.
In a third aspect, the invention provides an isocyanate prepolymer prepared by the above preparation method.
Preferably, in the isocyanate prepolymer of the present invention, the content of free isocyanate group in the isocyanate prepolymer is 15 to 42%, preferably 21 to 32%, and more preferably 23 to 30%.
The content of free isocyanate group (-NCO) is in the above range, which is beneficial for adjusting the forming speed of the final composite material, the resin viscosity is increased too fast due to too low content, the material has cavity defects, and the forming process is slow due to too high content, and the mechanical properties of the final product are influenced.
In a fourth aspect, the invention provides a polyurethane resin prepared from the isocyanate prepolymer or the isocyanate prepolymer prepared by the preparation method.
Methods for preparing polyurethane resins from isocyanate prepolymers are well known in the art. The invention preferably adopts the following method to prepare polyurethane resin from isocyanate prepolymer: 500g of copolymer was weighed at room temperature4012 (water is removed to below 0.05%) is added into a reactor, and then the copolymers are added respectively4012 defoaming agent BYK066N in 0.01 wt% and dibutyltin dilaurate in 50ppm are uniformly mixed, isocyanate prepolymer is added according to the NCO/OH of 1.1, the isocyanate prepolymer is mechanically stirred for 5 minutes to be uniformly mixed, the mixture is vacuumized at room temperature to remove bubbles, the mixture is poured into a standard mold, the mixture is cured at 85 ℃ for 2 hours, and the polyurethane resin is finally obtained after the mixture is cured at room temperature for 24 hours.
In a fifth aspect, the present invention provides a polyurethane-fiber composite material prepared from the above polyurethane resin.
Methods for preparing polyurethane-fiber composites from polyurethane resins are well known in the art. The invention preferably adopts the following method to prepare the polyurethane-fiber composite material from the polyurethane resin: soaking the glass fiber in polyurethane resin, and performing and soaking at 25-35 deg.C and 5-10bar pressure on a pultrusion machine; then molding at 80-200 ℃ and 10-15bar pressure with molding traction speed of 0.5-1.0m/min and resin curing condition controlled at 150-200 ℃ for about 1min, and finally cutting and molding to obtain the polyurethane-fiber composite material.
The technical scheme provided by the invention has the following beneficial effects:
according to the invention, researches show that polyether polyol with a specific structure is introduced to carry out prepolymerization on an aliphatic polyisocyanate component, and alicyclic diisocyanate with a specific content is introduced to carry out blending modification, so that the prepared isocyanate prepolymer has the characteristics of low viscosity, good mechanical property and simple process, and can greatly improve the dipping efficiency and the comprehensive mechanical property of the prepared polyurethane-fiber composite material, thereby being particularly suitable for preparing the polyurethane-fiber composite material.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials and sources used in the following examples and comparative examples of the present invention are as follows:
dicyclohexylmethane diisocyanate, having a viscosity of 30 cps at 25 ℃, available from wanhua chemical group ltd;
hexamethylene diisocyanate; a viscosity of 6 centipoise at 25 ℃ from Wanhua chemical group, Inc.;
pentamethylene diisocyanate, having a viscosity of 5 cps at 25 ℃, available from mitsubishi chemical corporation;
wanol R2305, a polypropylene oxide ether polyol having an average functionality of 3, a molecular weight of about 498g/mol, a moisture content of <500ppm, available from Wanol chemical group, inc;
wanol R2307, a polypropylene oxide ether polyol having an average functionality of 3, a molecular weight of about 696g/mol, a moisture content of <500ppm, available from Wanol chemical group, inc;
TEP-406, a polypropylene oxide ether polyol having an average functionality of 4, a molecular weight of about 600g/mol, a moisture content of <500ppm, available from Tianjin third petrochemical plant;
wanol C2010, a polypropylene oxide ether polyol having an average functionality of 2, a molecular weight of about 1000g/mol, a moisture content of less than 500ppm, available from Wanol chemical group, inc;
n330, a polypropylene oxide ether polyol having an average functionality of 3, a molecular weight of about 3000g/mol, a moisture content of <500ppm, available from Jiangsu clock shan chemical Co., Ltd;
multranol @4012, a commonly used polyether polyol for polyurethane-fiber composites, having an average functionality of 2, was used as a copolymerization reactant for isocyanate prepolymers, and was purchased from Corsai Corp;
BYK 066N: antifoam agents, silicone antifoam agents, available from BYK company.
