CN117924621A - Multiphase structure modified styrene-butadiene copolymer composite latex - Google Patents
Multiphase structure modified styrene-butadiene copolymer composite latex Download PDFInfo
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- CN117924621A CN117924621A CN202410144609.XA CN202410144609A CN117924621A CN 117924621 A CN117924621 A CN 117924621A CN 202410144609 A CN202410144609 A CN 202410144609A CN 117924621 A CN117924621 A CN 117924621A
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- Prior art keywords
- styrene
- percent
- butadiene
- modified
- weight
- Prior art date
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Links
- 229920000126 latex Polymers 0.000 title claims abstract description 67
- 239000004816 latex Substances 0.000 title claims abstract description 66
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 46
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical class [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229910000271 hectorite Inorganic materials 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- -1 tertiary amine modified hectorite Chemical class 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 19
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 10
- 239000000123 paper Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 claims description 3
- OAKUJYMZERNLLT-UHFFFAOYSA-N 4-(dimethylamino)butyl 2-methylprop-2-enoate Chemical compound CN(C)CCCCOC(=O)C(C)=C OAKUJYMZERNLLT-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 11
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 abstract description 3
- 238000007872 degassing Methods 0.000 abstract description 2
- 229940094522 laponite Drugs 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 11
- 239000002174 Styrene-butadiene Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000011115 styrene butadiene Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 6
- 238000009775 high-speed stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000012802 nanoclay Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Paper (AREA)
Abstract
The invention relates to a multiphase structure modified styrene-butadiene copolymer composite latex, which consists of laponite particles, soft phase and hard phase three-phase copolymers and water, wherein at least one phase is formed by polymerizing butadiene, styrene, functional monomers and unsaturated carboxylic acid monomers through emulsion; the weight of the modified laponite accounts for 3-6wt% of the total weight of the monomer mixture; the weight of the monomer mixture of the soft phase copolymer accounts for 50-80 wt% of the total weight of the monomer mixture; the weight of the monomer mixture of the hard phase copolymer is 20-50% of the total weight of the monomer mixture; the preparation method comprises a first, a second and a third polymerization stage and a degassing stage. The butadiene-styrene copolymer latex with the three-phase structure has strong controllability of particle size and glass transition temperature, can adjust the particle size and the glass transition temperature of the product according to specific requirements, and has stronger product stability.
Description
[ Field of technology ]
The invention relates to the technical field of modified styrene-butadiene copolymer latex, in particular to a modified styrene-butadiene copolymer composite latex with a multiphase structure.
[ Background Art ]
The styrene-butadiene latex is an important component in the polymer synthesis industry, emulsion polymerization is a main production process of the styrene-butadiene latex, and the styrene-butadiene latex has wide application and relates to the aspects of paper coating, dipping products and the like. Styrene-butadiene latex is used as a binder to improve the adhesive strength of paper coating products and the morphological and dimensional stability of nonwoven/paperboard products, to improve the gloss, printing properties, stiffness of the products, and to improve or increase the water resistance among other properties. The binding properties of styrene-butadiene latex determine to a large extent the weight and overall properties of the final product, with the composition of the latex being the most important factor affecting the binding properties of the product.
The styrene-butadiene latex has excellent film forming property and adhesiveness as water-based polymer emulsion, is low in cost, safe and environment-friendly, and becomes a film forming substance which is most widely applied in papermaking and chemical fiber materials. However, in many applications, especially in paper coating, the adhesive strength, glossiness, printing performance and water resistance of the coated paper product cannot be effectively balanced, and in non-woven fabric/paperboard impregnation, the hand feeling, dimensional stability and stiffness of the product are contradicted and not ideal, so that a hot soft and cold crisp phenomenon can be generated; to solve these problems, it is often necessary to compound modify the styrene-butadiene latex. Among the numerous modification methods, the composite material of the modified styrene-butadiene latex of the inorganic nano material is one direction of the research of the modified styrene-butadiene latex.
