CN113150345B - High-strength moisture-proof polyurethane molded plate and preparation method thereof - Google Patents
High-strength moisture-proof polyurethane molded plate and preparation method thereof Download PDFInfo
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- CN113150345B CN113150345B CN202110593772.0A CN202110593772A CN113150345B CN 113150345 B CN113150345 B CN 113150345B CN 202110593772 A CN202110593772 A CN 202110593772A CN 113150345 B CN113150345 B CN 113150345B
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- polydimethylsiloxane
- guar gum
- polyurethane
- glass fiber
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920002907 Guar gum Polymers 0.000 claims abstract description 59
- 229960002154 guar gum Drugs 0.000 claims abstract description 59
- 235000010417 guar gum Nutrition 0.000 claims abstract description 59
- 239000000665 guar gum Substances 0.000 claims abstract description 59
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 49
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 49
- 229920001690 polydopamine Polymers 0.000 claims abstract description 49
- 239000003365 glass fiber Substances 0.000 claims abstract description 47
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004744 fabric Substances 0.000 claims abstract description 34
- 238000007598 dipping method Methods 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 28
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005098 hot rolling Methods 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 65
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 16
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 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 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- CMDKYFGIJALPLS-UHFFFAOYSA-N furan-2-thiol Chemical compound SC1=CC=CO1 CMDKYFGIJALPLS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 238000011417 postcuring Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 40
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- 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
- C08J2375/06—Polyurethanes from polyesters
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
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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)
- Polyurethanes Or Polyureas (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a high-strength moisture-proof polyurethane molded plate and a preparation method thereof. The polyurethane molded plate is obtained by hot rolling a plurality of prepregs; the prepreg comprises glass fiber cloth and resin dipping solution. Has the advantages that: (1) guar gum/polydimethylsiloxane is prepared to be used as an internal crosslinking agent of polyurethane resin, and the compatibility of the polydimethylsiloxane is enhanced and the migration is inhibited by utilizing the affinity and the reactivity; the reaction is utilized to increase the crosslinking degree and improve the tensile strength and the moisture resistance synergistically; (2) n- (2-hydroxyethyl) maleimide is used as a chain extender of the polyurethane resin and reacts with furan polydopamine particles serving as fillers to increase the crosslinking degree among the polyurethane resins, so that the strength and the moisture resistance of the molded plate are remarkably increased. (3) Polydopamine particles with small particle size are prepared through a spraying method, and the dispersity of the furan-modified polydopamine particles in the resin dipping solution is improved through surface furylation, so that the stability of the resin dipping solution is ensured.
Description
Technical Field
The invention relates to the technical field of polyurethane molded plates, in particular to a high-strength moisture-proof polyurethane molded plate and a preparation method thereof.
Background
Polyurethane is a polymer material known as "fifth plastic", and is widely used in various fields such as electronics, building materials, aerospace and the like because of its excellent properties such as good flexibility and designability of structure. The molded plate is formed by compounding thermoplastic polyurethane resin and glass fiber cloth, and a uniform continuous phase is formed between the thermoplastic polyurethane resin and the glass fiber cloth, so that the molded plate has excellent performance, is easy to process and can be recycled, and the molded plate becomes a main consumable material of shells of electronic products such as mobile phone shells, notebook computers and the like. Most of the common molded plates in the market at present are mainly made of epoxy resin, but the epoxy resin has poor elastic modulus and weak molecular design. The polyurethane resin can be controlled and adjusted to have different mechanical properties by controlling and adjusting the hard segment and the soft segment.
However, the polyurethane molded plate has poor water resistance and low strength due to more hydrophilic groups, and the application of the polyurethane molded plate is greatly limited. Inorganic materials such as graphene and carbon nanotubes are generally used to enhance mechanical strength, and organic particles are rarely used. However, due to poor dispersibility of inorganic materials such as graphene, the stability of the dipping solution is reduced, the adhesion of the dipping solution on the glass fiber cloth is affected, and the surface roughness of the polyurethane film pressing plate is obviously increased due to the addition of the inorganic filler, so that the product appearance is affected.