Unless otherwise specified, the contents in the present invention are all mass contents.
In the following examples and comparative examples of the present invention,
the NCO content test is according to the standard GB/T12009.4;
the content test of the free isocyanate monomer adopts the national standard GB/T18446-;
the dynamic viscosity was measured at 25 ℃ using a spindle viscometer (Brookfield DV-11).
Example 1
The preparation method of the isocyanate prepolymer in the embodiment comprises the following steps: under the protection of nitrogen, 0.638kg of hexamethylene diisocyanate is added into a reaction kettle, the mixture is heated to 80 ℃ under stirring, then 0.70kg of polyether polyol Wanol R2307 is added into the reaction kettle in a slow dropwise adding mode, after the dropwise adding is finished, dibutyltin dilaurate accounting for 0.02 percent of the total mass of the hexamethylene diisocyanate and the polyether polyol is added, the reaction is continued for 2 hours under stirring at the temperature of 80 ℃, then 2.01kg of dicyclohexylmethane diisocyanate is added, and the mixture is uniformly stirred, so that isocyanate prepolymer No. 1 is obtained. Through determination, the NCO content of the isocyanate prepolymer 1# is 25.0%, the viscosity is 360cp/25 ℃, and the mass percentage of dicyclohexylmethane diisocyanate in the isocyanate prepolymer 1# is 60.1%.
Example 2
The preparation method of the isocyanate prepolymer in the embodiment comprises the following steps: under the protection of nitrogen, 0.702kg of hexamethylene diisocyanate is added into a reaction kettle, the mixture is heated to 45 ℃ under stirring, then 0.57kg of polyether polyol Wanol R2305 is added into the reaction kettle in a dropwise adding mode, dibutyltin dilaurate accounting for 0.04 percent of the total mass of the hexamethylene diisocyanate and the polyether polyol is added after dropwise adding is finished, the reaction is continued for 4 hours under stirring at 45 ℃, then 1.91kg of dicyclohexylmethane diisocyanate is added, and the mixture is uniformly stirred, so that an isocyanate prepolymer No. 2 is obtained. Through determination, the NCO content in the isocyanate prepolymer 2# is 25.7%, the viscosity is 233cp/25 ℃, and the mass percentage content of dicyclohexylmethane diisocyanate in the isocyanate prepolymer 2# is 60.0%.
Example 3
The preparation method of the isocyanate prepolymer in the embodiment comprises the following steps: under the protection of nitrogen, adding 1.040kg of hexamethylene diisocyanate into a reaction kettle, heating to 100 ℃ under stirring, then adding 0.55kg of polyether polyol TEP-406 into the reaction kettle in a dropwise adding mode, adding dibutyltin dilaurate accounting for 0.03 percent of the total mass of the hexamethylene diisocyanate and the polyether polyol after dropwise adding is finished, continuing to react for 0.5h at 120 ℃ under stirring, then adding 1.94kg of dicyclohexylmethane diisocyanate, and uniformly stirring to obtain an isocyanate prepolymer No. 3. Through determination, the NCO content of the isocyanate prepolymer 3# is 28.0%, the viscosity is 430cp/25 ℃, and the mass percentage of dicyclohexylmethane diisocyanate in the isocyanate prepolymer 3# is 55.0%.
