CN103319680A - Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate - Google Patents
Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate Download PDFInfo
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- CN103319680A CN103319680A CN2013102833369A CN201310283336A CN103319680A CN 103319680 A CN103319680 A CN 103319680A CN 2013102833369 A CN2013102833369 A CN 2013102833369A CN 201310283336 A CN201310283336 A CN 201310283336A CN 103319680 A CN103319680 A CN 103319680A
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- methyl
- acrylate
- ester
- composite emulsion
- polyurethane
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- 239000000839 emulsion Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 19
- 239000004814 polyurethane Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 40
- -1 (methyl) dimethylaminoethyl Chemical group 0.000 claims description 22
- 229940070721 polyacrylate Drugs 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- PVIQSDYZOCWZJD-UHFFFAOYSA-N (1-tert-butylcyclohexyl) but-2-enoate Chemical compound CC=CC(=O)OC1(C(C)(C)C)CCCCC1 PVIQSDYZOCWZJD-UHFFFAOYSA-N 0.000 claims description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- BMYQANDFJBPKIF-UHFFFAOYSA-M [Cl-].CC(C1=CC=CC=C1)([N+](C)(C)CC)OC(C=C)=O Chemical compound [Cl-].CC(C1=CC=CC=C1)([N+](C)(C)CC)OC(C=C)=O BMYQANDFJBPKIF-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 claims description 2
- ZUMGBVSYIVKLDH-UHFFFAOYSA-N cyclohexyl but-2-enoate Chemical compound CC=CC(=O)OC1CCCCC1 ZUMGBVSYIVKLDH-UHFFFAOYSA-N 0.000 claims description 2
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229960004194 lidocaine Drugs 0.000 claims description 2
- 229920001427 mPEG Polymers 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N tetramethylbenzene Natural products CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000009977 dual effect Effects 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 238000010422 painting Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate. The method comprises the following steps of: in synthesis polyurethane reaction, accessing polyacrylate containing terminated hydroxyl into a polyurethane molecular chain through the contained terminated hydroxyl, and forming a side chain of a polyurethane molecule, so as to obtain the composite emulsion combined with a chemical bond, wherein the side chain of the polyacrylate containing the terminated hydroxyl includes a cationic hydrophilic group, a non-ionic segment and a large-resistance group; preparing the polyacrylate containing terminated hydroxyl by using a uniform dripping method in preparation, and then neutralizing and emulsifying to obtain the composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate after reacting with common high-molecular polyol, isocyanate, a crosslinking agent and a common chain extender. The prepared composite emulsion integrates dual advantages of the polyurethane and polyacrylate materials, especially has excellent storage stability and electrolyte resistance, simultaneously has good water resistance and excellent mechanical property, and can be widely applied to the fields such as painting, ink, a binder and the like.
Description
Technical field
The present invention relates to the method for making of a kind of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion.This emulsion is applicable to fields such as coating, printing ink and tackiness agent.
Background technology
Water-base polyurethane material has been widely used in fields such as coating, printing ink and sizing agent at present owing to its excellent performance and environmental protection characteristics, but because the price of used starting material isocyanic ester is higher, has limited its application to a great extent.ACRYLIC EMULSION has ageing resistance and Bao Se gloss retention preferably, and cost is lower simultaneously, has well remedied the weak point of polyurethane material.Therefore, aqueous polyurethane and water polyacrylic acid are combined, prepare aquosity polyurethane-polyacrylate composite emulsion, can obtain the product of high performance-price ratio.In recent years, aquosity polyurethane-polyacrylate composite emulsion (hereinafter to be referred as the PUA composite emulsion) is comparatively fast developed.The method for preparing at present the PUA composite emulsion mainly comprises two kinds: one prepares aqueous polyurethane and water polyacrylic acid resin by " cold assembly "; Its two on the basis of aqueous polyurethane emulsion, dropwise addition of acrylic acid ester monomer polymerization, preparation " nuclear-shell " type composite emulsion.More than PUA composite emulsion its main body from essence of two kinds of methods preparation be still the physical mixed body of urethane and polyacrylic ester two components, and only have the problem of consistency by the composite emulsion of physical blending, can't bring into play the advantage of two components to greatest extent.Present research emphasis is how urethane and the polyacrylic ester component mode by chemical bond to be combined.Though existing several different methods is open, but, performance and the cost of the PUA composite emulsion that makes are difficult to take into account, and particularly there are deficiency in the electrolyte-resistant of PUA composite emulsion and stability in storage, and the water tolerance behind the emulsion film forming and mechanical property can not satisfy application requiring.On the other hand, carry out functional modification by the side chain to the PUA hybrid emulsion resins, can make prepared product obtain some specific performance properties, and then satisfy product some particular demands in actual applications.But still can not provide reliable preparation method at present.
