CN114555658B - 可通过共聚包含乙烯基单体和丁烯羧酸内酯单体的单体混合物获得的粘合剂聚合物 - Google Patents
可通过共聚包含乙烯基单体和丁烯羧酸内酯单体的单体混合物获得的粘合剂聚合物 Download PDFInfo
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- CN114555658B CN114555658B CN202080071310.6A CN202080071310A CN114555658B CN 114555658 B CN114555658 B CN 114555658B CN 202080071310 A CN202080071310 A CN 202080071310A CN 114555658 B CN114555658 B CN 114555658B
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- monomer
- vinyl
- adhesive polymer
- butenolide
- vinyl ether
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- 239000000178 monomer Substances 0.000 title claims abstract description 121
- 239000002998 adhesive polymer Substances 0.000 title claims abstract description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 37
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- SQEBMLCQNJOCBG-HVHJFMEUSA-N (5s)-3-(hydroxymethyl)-5-methoxy-4-methyl-5-[(e)-2-phenylethenyl]furan-2-one Chemical compound C=1C=CC=CC=1/C=C/[C@]1(OC)OC(=O)C(CO)=C1C SQEBMLCQNJOCBG-HVHJFMEUSA-N 0.000 title claims abstract description 26
- FBMORZZOJSDNRQ-UHFFFAOYSA-N Demethoxy,B,HCl-Adriamycin Natural products C1C2C(=C)CCCC2(C)CC2(O)C1=C(C)C(=O)O2 FBMORZZOJSDNRQ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- JUTMAMXOAOYKHT-UHFFFAOYSA-N karrikinolide Natural products C1=COC=C2OC(=O)C(C)=C21 JUTMAMXOAOYKHT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 239000008199 coating composition Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
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- 125000000962 organic group Chemical group 0.000 claims abstract description 5
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- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 claims description 5
