CN102432777A - Method for modifying cellulose acetate butyrate (CAB) for electro-silvered simulating coating - Google Patents
Method for modifying cellulose acetate butyrate (CAB) for electro-silvered simulating coating Download PDFInfo
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- CN102432777A CN102432777A CN2011102502475A CN201110250247A CN102432777A CN 102432777 A CN102432777 A CN 102432777A CN 2011102502475 A CN2011102502475 A CN 2011102502475A CN 201110250247 A CN201110250247 A CN 201110250247A CN 102432777 A CN102432777 A CN 102432777A
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- 229920006217 cellulose acetate butyrate Polymers 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- -1 vinylformic acid cycloalkyl ester Chemical class 0.000 claims description 41
- 230000004048 modification Effects 0.000 claims description 24
- 238000012986 modification Methods 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- HXTCWLNZDIPLCA-UHFFFAOYSA-N dodecanoic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCCCCCCCCC(O)=O HXTCWLNZDIPLCA-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 claims description 2
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 125000002277 benzylpenicilloyl group Chemical group C(=O)(O)[C@@H]1N[C@H](SC1(C)C)[C@@H](C(=O)*)NC(CC1=CC=CC=C1)=O 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for modifying cellulose acetate butyrate (CAB) for electro-silvered simulating coating. The method comprises the following steps of: after introducing inert gas in a container, adding 60-80% of reaction solvent by weight, stirring while heating, adding the CAB below 70-100 DEG C, after completely dissolving, stabilizing at 120-200 DEG C for 5-10 min, adding catalyst, a monomer and remained 20-40% of the reaction solvent, reacting at 120-200 DEG C for 3-15 h, and obtaining the CAB containing unsaturated double bond; and then adding a solvent for coating to dilute the solution, adding a mixture solution of a copolymerization monomer and an initiator in the mixed solution in a dropping manner, and reacting for 2-5 h again to obtain the modified CAB mixed solution for coating. The CAB for the electro-silvered simulating coating modified by using the method disclosed by the invention is high in wearable property of coating film, solvent resistant property and hardness; simultaneously, the metallic feel and the mirror effect of the coating cannot be lost.
Description
Technical field
The present invention relates to cellulose acetate butyrate, particularly relate to a kind of method of modifying that is used for the cellulose acetate butyrate (CAB) of imitative electrosilvering coating.
Background technology
Cellulose acetate butyrate (CAB) is widely used a kind of cellulose organic ester auxiliary agent in effect pigment at present; Have excellent water tolerance, weathering resistance, film-forming flexibility, high-clarity and stable advantages such as metal oriented alignment property; But it also has hardness not high, shortcomings such as scratch-proofness, organic solvent resistance difference.At present, the CAB method of modifying is mainly contained following several kinds:
(1) isocyanide ester prepolymer through containing vinyl and CAB go up remaining hydroxyl reaction, again with the vinyl monomer copolymerization, prepare the CAB of coating material solidified or other purposes of the UV of modification at last;
(2) with propenoate or methyl acrylic ester monomer polymeric method in being dissolved with the solution of CAB CAB is carried out modification, the CAB solution that obtains modification can directly be used for coating;
(3) through ATRP method grafted ethene base class monomers on CAB such as (ATRP), with performances such as the solvability that changes CAB, stability;
(4) with maleic acid ester or fumarate as modified monomer modified CA B, make CAB have the good solubility ability.
The subject matter that at present the CAB graft modification is existed has: the isocyanide ester prepolymer that vinyl is contained in (1) has severe toxicity, during as reactant, in practical application, needs special protective measures, and production cost is higher; (2) the polymeric method is to the CAB modification in being dissolved with the solution of CAB with propenoate or methyl acrylic ester monomer, and performances such as its solvent resistance of finally filming, hardness significantly do not improve, but the mirror effect of filming loss is bigger; (3) with ATRP method modified CA B, modified technique is complicated, and cost is higher to be difficult for being applied to factory's scale operation; (4) maleic acid ester or fumaric acid esters raw material monomer cost are higher, have improved the production cost of enterprise.