Therefore, it is important to solve the above problems and to prepare a high-strength moisture-resistant polyurethane molded plate.
Disclosure of Invention
The present invention is directed to a high-strength moisture-resistant polyurethane molded board and a method for manufacturing the same, which solves the above-mentioned problems of the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a high-strength moisture-resistant polyurethane molded plate is obtained by hot rolling a plurality of prepregs; the prepreg comprises glass fiber cloth and resin impregnation liquid; the resin dipping solution comprises the following raw materials: 100-125 parts of polyurethane resin, 30-50 parts of acetone, 5-10 parts of curing agent and 6-8 parts of furan polydopamine particles.
Preferably, the average particle size of the furan poly-dopamine particles is 80-200 nm.
Preferably, the raw materials of the polyurethane resin comprise the following components: 28-35 parts of isophorone diisocyanate, 32-45 parts of polyester polyol, 8-12 parts of guar gum/polydimethylsiloxane and 8-15 parts of chain extender.
Preferably, the raw material of the guar gum/polydimethylsiloxane comprises the following components: 15-22 parts of isocyanate, 22-32 parts of amino guar gum and 30-45 parts of amino polydimethylsiloxane.
Preferably, the chain extender is N- (2-hydroxyethyl) maleimide.
Preferably, the preparation method of the high-strength moisture-proof polyurethane molded plate comprises the following steps:
step 1: pretreatment of glass fiber cloth: arranging the glass fiber in acid liquor, washing and drying to obtain pretreated glass fiber cloth;
and 2, step: arranging the pretreated glass fiber on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, continuously drying, and initially curing to obtain a prepreg;
and step 3: and (3) superposing at least one layer of prepreg in a hot-pressing roller, hot-rolling and curing to obtain the molded plate.
In a more optimal way, the device is provided with a plurality of the following components,
step 1: pretreatment of glass fiber cloth: placing glass fibers in a 0.2-0.6 mol/L sulfuric acid solution for dipping for 1-2 hours, and washing and drying to obtain pretreated glass fiber cloth;
step 2: dissolving polyurethane resin in acetone, adding furan poly dopamine particles, stirring and mixing for 30-40 minutes, adding a curing agent, and continuously stirring for 30-40 minutes; obtaining resin dipping solution; arranging the pretreated glass fibers on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, setting the coating speed to be 5-8 m/min, continuously drying for 6-8 hours at the temperature of 80-100 ℃, and initially curing to obtain a prepreg;
and step 3: superposing at least one layer of prepreg in a hot-pressing roller at a set temperature of 160 to 210 ℃ and a pressure of 20 to 30kgf/cm2And the time is 5-10 minutes, hot rolling and post-curing to obtain the die-pressed plate.
Preferably, the preparation method of the furan poly dopamine particles comprises the following steps: mixing and stirring ethanol, ammonium hydroxide and deionized water in a volume ratio of (35-38) - (1-1.2) - (15-18) for 10-20 minutes to obtain a mixed solvent; dissolving dopamine hydrochloride in deionized water to obtain 25-50 g/L dopamine solution, injecting the dopamine solution into a mixed solvent in a spraying mode, stirring for 24 hours, carrying out centrifugal separation, washing, filtering and drying to obtain polydopamine nanoparticles; dispersing the poly-dopamine in ethanol to form a suspension, dropwise adding triethylamine, adjusting the pH value to 8.8-9.2, setting the temperature to be 58-65 ℃, dropwise adding furanthiol, reacting for 8-10 hours, filtering, washing and drying to obtain the furanized poly-dopamine particles.
Preferably, the preparation method of the polyurethane resin comprises the following steps: sequentially adding isophorone diisocyanate, polycaprolactone diol and 2, 2-dimethylolbutyric acid into a reaction kettle, and reacting for 2-3 hours at the set temperature of 80-82 ℃ in the nitrogen atmosphere; adding guar gum/polydimethylsiloxane, and continuously reacting for 1-2 hours; cooling to 75-78 ℃, adding N- (2-hydroxyethyl) maleimide, a catalyst and methyl ethyl ketone, and continuing to react for 3-4 hours for chain extension; and cooling to 38-45 ℃, adding triethylamine for neutralization, filtering and washing to obtain the polyurethane resin.