In recent years, solid particle stabilized emulsions, i.e. Pickering emulsions, have been rapidly developed and have attracted considerable attention in recent years because of their avoidance of negative effects (e.g. foaming, toxicity, affecting material properties) and unique interfacial particle self-assembly effects. However, the electrostatic attraction of silicate lamellar and interlayer ions makes the preparation of the exfoliated nanocomposite quite difficult, and the exfoliated polymer/clay nanocomposite prepared at home and abroad is less. The patent CN201711167541.3 prepares the aqueous acrylic resin/hectorite organic-inorganic composite leather finishing agent, which is characterized in that nano-particle hectorite is used as a stabilizer to replace the traditional organic surfactant, and the emulsion polymerization technology is adopted to prepare the aqueous acrylic resin/hectorite composite leather finishing agent which takes acrylate polymer as a core and inorganic nano-particles as a shell, thereby not only avoiding the use of the organic surfactant in the traditional emulsion polymerization method and solving the problem of toxicity of the organic emulsifier and the negative influence on the film forming performance in the later period of emulsion, but also the used stabilizer hectorite nano-particles are nano-clay with a lamellar structure, can be used as a reinforcing modifier of acrylic resin, and remarkably improve the mechanical property, wear resistance and thermal stability of the finishing agent and endow a coating film with good ultraviolet aging resistance. However, this patent does not disclose or address the greatest concerns and drawbacks of the Pickering emulsion polymerization process: the nano-particle hectorite is used as a stabilizer and has key performances such as mechanical stability, chemical stability, storage stability and the like. It has been noted that laponite is a highly hydrophilic, artificially synthesized layered silicate having a nano platelet structure, whose particle diameter is concentrated in 25 to 35nm, platelet thickness is 1nm, size is controllable and hydrophilicity is high, and it can be exfoliated into a platelet structure in water to finally form a colorless transparent colloidal dispersion, so that it has been widely used as an additive and a rheological agent in industrial and consumer products such as paint, varnish, printing, toothpaste, and its colloidal characteristics make it exhibit unique advantages in stabilizing emulsion or emulsion particles. In fact, some researches have reported that the nanoclay-modified styrene-butadiene polymer, such as patent CN200810200760.1, is modified with sodium bentonite-modified styrene-butadiene latex, which is prepared by mixing sodium bentonite and styrene-butadiene latex in a mechanical blending manner at a mixing ratio of 10%, and the obtained bentonite-modified styrene-butadiene latex improves the adhesive property of the latex. However, the patent does not disclose or examine the key properties such as stability of the composite emulsion, and the inorganic nanoclay has the problem of poor compatibility with the organic polymer.
The Chinese patent application with the application number of CN201810174129.2 discloses a preparation method of modified styrene-butadiene latex with a core-shell structure, wherein the inner core of the modified styrene-butadiene latex consists of butadiene, styrene, alkenyl carboxylic acid, nitrile monomer and organosilicon monomer, and the outer shell consists of alkyl methacrylate, alkyl acrylate, alkenyl carboxylic acid, cross-linking agent and adhesive force monomer, so that the modified styrene-butadiene latex with the core-shell structure is prepared, has stepped glass transition temperature, good film forming property and can greatly improve the water resistance and adhesive strength of the styrene-butadiene latex; however, the use of the cross-linking agent increases the gel content, which is unfavorable for the film forming property and the evenness of the paper coating during coating, and the difficult problem that the glossiness and the bonding strength of the styrene-butadiene latex are difficult to balance is not effectively solved or improved. A styrene-butadiene latex with similar core-shell structure or multiphase structure, such as China patent application numbers 201910648658.6, 201910648556.4 and 201910648534.8, relates to paper Tu Buding diene-styrene copolymer latex with a core-shell or multiphase structure or a core-shell structure, and solves the balance of glossiness and bonding strength to a certain extent.