- LRHFWTSUYLXTPU-UHFFFAOYSA-N 2-methoxy-2h-furan-5-one Chemical compound COC1OC(=O)C=C1 LRHFWTSUYLXTPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 claims description 3
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 claims description 3
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 claims description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 3
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 claims description 3
- WBZPMFHFKXZDRZ-UHFFFAOYSA-N ethenyl 6,6-dimethylheptanoate Chemical compound CC(C)(C)CCCCC(=O)OC=C WBZPMFHFKXZDRZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 238000000034 method Methods 0.000 description 3
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical group 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VIHAEDVKXSOUAT-UHFFFAOYSA-N but-2-en-4-olide Chemical class O=C1OCC=C1 VIHAEDVKXSOUAT-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 102220005453 rs34890875 Human genes 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- XJDDLMJULQGRLU-UHFFFAOYSA-N 1,3-dioxane-4,6-dione Chemical compound O=C1CC(=O)OCO1 XJDDLMJULQGRLU-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical class C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 102100040409 Ameloblastin Human genes 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- 125000004036 acetal group Chemical group 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D137/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
-
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Abstract
本发明涉及粘合剂聚合物，其可通过包含乙烯基单体M1和丁烯羧酸内酯单体M2的单体混合物的共聚获得，其中乙烯基单体M1为通式R1‑O‑CH＝CH2的乙烯基醚，通式R2‑C(O)‑O‑CH＝CH2的乙烯基酯，或它们的组合，其中R1和R2各自独立地为含有4‑18个碳原子的有机基团，并且其中丁烯羧酸内酯单体M2是如下通式的5‑烷氧基‑2(5H)‑呋喃酮，其中R3为含有1‑12个碳原子的烷基。本发明进一步涉及包含该粘合剂聚合物的涂料组合物和涂覆有由该涂料组合物沉积的涂层的基材。
Description
发明领域
本发明涉及可通过使包含乙烯基单体和丁烯羧酸内酯单体的单体混合物共聚获得的粘合剂聚合物，涉及包含该粘合剂聚合物的涂料组合物，以及涂覆有由该涂料组合物沉积的涂层的基材。
发明背景