Summary of the invention
The objective of the invention is to problem to existing method of modifying existence; Provide a kind of and can improve coating wear resisting property, solvent resistance and hardness; Simultaneously can not lose the metal sense of coating and the CAB method of modifying of mirror effect, this method was both safe, easy, obvious, the easy industriallization of effect again.
The present invention carries out transesterification reaction through containing propenoate or methyl acrylic ester monomer and CAB, makes the unsaturated double-bond that can carry out radical polymerization in the CAB grafting, and then with the monomer modified CAB with different qualities, finally improves the performance of CAB.
The object of the invention is realized through following technical scheme:
A kind of method of modifying that is used for the cellulose acetate butyrate of imitative electrosilvering coating comprises the steps:
(1) in container, led to inertia class gas 3-10 minute, add the reaction solvent of 60-80% quality, while stirring heating; Add dried CAB down at 70 ℃-100 ℃; After treating to dissolve fully, and, add the reaction solvent of catalyzer, monomer and residue 20-40% at 120-200 ℃ of stable 5-10 minute; Reacted 3-15 hour down at 120-200 ℃, promptly get the CAB that contains unsaturated double-bond; Said monomer is propenoate or methacrylate monomers;
(2) in the solution of gained, add coating and use solvent cut solution, and controlled temperature is to 75-140 ℃; Mixture solution at mixed solution and dripping comonomer and initiator; And dripped off at 30-180 minute, reacting again 2-5 hour, the coating that promptly gets after the modification is used the CAB mixing solutions;
In mass fraction, said composition of raw materials consumption is:
Said reaction solvent is that aromatic solvents, carbon atom number are that individual ketones solvent of 4-7 and carbon atom number are one or more in the individual alkane solvents of 7-11; Said aromatic solvents is toluene or YLENE;
Described catalyzer is a triethyl White tin oxide, one or more in diethylammonium White tin oxide, Dibutyltin oxide, the Mono-n-butyltin;
Described monomer is one or more in alkyl acrylate, vinylformic acid cycloalkyl ester, alkyl methacrylate and the methylacrylic acid cycloalkyl ester;
Described coating uses solvent to be in ETHYLE ACETATE, butylacetate, isopropylcarbinol, propyl carbinol, acetone, butanone, ethylene glycol monobutyl ether, YLENE and the toluene one or more;
Described initiator is one or more in peroxide initiator or the azo-initiator;
Described comonomer is to contain vinyl monomer, propenoate or methacrylate monomers, acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate class monomer, alpha-beta unsaturated carboxylic acid class monomer, acrylic amide or methacryloyl amine monomer and contain in the vinyl dehydrated glyceride class monomer one or more;
The said vinyl monomer that contains is vinylbenzene, vinyl toluene, vinyl-acetic ester or ethene nitrile;
Said propenoate or methacrylate monomers are one or more in methyl acrylate, Bing Xisuandingzhi, vinylformic acid laurate, TEB 3K, NSC 20956 and the methylacrylic acid laurate;
Said acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate class monomer are Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400 or Rocryl 410;
Said alpha-beta unsaturated carboxylic acid class monomer is vinylformic acid, methylacrylic acid, methylene-succinic acid or butenoic acid;
Said acrylic amide or methacryloyl amine monomer are acrylic amide, N methacrylamide, N-ethyl acrylamide, N; N-DMAA, N-hydroxypropyl acrylic amide, USAF RH-1, N-methyl-USAF RH-1, N-ethyl-USAF RH-1, N, N-dimethyl--methyl-acrylic amide or N-hydroxypropyl-USAF RH-1;
The said vinyl dehydrated glyceride class monomer that contains is vinylformic acid dehydrated glyceride, methacrylic dehydrated glyceride or dehydration R-Glyceric acid allyl ester.
Further, one or more among the preferred CAB-151-0.7 of described CAB, CAB-151-0.3, CAB-381-0.1, CAB-381-0.5, CAB-381-2, CAB-381-20, CAB-551-0.01 and the CAB-551-0.2.
Described drying is that oven temperature was 35 ℃-100 ℃ with CAB in vacuum drying oven dry 4-12 hour.
Described carbon atom number be 7-11 alkane solvents be heptane, octane, nonane, decane or undecane.