Based on the technical conditions, the invention discovers that the polymerization method can well solve the problem that the inorganic nano material and the organic polymer have poor compatibility all the time, and the solid particle emulsifier for stabilizing the emulsion has the advantages of low cost, no toxicity, no pollution and the like, and the prepared polymer emulsion does not need complex post-treatment, so that the composite modified styrene-butadiene copolymer latex is developed to overcome the defects of the prior art, and the defects of unstable polymerization, poor stability and the like of the product in the prior art are overcome.
[ Invention ]
The invention aims to overcome the defects of the prior art and provides a modified styrene-butadiene copolymer composite latex with a multiphase structure.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: the composite latex consists of modified hectorite, soft phase copolymer, hard phase copolymer and water, wherein the weight of the modified hectorite accounts for 3-6wt% of the total weight of the monomer mixture, the weight of the monomer mixture of the soft phase copolymer accounts for 50-80wt% of the total weight of the monomer mixture, and the weight of the monomer mixture of the hard phase copolymer accounts for 20-50wt% of the total weight of the monomer mixture; the copolymer composite latex has 49-51% of solid content, 6.0-8.0 of pH, 100-300 mPa.S of viscosity, 36-46 mN/m of surface tension, 140-170 nm of particle size, 10-30 mv of potential, 70-90% of gel content and glass transition temperature of-5-15 ℃ and 20-30 ℃.
Furthermore, in the above technical scheme, the weight of the modified hectorite accounts for 3 to 6 weight percent of the total weight of the monomer mixture, and the modified hectorite comprises the following components: nano hectorite, dispersose-AYD W-15 dispersant, reactive tertiary amine; the reactive tertiary amine is one or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate and dimethylaminobutyl methacrylate.
Furthermore, in the above technical solution, the multiphase structure includes: modified hectorite, soft phase copolymer, and hard phase copolymer; the weight of the monomer mixture of the soft phase copolymer is 50-80 wt% of the total weight of the monomer mixture, and the specific components and the proportion are as follows: butadiene monomer 20-40 wt%, styrene monomer 20-40 wt% and unsaturated amide 1-3 wt%; the weight of the monomer mixture of the hard phase copolymer accounts for 20-50 wt% of the total weight of the monomer mixture, and the hard phase copolymer comprises the following specific components in percentage: 10 to 20 percent by weight of butadiene monomer, 10 to 30 percent by weight of styrene monomer and 2 to 5 percent by weight of unsaturated carboxylic acid.
In the technical scheme, the preparation method of the modified styrene-butadiene copolymer composite latex with the multiphase structure adopts the following technical scheme that:
(1) Modified hectorite: adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 0.5-1.0 g of reactive tertiary amine monomer is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
(2) Soft phase pre-polymerization: adding 46-92 g of the reactive tertiary amine modified hectorite sol into a reaction kettle, replacing nitrogen, stirring at a high speed, heating to 80 ℃, then dropwise adding a mixed solution consisting of 20-40% of butadiene, 20-40% of styrene, 0.1-0.2% of molecular weight regulator, 1-3% of unsaturated amide monomer, 0.1-0.2% of emulsifier, 0.01% of chelating agent, 0.3-0.6% of initiator and a proper amount of deionized water into the high-pressure reaction kettle, starting to react for 45 minutes after dropwise adding, and reacting for 15 minutes after dropwise adding;
(3) Hard continuous polymerization: after the reaction is carried out for 60 minutes, respectively dripping a mixed solution of 2 to 5 percent of unsaturated carboxylic acid, 0.4 to 1.2 percent of emulsifier, and a mixed solution of one or more of 0.8 to 1.0 percent of molecular weight regulator, 2 to 10 percent of methyl methacrylate, methyl styrene, acrylonitrile and hydroxyethyl methacrylate, 10 to 20 percent of butadiene and 10 to 30 percent of styrene for 4 hours, and 3 to 6 percent of 20 percent of initiator aqueous solution for 5 hours, and preserving the temperature for 2 hours at 85 ℃ after the complete dripping;
(4) Post-treatment: slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 3-6% of 20% concentration tert-butyl hydroperoxide aqueous solution and 3-6% of 20% concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.0-7.0 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