Preferably, the preparation method of the guar gum/polydimethylsiloxane comprises the following steps: respectively dissolving amino polydimethylsiloxane, isocyanate and amino guar gum in an acetone solvent to obtain 15-20 g/L, 30-40 g/L and 10-15 g/L guar gum solutions; mixing and homogenizing the isocyanate solution and the amino polydimethylsiloxane solution for 20-40 seconds to obtain a mixed solution; and (3) dripping the guar gum into a guar gum solution for 1-3 hours, and continuously stirring for 3-8 minutes after dripping is finished to obtain the guar gum/polydimethylsiloxane.
According to the technical scheme, glass fiber cloth is used as a reinforcing material, resin impregnation liquid is coated on two surfaces of the glass fiber cloth, prepreg is obtained through initial curing, and then a plurality of prepregs are subjected to hot rolling at high temperature to obtain the molded plate. The moisture resistance and the strength of the molded plate are synergistically increased by utilizing the designed and prepared polyurethane resin and the furan polydopamine particles.
First, a polyurethane resin is designed, the polyurethane usually contains hard segments of carboxyl groups and soft satin of amino groups, and the water resistance of the polyurethane depends on the type of soft satin and the distribution of hydrophilic groups. The material commonly used for modifying the polyurethane soft satin is hydrophobic hydroxyl-terminated polydimethylsiloxane, but the material has poor compatibility in the modification process, so that the distribution is uneven, and the mechanical capacity of the polyurethane is reduced; meanwhile, the substance is easy to migrate to the surface of polyurethane to influence the dispersibility of the substance, so that the polyurethane glue solution is unstable. Therefore, in the scheme, isocyanate is used as a strong hydrogen donor and an acceptor, guar gum/polydimethylsiloxane is obtained by the reaction between isocyanate groups and amino groups in amino polydimethylsiloxane and amino guar gum, the guar gum/polydimethylsiloxane is used as an internal crosslinking agent of polyurethane, the affinity between ester groups in the chain break of the guar gum/polydimethylsiloxane and ester groups of other substances in a raw material of polyurethane resin is utilized, the reaction between residual isocyanate groups in a molecular chain and soft segment amino groups in the polyurethane resin and the reaction between amino groups in the molecular chain and isocyanate groups in the polyurethane resin are utilized, and the compatibility of the polydimethylsiloxane is enhanced through the affinity and the reactivity, and the specific process comprises the following steps: because hydroxyl in guar gum and isocyanate in polyurethane raw materials can form more polyurethane bonds, the crosslinking degree in polyurethane resin is increased, the expansion of water absorption chain break is inhibited, the moisture resistance is improved, and the migration of polydimethylsiloxane chain break is also inhibited. It should be noted that the amount of the substance added is not too large, because unstable hydrogen bonds are formed between amino groups and carboxyl groups, which may cause excessive cross-linking and disturb molecular order, thereby reducing tensile strength.
In addition, N- (2-hydroxyethyl) maleimide is used as a chain extender to form an end cap of polyurethane, and the end cap reacts with the furan poly-dopamine particles to increase the strength of a molded plate.
Second, dopamine is an adhesive having excellent waterproof adhesive power, and is added to a polyurethane glue solution to increase the adhesive power with glass cloth. In the scheme, the poly-dopamine particles are prepared, the surfaces of the poly-dopamine particles are modified, the furylated poly-dopamine particles are obtained, and the mechanical property and the moisture resistance of the molded plate are improved.