Described peroxide initiator initiator is Lucidol, lauroyl peroxide, tert-butyl hydroperoxide or cumene hydroperoxide.
The present invention compares with existing C AB method of modifying, has following advantage:
When (1) wear resisting property, solvent resistance and the hardness of the cellulose acetate butyrate coating paint film that is used for imitative electrosilvering coating through the inventive method modification increase, can not lose the metal sense and the mirror effect of coating;
(2) method of modifying reactant toxicity of the present invention is little, and practical application safety does not need specific installation;
(3) method of modifying technology of the present invention is simple, easy to operate, and production cost is low.
Description of drawings
Fig. 1 is the infrared spectrogram of CAB graft acrylic acid methyl esters (CAB-g-MA) among the embodiment 1;
Fig. 2 is the infrared spectrogram of CAB grafted propylene acid butyl ester (CAB-g-BA) among the embodiment 2;
Fig. 3 is the infrared spectrogram of CAB grafting NSC 20956 (CAB-g-BMA) among the embodiment 3;
Fig. 4 is the infrared spectrogram of CAB grafting TEB 3K (CAB-g-MMA) among the embodiment 4;
Fig. 5 is the infrared spectrogram of CAB grafting TEB 3K (CAB-g-MMA) among the embodiment 5;
Fig. 6 is that CAB directly reacts the infrared spectrogram of (CAB-MMA) in the Comparative Examples 1 with TEB 3K.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1:
Logical nitrogen is 5 minutes in four-hole boiling flask, and the YLENE that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-381-20 are added in the containers (drying is that oven temperature was 35 ℃ with CAB-381-20 in vacuum drying oven dry 12 hours); Continue to heat up; Make homo(io)thermism at 145 ℃, treat that CAB dissolves fully after, add 28 parts of methyl acrylates, 8 parts Dibutyltin oxide and the mixing solutions of 127.5 parts of YLENE; After reacting 6 hours under 145 ℃; Add 267 parts of ETHYLE ACETATE and 167 parts of butyl glycol ethers, cool the temperature to 95 ℃ after, begin to drip following mixture: 167 parts of TEB 3Ks, 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs; And about 2 hours, drip, react the CAB that promptly gets the methyl methacrylate-grafted modification after 3 hours.To carrying out infrared test after the methyl acrylate transesterify grafted CAB purification; As shown in Figure 1; 1642.9cm-1 has occurred-the stretching vibration absorption peak of C=C-in spectrogram, shows that to adopt the graft modification of methacrylate monomer ester-interchange method to make CAB contain two key methods feasible.
Embodiment 2:
Logical nitrogen is 5 minutes in container, and the butanone that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-381-20 are added in the containers (drying is that oven temperature was 100 ℃ with CAB-381-20 in vacuum drying oven dry 4 hours); Continue to heat up; Make homo(io)thermism at 145 ℃, treat that CAB dissolves fully after, add 41 parts of Bing Xisuandingzhis, 8 parts triethyl White tin oxide and the mixing solutions of 127.5 parts of YLENE; After reacting 6 hours under 145 ℃; Add 267 parts of ETHYLE ACETATE and 167 parts of butylacetates, cool the temperature to 95 ℃ after, begin to drip following mixture: 167 parts of TEB 3Ks, 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs; And about 2 hours, drip, react the CAB that promptly gets the methyl methacrylate-grafted modification after 3 hours.To carrying out infrared test after the Bing Xisuandingzhi transesterify grafted CAB purification; As shown in Figure 2; 1633.1cm-1 has occurred-the stretching vibration absorption peak of C=C-in spectrogram, shows that to adopt the graft modification of Butyl Acrylate Monomer ester-interchange method to make CAB contain two key methods feasible.
