CN115584008A - 一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯及制备 - Google Patents
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯及制备 Download PDFInfo
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 239000004814 polyurethane Substances 0.000 title claims abstract description 19
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 alcohol compound Chemical class 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 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 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000002009 diols Chemical class 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000013638 trimer Substances 0.000 claims description 4
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VLGNTAHJZQOHJE-UHFFFAOYSA-N (6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical compound OC1(C(C(=O)C2=CC=CC=C2)C=CC=C1)C VLGNTAHJZQOHJE-UHFFFAOYSA-N 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- UQBRAHLFLCMLBA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1 Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1 UQBRAHLFLCMLBA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 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
- 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
- C08G18/44—Polycarbonates
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08J5/18—Manufacture of films or sheets
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- 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
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
本发明涉及C09D175/14,具体涉及一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯及制备。包括以下原料:按质量份计,异氰酸酯10‑30份,丙烯酸酯50‑70份,二元醇类化合物1.5‑2.5份,催化剂0.01‑0.05份,光引发剂0.1‑0.5。本发明具有良好的耐高温性,兼具高硬度和高柔韧性的同时还具有良好的手感。
Description
技术领域
本发明涉及C09D175/14,具体涉及一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯及制备。
背景技术
聚氨酯丙烯酸酯结合了聚氨酯和聚丙烯酸酯的优点,被广泛地应用于涂料、印刷和油墨等各个领域。
专利CN202010322932.3UV固化高耐磨高韧性聚氨酯丙烯酸酯树脂及其制备方法通过羟基丙烯酸酯,第一类异氰酸酯,第二类异氰酸酯等为主要原料,采用一步法进行反应制得的聚氨酯丙烯酸酯树脂具有耐摩擦和耐溶剂性好,抗开裂等优异性能。