In the above technical scheme, the dispersose-AYD W-15 dispersant comprises modified thermoplastic polypropylene resin, acrylic resin and propylene glycol monomethyl ether acidic solution PM Aceta. The dispersose-AYD W-15 dispersing agent is dispersose-AYD series dispersing agent of Daniel Products Co. In the United states, is a mixture of several surfactants, can cooperate with each other to moisten pigment, resist pigment flocculation, stabilize the dispersion after coating, has the functions of dispersing agent and the like, is mainly suitable for preparing high-concentration pigment dispersion, has good compatibility with various resins in pigment dispersion systems prepared by AYD-15, and can be used for preparing Products with good chemical stability. The weight ratio of the consumption of the DISPERSE-AYD W-15 dispersing agent to the dry weight of the hectorite is 1:65, the weight ratio of the usage amount of the reactive tertiary amine monomer to the dry weight of the hectorite is 5-10: 65. The dry weight of the reactive tertiary amine modified hectorite is 3.75-12% of the weight of the soft phase pre-polymerized monomer; the butadiene in the soft phase prepolymerization stage accounts for 35-50% of the total monomer in the soft phase prepolymerization stage; butadiene in the continuous polymerization stage accounts for 25-40% of the total monomers in the continuous polymerization stage.
In the above technical scheme, the unsaturated carboxylic acid is one or more selected from acrylic acid, methacrylic acid, itaconic acid and fumaric acid.
In the above technical scheme, the unsaturated amide is one or more selected from acrylamide, methacrylamide, N-dimethylacrylamide and methylol acrylamide.
Further, in the above technical solution, the emulsifier is sodium dodecyl benzene sulfonate, or sodium dodecyl sulfate, sodium alkyl diphenyl ether disulfate; the chelating agent is sodium ethylenediamine tetraacetate, abbreviated EDTA; the molecular weight regulator is tert-dodecyl mercaptan; the initiator is ammonium persulfate, potassium persulfate and sodium persulfate can also be used.
Furthermore, in the above technical scheme, the redox initiation system composed of tert-butyl hydroperoxide and diabolo can also be persulfate and sodium bisulfite, persulfate and mercaptan, persulfate and diabolo (formaldehyde sodium bisulfite); preferably, the initiator is tert-butyl hydroperoxide and diabolo, and the weight ratio of the tert-butyl hydroperoxide to the diabolo is 1:0.75 to 1:1, the t-butyl hydroperoxide was used in an amount of 50% by weight based on the total weight of residual monomers.
Further, in the above technical scheme, the composite latex prepared by the preparation method is used for application as an adhesive in the field of paper coating.
In combination with the above, the invention takes nano hectorite as an inorganic material, and prepares the core-shell structure modified styrene-butadiene copolymer latex containing the hectorite through the steps of hectorite reactive tertiary amine modification, prepolymerization reaction, continuous polymerization reaction, post-treatment stage and the like, and the final product has excellent stability.
Compared with the prior art, the invention has the following positive effects: the latex of the invention is prepared by adopting a semi-continuous polymerization process, the process is simple, the reaction process is stable, the reaction time is short, and the polymerization conversion rate is high; the reaction process does not require a low temperature cryogen and a complex monomer recovery and degassing process. The copolymer emulsion has excellent mechanical stability, chemical stability and storage stability, moderate glass transition temperature, high napping strength of paper coating products and high glossiness. The latex and the paint complex thereof have excellent stability, and no excessive screen residue condition occurs in practical application and long-term storage.
[ Detailed description ] of the invention
Specific embodiments of a butyl benzene copolymer composite latex, a preparation method and application thereof according to the present invention are provided below.
The total monomer addition in the examples and comparative examples was IOOwt% by weight.
Emulsion polymerization was carried out in a stainless steel reactor, which was replaced with nitrogen and equipped with a stirrer and temperature was adjusted.
