CN115181231A - Liquid composition and prepreg and composite material prepared from same - Google Patents
Liquid composition and prepreg and composite material prepared from same Download PDFInfo
- Publication number
- CN115181231A CN115181231A CN202110362672.7A CN202110362672A CN115181231A CN 115181231 A CN115181231 A CN 115181231A CN 202110362672 A CN202110362672 A CN 202110362672A CN 115181231 A CN115181231 A CN 115181231A
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- Prior art keywords
- liquid composition
- polyurethane
- isocyanate
- prepreg
- component
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- 239000007788 liquid Substances 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000004814 polyurethane Substances 0.000 claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 claims abstract description 64
- 239000000835 fiber Substances 0.000 claims abstract description 52
- 239000012948 isocyanate Substances 0.000 claims abstract description 45
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 25
- 239000012779 reinforcing material Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims description 55
- 229920005862 polyol Polymers 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000002118 epoxides Chemical class 0.000 claims description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- -1 carbonate polyols Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 10
- 239000008158 vegetable oil Substances 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 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 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 230000005670 electromagnetic radiation Effects 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 235000019766 L-Lysine Nutrition 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000011325 microbead Substances 0.000 claims description 3
- 239000002557 mineral fiber Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims 1
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 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 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- 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
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present application provides a liquid composition and prepregs and composites made therefrom. The liquid composition comprises a polyurethane-forming component, a reaction catalyst and a reinforcing material, wherein the polyurethane-forming component comprises a) an isocyanate component and B) an isocyanate-reactive component, the liquid composition has an initial viscosity at 25 ℃ of from 50 to 5000mpa.s (measured according to DIN EN 53019), and the ratio of the number of NCO groups in the a) isocyanate component to the number of OH groups in the B) isocyanate-reactive component is 0.5:1-1.2:1. the liquid composition is contacted with the fiber base material under the condition of excess amount, the fiber base material can be fully soaked in a short time, the polyurethane prepreg prepared by the method has the advantages of storage resistance and easiness in processing, and the polyurethane prepreg is completely cured under high temperature and high pressure to obtain the polyurethane composite material which has the advantages of excellent mechanical property and long service life.
Description
Technical Field
The invention relates to the field of polyurethane composite materials, in particular to a liquid composition, and a prepreg and a composite material prepared from the liquid composition, and especially relates to a method for preparing the prepreg and the composite material.
Background
The polyurethane resin has excellent fatigue resistance, and in the preparation process of the polyurethane resin, the resin matrix is used for impregnating continuous fibers or fiber fabrics under certain conditions to prepare prepreg, the prepreg is heated and melted when needed to form a required shape, and then the prepreg is cured to obtain the polyurethane composite material. The prepreg prepared by the method can be cured within a short time, is not beneficial to cutting, and is also not beneficial to laying the prepreg in a mould with a certain shape to press a product with a complex shape.
Disclosure of Invention
The present application provides a liquid composition and prepregs and composites made therefrom, and methods of making the same, including the following embodiments:
embodiment 1. A liquid composition useful for preparing a prepreg, comprising a polyurethane-forming component, a reaction catalyst, and a reinforcing material, wherein,
the polyurethane-forming component comprising A) an isocyanate component and B) an isocyanate-reactive component,
the A) isocyanate component includes one or more selected from the group consisting of: diisocyanates and polyisocyanates;
said B) isocyanate-reactive component comprises:
b1 One or more organic polyols having a hydroxyl number of from 10 to 1000mg KOH/g and a functionality of from 2 to 6;
b2 One or more epoxides having an epoxide equivalent weight of from 100 to 500g/eq,
wherein the liquid composition has an initial viscosity at 25 ℃ of from 50 to 5000mPa.s (measured according to DIN EN 53019) and the ratio of the number of NCO groups in the A) isocyanate component to the number of OH groups in the B) isocyanate-reactive component is from 0.5:1-1.2:1.
embodiment 2. The liquid composition useful for preparing a prepreg according to embodiment 1, further comprising at least one auxiliary agent selected from the group consisting of: defoaming agent, release agent, flatting agent, durability assistant, flow assistant, organic toner, inorganic toner and color paste.
Embodiment 3. The liquid composition useful for preparing a prepreg according to embodiment 1, wherein the reaction catalyst is a latent catalyst that catalyzes at a temperature of 60 ℃ to 100 ℃, and the reaction catalyst is contained in an amount of 0.01 to 6 parts by weight, based on 100 parts by weight of the polyurethane-forming component.
Embodiment 4. The liquid composition useful for preparing a prepreg according to embodiment 1, wherein the B2) one or more epoxides comprises one or more selected from the group consisting of: epoxy resins based on diglycidyl ethers of bisphenol a, epoxy resins based on diglycidyl ethers of bisphenol F.