Summary of the invention
The objective of the invention is: a kind of have excellent storage stability, good electrolyte-resistant and the preparation method of alkali-proof positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion are provided.
The technical scheme that realizes the object of the invention is: the method for making of a kind of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, it is characterized in that, in the synthesis of polyurethane reaction, the polyacrylic ester that will contain terminal hydroxy group inserts the polyurethane molecular chain by contained terminal hydroxy group and becomes the side chain of polyurethane molecular, obtain urethane and polyacrylic ester by the composite emulsion of chemical bond combination, its side chain that contains the polyacrylic ester of terminal hydroxy group has cationic hydrophilic radical, non-ionic segments and big steric group, and concrete preparation process is as follows:
1. preparation contains the polyacrylic ester of terminal hydroxy group
With the mixture of whole monomers, chain-transfer agent and initiator, evenly be added drop-wise to and carry out in the solvent that radical polymerization forms, concrete operations are as follows:
In reaction vessel, the solvent that adds 20～50wt% is bed material, under 50～130 ℃, vinyl monomer with 10～20wt% cation type hydrophilic radical, 14～35wt% contains the acrylate monomer of non-ionic segments, 6～25wt% contains the acrylate monomer of big steric group, other contain the monomer of vinyl structure 2～15wt%, 0.5～8wt% contains the mixture that sulfydryl dibasic alcohol chain-transfer agent and 0.05～3wt% initiator mix and stir, in 3～5 hours, evenly be added drop-wise in the solvent in the reaction vessel, drip the insulation under 50～130 ℃ of end back and made the polyacrylic ester that contains terminal hydroxy group in 3～10 hours, above-mentioned each raw material consumption sum is 100%, wherein, the vinyl monomer of cation type hydrophilic radical is (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid dimethylamino propyl ester, (methyl) vinylformic acid lignocaine ethyl ester, vinylformic acid diethylin propyl ester, methacrylic acid-2-tertiary butyl amino ethyl ester, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, in (methyl) acrylyl oxy-ethyl dimethyl benzyl ammonium chloride one or more; The acrylate monomer that contains big steric group is one or more in (methyl) isobornyl acrylate, (methyl) vinylformic acid methyl ring pentyl ester, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid tert-butylcyclohexyl ester, (methyl) vinylformic acid front three cyclohexyl ester; Other monomers that contain vinyl structure are one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) propyl acrylate, the own monooctyl ester of (methyl) vinylformic acid, ethyl acrylate, (methyl) vinylformic acid n-octyl, benzyl acrylate, vinylbenzene, the alpha-methyl styrene; Containing sulfydryl dibasic alcohol chain-transfer agent is 3-Mercapto-1,1, one or more in the 4-DTT; Initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo dicyclohexyl formonitrile HCN, hydrogen peroxide, dibenzoyl peroxide, the tert-butyl peroxide; Solvent is acetone, butanone, 1-Methyl-2-Pyrrolidone, N, one or more in dinethylformamide, the 1-Methoxy-2-propyl acetate; The acrylate monomer that contains non-ionic segments has following structure:
R wherein
1Be H or CH
3, R
2Be methyl or ethyl or butyl, the scope of n is 7～35;
2. prepare positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion
In reaction vessel, add the polyacrylic ester that contains terminal hydroxy group that 1. 10～30wt% step makes, the common macromolecular polyol of 2～10wt% and 5～20wt% isocyanic ester, mix the back and react 2～3h down at 80～90 ℃, add 0.2～4wt% linking agent then successively, 0.1 the common chainextender of～5wt%, 5～20wt% solvent, react 2～4h down at 70～80 ℃, add 0.005～0.3wt% catalyzer again, obtain polyurethane prepolymer solution behind reaction 3～5h down at 60～70 ℃, reactant is moved in the dispersion machine, under 2000 rev/mins stirring velocity, add the neutralization of 1～8wt% neutralizing agent, add again after 40～70wt% deionized water and stirring is uniformly dispersed, desolventizing after the underpressure distillation obtains positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, and above-mentioned each raw material consumption sum is 100%.