Example 1
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, the pH of the solution is regulated to 2.5-3.0 by hydrochloric acid under the stirring condition, 0.75 g of dimethylaminoethyl methacrylate is added, and the solution is stirred and dispersed for 3 hours to obtain the reactive tertiary amine modified hectorite sol with the solid content of 6.5 percent.
46G of the reactive tertiary amine modified hectorite sol is subjected to nitrogen replacement, high-speed stirring and heating to 80 ℃, and then a mixed solution consisting of 20% of butadiene, 29% of styrene, 0.2% of tertiary dodecyl mercaptan, 1% of acrylamide monomer, 0.2% of sodium dodecyl benzene sulfonate, 0.01% of chelating agent EDTA, 0.5% of ammonium persulfate and a proper amount of deionized water is dropwise added into a high-pressure reaction kettle, the reaction is started, the dropwise addition time is 45 minutes, and the reaction is completed for 15 minutes.
After the reaction was carried out for 60 minutes, a mixed solution of 5% acrylic acid, 1.0% sodium dodecylbenzenesulfonate and a mixed solution of 0.8% tertiary dodecylmercaptan, 2.5% methyl styrene, 2.5% acrylonitrile, 15% butadiene and 25% styrene were started to be added dropwise, respectively, for 4 hours, and a 5% aqueous solution of 20% ammonium persulfate was prepared at 20% concentration for 5 hours, and the mixture was kept at 85℃for 2 hours after the completion of all the dropwise addition;
Slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 5 percent of 20 percent concentration tertiary butyl hydroperoxide aqueous solution and 5 percent of 20 percent concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting p H to 6.6 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
Example 2
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 1.0 g of dimethylaminoethyl methacrylate monomer is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
69 g of the reactive tertiary amine modified hectorite sol is subjected to nitrogen replacement, high-speed stirring and heating to 80 ℃, 25% of butadiene, 35% of styrene, 0.16% of tertiary dodecyl mercaptan, 2% of acrylamide monomer, 0.16% of sodium dodecyl benzene sulfonate, 0.01% of chelating agent EDTA, 0.6% of ammonium persulfate and a proper amount of deionized water are dropwise added into a high-pressure reaction kettle, the reaction is started, the dropwise adding time is 45 minutes, and the reaction is completed for 15 minutes;
After the reaction was carried out for 60 minutes, a mixed solution of 4% of acrylic acid, 0.8% of sodium dodecylbenzenesulfonate, and a mixed solution of 0.8% of dodecylmercaptan, 2% of methyl methacrylate, 2% of methyl styrene, 12% of butadiene and 18% of styrene were respectively added dropwise, for 4 hours, a 3% aqueous solution of ammonium persulfate at 20% concentration was added dropwise, and after completion of all the dropwise addition, the mixture was kept at 85℃for 2 hours;
Slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 3 percent of 20 percent concentration tertiary butyl hydroperoxide aqueous solution and 3 percent of 20 percent concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.4 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
Example 3
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 1.0 g of dimethylaminoethyl acrylate monomer is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
92 g of the reactive tertiary amine modified hectorite sol is subjected to nitrogen replacement, high-speed stirring and heating to 80 ℃, then 30% of butadiene, 35% of styrene, 0.15% of tertiary dodecyl mercaptan, 2% of methacrylamide monomer, 0.12% of sodium dodecyl benzene sulfonate, 0.01% of chelating agent EDTA, 0.4% of ammonium persulfate and a proper amount of deionized water are dropwise added into a high-pressure reaction kettle, the reaction is started, the dropwise adding time is 45 minutes, and the reaction is completed for 15 minutes;
after the reaction is carried out for 60 minutes, a mixed solution of 3 percent of methacrylic acid, 0.65 percent of sodium dodecyl benzene sulfonate and a mixed solution of 0.8 percent of tertiary dodecyl mercaptan, 5 percent of hydroxyethyl methacrylate, 8 percent of butadiene and 17 percent of styrene are respectively dripped for 4 hours, a 20 percent ammonium persulfate aqueous solution with the concentration of 3 to 6 percent is dripped for 5 hours, and the temperature is kept at 85 ℃ for 2 hours after the dripping is completed;
Slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 3-6% of 20% concentration tert-butyl hydroperoxide aqueous solution and 3-6% of 20% concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.5 to obtain the modified styrene-butadiene copolymer composite latex with a multiphase structure.