Embodiment 5. The liquid composition useful for making a prepreg according to embodiment 1, wherein the B1) one or more organic polyols comprise one or more selected from the group consisting of: pentaerythritol, ethylene Glycol (EG), 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol (NPG), diethylene glycol (EG), dipropylene glycol, trimethylolpropane (TMP), glycerol, diethylene glycol, methylpropylene glycol, polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols or polyols based on vegetable oils.
Embodiment 6 the liquid composition useful for preparing a prepreg according to embodiment 1, wherein the diisocyanate comprises at least one selected from the group consisting of: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI);
the polyisocyanate includes at least one selected from the group consisting of: polyphenyl polymethylene polyisocyanates (PAPI), triphenylmethane triisocyanate, L-lysine triisocyanate, oligomers containing multiple isocyanate groups.
Embodiment 7. The liquid composition useful for making a prepreg according to embodiment 1, wherein the reinforcing material comprises one or more selected from the group consisting of: inorganic filler, short fiber, fiber powder, glass micro-beads; wherein the reinforcing material is contained in an amount of 0.01 to 100 parts by weight, based on 100 parts by weight of the polyurethane-forming component.
Embodiment 8 the liquid composition useful for making a prepreg according to embodiment 1, further comprising a fibrous substrate comprising one or more selected from the group consisting of: glass fibers, carbon fibers, natural fibers, mineral fibers, (aromatic) polyamide fibers or polyester fibers, optionally the fibrous substrate comprises long fibers, optionally the fibrous substrate is in the form of a sheet-like textile structure, optionally the sheet-like textile structure is formed from at least one fabric in the form of: non-woven, knitted, loop-forming knitted, stretch-loop knitted, non-woven structures such as woven, laid mesh or knits.
Embodiment 9. A method of making a polyurethane prepreg, comprising:
procedure for preparation of liquid composition: mixing the components of the liquid composition of any one of embodiments 1 to 7 under conditions that substantially no chemical reaction occurs to provide a liquid composition;
a fiber substrate contacting step: contacting the liquid composition in excess with a fibrous substrate under conditions where substantially no chemical reaction occurs and sufficiently wetting the fibrous substrate to obtain a wetted fibrous substrate,
removal of excess liquid composition: pressing the wetted fibrous substrate to remove excess liquid composition to obtain a pressed fibrous substrate comprising the liquid composition,
pre-curing: and (c) subjecting the liquid composition in the extruded fibrous substrate to a pre-curing reaction under polyurethane-forming conditions to obtain a polyurethane prepreg.
Embodiment 10. The method of preparing a polyurethane prepreg according to embodiment 9, wherein,
the step of preparing the liquid composition comprises: first mixing said B) isocyanate-reactive component, said reaction catalyst and said reinforcing material to obtain a first component, mixing said A) isocyanate component with said first component to obtain said liquid composition.
Embodiment 11. The method of manufacturing a polyurethane prepreg according to embodiment 9, wherein the condition that substantially no chemical reaction occurs means at least one of the following conditions; ambient temperature, ambient atmospheric pressure.
Embodiment 12. The method of preparing a polyurethane prepreg according to embodiment 9, wherein the substantially non-chemically reactive condition is at a temperature of 10 ℃ to 60 ℃.
Embodiment 13. The method of making a polyurethane prepreg according to embodiment 9, wherein the conditions under which the polyurethane is formed refer to conditions under which the isocyanate and isocyanate-reactive component react, such as one or more of heat, electromagnetic radiation, or plasma.
Embodiment 14. The method of preparing a polyurethane prepreg according to embodiment 9, wherein the content of the fiber base material in the polyurethane prepreg is 50 to 90wt%, preferably 60 to 80wt%.
Embodiment 15 the method of preparing a polyurethane prepreg according to embodiment 9, further comprising covering both sides of the fibrous substrate with a release paper or a release film after the fibrous substrate contacting step and before the pre-curing step.
Embodiment 16 a prepreg made according to the method of any one of embodiments 9 to 15.
Embodiment 17. A method of making a polyurethane composite comprising
Subjecting a prepreg prepared according to the method of any one of embodiments 9 to 15 to full cure at high temperature and high pressure to give a polyurethane composite.
Embodiment 18. The method of preparing a polyurethane composite of embodiment 17, wherein the elevated temperature is 80 to 160 ℃, the elevated pressure is 2 to 100bar, and the curing step is performed for a time period of 1 to 10 minutes.
According to the polyurethane prepreg prepared from the liquid composition disclosed by the application, the fiber base material is soaked by the excessive liquid composition containing the unpolymerized monomer, and the fiber base material can be well soaked in a short time due to the low viscosity and good fluidity of the monomer and the excessive proportion, so that the preparation process is simple, and the fiber base material can be stored for a long time. The composite material produced has excellent low temperature performance and excellent mechanical performance.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings of the embodiments will be briefly introduced below, and it is apparent that the drawings in the following description relate only to some embodiments of the present disclosure and are not limiting to the present disclosure.