In the preparation process, dopamine hydrochloride is injected into the mixed solvent in a nitrogen spraying mode, so that the reaction force is increased, and the particle size of the polydopamine particles is reduced. Thereby better dispersing in the resin dipping solution. The particles increase cross-linking points in the curing process, and have surface interaction with a urethane resin network, so that the migration of polymer chains is inhibited, and the tensile strength and the heat resistance are enhanced; the water absorption and degradation of the polyurethane network are inhibited, and the moisture resistance is enhanced. Specifically, the method comprises the following steps: the furan rings on the surface of the particles and the maleic amide in the polyurethane resin can generate cycloaddition reaction at high temperature, so that the crosslinking degree of the resin dipping solution is obviously increased by curing. Thereby significantly increasing the strength and moisture resistance of the molded board. Meanwhile, due to the reactivity after modification, excellent compatibility is formed, the cohesive force of the resin glue solution is improved, and higher strength is obtained.
Compared with the prior art, the invention has the following beneficial effects: (1) guar gum/polydimethylsiloxane is prepared as an internal crosslinking agent of the polyurethane resin, and the compatibility of the polydimethylsiloxane is enhanced and the migration is inhibited by utilizing the affinity and the reactivity; the crosslinking degree is increased by utilizing the reaction, and the tensile strength and the moisture resistance of the polyurethane resin are improved by the cooperation of the guar gum and the polydimethylsiloxane; (2) n- (2-hydroxyethyl) maleimide is used as a chain extender of the polyurethane resin, and the N- (2-hydroxyethyl) maleimide and the furan polydopamine particles generate cycloaddition reaction in the high-temperature curing process, so that the crosslinking degree between the polyurethane resins is increased, and the strength and the moisture resistance of the molded plate are obviously increased. (3) Polydopamine particles with small particle size are prepared through a spraying method, and surface furylation is performed, so that the dispersibility of the furylated polydopamine particles in the resin dipping solution is improved, and the stability of the resin dipping solution is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
step 1: pretreatment of glass fiber cloth: placing glass fiber in 0.4mol/L sulfuric acid solution for dipping for 1-2 hours, washing and drying to obtain pretreated glass fiber cloth;
step 2:
(1) mixing and stirring ethanol, ammonium hydroxide and deionized water for 15 minutes, wherein the volume ratio is 36:1.1: 16; dissolving dopamine hydrochloride in deionized water to obtain a solution of 30g/L, injecting the solution into a mixed solvent in a spraying mode, stirring for 24 hours, centrifugally separating, washing, filtering and drying to obtain poly-dopamine nano particles; dispersing the poly-dopamine in ethanol to form a suspension, dropwise adding triethylamine, adjusting the pH value to 9, setting the temperature to be 60 ℃, dropwise adding furanthiol, reacting for 9 hours, filtering, washing and drying to obtain furanized poly-dopamine particles;
(2) respectively dissolving amino polydimethylsiloxane, isocyanate and amino guar gum in an acetone solvent to obtain 18g/L, 35g/L and 12g/L guar gum solutions; mixing and homogenizing the isocyanate solution and the amino polydimethylsiloxane solution for 30 seconds to obtain a mixed solution; dripping the guar gum into guar gum solution for 1.5 hours, and continuing stirring for 5 minutes after dripping is finished to obtain guar gum/polydimethylsiloxane for later use; adding isophorone diisocyanate, polycaprolactone diol and 2, 2-dimethylolbutyric acid into a reaction kettle in sequence, and reacting at 81 ℃ for 2.5 hours under the atmosphere of nitrogen; adding guar gum/polydimethylsiloxane, and continuing to react for 1.5 hours; cooling to 76 ℃, adding N- (2-ethoxyl) maleimide, a catalyst and methyl ethyl ketone, and continuing to react for 3.5 hours for chain extension; cooling to 40 ℃, adding triethylamine for neutralization, filtering and washing to obtain the polyurethane resin.
(3) Dissolving polyurethane resin in acetone, adding furan poly dopamine particles, stirring and mixing for 35 minutes, adding a curing agent, and continuing stirring for 35 minutes; obtaining resin dipping solution;
(4) arranging the pretreated glass fiber on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, setting the coating speed to be 6m/min, continuously drying for 7 hours at the temperature of 90 ℃, and primarily curing to obtain a prepreg;
and step 3: superposing at least one layer of prepreg in a hot-pressing roller, setting the temperature at 180 ℃ and the pressure at 25kgf/cm2Hot rolling for 8 minutes, and post-curing to obtain the molded plate.