In the method for making of above-mentioned composite emulsion, 1. step prepares the used acrylate monomer that contains non-ionic segments of polyacrylic ester that contains terminal hydroxy group is in methoxy poly (ethylene glycol) list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate one or more.
In the method for making of above-mentioned composite emulsion, 2. step prepares in the raw material of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, and described common macromolecular polyol is one or more in polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran ethoxylated polyhydric alcohol, polyethylene oxide polyvalent alcohol, poly(propylene oxide) polyvalent alcohol, hydroxy-terminated polybutadienes polyvalent alcohol, the polyester polyol; Described isocyanic ester is isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4,4 '-dicyclohexyl methyl hydride-vulcabond, xylylene diisocyanate, tetramethyl-benzene dimethyl vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, 1, one or more in 5-naphthalene diisocyanate, the poly methylene poly phenyl poly isocyanate; Described linking agent is one or more in TriMethylolPropane(TMP), glycerol, tetramethylolmethane, Dipentaerythritol, the Sorbitol Powder; Described common chainextender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 2,3-butyleneglycol, 1, one or more in 6-hexylene glycol, neopentyl glycol, glycol ether, the hydroxymethyl-cyclohexane; Described solvent is acetone, butanone, 1-Methyl-2-Pyrrolidone, N, one or more in the dinethylformamide; Described catalyzer is one or more in triethylamine, triethylene diamine, dibutyl tin laurate, the stannous octoate; Described neutralizing agent is one or more in lactic acid, acetic acid, the phosphoric acid.
Technique effect of the present invention is: prepare the method for aquosity polyurethane-polyacrylate composite emulsion in the technical solution of the present invention compared with prior art, have following advantage:
(1) 1. step prepares in the used monomer of the polyacrylic ester that contains terminal hydroxy group, has comprised 3 kinds of functional monomers simultaneously namely: the vinyl monomer of cation type hydrophilic radical, contain non-ionic segments acrylate monomer, contain the acrylate monomer of big steric group.The side chain of the polyacrylic ester that contains terminal hydroxy group that makes like this, contains non-ionic segments, cationic hydrophilic radical and big steric group simultaneously.Contain the cationic hydrophilic radical in the polyacrylic ester of terminal hydroxy group, make that preparing the hydrophilic monomer or the wetting ability chainextender that need not in the urethane process to add for self-emulsifying subsequently just can realize Water-borne modification, makes formula for a product simpler; The non-ionic segments that contains in the polyacrylic ester of terminal hydroxy group is positioned at the side chain of polyurethane molecular and distributes comparatively concentrated, therefore, can bring into play the synergy of non-ionic segments, more excellent electrolyte-resistant is provided, the price of the acrylate monomer that contains non-ionic segments that in addition, the present invention is used is lower than the used polyether Glycols of common introducing side chain non-ionic segments; Contain weakened reactive force between molecular chain of big steric group in the polyacrylic ester of terminal hydroxy group, the polyacrylate solution viscosity that contains terminal hydroxy group is reduced, also simplified the synthetic operation of follow-up urethane, in addition, big steric group can also guarantee to have more excellent water tolerance behind the emulsion film forming;
When (two) 1. step prepares the polyacrylic ester that contains terminal hydroxy group, employing feeds intake the mode that each monomer mixture evenly drips, the composition of polyacrylic ester that can guarantee to contain terminal hydroxy group is consistent with the raw material composition, and then can effectively improve the performance of corresponding urethane.Having overcome polymkeric substance that reactivity ratio difference because of different monomers that prior art adopts a step feeding mode to cause causes forms with used monomer and forms inconsistent shortcoming;
(3) step urethane synthetic reaction process 2., the polyacrylic ester that will contain terminal hydroxy group inserts the polyurethane molecular chain by contained terminal hydroxy group and becomes the side chain of polyurethane molecular, make urethane and polyacrylic ester by the composite emulsion of chemical bond combination, make composite emulsion have both the advantage of two kinds of components, and make the side chain of PUA hybrid emulsion resins obtain functional modification, overcome and adopted physical cold to piece together the shortcoming that the composite emulsion component compatibility is relatively poor and application performance is restricted of preparation;
(4) step urethane building-up process has 2. been introduced linking agent, makes the composite emulsion molecule of preparation have crosslinking structure, effectively raises the mechanical property behind the emulsion film forming, has solved the relatively poor problem of pectination material mechanical performance.