专利CN201511019707.8紫外光固化聚氨酯丙烯酸酯及其制备方法通过引入改性剂对二异氰酸酯改性,继续与二元醇、多羟基羧酸等发生反应制备得到的聚氨酯丙烯酸酯树脂操作简单,易于工业化生产。
但现有技术中制备得到聚氨酯丙烯酸酯耐高温、柔韧性等性能较差,无法长时间应用于手机、电脑及移动设备领域。
发明内容
为了解决上述技术问题,本发明的第一个方面提供了一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,包括以下原料:按质量份计,异氰酸酯10-30份,丙烯酸酯50-70份,二元醇类化合物1.5-2.5份,催化剂0.01-0.05份,光引发剂0.1-0.5。
优选的,所述异氰酸酯包括甲苯二异氰酸酯、六亚甲基二异氰酸酯、六亚甲基二异氰酸酯三聚体、二苯基甲烷二异氰酸酯、氢化苯甲基二异氰酸酯、2.4-甲苯二异氰酸酯三聚体、异氟尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯的至少一种。
进一步优选的,所述异氰酸酯包括甲苯二异氰酸酯和异氟尔酮二异氰酸酯。所述甲苯二异氰酸酯和异氟尔酮二异氰酸酯的质量比为(3-5):(5-8)。
优选的,所述丙烯酸酯包括含羟基丙烯酸酯、含氨基丙烯酸酯、含烷氧基丙烯酸酯的至少一种。
进一步优选的,所述丙烯酸酯为含羟基丙烯酸酯。
优选的,所述含羟基丙烯酸酯包括丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、三羟甲基丙烷三丙烯酸酯、双-三羟甲基丙烷四丙烯酸酯、季戊四醇三丙烯酸酯、己二醇二丙烯酸酯、2-羟基-3-苯氧基丙烯酸丙酯、新戊二醇二丙烯酸酯的至少一种。
进一步优选的,所述丙烯酸酯为包括丙烯酸羟乙酯和季戊四醇三丙烯酸酯。所述丙烯酸羟乙酯和季戊四醇三丙烯酸酯的质量比为1:(2-4)。
优选的,所述二元醇类化合物包括聚碳酸酯二元醇、聚己内酯二元醇、聚醚二元醇、聚四氢呋喃醚二元醇的的一种或几种。
优选的,所述二元醇类化合物的平均分子量为1500-2500。
优选的,所述二元醇类化合物的羟基含量1.5-2.0wt%。
优选的,所述二元醇类化合物75℃下的粘度为1700-2300cps。
进一步优选的,所述二元醇类化合物为聚碳酸酯二元醇。
优选的,所述催化剂包括五甲基二乙烯三胺、二甲基环己胺、二月桂酸二丁基锡、有机铋、三嗪类三聚催化剂等中的至少一种。
优选的,所述光引发剂包括2-羟基-2-甲基苯酮、1-羟基环己基苯酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦的至少一种。
进一步优选的,所述光引发剂为1-羟基环己基苯酮。
优选的,所述一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,所述原料还包括抗氧剂0.1-1份,流平剂0.1-0.3份,润湿剂1-3份。
优选的,所述抗氧剂包括过氧化物分解型抗氧剂、酚型抗氧剂、胺型抗氧剂、硫型抗氧剂、磷型抗氧剂的至少一种。
进一步优选的,所述抗氧剂包括酚型抗氧剂。
优选的,所述酚型抗氧剂包括2,5-二叔丁基对苯二酚,2,6-二叔丁基对苯二酚,2,5-二特丁基对苯二酚,2,2二甲基-双(4-甲基-6-叔丁基苯酚)。
进一步优选的,所述酚型抗氧剂为2,5-二叔丁基对苯二酚。
优选的,所述流平剂包括聚醚硅氧烷共聚物,聚酯硅氧烷共聚,物,烷基改性硅氧烷,聚丙烯酸酯的至少一种。
优选的,所述流平剂在25℃下的粘度为80-120mPa·s。
进一步优选的,所述流平剂包括聚醚硅氧烷共聚物。
优选的,所述润湿剂包括烷氧基表面活性剂、硅表面活性剂、磺基琥珀酸酯类化合物的至少一种。
优选的,所述润湿剂包括硅表面活性剂,磺基琥珀酸酯类化合物。所述硅表面活性剂,磺基琥珀酸酯类化合物的质量比为(1.0-1.5):(0.8-1.2)。
本发明的第二个方面提供了一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯的制备方法,包括以下步骤:
(1)将催化剂分为两份,第一份催化剂与异氰酸酯、溶剂混合均匀,升温至40-60℃,加入二元醇类化合物反应3-5h得到混合物A;
(2)将混合物A与丙烯酸酯,第二份催化剂混合均匀,升温到60-70℃,反应1-2h,加入剩余原料搅拌混合混匀即得。
有益效果:
1)本发明通过采用特定含量和特定种类的原料,对体系中各物质加以限定,反应制得的耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯同时兼具高硬度和高柔韧性,而且耐高温性好,特别适合手机背壳的应用,对手机具有良好保护效果的同时还具有良好的手感。