In this example, the raw materials of the polyurethane molded plate include the following components: 65% of glass fiber cloth and 35% of resin dipping solution by weight percentage; the resin dipping solution comprises the following raw materials: by weight, 110 parts of polyurethane resin, 42 parts of acetone, 6 parts of isocyanate curing agent and 7 parts of furan-modified polydopamine particles; the polyurethane resin comprises the following raw materials: 31 parts of isophorone diisocyanate, 36 parts of polyester polyol, 10 parts of guar gum/polydimethylsiloxane and 12 parts of N- (2-hydroxyethyl) maleimide by weight; the raw materials of the guar gum/polydimethylsiloxane comprise the following components: 18 parts of isocyanate, 28 parts of amino guar gum and 40 parts of amino polydimethylsiloxane; the average particle size of the furan polydopamine particles is 92 nm.
Example 2:
step 1: pretreatment of glass fiber cloth: placing glass fiber in 0.2mol/L sulfuric acid solution for dipping for 1 hour, washing and drying to obtain pretreated glass fiber cloth;
step 2:
(1) mixing and stirring ethanol, ammonium hydroxide and deionized water for 10 minutes, wherein the volume ratio is 35:1: 15; dissolving dopamine hydrochloride in deionized water to obtain a solution of 25g/L, injecting the solution into a mixed solvent in a spraying mode, stirring for 24 hours, carrying out centrifugal separation, washing, filtering and drying to obtain poly-dopamine nanoparticles; dispersing the poly-dopamine in ethanol to form a suspension, dropwise adding triethylamine, adjusting the pH value to 8.8, setting the temperature to be 58 ℃, dropwise adding furanthiol, reacting for 8 hours, filtering, washing and drying to obtain furanized poly-dopamine particles;
(2) respectively dissolving amino polydimethylsiloxane, isocyanate and amino guar gum into an acetone solvent to obtain 15g/L, 30g/L and 10g/L guar gum solutions; mixing and homogenizing the isocyanate solution and the amino polydimethylsiloxane solution for 20 seconds to obtain a mixed solution; dripping the guar gum into guar gum solution for hours, and continuously stirring for 3 minutes after the dripping is finished to obtain guar gum/polydimethylsiloxane for later use; adding isophorone diisocyanate, polycaprolactone diol and 2, 2-dimethylolbutyric acid into a reaction kettle in sequence, and reacting for 2 hours at the set temperature of 80 ℃ in a nitrogen atmosphere; adding guar gum/polydimethylsiloxane, and continuing to react for 1 hour; cooling to 75 ℃, adding N- (2-ethoxyl) maleimide, a catalyst and methyl ethyl ketone, and continuing to react for 3 hours for chain extension; cooling to 38 ℃, adding triethylamine for neutralization, filtering and washing to obtain the polyurethane resin.
(3) Dissolving polyurethane resin in acetone, adding furan poly dopamine particles, stirring and mixing for 30 minutes, adding a curing agent, and continuing stirring for 30 minutes; obtaining resin dipping solution;
(4) arranging the pretreated glass fiber on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, setting the coating speed to be 8m/min, continuously drying for 6 hours at the temperature of 80 ℃, and carrying out primary curing to obtain a prepreg;
and step 3: superposing at least one layer of prepreg in a hot-pressing roller at 160 deg.C and 20kgf/cm2Hot rolling for 10 minutes, and post-curing to obtain a molded plate.
In this example, the raw materials of the polyurethane molded plate include the following components: 60% of glass fiber cloth and 40% of resin dipping solution in percentage by weight; the resin dipping solution comprises the following raw materials: by weight, 100 parts of polyurethane resin, 30 parts of acetone, 5 parts of isocyanate curing agent and 6 parts of furan-modified polydopamine particles; the polyurethane resin comprises the following raw materials: 28 parts of isophorone diisocyanate, 32 parts of polyester polyol, 8 parts of guar gum/polydimethylsiloxane and 8 parts of N- (2-hydroxyethyl) maleimide by weight; the raw materials of the guar gum/polydimethylsiloxane comprise the following components: 15 parts of isocyanate, 22 parts of amino guar gum and 30 parts of amino polydimethylsiloxane; the average particle size of the furan polydopamine particles is 80 nm.