Embodiment
Be described further below in conjunction with the present invention of embodiment, but be not limited to this.
The used starting material of embodiment and Comparative Examples unless otherwise indicated are commercially available industrial goods, can buy by the commercial channel.
Embodiment 1～3
1. preparation contains the polyacrylic ester of terminal hydroxy group
With the mixture of whole monomers, chain-transfer agent and initiator, evenly be added drop-wise to and carry out in the solvent that radical polymerization forms.
A) prescription sees Table 1.
Table 1
B) concrete operations
The prescription that provides by table 1, agitator is being housed, thermometer, adding solvent in the four-hole boiling flask of drying nitrogen conduit and reflux condensing tube is bed material, under 75～85 ℃ with the vinyl monomer of cation type hydrophilic radical, the acrylate monomer that contains non-ionic segments, the acrylate monomer that contains big steric group, other contain the monomer of vinyl structure, contain the mixture that sulfydryl dibasic alcohol chain-transfer agent and initiator mix and stir, in 3 hours, evenly be added drop-wise in the solvent in the four-hole boiling flask, drip the end back and be incubated 5 hours down at 80 ℃, make the polyacrylic ester that contains terminal hydroxy group of embodiment 1～3 respectively, its solids content is 66.67wt%, preserves standby.
2. prepare positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion
A) prescription sees Table 2.
Table 2
B) concrete operations
In the container that agitator, thermometer and condenser are housed, contain the polyacrylic ester of terminal hydroxy group, common macromolecular polyol and isocyanic ester by the adding of table 2 formula ratio, mix the back and react 2h down at 90 ℃, add linking agent, common chainextender, solvent then successively, react 3h down at 70～80 ℃, add catalyzer again, obtain polyurethane prepolymer solution behind the reaction 4h down at 60～70 ℃.Reactant is moved in the high speed shear dispersion machine, under 2000 rev/mins stirring velocity, add the neutralizing agent neutralization, add again after deionized water and stirring is uniformly dispersed, desolventizing after the underpressure distillation, obtain positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of embodiment 1～3 respectively, its solids content is 33.3wt%, and the pH value is 6～7.
Comparative Examples 1～3
1. preparation contains the polyacrylic ester of terminal hydroxy group
A) prescription sees Table 3.
Table 3
B) concrete operations
Except the prescription difference, all the other all make the polyacrylic ester that contains terminal hydroxy group of Comparative Examples 1～3 respectively by the method for embodiment, standby.
2. prepare positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion
A) prescription sees Table 4.
Table 4
B) concrete operations
Except the prescription difference, all the other all make the positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of Comparative Examples 1～3 respectively by the method for embodiment.
Detect the performance of the positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of embodiment and Comparative Examples
(1) detection method
1. viscosity
Mensuration contains the viscosity of the polyacrylic ester of terminal hydroxy group.Adopt model to measure for the NDJ-1 rotational viscosimeter down at 25 ℃.
2. electrolyte-resistant
Get composite emulsion 20 gram, contain more chemical industry company limited product of electrolyte solution YK-L360(Shanghai but slowly add 10 grams) mix after, be positioned in 50 ℃ of baking ovens 3 months, observe and have or not precipitation and throw out generation.Electrolyte-resistant is divided into 3 grades: 1 grade is homogeneous solution, does not have precipitation, no layering; 2 grades is little turbid solution, does not have precipitation, no layering; 3 grades are flocculation, and precipitation is arranged at the bottom, layering.1 grade best, and 3 grades the poorest.