Example 4
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 0.80 g of dimethylaminopropyl methacrylate monomer is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
69 g of the reactive tertiary amine modified hectorite sol is subjected to nitrogen replacement, high-speed stirring and heating to 80 ℃, and then 30% of butadiene, 30% of styrene, 0.2% of tertiary dodecyl mercaptan, 3% of methacrylamide monomer, 0.15% of sodium dodecyl benzene sulfonate, 0.01% of chelating agent EDTA, 0.5% of ammonium persulfate and a proper amount of deionized water are dropwise added into a high-pressure reaction kettle, the reaction is started, the dropwise adding time is 45 minutes, and the reaction is completed for 15 minutes;
After the reaction is carried out for 60 minutes, a mixed solution of 2% of itaconic acid and 1.2% of sodium dodecyl benzene sulfonate and a mixed solution of 0.8% of tertiary dodecyl mercaptan, 2% of methyl styrene, 1% of acrylonitrile, 12% of butadiene and 20% of styrene are respectively dripped for 4 hours, a 20% concentration ammonium persulfate aqueous solution of 3-6% is dripped for 5 hours, and the temperature is kept at 85 ℃ for 2 hours after the dripping is completed;
Slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 6 percent of 20 percent concentration tertiary butyl hydroperoxide aqueous solution and 5 percent of 20 percent concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.5 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
Example 5
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 0.5 g of dimethylaminoethyl methacrylate is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
75 g of the reactive tertiary amine modified hectorite sol is subjected to nitrogen replacement, high-speed stirring and heating to 80 ℃, 23% of butadiene, 36% of styrene, 0.2% of tertiary dodecyl mercaptan, 1.5% of methylol acrylamide monomer, 0.2% of sodium dodecyl benzene sulfonate, 0.01% of chelating agent EDTA, 0.5% of ammonium persulfate and a proper amount of deionized water are dropwise added into a high-pressure reaction kettle, and the dropwise addition is started for 45 minutes after the reaction is started, and the dropwise addition is completed for 15 minutes;
After the reaction is carried out for 60 minutes, a mixed solution of 3.5 percent of fumaric acid, 0.65 percent of sodium dodecyl benzene sulfonate, and a mixed solution of one or more of 0.8 percent of tertiary dodecyl mercaptan, 2 methyl styrene and 1 percent of hydroxyethyl methacrylate, 13 percent of butadiene and 20 percent of styrene are respectively dripped for 4 hours, a 4 percent of 20 percent concentration ammonium persulfate aqueous solution is dripped for 5 hours, and the temperature is kept at 85 ℃ for 2 hours after the dripping is completed;
Slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dropwise adding 4% of 20% concentration tert-butyl hydroperoxide aqueous solution and 4% of 20% concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.6 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
Example 6
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 1.0 g of dimethylaminobutyl methacrylate is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
58 g of the reactive tertiary amine modified hectorite sol is subjected to nitrogen replacement, high-speed stirring and heating to 80 ℃, 25% of butadiene, 33% of styrene, 0.15% of tertiary dodecyl mercaptan, 2% of N, N-dimethylacrylamide, 0.2% of sodium dodecyl benzene sulfonate, 0.01% of chelating agent EDTA, 0.45% of ammonium persulfate and a proper amount of deionized water are dropwise added into a high-pressure reaction kettle, and the dropwise addition is started for 45 minutes after the reaction is started, and the dropwise addition is completed for 15 minutes;
After the reaction was carried out for 60 minutes, a mixed solution of 2% of acrylic acid, 0.82% of sodium dodecylbenzenesulfonate and a mixed solution of 0.8% of tertiary dodecyl mercaptan, 2% of methyl styrene, 1% of hydroxyethyl methacrylate, 12% of butadiene and 23% of styrene were respectively added dropwise, 5% of a 20% strength ammonium persulfate aqueous solution for 5 hours, and after all the dropwise addition was completed, the mixture was kept at 85℃for 2 hours;
Slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 3 percent of 20 percent concentration tertiary butyl hydroperoxide aqueous solution and 3 percent of 20 percent concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.7 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
Comparative example 1
Adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of DISPESE-AYD W-15 dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, the pH value of the solution is regulated to 2.7 by hydrochloric acid under the stirring condition, and the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained after stirring and dispersing for 3 hours.