Figure 1 shows a process flow for making a polyurethane prepreg.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be described clearly and completely with reference to the drawings of the embodiments of the present disclosure. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without inventive step, are within the scope of protection of the disclosure.
The present invention is directed to solving at least one of the problems of the prior art or the related art.
To this end, one aspect of the present invention provides a liquid composition useful for preparing a prepreg comprising a polyurethane-forming component, a reaction catalyst and a reinforcing material, wherein the polyurethane-forming component comprises A) an isocyanate component and B) an isocyanate-reactive component,
the A) isocyanate component includes one or more selected from the group consisting of: diisocyanates and polyisocyanates;
said B) isocyanate-reactive component comprises:
b1 One or more organic polyols having a hydroxyl number of from 10 to 1000mg KOH/g and a functionality of from 2 to 6;
b2 One or more epoxides having an epoxide equivalent weight of from 100 to 500g/eq,
wherein the liquid composition has an initial viscosity at 25 ℃ of from 50 to 5000mPa.s (measured according to DIN EN 53019) and the ratio of the number of NCO groups in the A) isocyanate component to the number of OH groups in the B) isocyanate-reactive component is from 0.5:1-1.2:1. in some embodiments, the liquid composition has an initial viscosity at 25 ℃ of 50 to 1000mpa.s (measured according to DIN EN 53019). The initial viscosity of the liquid composition at 25 ℃ may also be any other value, for example, 50 to 100mPa.s,150 to 200mPa.s,250 to 500mPa.s,600 to 1000mPa.s,1000 to 1500mPa.s,2000 to 3000mPa.s, etc. In the present application, the number of OH groups in the isocyanate-reactive component of B) is calculated as the number of hydroxyl groups and one epoxy group is also calculated as one OH group. It is understood by those skilled in the art that the ratio of the number of NCO groups in the A) isocyanate component to the number of OH groups in the B) isocyanate-reactive component is 1:1, the chemical reaction can be completed with the best chemical ratio. However, the polyurethane-forming reaction is very complicated, and there is a possibility that some chemical reactions may occur between isocyanate and hydroxyl groups in addition to the reaction between isocyanate and hydroxyl groups, and therefore, outside the range of 1. In some embodiments, the ratio of the number of NCO groups in the a) isocyanate component to the number of OH groups in the B) isocyanate-reactive component is 0.7:1-0.8:1, or in the range of 0.75.
In some embodiments, the liquid composition useful for preparing a prepreg further comprises at least one auxiliary agent selected from the group consisting of: defoaming agent, release agent, flatting agent, durability assistant, flow assistant, organic toner, inorganic toner and color paste.
In some embodiments, the liquid composition useful for preparing a prepreg, wherein the reaction catalyst is a latent catalyst that catalyzes at a temperature of 60 ℃ to 100 ℃, and the reaction catalyst is present in an amount of 0.01 to 6 parts by weight, based on 100 parts by weight of the polyurethane-forming component. The temperature range may also be 70 to 80 ℃,90 to 100 ℃ and the like. The reaction catalyst may also be present in an amount of 0.05 to 5 parts by weight, 0.1 to 4 parts by weight, 0.5 to 3 parts by weight, 1 to 2 parts by weight, 1.5 to 2.5 parts by weight. The type of catalyst used in the present application is not limited as long as it is suitable for the chemical reaction in the present application, and in some embodiments, the reaction catalyst may be one or more of aromatic amines, imidazoles, acid anhydrides, dicyandiamide, organic hydrazide compounds such as cyanoguanidine, 4' -diaminodiphenyl sulfone, N-acylimidazole compounds, cyanoacetyl compounds such as Aradur 3380 available from henseme advanced chemicals limited, which is an acid anhydride curing agent used in the examples of the present application.
In some embodiments, the liquid composition useful for preparing a prepreg, wherein the B2) one or more epoxides comprises one or more selected from the group consisting of: epoxy resins based on diglycidyl ethers of bisphenol a, epoxy resins based on diglycidyl ethers of bisphenol F.
In some embodiments, the liquid composition useful for preparing a prepreg, wherein the B1) one or more organic polyols comprises one or more selected from the group consisting of: pentaerythritol, ethylene Glycol (EG), 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol (NPG), diethylene glycol (EG), dipropylene glycol, trimethylolpropane (TMP), glycerol, diethylene glycol, methylpropylene glycol, polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols or polyols based on vegetable oils. Reference may be made to CN10899426A as examples of such organic polyols.
Polyether polyols may be prepared by known processes, for example, by reacting an olefin oxide with an initiator in the presence of a catalyst.
Polyether carbonate polyols can be prepared by the addition of carbon dioxide and alkylene oxides onto active hydrogen-containing starters using double metal cyanide catalysts.