Example 3: step 1: pretreatment of glass fiber cloth: placing glass fibers in a 0.6mol/L sulfuric acid solution, soaking for 1-2 hours, washing and drying to obtain pretreated glass fiber cloth;
step 2:
(1) mixing and stirring ethanol, ammonium hydroxide and deionized water for 20 minutes, wherein the volume ratio is 38:1.2: 18; dissolving dopamine hydrochloride in deionized water to obtain a solution of 25-50 g/L, injecting the solution into a mixed solvent in a spraying mode, stirring for 24 hours, carrying out centrifugal separation, washing, filtering and drying to obtain polydopamine nanoparticles; dispersing the poly-dopamine in ethanol to form a suspension, dropwise adding triethylamine, adjusting the pH value to 9.2, setting the temperature to 65 ℃, dropwise adding furanthiol, reacting for 10 hours, filtering, washing and drying to obtain furanized poly-dopamine particles;
(2) respectively dissolving amino polydimethylsiloxane, isocyanate and amino guar gum in an acetone solvent to obtain 20g/L, 40g/L and 115g/L guar gum solutions; mixing and homogenizing the isocyanate solution and the amino polydimethylsiloxane solution for 40 seconds to obtain a mixed solution; dripping the guar gum into guar gum solution for 3 hours, and continuing stirring for 8 minutes after the dripping is finished to obtain guar gum/polydimethylsiloxane for later use; adding isophorone diisocyanate, polycaprolactone diol and 2, 2-dimethylolbutyric acid into a reaction kettle in sequence, and reacting for 3 hours at 82 ℃ in a nitrogen atmosphere; adding guar gum/polydimethylsiloxane, and continuing to react for 2 hours; cooling to 78 ℃, adding N- (2-ethoxyl) maleimide, a catalyst and methyl ethyl ketone, and continuing to react for 4 hours for chain extension; cooling to 45 ℃, adding triethylamine for neutralization, filtering and washing to obtain the polyurethane resin.
(3) Dissolving polyurethane resin in acetone, adding furan poly dopamine particles, stirring and mixing for 40 minutes, adding a curing agent, and continuing stirring for 40 minutes; obtaining resin dipping solution;
(4) arranging the pretreated glass fiber on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, setting the coating speed to be 5m/min, continuously drying for 8 hours at the temperature of 100 ℃, and carrying out primary curing to obtain a prepreg;
and step 3: superposing at least one layer of prepreg in a hot-press roller at 210 deg.C and 30kgf/cm2Hot rolling for 5 minutes, and post-curing to obtain a molded plate.
In this example, the raw materials of the polyurethane molded plate include the following components: 70% of glass fiber cloth and 30% of resin dipping solution according to weight percentage; the resin dipping solution comprises the following raw materials: 125 parts of polyurethane resin, 50 parts of acetone, 10 parts of isocyanate curing agent and 8 parts of furan poly dopamine particles; the polyurethane resin comprises the following raw materials: 35 parts of isophorone diisocyanate, 45 parts of polyester polyol, 12 parts of guar gum/polydimethylsiloxane and 15 parts of N- (2-hydroxyethyl) maleimide by weight; the raw materials of the guar gum/polydimethylsiloxane comprise the following components: 22 parts of isocyanate, 32 parts of amino guar gum and 45 parts of amino polydimethylsiloxane; the average particle size of the furan polydopamine particles is 200 nm.
Example 4: no guar/dimethicone was added; adding the amino guar gum and the amino polydimethylsiloxane directly; the rest is the same as in example 1.
In this embodiment, the raw materials of the polyurethane resin include the following components: 31 parts of isophorone diisocyanate, 36 parts of polyester polyol, 4 parts of amino guar gum, 6 parts of amino polydimethylsiloxane and 12 parts of N- (2-hydroxyethyl) maleimide.