3. stability in storage
Get 20 gram composite emulsion and pour in the airtight vial, be positioned over 50 ℃ of baking ovens interior 3 months, observe to have or not and precipitate and the throw out generation.
4. water tolerance
Composite emulsion is sprayed on the steel plate galvanized after the polishing, and film thickness monitoring behind the surface drying, is put into 80 ℃ of oven dryings and was obtained model to be measured in 30 minutes under the room temperature between 15～20 μ m.In the water with 25 ℃ of model immersions to be measured, observe the model changing conditions after 48 hours.Outward appearance situation according to soaking the back model is divided into 3 grades with water tolerance: 1 grade is the basic no change of model; 2 grades is the model surface blistering, little turning white; 3 grades is to film on the model to come off, and turns white fully.1 grade best, and 3 grades the poorest.
5. tensile strength
Pour composite emulsion on polyfluortetraethylene plate film forming, film thickness monitoring is treated to test according to the standard A STMD412-87 of American Society Testing and Materials behind the glued membrane complete drying between 1～2mm.
(2) detected result sees Table 5
Table 5
A is the polyacrylic ester that contains terminal hydroxy group in the table 5
By the test result of table 5 as can be known, the prepared polyacrylic ester modest viscosity that contains terminal hydroxy group in the embodiment of the invention 1～3 is conducive to the synthetic of follow-up urethane.Prepared positively charged ion-non-ionic water polyurethane-acrylate composite emulsion combines the two-fold advantage of urethane and polyacrylate material in the embodiment of the invention 1～3, particularly have more excellent stability in storage and electrolyte-resistant performance, have water tolerance and excellent mechanical property preferably simultaneously, can be widely used in fields such as coating, printing ink and tackiness agent.
By the detected result of table 5 also as can be known, compare with the embodiment of the invention 1～3, because Comparative Examples 1 does not add the acrylate monomer that contains non-ionic segments in containing the polyacrylic ester preparation process of terminal hydroxy group, therefore, the electrolyte-resistant of Comparative Examples 1 composite emulsion stability and the obvious variation of stability in storage; Because Comparative Examples 2 does not add the acrylate monomer that contains big steric group in containing the polyacrylic ester preparation process of terminal hydroxy group, therefore, the viscosity of the polyacrylic ester that contains terminal hydroxy group of Comparative Examples 2 is higher, is unfavorable for follow-up polyurethane preparation.Simultaneously, the water tolerance of corresponding composite emulsion is also relatively poor; Because Comparative Examples 3 does not add linking agent in preparation urethane process, therefore, the tensile strength of the compound emulsion film of Comparative Examples 3 correspondences is lower, and mechanical property is obviously relatively poor.Proved that thus the present invention is when preparation contains the polyacrylic ester of terminal hydroxy group, use contain non-ionic segments acrylate monomer, contain the acrylate monomer of big steric group and when preparation urethane, adopt linking agent, the performance that improves after composite emulsion and the film forming is had positive effect.