Polyester polyols are prepared by reacting dicarboxylic acids or dicarboxylic acid anhydrides with polyols. The dicarboxylic acids are preferably, but not limited to, aliphatic carboxylic acids having 2 to 12 carbon atoms.
Polycarbonate diols may be prepared by reacting diols with dihydroxy or diaryl carbonates or phosgene.
The vegetable oil-based polyol includes a vegetable oil, a vegetable oil polyol, or a modified product thereof. Vegetable oils are compounds prepared from unsaturated fatty acids and glycerol or oils and fats extracted from fruits, seeds, germs of plants, preferably but not limited to peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, palm oil. The plant polyol is a polyol initiated by one or more plant oils. Synthetic vegetable oil polyol starters include, but are not limited to, soybean oil, palm oil, peanut oil, canola oil, and castor oil. The vegetable oil polyol starter may be used to introduce hydroxyl groups by cleavage, oxidation, or transesterification, and the corresponding vegetable oil polyol may be prepared by processes well known to those skilled in the art for preparing organic polyols.
In some embodiments, the liquid composition useful for preparing a prepreg, wherein the diisocyanate comprises at least one selected from the group consisting of: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI);
the polyisocyanate includes at least one selected from the group consisting of: polyphenyl polymethylene polyisocyanates (PAPI), triphenylmethane triisocyanate, L-lysine triisocyanate, oligomers containing multiple isocyanate groups.
In some embodiments, the liquid composition useful for preparing a prepreg, wherein the reinforcement material comprises one or more selected from the group consisting of: inorganic filler, short fiber, fiber powder, glass micro-beads; wherein the reinforcing material is contained in an amount of 0.01 to 100 parts by weight, for example, 1 to 80 parts by weight, 2 to 70 parts by weight, 3 to 60 parts by weight, 4 to 50 parts by weight, 5 to 40 parts by weight, 10 to 30 parts by weight, 25 to 35 parts by weight, based on 100 parts by weight of the polyurethane-forming component.
In some embodiments, the liquid composition useful for preparing a prepreg further comprises a fibrous substrate comprising one or more selected from the group consisting of: glass fibers, carbon fibers, natural fibers, mineral fibers, (aromatic) polyamide fibers or polyester fibers, optionally the fibrous substrate comprises long fibers, optionally the fibrous substrate is in the form of a sheet-like textile structure, optionally the sheet-like textile structure is formed from at least one fabric in the form of: non-woven, knitted, loop-forming knitted, stretch-loop knitted, non-woven structures such as woven, laid-up scrim or knits.
In yet another aspect of the present invention, a method of making a polyurethane prepreg is provided. It includes:
procedure for preparation of liquid composition: mixing the components of the liquid composition of any one of the preceding claims under conditions that do not substantially chemically react to provide a liquid composition;
a fiber substrate contacting step: contacting the liquid composition in excess with a fibrous substrate under conditions where substantially no chemical reaction occurs and sufficiently wetting the fibrous substrate to obtain a wetted fibrous substrate,
removal of excess liquid composition: pressing the wetted fibrous substrate to remove excess liquid composition to obtain a pressed fibrous substrate comprising the liquid composition,
pre-curing: and (c) subjecting the liquid composition in the extruded fibrous substrate to a pre-curing reaction under polyurethane-forming conditions to obtain a polyurethane prepreg.
In some embodiments, the step of preparing a liquid composition comprises: first mixing said B) isocyanate-reactive component, said reaction catalyst and said reinforcement material to obtain a first component, mixing said A) isocyanate component with said first component to obtain said liquid composition.
In some embodiments, the conditions under which substantially no chemical reaction occurs are at least one of the following; ambient temperature, ambient atmospheric pressure.
In some embodiments, the condition that substantially no chemical reaction occurs refers to a condition of 10 ℃ to less than 60 ℃. By substantially non-chemically reacting, it is meant herein that the amount of reaction between the isocyanate component and the isocyanate-reactive component in the liquid composition is below 5%, and it is understood by those skilled in the art that the higher the temperature, the easier the reaction proceeds, and to prevent excessive progress of the chemical reaction, it is possible to control by lowering the ambient temperature and/or shortening the reaction time, and the higher the temperature, the faster the mixing of the liquid composition and the contacting of the fibrous substrate should proceed.
In some embodiments, the polyurethane-forming conditions refer to conditions under which the isocyanate and isocyanate-reactive component are reacted, such as one or more of heat, electromagnetic radiation, or plasma.
In some embodiments, the fibrous substrate is present in the polyurethane prepreg in an amount of from 50 to 90wt%, preferably from 60 to 80wt%, such as from 55 to 85wt%, from 65 to 75wt%, and the like.