Example 5: no guar gum was added; otherwise, the same as example 1;
example 6: replacing the chain extender N- (2-hydroxyethyl) maleimide with 1, 4-dibutanol; otherwise, the same as example 1;
example 7: no furylated polydopamine particles were added; otherwise, the same as example 1;
example 8: the procedure of example 1 was repeated except that the polydopamine particles were used as they were without being furylated;
experiment: cutting a high-strength moisture-proof polyurethane molded plate prepared in examples 1-8 into a square of 8cm multiplied by 8cm, (1) testing the tensile strength (MPa) and the flexural modulus (GPa) by adopting a GB/T528-1992 standard testing method and a universal material testing machine; (2) the weight of the polyurethane molded plate before soaking is measured as m1(ii) a Soaking in distilled water at normal temperature for 7 days, taking out, removing surface water with absorbent paper, and weighing to obtain m2Moisture absorption rate ═ m2－m1)/m1X 100%, the results obtained are shown in the following table:
and (4) conclusion: the data of comparative examples 1-3 show that the prepared polyurethane molded plate has the tensile strength of more than 350MPa, the flexural modulus of more than 16GPa, the moisture absorption rate of less than 1 percent and good moisture resistance.
The data of comparative example 4 can find that the mechanical properties are reduced because: the amino guar gum and the amino polydimethylsiloxane are directly added, so that the migration of the polydimethylsiloxane cannot be inhibited, the compatibility is poor, and the mechanical property is reduced; and because the polydimethylsiloxane is not anchored in the internal cross-linked network of the polyurethane, the internal swelling is reduced, and the moisture absorption rate is increased. In the data of comparative example 5, it can be found that the mechanical properties are greatly reduced and the moisture absorption rate is obviously increased because: because hydroxyl in guar gum and isocyanate in polyurethane raw materials can form more polyurethane bonds, the crosslinking degree in polyurethane resin is increased, the expansion of water absorption chain break is inhibited, the moisture resistance is improved, and the migration of polydimethylsiloxane chain break is also inhibited. There is a synergistic effect between the two substances.
Similarly, the data of comparative examples 6 to 8 show that the mechanical properties are decreased and the moisture absorption rate is increased. The reason is that: the polydopamine particles are prepared from waterproof adhesive dopamine, and can be added into polyurethane glue solution to increase the adhesive force between the polydopamine particles and glass fiber cloth, and have an acting force with polyurethane resin to increase the mechanical property. Meanwhile, N- (2-hydroxyethyl) maleimide is used as a chain extender of the polyurethane resin, and the N- (2-hydroxyethyl) maleimide and the furan polydopamine particles generate cycloaddition reaction in the high-temperature curing process, so that the crosslinking degree among the polyurethane resins is increased, and the strength and the moisture resistance of the molded plate are obviously increased.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A high-strength moisture-proof polyurethane molded plate is characterized in that: the polyurethane molded plate is obtained by hot rolling a plurality of prepregs; the prepreg comprises glass fiber cloth and resin impregnation liquid; the resin dipping solution comprises the following raw materials: 100-125 parts of polyurethane resin, 30-50 parts of acetone, 5-10 parts of curing agent and 6-8 parts of furan polydopamine particles by weight;
the preparation method of the polyurethane resin comprises the following steps: adding isophorone diisocyanate, polycaprolactone diol and 2, 2-dimethylolbutyric acid into a reaction kettle in sequence, and reacting for 2-3 hours at the set temperature of 80-82 ℃ in a nitrogen atmosphere; adding guar gum/polydimethylsiloxane, and continuously reacting for 1-2 hours; cooling to 75-78 ℃, adding N- (2-hydroxyethyl) maleimide, a catalyst and methyl ethyl ketone, and continuing to react for 3-4 hours for chain extension; cooling to 38-45 ℃, adding triethylamine for neutralization, filtering and washing to obtain polyurethane resin;
the preparation method of the guar gum/polydimethylsiloxane comprises the following steps: respectively dissolving amino polydimethylsiloxane, isocyanate and amino guar gum in an acetone solvent to obtain solutions of 15-20 g/L, 30-40 g/L and 10-15 g/L; mixing and homogenizing the isocyanate solution and the amino polydimethylsiloxane solution for 20-40 seconds to obtain a mixed solution; dripping the guar gum into a guar gum solution for 1-3 hours, and continuing stirring for 3-8 minutes after dripping is finished to obtain guar gum/polydimethylsiloxane;
the preparation method of the furan poly dopamine particle comprises the following steps: mixing and stirring ethanol, ammonium hydroxide and deionized water in a volume ratio of (35-38) - (1-1.2) - (15-18) for 10-20 minutes to obtain a mixed solvent; dissolving dopamine hydrochloride in deionized water to obtain 25-50 g/L dopamine solution, injecting the dopamine solution into a mixed solvent in a spraying manner, stirring for 24 hours, carrying out centrifugal separation, washing, filtering and drying to obtain polydopamine nanoparticles; dispersing the poly-dopamine in ethanol to form a suspension, dropwise adding triethylamine, adjusting the pH value to 8.8-9.2, setting the temperature to be 58-65 ℃, dropwise adding furanthiol, reacting for 8-10 hours, filtering, washing and drying to obtain the furanized poly-dopamine particles.
