CN105037632A - Starch-based bio-latex with core-shell structure and preparation method thereof - Google Patents
Starch-based bio-latex with core-shell structure and preparation method thereof Download PDFInfo
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- CN105037632A CN105037632A CN201510354361.0A CN201510354361A CN105037632A CN 105037632 A CN105037632 A CN 105037632A CN 201510354361 A CN201510354361 A CN 201510354361A CN 105037632 A CN105037632 A CN 105037632A
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- starch
- latex
- monomer
- alkene class
- nucleocapsid structure
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Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 70
- 235000019698 starch Nutrition 0.000 title claims abstract description 70
- 239000008107 starch Substances 0.000 title claims abstract description 69
- 239000004816 latex Substances 0.000 title claims abstract description 55
- 229920000126 latex Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011258 core-shell material Substances 0.000 title claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 150000001336 alkenes Chemical class 0.000 claims abstract description 32
- 229920000881 Modified starch Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 235000019426 modified starch Nutrition 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims abstract description 6
- 239000012792 core layer Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004160 Ammonium persulphate Substances 0.000 claims description 9
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 4
- 230000002255 enzymatic effect Effects 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-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
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 claims description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract 2
- 239000002002 slurry Substances 0.000 abstract 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- 238000009795 derivation Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 108010027529 Bio-glue Proteins 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical class NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
- Paper (AREA)
Abstract
The invention relates to starch-based bio-latex with a core-shell structure and a preparation method thereof. The latex is of a two-layer core-shell structure, the core layer is a crosslinked copolymer mainly including starch derivatives and hard alkene monomers, and the shell layer is a copolymer mainly including soft alkene monomers. The preparation method of the bio-latex includes the following steps: (1) stirring uniformly the starch derivatives and water, heating and gelatinizing to prepare starch slurry; (2) adding a part of monomers, an initiator, an emulsifier and crosslinking monomers into the starch slurry to prepare shell-layer polymer; (3) adding the remaining monomers, the emulsifier and the initiator, and wrapping the core-layer polymer with the shell-layer polymer; (4) filtering the reaction product to obtain the starch-based bio-latex with the core-shell structure. Compared with the preparation method of conventional starch-based bio-latex, the preparation method provided by the invention can improve the performance of bio-latex on the premise that the cost is not increased; the bio-latex provided by the invention can be used to partially or completely replace carboxylic butadiene-styrene latex or styrene-acrylate latex commonly used in the current papermaking field.
Description
Technical field
The present invention relates to a kind of starch-based biological latex and preparation method thereof, particularly relate to a kind of starch-based biological latex with nucleocapsid structure and preparation method thereof, belong to chemical field.
Background technology
The quality of White Board determines primarily of bodystock paper, sizing agent, pigment and auxiliary agent, and wherein sizing agent plays an important role.Pigment particles bonds by sizing agent mutually, and pigment is bonded in bodystock paper surface, also plays simultaneously and regulates printing-ink to absorb, maintain the effect of paint stability and mobility.At present, in White Board production, sizing agent used mainly contains natural glue and synthetic sizing agent two kinds, the most frequently used in natural glue is exactly various treated starches, and topmost in synthetic sizing agent is exactly various latex, as carboxylic styrene butadiene latex, styrene-acrylic latex, pure third latex etc.In actual production, for the consideration of cost and aspect of performance, papermaking enterprise usually by modified starch and latex used in combination, but the ratio of starch usually can not higher than 30%.
The synthetic tamanoris such as carboxylic styrene butadiene latex are all with petroleum derivation product, as vinylbenzene, divinyl, acrylic ester monomer polymerization obtain.In recent years, because oil price rises steadily, the raw materials cost producing latex is caused constantly to rise.In order to reduce costs, papermaking enterprise selects the ratio increasing starch in sizing agent.Some enterprise developments go out starch-based biological latex, and the starch content that these starch-based biological latexes contain is very high, although can reduce costs, cause disadvantageous effect to the performance of coating and White Board simultaneously.Containing a large amount of hydroxyls in starch molecule, oh group has stronger wetting ability, causes the paper water-absorbent grow of production, wet tenacity to decline.
For the negative impact avoiding the great amount of hydroxy group in starch molecule to cause coating and paper performance, adopt hud polymerization method, by regulating formula and technique, starch molecule is made mainly to be distributed in stratum nucleare, in follow-up building-up reactions, continue encasement one polymer on stratum nucleare, manage to avoid latex particle surface to there is much starch molecule.