In some embodiments, the method for preparing a polyurethane prepreg further comprises covering both sides of the fibrous substrate with a release paper or a release film after the fibrous substrate contacting step and before the pre-curing step.
In a third aspect of the present invention there is provided a prepreg, prepared by a method according to any one of the preceding claims.
In a fourth aspect of the present invention, a method of preparing a polyurethane composite is provided. Which comprises subjecting a prepreg prepared according to any one of the preceding methods to full cure at elevated temperature and pressure to give a polyurethane composite.
In some embodiments, the elevated temperature is from 80 to 160 ℃, e.g., from 90 to 150 ℃, from 100 to 140 ℃, from 110 to 130 ℃, from 115 to 125 ℃, the elevated pressure is from 2 to 100bar, e.g., from 5 to 80bar, from 10 to 70bar, from 20 to 60bar, from 30 to 50bar, from 35 to 45bar, and the curing step is carried out for a time period of from 1 to 10 minutes, e.g., from 1.5 minutes to 9 minutes, from 2 minutes to 8 minutes, from 3 minutes to 7 minutes, from 4 minutes to 6 minutes.
The composite material prepared by the composition and the method has excellent low-temperature performance and mechanical performance, and is not limited by theory, the composition is considered to be in contact with a fiber base material in a low-viscosity state, the fiber base material can be fully infiltrated, and a polyurethane polymer network and an epoxy resin polymer network are formed simultaneously after the composition is cured, so that the whole composite material forms an interpenetrating polymer network, the mechanical performance of the composite material is greatly improved, the capability of adapting to temperature change is realized, and the mechanical performance of the composite material is even improved after the composite material is subjected to low temperature.
The ranges described above may be used alone or in combination. The present application can be more easily understood by the following examples.
Examples
The raw materials and sources used in this example are shown in table 1 below:
TABLE 1
Example 1 (method of preparing liquid composition)
This example discloses a method of making a liquid composition useful for making prepregs.
The liquid composition is formed by mixing a polyurethane-forming component, a reaction catalyst, a reinforcing material and an auxiliary agent, wherein the polyurethane-forming component comprises A) an isocyanate component and B) an isocyanate-reactive component. The A) isocyanate component comprises diisocyanate and polyisocyanate. The B) isocyanate-reactive component includes B1) an organic polyol and B2) an epoxide.
In this example, the polyisocyanate component includes isocyanate 1 and isocyanate 2; the B1) organic polyol adopts polyether 1 and polyether 4; the B2) epoxide is epoxide 2;
the reaction catalyst is an anhydride curing agent Aradur 3380;
the reinforcing material is aluminum hydroxide;
the auxiliary agent is defoaming agent BYK-A535.
The liquid composition comprises the following components in parts by weight:
35 parts of polyether 1, 35 parts of polyether 4, 30 parts of epoxide 2,0.3 part of reaction catalyst, 0.5 part of defoaming agent, 35 parts of isocyanate 1, 35 parts of isocyanate 2 and 5 parts of reinforcing material. The ratio of the number of NCO groups in the isocyanate component to the number of OH groups in the isocyanate-reactive component is from about 0.7 to 0.8:1.
the liquid composition is prepared as follows:
step 1, fully mixing the isocyanate reactive component B), the reaction catalyst, the reinforcing material and the auxiliary agent at the temperature of 10-60 ℃ to obtain a component I.
And 2, fully mixing the A) isocyanate component and the component I at the temperature of about 15 ℃ to obtain the liquid composition.
The initial viscosity of the resulting liquid composition at 25 ℃ was tested and determined to be 500mPa.s according to DIN EN 53019.
Example 2 (method of preparing liquid composition)
This example discloses a method of making a liquid composition useful for making prepregs.
The liquid composition is formed by mixing a polyurethane-forming component, a reaction catalyst, a reinforcing material and an auxiliary agent, wherein the polyurethane-forming component comprises A) an isocyanate component and B) an isocyanate-reactive component. The B) isocyanate-reactive component includes B1) an organic polyol and B2) an epoxide.
In this example, the isocyanate component includes isocyanate 1 and isocyanate 3; the B1) organic polyol adopts polyether 1, polyether 3 and polyether 4; the B2) epoxide is epoxide 2;
the reaction catalyst, namely the anhydride curing agent, aradur 3380;
the reinforcing material is aluminum hydroxide.
The auxiliary agent is defoaming agent BYK-A535.
The liquid composition comprises the following components in parts by weight:
35 parts of polyether 1,5 parts of polyether 3, 30 parts of polyether 4, 30 parts of epoxide 2,0.7 part of reaction catalyst, 0.5 part of defoaming agent, 30 parts of reinforcing material, 50 parts of isocyanate 1 and 20 parts of isocyanate 3. The ratio of the number of NCO groups in the isocyanate component to the number of OH groups in the isocyanate-reactive component is from about 0.8 to 0.9:1.
the liquid composition is prepared as follows:
step 1, fully mixing the isocyanate reactive component B), the reaction catalyst, the reinforcing material and the auxiliary agent at the temperature of 10-60 ℃ to obtain a component I.