Embodiment 3:
Logical nitrogen is 5 minutes in container, and the YLENE that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-551-0.2 are added in the container, continue to heat up; Make homo(io)thermism at 145 ℃, treat that CAB dissolves fully after, add 45.3 parts of NSC 20956s, 8 parts diethylammonium White tin oxide and the mixing solutions of 127.5 parts of YLENE; After reacting 6 hours under 145 ℃; Add 267 parts of ETHYLE ACETATE and 167 parts of acetone, cool the temperature to 95 ℃ after, begin to drip following mixture: 167 parts of TEB 3Ks, 167 parts of acetone, 100 parts of butyl glycol ethers, 5 parts of BPOs; And about 2 hours, drip, react the CAB that promptly gets the methyl methacrylate-grafted modification after 3 hours.To carrying out infrared test after the NSC 20956 transesterify grafted CAB purification, as shown in Figure 3,1630.2cm in spectrogram
-1Occurred-the stretching vibration absorption peak of C=C-, shown that to adopt the graft modification of NSC 20956 monomeric ester exchange process to make CAB contain two key methods feasible.
Embodiment 4:
Logical nitrogen is 5 minutes in container, and the YLENE that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-151-0.7 are added in the container, continue to heat up; Make homo(io)thermism at 145 ℃, treat that CAB dissolves fully after, add 32 parts of TEB 3Ks, 8 parts Mono-n-butyltin and the mixing solutions of 127.5 parts of YLENE; After reacting 6 hours under 145 ℃; Add 267 parts of isopropylcarbinols and 167 parts of butyl glycol ethers, cool the temperature to 95 ℃ after, begin to drip following mixture: 135 parts of TEB 3Ks, 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs; And about 2 hours, drip, react the CAB that promptly gets the methyl methacrylate-grafted modification after 3 hours.To carrying out infrared test after the TEB 3K transesterify grafted CAB purification, as shown in Figure 4,1627.7cm in spectrogram
-1Occurred-the stretching vibration absorption peak of C=C-, shown that to adopt the graft modification of MMA MONOMER ester-interchange method to make CAB contain two key methods feasible.
Embodiment 5:
Logical nitrogen is 5 minutes in container, and the YLENE that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-381-0.1 are added in the container, continue to heat up; Make homo(io)thermism at 145 ℃; After treating that CAB dissolves fully, add 167 parts of TEB 3Ks, 8 parts Dibutyltin oxide and the mixing solutions of 127.5 parts of YLENE, after reacting 6 hours under 145 ℃; Add 267 parts of ETHYLE ACETATE and 167 parts of butyl glycol ethers; After cooling the temperature to 95 ℃, the following mixture of disposable adding: 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs, react the CAB that promptly gets the methyl methacrylate-grafted modification after 5 hours.To carrying out infrared test after the TEB 3K transesterify grafted CAB purification, as shown in Figure 5,1628.7cm in spectrogram
-1Occurred-the stretching vibration absorption peak of C=C-, shown that to adopt the graft modification of MMA MONOMER ester-interchange method to make CAB contain two key methods feasible.
Embodiment 6
Logical nitrogen is 5 minutes in container, and the pimelinketone that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-551-2 are added in the container, continue to heat up; Make homo(io)thermism at 145 ℃, treat that CAB dissolves fully after, add 32 parts of TEB 3Ks, 8 parts Dibutyltin oxide and the mixing solutions of 127.5 parts of pimelinketone; After reacting 6 hours under 145 ℃; Add 267 parts of ETHYLE ACETATE and 167 parts of butyl glycol ethers, cool the temperature to 95 ℃ after, begin to drip following mixture: 135 parts of TEB 3Ks, 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs; And about 2 hours, drip, react the CAB that promptly gets the methyl methacrylate-grafted modification after 3 hours.
Embodiment 7
Logical nitrogen is 5 minutes in container, and the YLENE that adds 340 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-551-0.01 are added in the container, continue to heat up; Make homo(io)thermism at 145 ℃; After treating that CAB dissolves fully, add 167 parts of TEB 3Ks, 8 parts Mono-n-butyltin and the mixing solutions of 127.5 parts of YLENE, after reacting 6 hours under 145 ℃; Add 267 parts of ETHYLE ACETATE and 167 parts of butyl glycol ethers; After cooling the temperature to 95 ℃, the following mixture of disposable adding: 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs, react the CAB that promptly gets the methyl methacrylate-grafted modification after 5 hours.