The remaining soft phase prepolymerization, hard phase continuous polymerization and post-treatment stages were the same as in example 1.
Comparative example 2
Example 2 was repeated except that 68 g of water was added to the non-reactive tertiary amine modified hectorite and the soft phase prepolymerized base material.
The modified styrene-butadiene copolymer composite latices of the multiphase structures obtained in examples 1 to 6 and comparative examples 1 to 2 were formulated into paper coating paints for paperboard coating, and the latex properties are shown in Table 1.
TABLE 1
As can be seen from Table 1, examples 1 to 6 all have better stability properties (the lower the number, the better the stability, the more 0.02% or less of the mechanical stability is acceptable, the less 0.02% or less of the chemical stability is acceptable, and the less 0.02% or less of the storage stability is acceptable) than comparative examples 1 to 2.
The properties of the modified styrene-butadiene copolymer composite latex coating materials having the multi-phase structure obtained in examples 1 to 6 and comparative examples 1 to 2 are shown in Table 2.
TABLE 2
As can be seen from Table 2, examples 1 to 6 each had a good galling strength and water resistance, while comparative examples 1 to 2 were lower in galling strength and lower in water resistance (the lower the wet abrasion, the better the water resistance).
The foregoing is merely illustrative of the technical solution of the embodiments of the present invention, and is not meant to be limiting, and those skilled in the art will understand that the technical solution of the embodiments of the present invention may be modified or equivalently replaced, and that the modified or equivalent replacement does not deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (9)
1. The modified styrene-butadiene copolymer composite latex with the multiphase structure is characterized by comprising modified hectorite, a soft phase copolymer, a hard phase copolymer and water, wherein the weight of the modified hectorite accounts for 3-6wt% of the total weight of the monomer mixture, the weight of the monomer mixture of the soft phase copolymer accounts for 50-80wt% of the total weight of the monomer mixture, and the weight of the monomer mixture of the hard phase copolymer accounts for 20-50wt% of the total weight of the monomer mixture;
The copolymer composite latex has 49-51% of solid content, 6.0-8.0 of pH, 100-300 mPa.S of viscosity, 36-46 mN/m of surface tension, 140-170 nm of particle size, 10-30 mv of potential, 70-90% of gel content and glass transition temperature of-5-15 ℃ and 20-30 ℃.
2. The modified styrene-butadiene copolymer composite latex of a heterogeneous structure according to claim 1, wherein the modified hectorite composition comprises: nano hectorite, a dispersing agent and reactive tertiary amine; the reactive tertiary amine is one or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylate and dimethylaminobutyl methacrylate.
3. The modified styrene-butadiene copolymer composite latex of a multiphase structure according to claim 1, wherein the multiphase structure comprises: modified hectorite, soft phase copolymer, and hard phase copolymer;
The weight of the monomer mixture of the soft phase copolymer is 50-80 wt% of the total weight of the monomer mixture, and the specific components and the proportion are as follows: butadiene monomer 20-40 wt%, styrene monomer 20-40 wt% and unsaturated amide 1-3 wt%;
The weight of the monomer mixture of the hard phase copolymer accounts for 20-50 wt% of the total weight of the monomer mixture, and the hard phase copolymer comprises the following specific components in percentage: 10 to 20 percent by weight of butadiene monomer, 10 to 30 percent by weight of styrene monomer and 2 to 5 percent by weight of unsaturated carboxylic acid.