Example 4
The preparation method of the isocyanate prepolymer in the embodiment comprises the following steps: under the protection of nitrogen, adding 1.32kg of hexamethylene diisocyanate into a reaction kettle, heating to 120 ℃ under stirring, then adding 1.07kg of polyether polyol Wanol R2305 into the reaction kettle in a dropwise adding mode, adding dibutyltin dilaurate accounting for 0.01 percent of the total mass of the hexamethylene diisocyanate and the polyether polyol after dropwise adding is finished, continuing to react for 1 hour under stirring at 100 ℃, then adding 1.95kg of dicyclohexylmethane diisocyanate, and uniformly stirring to obtain an isocyanate prepolymer No. 4. Through determination, the NCO content of the isocyanate prepolymer No. 4 is 23.4%, the viscosity is 610cp/25 ℃, and the mass percentage content of dicyclohexylmethane diisocyanate in the isocyanate prepolymer No. 4 is 45.2%. .
Example 5
The preparation method of the isocyanate prepolymer in the embodiment comprises the following steps: under the protection of nitrogen, adding 1.06kg of pentamethylene diisocyanate into a reaction kettle, heating to 60 ℃ under stirring, then adding 0.57kg of polyether polyol Wanol R2305 into the reaction kettle in a dropwise adding mode, adding dibutyltin dilaurate accounting for 0.06% of the total mass of dicyclohexylmethane diisocyanate and polyether polyol after dropwise adding, continuing to react for 1.5h at 90 ℃ under stirring, then adding 3.80kg of dicyclohexylmethane diisocyanate, and uniformly stirring to obtain an isocyanate prepolymer No. 5. Through determination, the NCO content of the isocyanate prepolymer 5# is 30.1%, the viscosity is 220cp/25 ℃, and the mass percentage content of dicyclohexylmethane diisocyanate in the isocyanate prepolymer 5# is 70.0%.
Comparative example 1
This comparative example differs from example 1 only in that: the polyether polyol Wanol R2307 in example 1 was replaced with polyether polyol Wanol C2010 (functionality of 2), and the remaining raw materials, experimental conditions and reaction steps were the same as in example 1.
Comparative example 2
This comparative example differs from example 4 only in that: 1.95kg of dicyclohexylmethane diisocyanate from example 4 was replaced with 0.865kg of dicyclohexylmethane diisocyanate (26.57% added), and the remaining raw materials, experimental conditions and reaction steps were the same as in example 4.
Comparative example 3
The comparative example only differs from example 3 in that: the polyether polyol TEP-406 from example 3 was replaced with polyether polyol N330 (molecular weight about 3000g/mol), and the remaining raw materials, experimental conditions and reaction steps were the same as in example 3.
Comparative example 4
This comparative example differs from example 2 only in that: 1.91kg of dicyclohexylmethane diisocyanate from example 2 was replaced by 1.91kg of hexamethylene diisocyanate, and the remaining raw materials, experimental conditions and reaction steps were the same as in example 2.
Comparative example 5
This comparative example differs from example 1 only in that: 0.7kg of polyether polyol Wanol R2307 in example 1 was replaced with 0kg of polyether polyol Wanol R2307, and the remaining raw materials, experimental conditions and reaction procedure were the same as in example 1.
Example 6
The preparation of the polyurethane resin of this example included the following steps: 500g of copolymer was weighed at room temperature4012 (water is removed to below 0.05%) is added into a reactor, and then the copolymers are added respectively4012, 0.01% by mass of defoamer BYK066N and 50ppm dibutyltin dilaurate, uniformly mixing, adding the isocyanate prepolymer of example 1 according to NCO/OH ratio of 1.1, mechanically stirring for 5 minutes to uniformly mix, vacuumizing at room temperature to remove bubbles, pouring the mixture into a standard mold, curing at 85 ℃ for 2 hours, and curing at room temperature for 24 hours to finally obtain the polyurethane resin.