The where the shoe pinches of this process is, hydrophilic hydroxyl trends towards entering aqueous phase, therefore phase reversion can occur in building-up process, is finally distributed in emulsion particle surface, makes latex show stronger wetting ability.For addressing this problem, need adjustment polymer formulators and synthetic method, such as in stratum nucleare polymer synthesis process, add hard monomer and cross-linking monomer, the network polymer of dimensional stabilizing is formed at stratum nucleare, thus avoid, in follow-up building-up process, phase reversion occurs, make starch molecule be covered by emulsion particle inside securely, avoid the disadvantageous effect that in starch, hydrophilic hydroxy group causes coating and paper performance.
In view of this, be necessary to improve existing starch-based biological latex and preparation method thereof, coating, the glue-applying technique of modern paper can be applied to better.
Summary of the invention
The object of the invention is to, a kind of starch-based biological latex with nucleocapsid structure and preparation method thereof is provided.
The technical scheme that technical solution problem of the present invention adopts is: a kind of starch-based biological latex with nucleocapsid structure, it is characterized in that: the latex particle that this starch-based biological latex contains has nucleocapsid structure, this coreshell type structure comprises the shell of outside and is positioned at the stratum nucleare of shell, described stratum nucleare and the shell component jointly containing following weight part: starch and 30 ~ 80 parts, derivative thereof; Alkene class hard monomer 10 ~ 80 parts; Alkene class soft monomer 20 ~ 80 parts; Cross-linking monomer 2 ~ 15 parts; Carboxylic vinyl monomer 3 ~ 10 parts; Initiator 0.2 ~ 5 part; Emulsifying agent 0.5 ~ 5 part; 50 ~ 200 parts, water.
The stratum nucleare of described nucleocapsid structure starch-based bio glue is the multipolymer of starch derivative, alkene class hard monomer, alkene class soft monomer and cross-linking monomer, and wherein the quality of starch derivative, alkene class hard monomer and cross-linking monomer accounts for 55 ~ 80% of polymeric core layer total mass; Shell is the multipolymer of alkene class hard monomer, alkene class soft monomer and carboxylic vinyl monomer, and wherein the quality of alkene class soft monomer accounts for 55 ~ 80% of polymeric shell layer total mass.
Described starch derivative is one or more in Sumstar 190, enzymatic starch, esterification starch, etherification starch, acidified starch, Zulkovsky starch, dextrin, graft copolymerization starch, pre-gelatinized starch.
Described alkene class hard monomer is one or more in vinylbenzene, vinyl toluene, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, t-butyl styrene.
Described alkene class soft monomer is one or more just in ester, Isooctyl acrylate monomer, isoprene, isoamyl acrylate of divinyl, methyl acrylate, ethyl propenoate, n-propyl, Propylene glycol monoacrylate, n-butyl acrylate, tert-butyl acrylate, vinylformic acid.
Described cross-linking monomer be methylene-bisacrylamide, oxalic dialdehyde, glutaraldehyde, Vinylstyrene, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, one or more in pentaerythritol tetramethylacrylate.
Described initiator is one or more in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, ceric ammonium nitrate, cerous sulfate, Sulfothiorine, sodium bisulfite.
Described carboxylic vinyl monomer is one or more in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid.
The described preparation process with the starch-based biological latex of nucleocapsid structure is:
(1) first, starch derivative and water are added reactor, stir and make its Homogeneous phase mixing, be heated to 60 ~ 90 DEG C and be incubated 0.5 ~ 1 hour, making its abundant gelatinization;
(2) under nitrogen protection, by account for whole alkene class hard monomer total mass 55 ~ 85% alkene class hard monomer, account for whole alkene class soft monomer total mass 15 ~ 45% alkene class soft monomer, accounting for the initiator solution of 40 ~ 80% of whole initiator total mass, partial cross-linked monomer and emulsifying agent joins in reactor, control temperature, at 40 ~ 90 DEG C, reacts 2 ~ 4 hours;
(3) remaining alkene class soft monomer, alkene class hard monomer, initiator, cross-linking monomer and emulsifying agent are added reactor, control temperature, at 40 ~ 90 DEG C, reacts 2 ~ 4 hours;
(4) keeping, under the state stirred, reactor being cooled to room temperature, filtering, obtaining the starch-based biological latex with nucleocapsid structure.
Compared with prior art, the beneficial effect that the present invention has is:
(1) replace part petroleum derivation product with starch derivative, decrease the consumption of petroleum derivation product, the raw materials cost of latex manufacturing enterprise can be reduced, be conducive to environment protection;
(2) compared with traditional starch radical biogum breast, the present invention is by regulating the distribution of starch molecule in emulsion particle, control the stratum nucleare that starch molecule is mainly distributed in emulsion particle, the disadvantageous effect that the hydroxyl avoiding starch molecule causes coating and ways and methods, achieves and improve starch-based biological latex performance under the prerequisite not increasing cost.