Comparative Examples 1:
Logical nitrogen is 5 minutes in four-hole boiling flask, and the YLENE that adds 467.5 parts adds in the container, heating while stirring; When temperature rises to 90 ℃, 100 parts of exsiccant CAB-381-20 are added in the container, continue to heat up; Make homo(io)thermism at 145 ℃, treat that CAB-381-20 dissolves fully after, add 267 parts of ETHYLE ACETATE and 167 parts of butyl glycol ethers; After cooling the temperature to 95 ℃; Begin to drip following mixture: 167 parts of TEB 3Ks, 167 parts of ETHYLE ACETATE, 100 parts of butyl glycol ethers, 5 parts of BPOs, and about 2 hours, drip, react the CAB that promptly gets the methyl methacrylate-grafted modification after 3 hours.Carry out infrared test after the CAB of above-mentioned TEB 3K modification purified, as shown in Figure 6, in spectrogram, do not occurred-the stretching vibration absorption peak of C=C-, show and adopt effectively modified CA B of this method, make it and contain-C=C-.
The performance test situation of embodiment 1-7 and comparative example's products obtained therefrom is as shown in table 1.The QYG type that wherein adopts Tianjin Expo great achievement glass Instr Ltd. the to produce clarity determinator of filming is measured.Drain after soaking in ethanol with cotton gauze, wipe examination lacquered surface same position repeatedly, measure wiping position is clipped the number of times that whiting obtains lacquer with a kgf.According to GB/T 6739-2006, adopt pencil hardness test.The DH48J type abrasion tester test of adopting the big gloomy Instr Ltd. in Dongguan City, Guangdong Province to produce.Can find out from table 1; When the CAB of process step of transesterification modification finally is applied to coating; Its film performance is compared with the CAB of not process step of transesterification modification; In clarity, solvent resistance, hardness and wear resistance improvement has in various degree been arranged all, this shows through ester exchange method can significantly improve the over-all properties that is applied to the CAB in the coating.
Table 1
Claims (5)
1. a method of modifying that is used for the cellulose acetate butyrate of imitative electrosilvering coating is characterized in that comprising the steps:
(1) in container, led to inertia class gas 3-10 minute, add the reaction solvent of 60-80% quality, while stirring heating; Add dried CAB down at 70 ℃-100 ℃; After treating to dissolve fully, and, add the reaction solvent of catalyzer, monomer and residue 20-40% at 120-200 ℃ of stable 5-10 minute; Reacted 3-15 hour down at 120-200 ℃, promptly get the CAB that contains unsaturated double-bond; Said monomer is propenoate or methacrylate monomers;
(2) in the solution of gained, add coating and use solvent cut solution, and controlled temperature is to 75-140 ℃; Mixture solution at mixed solution and dripping comonomer and initiator; And dripped off at 30-180 minute, reacting again 2-5 hour, the coating that promptly gets after the modification is used the CAB mixing solutions;
In mass fraction, said composition of raw materials consumption is:
100 parts of CAB
300-1000 parts of reaction solvents
0.1-5 parts of catalyzer
5-200 parts of monomers
Coating is with 100-1000 parts of solvents
20-500 parts of comonomers;
0.6-15 parts of initiators
Said reaction solvent is that aromatic solvents, carbon atom number are that individual ketones solvent of 4-7 and carbon atom number are one or more in the individual alkane solvents of 7-11; Said aromatic solvents is toluene or YLENE;
Described catalyzer is a triethyl White tin oxide, one or more in diethylammonium White tin oxide, Dibutyltin oxide, the Mono-n-butyltin;
Described monomer is one or more in alkyl acrylate, vinylformic acid cycloalkyl ester, alkyl methacrylate and the methylacrylic acid cycloalkyl ester;
Described coating uses solvent to be in ETHYLE ACETATE, butylacetate, isopropylcarbinol, propyl carbinol, acetone, butanone, ethylene glycol monobutyl ether, YLENE and the toluene one or more;
Described initiator is one or more in peroxide initiator or the azo-initiator;
Described comonomer is to contain vinyl monomer, propenoate or methacrylate monomers, acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate class monomer, alpha-beta unsaturated carboxylic acid class monomer, acrylic amide or methacryloyl amine monomer and contain in the vinyl dehydrated glyceride class monomer one or more;
The said vinyl monomer that contains is vinylbenzene, vinyl toluene, vinyl-acetic ester or ethene nitrile;
Said propenoate or methacrylate monomers are one or more in methyl acrylate, Bing Xisuandingzhi, vinylformic acid laurate, TEB 3K, NSC 20956 and the methylacrylic acid laurate;
Said acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate class monomer are Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400 or Rocryl 410;
Said alpha-beta unsaturated carboxylic acid class monomer is vinylformic acid, methylacrylic acid, methylene-succinic acid or butenoic acid;
Said acrylic amide or methacryloyl amine monomer are acrylic amide, N methacrylamide, N-ethyl acrylamide, N; N-DMAA, N-hydroxypropyl acrylic amide, USAF RH-1, N-methyl-USAF RH-1, N-ethyl-USAF RH-1, N, N-dimethyl--methyl-acrylic amide or N-hydroxypropyl-USAF RH-1;
The said vinyl dehydrated glyceride class monomer that contains is vinylformic acid dehydrated glyceride, methacrylic dehydrated glyceride or dehydration R-Glyceric acid allyl ester.