Examples 7 to 10 and comparative examples 6 to 10
The polyurethane resins of examples 7 to 10 and comparative examples 6 to 10 were prepared in the following manner with respect to example 6: the isocyanate prepolymers of example 1 were replaced with the isocyanate prepolymers of examples 2 to 5 and comparative examples 1 to 5, respectively, in this order, and the remaining reaction materials, reaction conditions and experimental procedures were the same as those of example 6.
Example 11
The preparation of the polyurethane-fiber composite of this example included the following steps: impregnating the polyurethane resin prepared in the embodiment 6 with glass fibers, and performing and impregnating on a pultrusion machine at 25-35 ℃ and 5-10bar pressure after the impregnation is finished; then molding at 80-200 ℃ and 10-15bar pressure with molding traction speed of 0.5-1.0m/min and resin curing condition controlled at 150-200 ℃ for about 1min, and finally cutting and molding to obtain the polyurethane-fiber composite material.
Examples 12 to 15 and comparative examples 11 to 15
The preparation of the polyurethane resins of examples 12 to 15 and comparative examples 11 to 15 differs from example 11 only in that: the polyurethane resin of example 6 was replaced with the isocyanate prepolymers of examples 7 to 10 and comparative examples 6 to 10, respectively, in this order, and the remaining reaction materials, reaction conditions and experimental procedures were the same as those of example 11.
Examples of the experimentsMechanical testing of polyurethane resin
The mechanical properties of the polyurethane resins prepared in examples 6 to 10 and comparative examples 6 to 10 were measured according to the following methods: the tensile strength and elongation at break of the polyurethane resin were measured according to standard ASTM D412, the tear strength of the polyurethane resin was measured according to standard ASTM D624, the impact strength of the polyurethane resin was measured according to standard ASTM D302, and the results of the experiments are shown in tables 1-1 and tables 1-2.
Tables 1-1 mechanical Property test results of the polyurethane resins of examples 6-10
Tables 1-2 mechanical property test results of the polyurethane resins of comparative examples 6-10
As can be seen from tables 1-1 and tables 1-2, the polyurethane resins of examples 6-10 all have good mechanical properties, while the polyurethane resins of comparative examples 6-10 have poor mechanical properties, which are partially indicative of poor mechanical properties, and are liable to cause application defects and deficiencies in composite materials.
Examples of the experimentsPolyurethane-fiber composite Performance testing
The mechanical properties of the polyurethane-fiber composites prepared in examples 11 to 15 and comparative examples 11 to 15 were measured according to the following methods: the tensile strength test of the polyurethane-fiber composite material is in accordance with standard ISO 527; the tensile modulus test of the polyurethane-fiber composite material is in accordance with standard ISO 527; elongation testing of the polyurethane-fiber composite material follows standard ISO 527; the compressive strength test of the polyurethane-fiber composite material is in accordance with the standard GB-T1448; the compression modulus test of the polyurethane-fibre composite material is in accordance with the standard GB-T1448. The specific experimental results are shown in tables 2-1 and 2-2.
Table 2-1 results of performance testing of polyurethane-fiber composites of examples 11-15
Tables 2-2 results of the Performance test of the polyurethane-fiber composites of comparative examples 11-15
As can be seen from tables 2-1 and 2-2, the polyurethane-fiber composites prepared in examples 11-15 exhibited good compressive strength, tensile strength, elongation, and other indicators, and the overall properties were better; the polyurethane resins prepared in comparative examples 11 to 15 obviously have poor indexes and poor comprehensive performance.