聚丙烯酸酯或其他加聚物被广泛用作油漆和涂料中的成膜聚合物。成膜聚合物也称为粘合剂聚合物，因为该类聚合物具有将任何颗粒材料如颜色颜料和体质颜料粘合在一起的作用。
聚丙烯酸酯或其他加聚物通常通过具有烯属不饱和基团如丙烯酸类基团、甲基丙烯酸类基团或乙烯基的单体的自由基聚合来制备。该类单体的实例包括丙烯酸、甲基丙烯酸、(甲基)丙烯酸的烷基酯、苯乙烯、烷基取代的苯乙烯、乙烯基酯和乙烯基醚。所述单体通常由石化原料制备。
对由可再生原料制备的化学产品的需求不断增加。至少部分地由可再生原料制备的粘合剂聚合物是本领域已知的。例如，醇酸树脂包含较高含量的由植物油获得的脂肪酸。
WO 2009/080599公开了一种由植物油制备可聚合的烯属不饱和大分子单体的方法，该方法可用于制备用于涂料组合物的加聚物。
丁烯羧酸内酯是可以由碳水化合物(即可再生原料)制备的烯属不饱和呋喃化合物。碳水化合物原料如淀粉、纤维素或含碳水化合物的生物废物可通过脱水转化为糠醛、羟甲基糠醛或相关的呋喃衍生物，然后氧化成内酯或其他丁烯羧酸内酯。丁烯羧酸内酯的制备例如描述于J.C.de Jong，Asymmetric Diels-Alder reactions with 5-menthyloxy-2(5H)-furanones，Thesis University of Groningen，2006第II章中，可通过以下方式访问：
https://www.rug.nl/research/portal/en/publications/asymmetric- dielsalder-reactions-with-5menthyloxy25hfuranones(f0ab6c00-8c6c-4ccc-90aa- 3ef05f759fa4).html。
Poskonin等在Russian Journal of Organic Chemistry 35(1999)721-726中公开了通过4-烷氧基-2-丁烯羧酸内酯(5-烷氧基-2(5H)-呋喃酮)和苯乙烯、甲基丙烯酸甲酯或乙酸乙烯酯的自由基聚合制备的共聚物。建议使用该共聚物来合成生理活性物质。
需要可从可再生原料获得的粘合剂聚合物。
发明概述
现已发现，如果将5-烷氧基-2(5H)-呋喃酮与特定的乙烯基单体共聚，则可以制备可合适地用作涂料组合物中的粘合剂聚合物的共聚物。
因此，在第一方面中，本发明提供了一种粘合剂聚合物，其可通过使包含乙烯基单体M1和丁烯羧酸内酯单体M2的单体混合物共聚而获得，其中乙烯基单体M1是通式(I)的乙烯基醚：
R1-O-CH＝CH2 (I)
通式(II)的乙烯基酯：
R2-C(O)-O-CH＝CH2 (II)
或其组合，
其中R1和R2各自独立地为含有4-18个碳原子的有机基团，
并且其中丁烯羧酸内酯单体M2为通式(III)的5-烷氧基-2(5H)-呋喃酮：
其中R3为含有1-12个碳原子的烷基。
已经发现，如果将所述粘合剂聚合物施加到基材上并使其干燥，则该粘合剂聚合物可提供具有良好硬度性能的无粘性涂膜。
所述粘合剂聚合物具有含缩醛官能团的聚合物主链，这有利地提供了交联的可能性。
因此，在第二方面中，本发明提供了一种涂料组合物，其包含根据本发明第一方面的粘合剂聚合物。
在最后一个方面中，本发明提供了一种基材，其涂覆有由根据本发明第二方面的涂料组合物沉积的涂层。
发明详述
本发明的粘合剂聚合物可通过使包含乙烯基单体M1和丁烯羧酸内酯单体M2的单体混合物共聚而获得。
乙烯基单体M1为通式(I)的乙烯基醚或通式(II)的乙烯基酯或其组合。
通式(I)为：
R1-O-CH＝CH2 (I)
通式(II)为：
R2-C(O)-O-CH＝CH2 (II)
其中R1和R2各自独立地为含有4-18个碳原子，优选4-12个碳原子的有机基团。R1和R2各自可为芳族或脂族有机基团，并且可为支化或非支化的。优选地，R1和R2各自为任选被OH基团取代的烃基，更优选为任选被OH基团取代的支化或未支化的脂族烃基团。优选地，乙烯基单体M1为新癸酸乙烯酯、新壬酸乙烯酯、癸酸乙烯酯、正丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚、苯基乙烯基醚、2-乙基己基乙烯基醚、正十二烷基乙烯基醚、十八烷基乙烯基醚，4-羟丁基乙烯基醚，或其两种或更多种的混合物。