Embodiment
In order to make the object, technical solutions and advantages of the present invention clearly, describe the present invention below in conjunction with specific embodiment.
Embodiment 1
Nucleocapsid structure starch-based biological latex is filled a prescription, and each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
Under nitrogen protection, by whole enzymatic starch and 80% water Homogeneous phase mixing, be heated to 80 DEG C and be incubated 30 minutes, make its abundant gelatinization, add the vinylbenzene and methyl methacrylate that account for 80% in above-mentioned reactant formula, the ammonium persulphate of 60% and sodium bisulfite, the methylene-bisacrylamide of 85%, the butyl acrylate of 30% and sodium lauryl sulphate, react 2 hours at 80 DEG C, by whole methylene-succinic acids and remaining vinylbenzene, methyl methacrylate, butyl acrylate, methylene-bisacrylamide, sodium lauryl sulphate and water mixing, remaining ammonium persulphate and sodium bisulfite are mixed with solution, slowly be added drop-wise to respectively in flask, rate of addition controls to dropwise at 1 hours, temperature controls to continue reaction 3 hours at 80 DEG C, keeping stopping heating under the state stirred, filter after being down to room temperature, obtain the starch-based biological latex with nucleocapsid structure, its physical property measurement the results are shown in Table 1.
Embodiment 2:
Nucleocapsid structure starch-based biological latex is filled a prescription, and each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
Under nitrogen protection, by whole enzymatic starch and Sumstar 190 and 80% water Homogeneous phase mixing, be heated to 80 DEG C and make its abundant gelatinization, add the vinyl toluene accounting for 80% in above-mentioned reactant formula, the ammonium persulphate of 65% and cerous sulfate, the isoprene of 20% and Isooctyl acrylate monomer, the Sodium dodecylbenzene sulfonate of 30% and whole glutaraldehyde, react 3 hours at 80 DEG C, then by whole methacrylic acids and remaining vinyl toluene, isoprene, drip gradually after Sodium dodecylbenzene sulfonate and water mix, remaining ammonium persulphate and cerous sulfate are mixed with 10% aqueous solution respectively drip simultaneously, after whole monomer and initiator dropwise, temperature controls 70 DEG C of reactions 4 hours, keeping stopping heating under the state stirred, filter after being down to room temperature, obtain the starch-based biological latex with nucleocapsid structure, its physical property measurement the results are shown in Table 1.
Embodiment 3:
Nucleocapsid structure starch-based biological latex is filled a prescription, and each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
Under nitrogen protection, by whole dextrin and 70% water Homogeneous phase mixing, be heated to 80 DEG C and make its abundant gelatinization, add the vinylbenzene and the methyl methacrylate that account in above-mentioned reactant formula 75%, the Sodium Persulfate of 65%, the ethyl propenoate of 25% and Isooctyl acrylate monomer, whole oxalic dialdehydes, react 2 hours at 80 DEG C, by whole methylene-succinic acids and sodium stearate, remaining vinylbenzene, methyl methacrylate, Sodium Persulfate, ethyl propenoate, Isooctyl acrylate monomer fully mixes with water, be divided into 5 equal portions, dripped once every 10 minutes, after dropwising, temperature controls 80 DEG C of reactions 4 hours, keeping stopping heating under the state stirred, filter after being down to room temperature, obtain the starch-based biological latex with nucleocapsid structure, its physical property measurement the results are shown in Table 1.
Embodiment 4:
Nucleocapsid structure starch-based biological latex is filled a prescription, and each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
Under nitrogen protection, by whole acidified starch and 75% water Homogeneous phase mixing, being heated to 80 DEG C makes it fully dissolve gelatinization, add the vinyl toluene and methyl methacrylate that account for 80% in above-mentioned reactant formula, the Propylene glycol monoacrylate of 20% and butyl acrylate, whole ceric ammonium nitrates and methylene-bisacrylamide, react 2 hours at 40 DEG C, then by whole vinylformic acid, whole Tween80 and sodium lauryl sulphate, remaining vinyl toluene, methyl methacrylate, butyl acrylate, Propylene glycol monoacrylate fully mixes with water, ammonium persulphate is made into the solution of 20%, first drip monomer mixture, start to drip ammonium persulfate solution after 10 minutes, after whole monomer and initiator dropwise, temperature controls 70 DEG C of reactions 3 hours, keeping stopping heating under the state stirred, filter after being down to room temperature, obtain the starch-based biological latex with nucleocapsid structure, its physical property measurement the results are shown in Table 1.