2)本发明通过引入聚碳酸酯二元醇对异氰酸酯进行处理,增加了体系中软段结构,使制备得到的聚氨酯丙烯酸酯具有更好的柔韧性,提高了拉伸强度。尤其是当平均分子量为1500-2500;羟基含量1.5-2.0wt%时,具有适宜的反应速度,避免由于分子量过高导致双键密度降低,硬度和耐热稳定性下降。
3)聚碳酸酯二元醇的加入,提高柔韧性和拉伸强度的同时,由于C-O键的键能较小,容易导致聚氨酯丙烯酸酯的热稳定性较差,本发明通过采用丙烯酸羟乙酯和季戊四醇三丙烯酸酯极性复配,尤其是质量比为1:(2-4)时,与制备得到的聚氨酯预聚物共同作用,控制交联速率,加快涂膜干燥速度,提高附着力,同时避免固化膜在较高的温度下,发生软化变形。
4)本发明采用甲苯二异氰酸酯和异氟尔酮二异氰酸酯,活性基团之间具有不同的反应活性,控制体系反应,与本发明所述2,5-二叔丁基对苯二酚共同作用,具有更高的柔韧性,硬度和耐热性,同时与本发明所述1-羟基环己基苯酮,25℃下的粘度为100mPa·s的聚醚硅氧烷共聚物等物质共同作用,得到的固化膜具有更高的透明性和防雾性,无起泡发皱,光泽度高。
5)本发明制得的耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯还具有机械强度高,具有较好的抗磨擦性和耐候性,耐腐蚀性等优异性能。
具体实施方式
实施例
实施例1
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,包括以下原料:按质量份计,异氰酸酯20份,丙烯酸酯60份,二元醇类化合物2份,抗氧剂0.8份,催化剂0.04份,光引发剂0.25份,流平剂0.2份,润湿剂2份。
所述异氰酸酯包括甲苯二异氰酸酯和异氟尔酮二异氰酸酯。所述甲苯二异氰酸酯和异氟尔酮二异氰酸酯的质量比为4:7。所述甲苯二异氰酸酯包括2,4二甲苯二异氰酸酯80%和2,6二甲苯二异氰酸酯20%,所述甲苯二异氰酸酯购自山东京昊化工有限公司。所述异氟尔酮二异氰酸酯包括75%顺式和25%反式异构体,NCO的质量分数≥37.5%,所述异氟尔酮二异氰酸酯购自广州昊毅新材料科技股份有限公司,型号:科思创(原拜耳)DesmodurI。
所述丙烯酸酯为含羟基丙烯酸酯。所述丙烯酸酯为包括丙烯酸羟乙酯和季戊四醇三丙烯酸酯。所述丙烯酸羟乙酯和季戊四醇三丙烯酸酯的质量比为1:3。
所述二元醇类化合物包括聚碳酸酯二元醇。所述二元醇类化合物的平均分子量为2000。所述二元醇类化合物的羟基含量1.7wt%。所述二元醇类化合物75℃下的粘度为1960cps。所述二元醇类化合物购自广州昊毅新材料科技股份有限公司,型号:PCDL 1022。
所述催化剂为二月桂酸二丁基锡。
所述光引发剂为1-羟基环己基苯酮。所述光引发剂购自广州昊毅新材料科技股份有限公司,型号:光引发剂184。
所述抗氧剂包括2,5-二叔丁基对苯二酚。所述抗氧剂购自宜兴市天使合成化学有限公司,型号:抗氧剂DTBHQ。
所述流平剂在25℃下的粘度为100mPa·s。所述流平剂包括聚醚硅氧烷共聚物。所述流平剂购自凯茵化工,型号:迪高流平剂Flow 425。
所述润湿剂包括硅表面活性剂,磺基琥珀酸酯类化合物。所述硅表面活性剂,磺基琥珀酸酯类化合物的质量比为1.2:1。所述硅表面活性剂为Hydropalat WE 3240,所述磺基琥珀酸酯类化合物为Hydropalat WE 3488。所述润湿剂均购自广州昊毅新材料科技股份有限公司。
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯的制备方法,包括以下步骤:
(1)将催化剂分为两份,第一份催化剂(占催化剂总质量的40%)与异氰酸酯、溶剂混合均匀,升温至50℃,加入二元醇类化合物反应4h得到混合物A;
(2)将混合物A与丙烯酸酯,第二份催化剂(占催化剂总质量的60%)混合均匀,升温到65℃,反应1.5h,加入剩余原料搅拌混合混匀即得。
实施例2
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,具体实施方式同实施例1,不同之处在于所述甲苯二异氰酸酯和异氟尔酮二异氰酸酯的质量比为5:8。
实施例3
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,具体实施方式同实施例1,不同之处在于所述原料包括异氰酸酯30份,丙烯酸酯70份,二元醇类化合物2.5份,抗氧剂1份,催化剂0.05份,光引发剂0.5份,流平剂0.3份,润湿剂3份。