在一个实施方案中，乙烯基单体M1为新癸酸乙烯酯或新癸酸乙烯酯和新壬酸乙烯酯的混合物。
在另一个实施方案中，乙烯基单体M1为乙烯基醚，优选为正丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚、苯基乙烯基醚、2-乙基己基乙烯基醚、正十二烷基乙烯基醚、4-羟丁基乙烯基醚，或其两种或多种的混合物。已发现，与通式(II)的乙烯基单体M1，即乙烯基酯相比，通式(I)的乙烯基单体M1，即乙烯基醚，与丁烯羧酸内酯单体M2以更高的反应速率共聚。
丁烯羧酸内酯单体M2为通式(III)的5-烷氧基-2(5H)-呋喃酮：
其中R3为含有1-12个碳原子的烷基。烷基可以是支化的、未支化的、直链的或环状的。合适的烷基的实例为甲基、乙基、正丙基、异丙基、正丁基、叔丁基、仲丁基、异丁基、己基、薄荷基(2-异丙基-5-甲基环己烷-1-基)。优选地，烷基具有1-6个碳原子，更优选1-4个碳原子。特别优选的单体M2为5-甲氧基呋喃-2(5H)-酮(R3为CH3)。
所述单体混合物可具有任何合适的乙烯基单体M1与丁烯羧酸内酯单体M2的摩尔比。优选地，乙烯基单体M1与丁烯羧酸内酯单体M2的摩尔比为1:10至10:1，更优选为1:5至5:1，甚至更优选为1:3至3:1，仍更优选为1:2至2:1，或者甚至为1:1.5至1.5:1。
所述单体混合物可包含除乙烯基单体M1和丁烯羧酸内酯单体M2以外的其他烯属不饱和单体，它们可以通过自由基聚合进行共聚。该类其他单体的实例为丙烯酸、甲基丙烯酸、(甲基)丙烯酸烷基酯、苯乙烯、亚甲基丙二酸酯、衣康酸、乙酸乙烯酯、二乙烯基醚如乙二醇二乙烯基醚、二甘醇二乙烯基醚、三甘醇二乙烯基醚、1,4-丁二醇二乙烯基醚和三乙烯基醚如三羟甲基丙烷三乙烯基醚。所述单体混合物中的二乙烯基醚的存在提供了具有交联官能团的粘合剂聚合物。
优选地，所述单体混合物包含小于50摩尔％，更优选小于30摩尔％，甚至更优选小于20摩尔％，或者甚至小于10摩尔％的其他烯属不饱和单体。在一个实施方案中，所述单体混合物包含1-50摩尔％，优选2-30％，更优选5至20摩尔％的其他烯属不饱和单体。
在另一个实施方案中，所述单体混合物不含其他烯属不饱和单体。
共聚是自由基聚合过程。允许单体通过自由基聚合共聚成加聚物的条件在本领域中是众所周知的。合适的条件通常包括引发剂的存在。
共聚可以在有机溶剂中进行(溶剂聚合)。在溶剂聚合中，将单体混合物溶解在合适的有机溶剂中，加热到所需的反应温度并以合适的量加入合适的引发剂。通常，溶剂聚合期间的温度为50-180℃，优选为70-160℃。应当理解，最佳聚合温度取决于所用引发剂的分解温度和任何单体在进行聚合的压力下的沸点。在共聚期间，所述单体混合物可以溶解在任何合适的溶剂中。合适的有机溶剂是单体混合物中的所有单体和所得共聚物在聚合条件下溶解的溶剂。优选地，有机溶剂为含氧有机溶剂，例如醇、二醇醚、二醇酯、乙酸烷基酯、酮、酯或二醇醚/酯。更优选地，溶剂为二醇醚或乙酸烷基酯。1-甲氧基-2-丙醇和乙酸丁酯是特别优选的溶剂。
或者，共聚可作为乳液聚合方法进行，其中将单体乳化在水相中，然后共聚。乳液聚合通常可在15-90℃的温度下进行。
可以使用任何合适的引发剂。合适的引发剂是本领域所已知的，包括有机过氧化物和偶氮引发剂。偶氮引发剂的实例包括偶氮二异丁腈(AIBN)和2,2'-偶氮二(2-甲基丁腈)(AMBN)。合适的有机过氧化物的实例包括过氧化3,5,5-三甲基己酸叔丁酯、过氧化苯甲酰、过氧化月桂酰、过氧化二叔丁基、过氧化乙酰、过氧化2-乙基己基碳酸叔丁酯、过氧化辛酸叔丁酯、过氧化辛酸叔戊酯和过氧化苯甲酸叔丁酯。引发剂可以以任何合适的量添加，通常基于烯属不饱和单体的总摩尔为至多6摩尔％，优选为1-4摩尔％。引发剂的总量可以分两步或三步添加，即在聚合开始时的第一量和在聚合反应期间的另外量。
任选地，在聚合期间使用链转移剂。可以以合适的量使用任何合适的链转移剂。合适的链转移剂是本领域所已知的并且包括巯基丙酸甲酯、1-十二硫醇、1-辛硫醇、硫代乙醇酸、2-羟基-1-乙硫醇和丁烯二醇。
共聚可以间歇进行，即通过在聚合开始时加入所有单体和引发剂，或通过在共聚期间逐渐加入部分单体和/或引发剂，即在所谓的饥饿进料条件下。