Embodiment 5
Nucleocapsid structure starch-based biological latex is filled a prescription, and each component content is calculated in mass, and unit is gram (g):
Synthesis technique:
Under nitrogen protection, by whole Sumstar 190 and 80% water Homogeneous phase mixing, being heated to 80 DEG C makes it fully dissolve gelatinization, add the vinyl toluene accounting for 80% in above-mentioned reactant formula, the ammonium persulphate of 60%, the butyl acrylate of 10% and OP-10, whole methylene-bisacrylamides, react 2 hours at 80 DEG C, by whole vinylformic acid and remaining vinyl toluene, ammonium persulphate, butyl acrylate, OP-10 and water mixing, be divided into 5 equal portions, dripped once every 10 minutes, after dropwising, temperature controls 80 DEG C of reactions 3 hours, keeping stopping heating under the state stirred, filter after being down to room temperature, obtain the starch-based biological latex with nucleocapsid structure, its physical property measurement the results are shown in Table 1.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.Anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Table 1
Claims (9)
1. one kind has the starch-based biological latex of nucleocapsid structure, it is characterized in that: the latex particle that this starch-based biological latex contains has nucleocapsid structure, this coreshell type structure comprises the shell of outside and is positioned at the stratum nucleare of shell, described stratum nucleare and the shell component jointly containing following weight part:
2. the starch-based biological latex with nucleocapsid structure according to claim 1, it is characterized in that: the stratum nucleare of latex particle is the multipolymer of starch derivative, alkene class hard monomer, alkene class soft monomer and cross-linking monomer, and wherein the quality of starch derivative, alkene class hard monomer and cross-linking monomer accounts for 55 ~ 80% of polymeric core layer total mass; Shell is the multipolymer of alkene class hard monomer, alkene class soft monomer and carboxylic vinyl monomer, and wherein the quality of alkene class soft monomer accounts for 55 ~ 80% of polymeric shell layer total mass.
3. the starch-based biological latex with nucleocapsid structure according to claim 1, is characterized in that: described starch derivative is one or more in Sumstar 190, enzymatic starch, esterification starch, etherification starch, acidified starch, Zulkovsky starch, dextrin, graft copolymerization starch, pre-gelatinized starch.
4. the starch-based biological latex with nucleocapsid structure according to claim 1, is characterized in that: described alkene class hard monomer is one or more in vinylbenzene, vinyl toluene, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, t-butyl styrene.
5. the starch-based biological latex with nucleocapsid structure according to claim 1, is characterized in that: described alkene class soft monomer is one or more just in ester, Isooctyl acrylate monomer, isoprene, isoamyl acrylate of divinyl, methyl acrylate, ethyl propenoate, n-propyl, Propylene glycol monoacrylate, n-butyl acrylate, tert-butyl acrylate, vinylformic acid.
6. the starch-based biological latex with nucleocapsid structure according to claim 1, is characterized in that: described cross-linking monomer be methylene-bisacrylamide, oxalic dialdehyde, glutaraldehyde, Vinylstyrene, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, one or more in pentaerythritol tetramethylacrylate.
7. the starch-based biological latex with nucleocapsid structure according to claim 1, is characterized in that: described initiator is one or more in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, ceric ammonium nitrate, cerous sulfate, Sulfothiorine, sodium bisulfite.
8. the starch-based biological latex with nucleocapsid structure according to claim 1, is characterized in that: carboxylic vinyl monomer is one or more in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid.
9. the preparation method with the starch-based biological latex of nucleocapsid structure described in any one of claim 1 ~ 8, is characterized in that, the step of described preparation method is:
(1) first, starch derivative and water are added reactor, stir and make its Homogeneous phase mixing, be heated to 60 ~ 90 DEG C and be incubated 0.5 ~ 1 hour, making its abundant gelatinization;
(2) under nitrogen protection, by account for whole alkene class hard monomer total mass 55 ~ 85% alkene class hard monomer, account for whole alkene class soft monomer total mass 15 ~ 45% alkene class soft monomer, accounting for the initiator solution of 40 ~ 80% of whole initiator total mass, partial cross-linked monomer and emulsifying agent joins in reactor, control temperature, at 40 ~ 90 DEG C, reacts 2 ~ 4 hours;
(3) remaining alkene class soft monomer, alkene class hard monomer, initiator, cross-linking monomer and emulsifying agent are added reactor, control temperature, at 40 ~ 90 DEG C, reacts 2 ~ 4 hours;
(4) keeping, under the state stirred, reactor being cooled to room temperature, filtering, obtaining the starch-based biological latex with nucleocapsid structure.
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