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. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (14)
1. A preparation method of an isocyanate prepolymer for a polyurethane-fiber composite material is characterized by comprising the following steps: adding aliphatic polyisocyanate with a selected weight into a reaction container under an inert atmosphere, heating to 45-120 ℃ under stirring, slowly dropwise adding polyether polyol with the selected weight into the reaction container, adding a catalyst with the selected weight after dropwise adding, continuously reacting for 0.5-4h at 45-120 ℃ under stirring, adding alicyclic diisocyanate with the selected weight, and uniformly stirring to obtain an isocyanate prepolymer; wherein,
the isocyanate prepolymer is prepared from the following raw material components:
(1) an aliphatic polyisocyanate; the aliphatic polyisocyanate is at least one selected from pentamethylene diisocyanate and hexamethylene diisocyanate;
(2) a polyether polyol having a molecular weight of 200-;
(3) an alicyclic diisocyanate; the alicyclic diisocyanate is selected from at least one of isophorone diisocyanate, dicyclohexyl methane diisocyanate and methyl cyclohexyl diisocyanate;
in the isocyanate prepolymer, the mass percentage of the alicyclic diisocyanate is 44-70%;
the addition amount of the aliphatic polyisocyanate is 10-40%, the addition amount of the polyether polyol is 5-25%, and the addition amount of the alicyclic diisocyanate is 44-70%, based on 100% of the sum of the mass of the aliphatic polyisocyanate, the mass of the polyether polyol and the mass of the alicyclic diisocyanate.
2. The method as claimed in claim 1, wherein the polyether polyol has a molecular weight of 490-1000 Dalton and an average functionality of 2.5-4.
3. The method for preparing an isocyanate prepolymer for a polyurethane-fiber composite material according to claim 1, wherein the aliphatic polyisocyanate is added in an amount of 19 to 31% based on 100% by mass of the sum of the aliphatic polyisocyanate, the polyether polyol and the alicyclic diisocyanate; and/or the addition amount of the polyether glycol is 10-25%.
4. The method for preparing an isocyanate prepolymer for a polyurethane-fiber composite material according to any one of claims 1 to 3,
the polyether polyol is selected from at least one of polypropylene oxide polyether polyol, polyethylene oxide polyether polyol and polypropylene oxide-ethylene oxide polyether polyol; and/or the presence of a gas in the gas,
the alicyclic diisocyanate is selected from isophorone diisocyanate and/or dicyclohexyl methane diisocyanate; and/or the presence of a gas in the gas,
the aliphatic polyisocyanate is selected from hexamethylene diisocyanate.
5. The method for preparing an isocyanate prepolymer for polyurethane-fiber composite according to claim 4,
the polyether polyol is selected from polypropylene oxide polyether polyol and/or polypropylene oxide-ethylene oxide polyether polyol.
6. The method for preparing an isocyanate prepolymer for polyurethane-fiber composite according to claim 5,
the polyether polyol is selected from polypropylene oxide polyether polyols.
7. The method of preparing an isocyanate prepolymer for polyurethane-fiber composite according to any one of claims 1 to 3 and 5 to 6,
the raw material components also comprise, by taking the total mass of the aliphatic polyisocyanate and the polyether polyol as 100%: the addition amount of the catalyst is 0.01-0.06%; and/or the catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, iron acetylacetonate, zinc octoate, lead octoate and potassium oleate.
8. The preparation method of the isocyanate prepolymer for the polyurethane-fiber composite material according to claim 7, wherein the addition amount of the catalyst is 0.02-0.04%; and/or the catalyst is selected from dibutyltin dilaurate and/or stannous octoate.
9. An isocyanate prepolymer prepared by the method of any one of claims 1 to 8.
10. The isocyanate prepolymer of claim 9, wherein the isocyanate prepolymer has a free isocyanate group content of 15 to 42%.
11. The isocyanate prepolymer of claim 10, wherein the isocyanate prepolymer has a free isocyanate group content of 21 to 32%.
12. The isocyanate prepolymer of claim 10, wherein the isocyanate prepolymer has a free isocyanate group content of 23 to 30%.
13. A polyurethane resin, which is characterized by being prepared from the isocyanate prepolymer prepared by the preparation method of any one of claims 1 to 8.
14. A polyurethane-fiber composite material characterized by being prepared from the polyurethane resin according to claim 13.
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