Step 2, mixing the A) isocyanate component and the first component at the temperature of 10-60 ℃ to obtain the liquid composition.
The initial viscosity of the resulting liquid composition at 25 ℃ was tested and was measured according to DIN EN 53019 and found to be 900mpa.s.
Example 3 (contacting excess liquid composition with fibrous substrate, precuring to form polyurethane, making prepreg)
This example discloses a method of making a polyurethane prepreg. The method comprises the following steps:
as shown in fig. 1, step 1, the liquid composition is prepared by the method described in example 1, the prepared liquid composition is continuously fed into the soaking tank at once, the feeding amount is controlled, the liquid level of the liquid composition is not too low, so as to completely soak the fiber substrate in the feeding tank, in this example, the liquid level is more than two thirds of the height of the soaking tank, so as to keep the excessive liquid composition completely submerging the fiber substrate, which is biaxial glass fiber cloth.
Step 2, fiber substrate contacting step: the fibrous substrate is contacted with an excess of the liquid composition in a steeping chamber under conditions substantially free of chemical reaction to obtain a wetted fibrous substrate. The condition under which substantially no chemical reaction occurs means a condition of 20 ℃ to 30 ℃.
And 3, extruding the infiltrated fiber base material through a compression roller, and removing excessive liquid composition to obtain an extruded fiber base material containing the liquid composition.
And 4, covering PE films on two sides of the extruded fiber base material through a press roller.
And 5, precuring, namely, precuring the liquid composition in the extruded fiber base material under the conditions of heating, electromagnetic radiation or plasma and the like to generate polyurethane to obtain a polyurethane prepreg, and collecting the polyurethane prepreg in a material collecting roller. The content of the fiber base material in the polyurethane prepreg is 70wt%, and the prepreg can be stored for 12 days at normal temperature and normal pressure.
Example 4
This example discloses a method of making a polyurethane prepreg. The method comprises the following steps:
as shown in fig. 1, step 1, the liquid composition is prepared by the method described in example 2, the prepared liquid composition is fed into the dipping tank continuously and immediately, the feeding amount is controlled, the liquid level of the liquid composition is not too low, so as to completely dip the fiber substrate in the feeding tank, in this example, the liquid level is more than two thirds of the height of the dipping tank, so as to keep the excessive liquid composition completely submerged in the fiber substrate, which is biaxial glass fiber cloth.
Step 2, fiber substrate contacting step: the fibrous substrate is contacted with an excess of the liquid composition in the steeping cistern 1 under substantially non-chemically reactive conditions to obtain a wetted fibrous substrate. The condition under which substantially no chemical reaction occurs means a condition of 10 ℃ to 20 ℃.
And 3, extruding the infiltrated fiber base material through a compression roller, and removing excessive liquid composition to obtain an extruded fiber base material containing the liquid composition.
And 4, covering PE films on two sides of the extruded fiber base material through a press roller.
And 5, precuring, namely, precuring the liquid composition in the extruded fiber base material under the conditions of heating, electromagnetic radiation or plasma and the like to generate polyurethane to obtain a polyurethane prepreg, and collecting the polyurethane prepreg in a material collecting roller. The content of the fiber base material in the polyurethane prepreg is 70wt%, and the prepreg can be stored for 7 days at normal temperature and normal pressure.
Example 5 (fully cured preparation-molded plate)
This example discloses a method for preparing a polyurethane composite. The method comprises the following steps:
the polyurethane prepreg of example 3 was used, laid in a mold and pressed, and completely cured under high temperature and high pressure conditions to obtain a polyurethane composite material, which was a molded board. The high temperature is 100 ℃, the high pressure is 20bar, and the curing time is 10 minutes.
Example 6 (fully cured preparation-molded plate)
The polyurethane prepreg of example 4 was used, laid in a mold for pressing, and completely cured under high temperature and high pressure conditions to obtain a polyurethane composite material, which was a molded board. The high temperature is 100 ℃, the high pressure is 20bar, and the curing time is 10 minutes.
Comparative example 1
Using a liquid composition formulation and method consistent with example 1, the prepared liquid composition is continuously fed into the dip tank 1 at once, and the feed rate is controlled at 10 ℃ to 60 ℃ so that the liquid level is maintained at about half the height of the dip tank, thereby allowing a portion of the fibrous substrate to be submerged by the liquid composition without excess, e.g., the lower surface of the fibrous substrate is brought into contact with the liquid level to obtain a wetted fibrous substrate.
Pressing the wetted fibrous substrate to obtain a pressed fibrous substrate comprising the liquid composition.