2. The high strength moisture resistant polyurethane molded board as claimed in claim 1, wherein: the average particle size of the furan polydopamine particles is 80-200 nm.
3. The high strength moisture resistant polyurethane molded board as claimed in claim 1, wherein: the polyurethane resin comprises the following raw materials: 28-35 parts of isophorone diisocyanate, 32-45 parts of polyester polyol, 8-12 parts of guar gum/polydimethylsiloxane and 8-15 parts of chain extender.
4. The high strength moisture resistant polyurethane molded board as claimed in claim 3, wherein: the raw materials of the guar gum/polydimethylsiloxane comprise the following components: 15-22 parts of isocyanate, 22-32 parts of amino guar gum and 30-45 parts of amino polydimethylsiloxane.
5. The high strength moisture resistant polyurethane molded board as claimed in claim 1, wherein: the preparation method of the polyurethane molded plate comprises the following steps:
step 1: pretreatment of glass fiber cloth: arranging the glass fiber in acid liquor, washing and drying to obtain pretreated glass fiber cloth;
step 2: arranging the pretreated glass fiber on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, continuously drying, and initially curing to obtain a prepreg;
and step 3: and (3) superposing at least one layer of prepreg in a hot-pressing roller, hot-rolling and curing to obtain the molded plate.
6. The high strength moisture resistant polyurethane molded board according to claim 5, wherein: the method comprises the following steps:
step 1: pretreatment of glass fiber cloth: placing glass fibers in a 0.2-0.6 mol/L sulfuric acid solution, soaking for 1-2 hours, washing and drying to obtain pretreated glass fiber cloth;
step 2: dissolving polyurethane resin in acetone, adding furan poly dopamine particles, stirring and mixing for 30-40 minutes, adding a curing agent, and continuously stirring for 30-40 minutes; obtaining resin gum dipping liquid; arranging the pretreated glass fibers on a coating machine, uniformly coating resin dipping solution on two sides of the pretreated glass fiber cloth, setting the coating speed to be 5-8 m/min, continuously drying for 6-8 hours at the temperature of 80-100 ℃, and initially curing to obtain a prepreg;
and step 3: superposing at least one layer of prepreg in a hot-pressing roller, wherein the set temperature is 160-210 ℃, and the pressure is 20-30 kgf/cm2And the time is 5-10 minutes, hot rolling and post-curing to obtain the die-pressed plate.
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| EP1642620A1 (en) * | 2004-10-04 | 2006-04-05 | L'oreal, S.A. | Hair cosmetic composition comprising hollow particles and silicone fixing polyurethane |
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| JP2001031783A (en) * | 1999-05-14 | 2001-02-06 | Toray Ind Inc | Prepreg and fiber-reinforced composite material |
| EP1642620A1 (en) * | 2004-10-04 | 2006-04-05 | L'oreal, S.A. | Hair cosmetic composition comprising hollow particles and silicone fixing polyurethane |
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