对比例1
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,具体实施方式同实施例1,不同之处在于所述聚碳酸酯二元醇的平均分子量为3000,羟值为37±3,75℃粘度为6500-9800,型号PH-300,购自广州昊毅新材料科技股份有限公司。
对比例2
一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,具体实施方式同实施例1,不同之处在于所述丙烯酸羟乙酯和季戊四醇三丙烯酸酯的质量比为1:6。
性能测试
使用条件:250W紫外灯光照射,灯距5cm,时间30s。
1.硬度:按照GB/T 6739-2006进行铅笔硬度试验;
2.柔韧性:按照GB/T 6742-2007进行弯曲试验,试板为钢板;
3.耐高温性:按照GB/T 1735进行耐热性试验,测试条件:试板:钢板,温度:90℃,时间:3h。
表1性能测试结果
硬度 | 柔韧性(2mm) | 耐热性 | |
实施例1 | 4H | 未开裂 | 无鼓泡起皱 |
实施例2 | 3H | 未开裂 | 无鼓泡起皱 |
实施例3 | 3H | 未开裂 | 无鼓泡起皱 |
对比例1 | 2H | 开裂 | 有鼓泡起皱 |
对比例2 | 2H | 开裂 | 有鼓泡起皱 |
Claims (10)
1.一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,包括以下原料:按质量份计,异氰酸酯10-30份,丙烯酸酯50-70份,二元醇类化合物1.5-2.5份,催化剂0.01-0.05份,光引发剂0.1-0.5。
2.根据权利要求1所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述异氰酸酯包括甲苯二异氰酸酯、六亚甲基二异氰酸酯、六亚甲基二异氰酸酯三聚体、二苯基甲烷二异氰酸酯、氢化苯甲基二异氰酸酯、2.4-甲苯二异氰酸酯三聚体、异氟尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯的至少一种。
3.根据权利要求1所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述丙烯酸酯包括含羟基丙烯酸酯、含氨基丙烯酸酯、含烷氧基丙烯酸酯的至少一种。
4.根据权利要求1所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述二元醇类化合物包括聚碳酸酯二元醇、聚己内酯二元醇、聚醚二元醇、聚四氢呋喃醚二元醇的的至少一种。
5.根据权利要求4所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述二元醇类化合物的羟基含量为1.5-2.0wt%。
6.根据权利要求1所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述催化剂包括五甲基二乙烯三胺、二甲基环己胺、二月桂酸二丁基锡、有机铋、三嗪类三聚催化剂等中的至少一种。
7.根据权利要求1所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述光引发剂包括2-羟基-2-甲基苯酮,1-羟基环己基苯酮,2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮,2,4,6-三甲基苯甲酰基-二苯基氧化膦的至少一种。
8.根据权利要求1-7任一项所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,所述原料还包括抗氧剂0.1-1份,流平剂0.1-0.3份,润湿剂1-3份,溶剂。
9.根据权利要求8所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯,其特征在于,所述抗氧剂包括过氧化物分解型抗氧剂、酚型抗氧剂、胺型抗氧剂、硫型抗氧剂、磷型抗氧剂的至少一种。
10.一种根据权利要求9所述的一种耐高温与高柔韧性高硬度的聚氨酯丙烯酸酯的制备方法,其特征在于,包括以下步骤:
(1)将催化剂分为两份,第一份催化剂与异氰酸酯、溶剂混合均匀,升温至40-60℃,加入二元醇类化合物反应3-5h得到混合物A;
(2)将混合物A与丙烯酸酯,第二份催化剂混合均匀,升温到60-70℃,反应1-2h,加入剩余原料搅拌混合混匀即得。
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