And (2) carrying out pre-curing reaction on the liquid composition in the extruded fiber base material under the condition of polyurethane generation by heating, electromagnetic radiation or plasma and the like to obtain a polyurethane prepreg, and collecting the polyurethane prepreg in a material collecting roller. The content of the fiber base material in the polyurethane prepreg was 70wt%. The prepreg can be stored for only 2 days at normal temperature and pressure.
And laying the polyurethane prepreg in a mould for pressing, and completely curing under the conditions of high temperature and high pressure to obtain the polyurethane composite material which is a mould pressing plate. The high temperature is 100 ℃, the high pressure is 20bar, and the curing time is 10 minutes.
Performance detection
Sending the sample to Shanghai Polymer materials research and development center according to GB/T1447-2005 tensile property test method for fiber reinforced plastics, GB/T1449-2005 tensile property test method for fiber reinforced plastics, GB/T1451-2005 simple beam impact toughness test method for fiber reinforced plastics, GB/T1043.1-2008 impact property determination part 1 for plastic simple beam: non-instrumented impact test, GB/T2411-2008 "hardness of plastic and hard rubber measured by durometer with indentation hardness (Shore hardness)", GB/T3960-2016 "test method for sliding friction and wear of plastic" GB/T1633-2000 determination of thermoplastic Vicat Softening Temperature (VST) and GB/T1034-2008 determination of water absorption of plastics, the test conditions were as follows:
1. impact toughness (notch): impact energy 7.5J;
2. performance retention after low temperature test = performance after low temperature test/performance before low temperature test × 100%, wherein performance after low temperature test means that the specimen was taken out after-196 ℃ × 48h and immediately tested in laboratory environment (23 ℃,53 ± 2% rh);
3. notched impact strength (-50 ℃): after 3 hours at-50 ℃ the plates were taken out one by one and tested at ambient laboratory temperature (23 ℃). The impact energy is 21J, the sample size is 1 type, and the thickness is 2.90mm;
4. notched impact strength (23 ℃): the impact energy is 23J, the sample size is 1 type, and the thickness is 2.90mm;
5. coefficient of friction: the sample size was 30mm × 7mm × 3.1mm;
6. shore D hardness: two layers were superimposed and read for 15 s.
The results of the tests obtained are shown in table 2:
TABLE 2
Example 7
Liquid compositions, prepregs and polyurethane composites were prepared similarly to examples 2, 4 and 6.
In this example, when preparing the liquid composition, the isocyanate component includes isocyanate 1 and isocyanate 2; the B1) organic polyol adopts polyether 1, polyether 2 and polyether 4; the B2) epoxide is epoxide 1.
The reaction catalyst is an acid anhydride curing agent Aradur 3380.
The reinforcing material is aluminum hydroxide.
The auxiliary agent is defoaming agent BYK-A535.
The liquid composition comprises the following components in parts by weight:
20 parts of polyether 1, 10 parts of polyether 2, 30 parts of polyether 4, 30 parts of epoxide 1,0.1 part of reaction catalyst, 0.5 part of defoaming agent, 30 parts of reinforcing material and 70 parts of isocyanate 1. The ratio of the number of NCO groups in the isocyanate component to the number of OH groups in the isocyanate-reactive component is from about 0.9 to 1.0:1.
the initial viscosity of the resulting liquid composition at 25 ℃ was tested and found to be 950mpa.s, measured in accordance with DIN EN 53019.
The liquid composition was used to prepare a prepreg similarly to example 4.
The prepreg was then used to prepare a polyurethane composite, molded board, similar to example 6.
The mechanical properties and low temperature properties of the molded plate prepared in this example were comparable to those measured in example 6.
The above description is intended to be exemplary of the present disclosure, and not to limit the scope of the present disclosure, which is defined by the claims appended hereto.
Claims (18)
1. A liquid composition useful for preparing prepregs comprising a polyurethane-forming component, a reaction catalyst and a reinforcing material, wherein
The polyurethane-forming component includes A) an isocyanate component and B) an isocyanate-reactive component,
the A) isocyanate component includes one or more selected from the group consisting of: diisocyanates and polyisocyanates;
said B) isocyanate-reactive component comprises:
b1 One or more organic polyols having a hydroxyl number of from 10 to 1000mg KOH/g and a functionality of from 2 to 6;
b2 One or more epoxides having an epoxide equivalent weight of from 100 to 500g/eq,
wherein the liquid composition has an initial viscosity at 25 ℃ of from 50 to 5000mPa.s (measured according to DIN EN 53019) and the ratio of the number of NCO groups in the A) isocyanate component to the number of OH groups in the B) isocyanate-reactive component is from 0.5:1-1.2:1.
2. the liquid composition useful for preparing a prepreg according to claim 1, further comprising at least one auxiliary agent selected from the group consisting of: defoaming agent, release agent, leveling agent, durability auxiliary agent, flow auxiliary agent, organic toner, inorganic toner and color paste.