已发现由此获得的共聚物具有使其适合用作涂料组合物中的粘合剂聚合物的性质。所述粘合剂聚合物具有相对高含量的丁烯羧酸内酯，一种可以由可再生原料获得的组分。特别地，可以获得具有+5℃至+80℃的玻璃化转变温度的粘合剂聚合物，根据ISO11357-2通过差示扫描量热法(DSC)使用20K/分钟的加热速率测量。所述粘合剂聚合物的另一个有利的性质是其具有含缩醛官能团的聚合物主链(在丁烯羧酸内酯单体处)。该缩醛基团可用于交联，例如与羟基或硫醇官能交联剂或与具有羟基或硫醇官能团的聚合物交联。
因此，本发明提供了一种包含粘合剂聚合物的涂料组合物，所述粘合剂聚合物可通过共聚包含如上所述的乙烯基单体M1和丁烯羧酸内酯单体M2的单体混合物而获得。
所述涂料组合物可以是溶剂型或水性液体涂料组合物，或粉末涂料组合物，优选液体涂料组合物，更优选其中粘合剂聚合物乳化在含水液相中的水性液体涂料组合物。
所述涂料组合物可包含其他常用于涂料组合物中的成分，例如颜色颜料、体质颜料、聚结溶剂和一种或多种添加剂，例如表面活性剂、消泡剂、增稠剂、流平剂和生物杀伤剂。
在最后一个方面中，本发明涉及一种涂覆有由本发明涂料组合物沉积的涂层的基材。所述基材可以是任何合适的基材，例如木材、聚合物、复合材料、金属或矿物基材。基材可以是涂底漆的或裸基材。
通过以下非限制性实施例进一步说明本发明。
实施例
使用以下乙烯基酯和乙烯基醚单体：
使用以下其他烯属不饱和单体：
-丙烯酸丁酯 BA
-甲基丙烯酸甲酯 MMA
-苯乙烯 STY
使用以下丁烯羧酸内酯单体：
使用以下溶剂：
-乙酸丁酯 BuAc
-1-甲氧基-2-丙醇(DowanolTMPM) DowPM
使用以下引发剂：
-2,2'-偶氮二(2-甲基丁腈) AMBM
-过氧化3,5,5-三甲基己酸叔丁酯 T42S
实施例1—由乙烯基酯或乙烯基醚和丁烯羧酸内酯获得的粘合剂聚合物
通过在装有回流冷凝器的三颈圆底烧瓶中加入丁烯羧酸内酯单体和溶剂来制备粘合剂聚合物。将混合物加热至125℃的温度并在2小时内加入在另外溶剂中的乙烯基单体和过氧化3,5,5-三甲基己酸叔丁酯(Trigonox 42S，获自Nouryon)，同时保持温度为125℃在回流条件下在氮气保护下。然后再加入一些引发剂，继续反应1小时；然后再加入另外的引发剂并继续反应1小时。将反应混合物冷却至室温。计算的固含量(单体和引发剂的重量，基于单体、引发剂和溶剂的总重量)为43重量％。
使用不同的单体制备不同的粘合剂聚合物。粘合剂聚合物1至8是本发明的粘合剂聚合物；粘合剂聚合物A至D是对比粘合剂聚合物。
根据ISO 3251测定所得聚合物溶液的固含量，初始样品质量为1.0g，测试时间为60分钟，温度为125℃。基于测得的固含量计算单体转化率。剩余的单体在测试条件下蒸发，而形成的任何聚合物都不会蒸发。
在减压(50毫巴)和80℃下，在旋转蒸发器(rotavapor)中从获得的聚合物溶液中蒸发溶剂。对由此获得的样品进行1H NMR光谱分析。1H NMR光谱与聚合物溶液的聚合物含量(来自固含量测定)相结合，很好地指示了具体单体的转化率。
对于一些粘合剂聚合物，数均和重均分子量使用凝胶渗透色谱法(GPC)在苯乙烯-二乙烯基苯柱上以四氢呋喃(THF)(+1％乙酸)作为洗脱剂(1ml/分钟)测定，其中使用聚苯乙烯标样校准。
表1显示了制得的不同粘合剂聚合物、所用单体的类型和摩尔比以及所用的溶剂和引发剂。
实施例2—由其他烯属不饱和单体和丁烯羧酸内酯获得的粘合剂聚合物(对比)
作为共聚物，对比粘合剂聚合物E和F如实施例1所述制备，其中使用5-甲氧基-2(5H)-呋喃酮作为丁烯羧酸内酯单体和除乙烯基单体M1以外的烯属不饱和单体。使用乙酸丁酯作为溶剂，使用Trigonox 42S作为引发剂。表2显示了所用单体的类型和比例。
表3显示了粘合剂聚合物1至8(本发明)和粘合剂聚合物A至F(对比)：单体转化率；制得的粘合剂聚合物溶液的固含量；由1H-NMR光谱观察内置单体。给出了粘合剂聚合物1至5、E和F的数均和重均分子量(Mn和Mw；均以g/mol计)和多分散指数(PDI)，即Mn/Mw。
表1实施例1—粘合剂聚合物的制备(本发明和对比)
a纯化至98％纯度的单体，
b聚合在80℃下进行。
表2实施例2—对比粘合剂聚合物的制备
表3实施例1和2中制备的粘合剂聚合物的特性