2. the method for modifying that is used for the cellulose acetate butyrate of imitative electrosilvering coating according to claim 1, it is characterized in that: described CAB is one or more among CAB-151-0.7, CAB-151-0.3, CAB-381-0.1, CAB-381-0.5, CAB-381-2, CAB-381-20, CAB-551-0.01 and the CAB-551-0.2.
3. the method for modifying that is used for the cellulose acetate butyrate of imitative electrosilvering coating according to claim 1 is characterized in that: described drying is that oven temperature was 35 ℃-100 ℃ with CAB in vacuum drying oven dry 4-12 hour.
4. the method for modifying that is used for the cellulose acetate butyrate of imitative electrosilvering coating according to claim 1 is characterized in that: described carbon atom number be 7-11 alkane solvents be heptane, octane, nonane, decane or undecane.
5. the method for modifying that is used for the cellulose acetate butyrate of imitative electrosilvering coating according to claim 1, it is characterized in that: described peroxide initiator initiator is Lucidol, lauroyl peroxide, tert-butyl hydroperoxide or cumene hydroperoxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103951789A (en) * | 2014-04-04 | 2014-07-30 | 广州伊德尔化学科技有限公司 | High-temperature-resistant mirror silver resin and preparation method thereof |
| CN104877082A (en) * | 2015-06-02 | 2015-09-02 | 清远雅克化工有限公司 | Preparation method of CAB (cellulose acetate butyrate) graft modified hydroxy acrylic resin for electrosilvering paint |
| CN106317230A (en) * | 2016-08-22 | 2017-01-11 | 四川北方硝化棉股份有限公司 | Preparation method of cellulose acetate butyrate nitrate |
| CN107603373A (en) * | 2017-09-29 | 2018-01-19 | 四川长虹电器股份有限公司 | One kind plating silver coating and preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103951789A (en) * | 2014-04-04 | 2014-07-30 | 广州伊德尔化学科技有限公司 | High-temperature-resistant mirror silver resin and preparation method thereof |
| CN103951789B (en) * | 2014-04-04 | 2017-03-15 | 广州伊德尔化学科技有限公司 | A kind of resistant to elevated temperatures minute surface silver resin and preparation method thereof |
| CN104877082A (en) * | 2015-06-02 | 2015-09-02 | 清远雅克化工有限公司 | Preparation method of CAB (cellulose acetate butyrate) graft modified hydroxy acrylic resin for electrosilvering paint |
| CN106317230A (en) * | 2016-08-22 | 2017-01-11 | 四川北方硝化棉股份有限公司 | Preparation method of cellulose acetate butyrate nitrate |
| CN106317230B (en) * | 2016-08-22 | 2018-06-12 | 四川北方硝化棉股份有限公司 | A kind of preparation method of acetate butyrate cellulose nitrate ester |
| CN107603373A (en) * | 2017-09-29 | 2018-01-19 | 四川长虹电器股份有限公司 | One kind plating silver coating and preparation method |
| CN107603373B (en) * | 2017-09-29 | 2020-01-31 | 四川长虹电器股份有限公司 | electrosilvering paint and preparation method thereof |
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