3. The liquid composition useful for preparing a prepreg according to claim 1, wherein the reaction catalyst is a latent catalyst that catalyzes at a temperature of 60 ℃ to 100 ℃, and the reaction catalyst is contained in an amount of 0.01 to 6 parts by weight, based on 100 parts by weight of the polyurethane-forming component.
4. The liquid composition useful for making a prepreg according to claim 1 wherein said B2) one or more epoxides comprises one or more selected from the group consisting of: epoxy resins based on diglycidyl ethers of bisphenol a, epoxy resins based on diglycidyl ethers of bisphenol F.
5. The liquid composition useful for making a prepreg according to claim 1 wherein said B1) one or more organic polyols comprise one or more selected from the group consisting of: pentaerythritol, ethylene Glycol (EG), 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol (NPG), diethylene glycol (EG), dipropylene glycol, trimethylolpropane (TMP), glycerol, diethylene glycol, methyl propylene glycol, polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols or polyols based on vegetable oils.
6. The liquid composition useful for preparing a prepreg according to claim 1, wherein the diisocyanate comprises at least one selected from the group consisting of: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI);
the polyisocyanate includes at least one selected from the group consisting of: polyphenyl polymethylene polyisocyanates (PAPI), triphenylmethane triisocyanate, L-lysine triisocyanate, oligomers containing multiple isocyanate groups.
7. The liquid composition useful for preparing a prepreg according to claim 1, wherein the reinforcing material comprises one or more selected from: inorganic filler, short fiber, fiber powder, glass micro-beads; wherein the reinforcing material is contained in an amount of 0.01 to 100 parts by weight, based on 100 parts by weight of the polyurethane-forming component.
8. The liquid composition useful for preparing a prepreg according to claim 1, further comprising a fibrous substrate,
the fibrous substrate comprises one or more selected from the group consisting of: glass fibers, carbon fibers, natural fibers, mineral fibers, ultra-high molecular weight polyethylene fibers, (aromatic) polyamide fibers or polyester fibers,
optionally the fibrous base material comprises long fibers,
optionally the fibrous substrate is in the form of a sheet-like textile structure,
optionally the sheet-like textile structure is formed from at least one fabric of the form: non-woven, knitted, loop-forming knitted, stretch-loop knitted, non-woven structures such as woven, laid-up scrim or knits.
9. A method of making a polyurethane prepreg comprising:
procedure for preparation of liquid composition: mixing the components of the liquid composition of any one of claims 1 to 7 under conditions that do not substantially chemically react to provide a liquid composition;
a fiber substrate contacting step: contacting the liquid composition in excess with a fibrous substrate and sufficiently wetting the fibrous substrate to obtain a wetted fibrous substrate, substantially without chemical reaction,
removal of excess liquid composition: pressing the wetted fibrous substrate to remove excess liquid composition to obtain a pressed fibrous substrate comprising the liquid composition,
pre-curing: and (c) subjecting the liquid composition in the extruded fibrous substrate to a pre-curing reaction under polyurethane-forming conditions to obtain a polyurethane prepreg.
10. The method of producing a polyurethane prepreg according to claim 9,
the step of preparing the liquid composition comprises: first mixing said B) isocyanate-reactive component, said reaction catalyst and said reinforcement material to obtain a first component, mixing said A) isocyanate component with said first component to obtain said liquid composition.
11. The method of producing a polyurethane prepreg according to claim 9, wherein said substantially chemically non-reactive condition is at least one of: ambient temperature, ambient atmospheric pressure.
12. The method of producing a polyurethane prepreg according to claim 9, wherein the condition that substantially no chemical reaction occurs means a condition of 10 ℃ to 60 ℃.
13. A method of producing a polyurethane prepreg according to claim 9 wherein the conditions under which polyurethane is produced refer to conditions under which the isocyanate and isocyanate-reactive component are reacted, for example one or more of heat, electromagnetic radiation or plasma.
14. A method of producing a polyurethane prepreg according to claim 9 wherein the content of fibrous substrate in the polyurethane prepreg is from 50 to 90wt%, preferably from 60 to 80wt%.
15. The method of producing a polyurethane prepreg according to claim 9, further comprising covering both sides of the fiber substrate with a release paper or a release film after the fiber substrate contacting step and before the pre-curing step.
16. A prepreg prepared according to the method of any one of claims 9 to 15.
17. A method of preparing a polyurethane composite comprising
Subjecting a prepreg prepared according to the method of any one of claims 9 to 15 to full cure at elevated temperature and pressure to give a polyurethane composite.
18. The method for preparing a polyurethane composite as claimed in claim 17, wherein the elevated temperature is 80 to 160 ℃, the elevated pressure is 2 to 100bar, and the curing step is performed for 1 to 10 minutes.
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