4. The modified styrene-butadiene copolymer composite latex of a multi-phase structure according to any one of claims 1 to 3, wherein the preparation method thereof comprises the steps of:
(1) Modified hectorite: adding 91.5 g of deionized water into a reactor with stirring, heating to 80 ℃, slowly adding 6.5 g of nano hectorite, adding 0.1 g of dispersing agent, stirring and dispersing for 2 hours, and uniformly dissolving to obtain a hectorite sol; then, under the stirring condition, hydrochloric acid is used for regulating the pH value of the solution to 2.5-3.0, 0.5-1.0 g of reactive tertiary amine monomer is added, and after stirring and dispersing for 3 hours, the reactive tertiary amine modified hectorite sol with the solid content of 6.5% is obtained;
(2) Soft phase pre-polymerization: adding 46-92 g of the reactive tertiary amine modified hectorite sol into a reaction kettle, replacing nitrogen, stirring at a high speed, heating to 80 ℃, then dropwise adding a mixed solution consisting of 20-40% of butadiene, 20-40% of styrene, 0.1-0.2% of molecular weight regulator, 1-3% of unsaturated amide monomer, 0.1-0.2% of emulsifier, 0.01% of chelating agent, 0.3-0.6% of initiator and a proper amount of deionized water into the high-pressure reaction kettle, starting to react for 45 minutes after dropwise adding, and reacting for 15 minutes after dropwise adding;
(3) Hard continuous polymerization: after the reaction is carried out for 60 minutes, respectively dripping a mixed solution of 2 to 5 percent of unsaturated carboxylic acid, 0.4 to 1.2 percent of emulsifier, and a mixed solution of one or more of 0.8 to 1.0 percent of molecular weight regulator, 2 to 10 percent of methyl methacrylate, methyl styrene, acrylonitrile and hydroxyethyl methacrylate, 10 to 20 percent of butadiene and 10 to 30 percent of styrene for 4 hours, and 3 to 6 percent of 20 percent of initiator aqueous solution for 5 hours, and preserving the temperature for 2 hours at 85 ℃ after the complete dripping;
(4) Post-treatment: slowly adding alkali into the latex to adjust the pH value to 5.0, respectively dripping 3-6% of 20% concentration tert-butyl hydroperoxide aqueous solution and 3-6% of 20% concentration diabolo aqueous solution, reacting for 4 hours, cooling and discharging, and adjusting the pH value to 6.0-7.0 to obtain the modified styrene-butadiene copolymer composite latex with the multiphase structure.
5. The multiphase structured modified styrene-butadiene copolymer composite latex of claim 4, wherein the dispersant comprises a modified thermoplastic polypropylene resin, an acrylic resin, and an acidic solution of propylene glycol monomethyl ether.
6. The modified styrene-butadiene copolymer composite latex of a heterogeneous structure of claim 4, wherein the unsaturated carboxylic acid is one or more selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and fumaric acid.
7. The modified styrene-butadiene copolymer composite latex with the multiphase structure according to claim 4, wherein the unsaturated amide is one or more selected from the group consisting of acrylamide, methacrylamide, N-dimethylacrylamide and methylol acrylamide.
8. The modified styrene-butadiene copolymer composite latex of the multiphase structure of claim 4, wherein the emulsifier is sodium dodecyl benzene sulfonate; the chelating agent is sodium ethylenediamine tetraacetate EDTA; the molecular weight regulator is tert-dodecyl mercaptan and the initiator is ammonium persulfate.
9. The modified styrene-butadiene copolymer composite latex with a multi-phase structure according to claim 4, wherein the composite latex is prepared by the preparation method for the application as an adhesive in the field of paper coating.
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