Claims (3)
1. the method for making of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, it is characterized in that, in the synthesis of polyurethane reaction, the polyacrylic ester that will contain terminal hydroxy group inserts the polyurethane molecular chain by contained terminal hydroxy group and becomes the side chain of polyurethane molecular, obtain urethane and polyacrylic ester by the composite emulsion of chemical bond combination, its side chain that contains the polyacrylic ester of terminal hydroxy group has cationic hydrophilic radical, non-ionic segments and big steric group, and concrete preparation process is as follows:
1. preparation contains the polyacrylic ester of terminal hydroxy group
With the mixture of whole monomers, chain-transfer agent and initiator, evenly be added drop-wise to and carry out in the solvent that radical polymerization forms, concrete operations are as follows:
In reaction vessel, the solvent that adds 20～50wt% is bed material, under 50～130 ℃, vinyl monomer with 10～20wt% cation type hydrophilic radical, 14～35wt% contains the acrylate monomer of non-ionic segments, 6～25wt% contains the acrylate monomer of big steric group, other contain the monomer of vinyl structure 2～15wt%, 0.5～8wt% contains the mixture that sulfydryl dibasic alcohol chain-transfer agent and 0.05～3wt% initiator mix and stir, in 3～5 hours, evenly be added drop-wise in the solvent in the reaction vessel, drip the insulation under 50～130 ℃ of end back and made the polyacrylic ester that contains terminal hydroxy group in 3～10 hours, above-mentioned each raw material consumption sum is 100%, wherein, the vinyl monomer of cation type hydrophilic radical is (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid dimethylamino propyl ester, (methyl) vinylformic acid lignocaine ethyl ester, vinylformic acid diethylin propyl ester, methacrylic acid-2-tertiary butyl amino ethyl ester, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, in (methyl) acrylyl oxy-ethyl dimethyl benzyl ammonium chloride one or more; The acrylate monomer that contains big steric group is one or more in (methyl) isobornyl acrylate, (methyl) vinylformic acid methyl ring pentyl ester, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid tert-butylcyclohexyl ester, (methyl) vinylformic acid front three cyclohexyl ester; Other monomers that contain vinyl structure are one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) propyl acrylate, the own monooctyl ester of (methyl) vinylformic acid, ethyl acrylate, (methyl) vinylformic acid n-octyl, benzyl acrylate, vinylbenzene, the alpha-methyl styrene; Containing sulfydryl dibasic alcohol chain-transfer agent is 3-Mercapto-1,1, one or more in the 4-DTT; Initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo dicyclohexyl formonitrile HCN, hydrogen peroxide, dibenzoyl peroxide, the tert-butyl peroxide; Solvent is acetone, butanone, 1-Methyl-2-Pyrrolidone, N, one or more in dinethylformamide, the 1-Methoxy-2-propyl acetate; The acrylate monomer that contains non-ionic segments has following structure:
R wherein
1Be H or CH
3, R
2Be methyl or ethyl or butyl, the scope of n is 7～35;
2. prepare positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion
In reaction vessel, add the polyacrylic ester that contains terminal hydroxy group that 1. 10～30wt% step makes, the common macromolecular polyol of 2～10wt% and 5～20wt% isocyanic ester, mix the back and react 2～3h down at 80～90 ℃, add 0.2～4wt% linking agent then successively, 0.1 the common chainextender of～5wt%, 5～20wt% solvent, react 2～4h down at 70～80 ℃, add 0.005～0.3wt% catalyzer again, obtain polyurethane prepolymer solution behind reaction 3～5h down at 60～70 ℃, reactant is moved in the dispersion machine, under 2000 rev/mins stirring velocity, add the neutralization of 1～8wt% neutralizing agent, add again after 40～70wt% deionized water and stirring is uniformly dispersed, desolventizing after the underpressure distillation obtains positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, and above-mentioned each raw material consumption sum is 100%.
2. according to the method for making of right 1 described composite emulsion, it is characterized in that 1. step prepares the used acrylate monomer that contains non-ionic segments of polyacrylic ester that contains terminal hydroxy group is in methoxy poly (ethylene glycol) list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate one or more.
3. according to the method for making of right 1 described composite emulsion, it is characterized in that, 2. step prepares in the raw material of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, and described common macromolecular polyol is one or more in polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran ethoxylated polyhydric alcohol, polyethylene oxide polyvalent alcohol, poly(propylene oxide) polyvalent alcohol, hydroxy-terminated polybutadienes polyvalent alcohol, the polyester polyol; Described isocyanic ester is isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4,4 '-dicyclohexyl methyl hydride-vulcabond, xylylene diisocyanate, tetramethyl-benzene dimethyl vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, 1, one or more in 5-naphthalene diisocyanate, the poly methylene poly phenyl poly isocyanate; Described linking agent is one or more in TriMethylolPropane(TMP), glycerol, tetramethylolmethane, Dipentaerythritol, the Sorbitol Powder; Described common chainextender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 2,3-butyleneglycol, 1, one or more in 6-hexylene glycol, neopentyl glycol, glycol ether, the hydroxymethyl-cyclohexane; Described solvent is acetone, butanone, 1-Methyl-2-Pyrrolidone, N, one or more in the dinethylformamide; Described catalyzer is one or more in triethylamine, triethylene diamine, dibutyl tin laurate, the stannous octoate; Described neutralizing agent is one or more in lactic acid, acetic acid, the phosphoric acid.
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