c基于溶剂蒸发后聚合物溶液的1H-NMR。
实施例3—涂层的制备
使用刮涂棒将3号粘合剂聚合物溶液的200μm湿膜刮涂到玻璃板上。使湿膜在23℃和50％相对湿度下干燥7天。在4小时内获得无粘性的透明涂层。根据ISO 1522测定在23℃和50％相对湿度下储存2周后的摆锤硬度(Persoz硬度)。摆锤的幅度从12°降至4°的时间为60秒。
该实施例表明形成粘合剂聚合物膜并且可以形成不粘且具有许多涂料应用可接受的硬度的涂层。
实施例4—不同单体组合的反应动力学
通过如下1H-NMR光谱法测定乙烯基单体和丁烯羧酸内酯单体的不同组合的反应动力学(聚合速率常数和最大转化率)。
向4mL带隔片的螺旋盖小瓶中加入2mmol乙烯基单体和2mmol丁烯羧酸内酯单体，1mL 1DowPM作为溶剂和1mmol 1,3,5-三甲氧基苯作为内标。将混合物加热至120℃并加入30mg T42S作为引发剂。将混合物回流2-4小时。以5分钟的间隔，取出50μL样品并快速冷冻以停止聚合。单体的绝对浓度通过1H-NMR光谱法使用每种单体特有的1H-NMR位移来确定。根据单体浓度随时间的降低，确定总聚合速率常数(以s-1计)和所达到的最大单体转化率(％)。结果在表4中给出。
表4—不同单体组合的聚合反应动力学
*对比实施例
在样品G中，内置于聚合物中的乙烯基单体多于丁烯羧酸内酯单体。
该实施例表明5-烷氧基-2(H)-呋喃酮与通式(I)的乙烯基单体以比2(5H)-呋喃酮更高的聚合速率聚合。此外，实现了更高的单体转化率和更好的丁烯羧酸内酯单体内置。
Claims (17)
1.一种粘合剂聚合物，其可通过使包含乙烯基单体M1和丁烯羧酸内酯单体M2的单体混合物共聚而获得，其中乙烯基单体M1是通式(I)的乙烯基醚：
R1-O-CH＝CH2 (I)
通式(II)的乙烯基酯：
R2-C(O)-O-CH＝CH2 (II)
或其组合，
其中R1和R2各自独立地为含有4-18个碳原子的有机基团，
并且其中丁烯羧酸内酯单体M2为通式(III)的5-烷氧基-2(5H)-呋喃酮：
其中R3为含有1-12个碳原子的烷基。
2.根据权利要求1所述的粘合剂聚合物，其中R3为含有1-6个碳原子的烷基。
3.根据权利要求2所述的粘合剂聚合物，其中R3为含有1-4个碳原子的烷基。
4.根据权利要求2所述的粘合剂聚合物，其中丁烯羧酸内酯单体M2为5-甲氧基-2(5H)-呋喃酮。
5.根据权利要求3所述的粘合剂聚合物，其中丁烯羧酸内酯单体M2为5-甲氧基-2(5H)-呋喃酮。
6.根据权利要求1-5中任一项所述的粘合剂聚合物，其中R1和R2各自独立地为含有4-12个碳原子的任选被OH基团取代的烃基。
7.根据权利要求1-5中任一项所述的粘合剂聚合物，其中乙烯基单体M1为新癸酸乙烯酯或新癸酸乙烯酯和新壬酸乙烯酯的混合物。
8.根据权利要求1-5中任一项所述的粘合剂聚合物，其中乙烯基单体M1为通式(I)的乙烯基醚。
9.根据权利要求8所述的粘合剂聚合物，其中乙烯基单体M1为正丁基乙烯基醚、异丁基乙烯基醚、环己基乙烯基醚、苯基乙烯基醚、2-乙基己基乙烯基醚、正十二烷基乙烯基醚、4-羟丁基乙烯基醚，或其两种或多种的混合物。
10.根据权利要求1-5中任一项所述的粘合剂聚合物，其中所述单体混合物包含摩尔比为1:5至5:1的乙烯基单体M1和丁烯羧酸内酯M2。
11.根据权利要求10所述的粘合剂聚合物，其中所述单体混合物包含摩尔比为1:2至2:1的乙烯基单体M1和丁烯羧酸内酯M2。
12.根据权利要求1-5中任一项所述的粘合剂聚合物，其中所述单体混合物包含1-50摩尔％的其他烯属不饱和单体。
13.根据权利要求12所述的粘合剂聚合物，其中所述单体混合物包含2-30摩尔％的其他烯属不饱和单体。
14.根据权利要求1-5中任一项所述的粘合剂聚合物，其中所述单体混合物不含其他烯属不饱和单体。
15.一种涂料组合物，其包含根据权利要求1-14中任一项所述的粘合剂聚合物。
16.根据权利要求15所述的涂料组合物，其中所述涂料组合物是包含乳化在水相中的粘合剂聚合物的水性液体涂料组合物。
17.一种涂覆有由根据权利要求15或16所述的涂料组合物沉积的涂层的基材。
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