CN118421221A - A modified styrene-butadiene latex binder and preparation method thereof - Google Patents
A modified styrene-butadiene latex binder and preparation method thereof Download PDFInfo
- Publication number
- CN118421221A CN118421221A CN202410833088.9A CN202410833088A CN118421221A CN 118421221 A CN118421221 A CN 118421221A CN 202410833088 A CN202410833088 A CN 202410833088A CN 118421221 A CN118421221 A CN 118421221A
- Authority
- CN
- China
- Prior art keywords
- butadiene latex
- titanium dioxide
- parts
- latex binder
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004816 latex Substances 0.000 title claims abstract description 55
- 229920000126 latex Polymers 0.000 title claims abstract description 55
- 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 51
- 239000011230 binding agent Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 229920001897 terpolymer Polymers 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- -1 acrylic ester Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 16
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 16
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 16
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 16
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- QGVQVNIIRBPOAM-UHFFFAOYSA-N dodecyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCCCCCCCCCC)=CC=CC2=C1 QGVQVNIIRBPOAM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 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 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 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
- 239000011976 maleic acid Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 abstract description 18
- 239000011115 styrene butadiene Substances 0.000 abstract description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 239000001257 hydrogen Chemical group 0.000 abstract description 3
- 229910052739 hydrogen Chemical group 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- RGIBXDHONMXTLI-UHFFFAOYSA-N chavicol Chemical compound OC1=CC=C(CC=C)C=C1 RGIBXDHONMXTLI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical group N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/16—Homopolymers or copolymers of alkyl-substituted styrenes
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
Description
技术领域Technical Field
本发明属于丁苯胶乳粘结剂的技术领域,涉及一种改性丁苯胶乳粘结剂及其制备方法。The invention belongs to the technical field of styrene butadiene latex binders and relates to a modified styrene butadiene latex binder and a preparation method thereof.
背景技术Background technique
纳米二氧化硅/二氧化钛粒子因其颗粒尺寸微小、比表面积广阔及表面能较高,极易发生团聚现象。这一现象导致二氧化硅/二氧化钛丁苯胶乳复合材料的黏度大幅上升,加工能耗显著增加,从而在一定程度上限制了其在各个领域的实际应用。Nano-silicon dioxide/titanium dioxide particles are very prone to agglomeration due to their tiny particle size, large specific surface area and high surface energy. This phenomenon leads to a significant increase in the viscosity of the silica/titanium dioxide styrene-butadiene latex composite material and a significant increase in processing energy consumption, which, to a certain extent, limits its practical application in various fields.
丁苯胶乳是一种由丁二烯和苯乙烯单体通过乳液共聚制得的聚合物胶乳。它具有良好的粘着性,并且由于其粒径小于天然胶乳的粒径,因此在浸渍制品时的扩散性更佳,但由于其非极性,与填料间的相容性较差。因此需要对丁苯胶乳进行改性,而羧基丁苯胶乳在此基础下加入微量不饱和羧酸经乳液聚合工艺精制而成。鉴于苯乙烯成分占比较高,胶乳本身具备卓越的稳定性、成膜性以及结膜性能。羧基的引入显著提升了胶乳的极性,进而一定促进了与填料的优良相容性,因此广泛应用于造纸、地毯及纺织等多个行业;但单一羧基的引入,对于填料的相容性依然存在相容性有待提高,附着力不足的问题。Styrene butadiene latex is a polymer latex made by emulsion copolymerization of butadiene and styrene monomers. It has good adhesion, and because its particle size is smaller than that of natural latex, it has better diffusion when impregnating products, but due to its non-polarity, its compatibility with fillers is poor. Therefore, it is necessary to modify the styrene butadiene latex, and carboxyl styrene butadiene latex is refined by emulsion polymerization by adding a trace amount of unsaturated carboxylic acid to this basis. In view of the high proportion of styrene components, the latex itself has excellent stability, film-forming properties and film-forming properties. The introduction of carboxyl groups significantly improves the polarity of the latex, which in turn promotes excellent compatibility with fillers, so it is widely used in papermaking, carpets, textiles and other industries; However, the introduction of a single carboxyl group still has problems with compatibility with fillers and insufficient adhesion.
发明内容Summary of the invention
本发明的目的在于提供一种改性丁苯胶乳粘结剂及其制备方法,本发明制得的三元共聚物包覆二氧化钛,提高了二氧化钛和二氧化硅在丁苯胶乳体系的分散性和相容性。其环氧基团可与丁苯胶乳的羧基和二氧化硅的羟基反应,形成化学键连接,另外脂肪族长侧链和氢氧化钠处理的二氧化硅羟基数量的增加,有利于二氧化硅在丁苯胶乳体系的流动,形成致密的交联网络结构,显著提高力学性能和粘结性能。加入季胺类丙烯酸酯,利用氨基与丁苯胶乳体系中的氢键、离子键相互作用力,提高粘结剂的力学性能,增强其在纸张或其他材料表面的附着力。The object of the present invention is to provide a modified styrene butadiene latex binder and a preparation method thereof. The terpolymer prepared by the present invention coats titanium dioxide, thereby improving the dispersibility and compatibility of titanium dioxide and silicon dioxide in the styrene butadiene latex system. The epoxy group thereof can react with the carboxyl group of the styrene butadiene latex and the hydroxyl group of silicon dioxide to form a chemical bond connection. In addition, the increase in the number of hydroxyl groups of silicon dioxide treated with aliphatic long side chains and sodium hydroxide is conducive to the flow of silicon dioxide in the styrene butadiene latex system, forming a dense cross-linked network structure, and significantly improving the mechanical properties and bonding properties. The addition of quaternary amine acrylate utilizes the interaction force between the amino group and the hydrogen bond and ionic bond in the styrene butadiene latex system to improve the mechanical properties of the binder and enhance its adhesion on the surface of paper or other materials.
本发明的目的可以通过以下技术方案实现:The purpose of the present invention can be achieved through the following technical solutions:
一种改性丁苯胶乳粘结剂,按重量份数包括以下组分:A modified styrene-butadiene latex binder comprises the following components in parts by weight:
功能单体 3-6份Functional monomer 3-6 parts
丙烯酸酯 70-80份Acrylate 70-80 parts
丁二烯 45-60份Butadiene 45-60 parts
甲基苯乙烯 90-100份Methyl styrene 90-100 parts
丙烯酸羟乙酯 3-5份Hydroxyethyl acrylate 3-5 parts
三元共聚物包覆二氧化钛 15-20份Terpolymer coated titanium dioxide 15-20 parts
二氧化硅 5-8份Silicon dioxide 5-8 parts
乳化剂 4-6份Emulsifier 4-6 parts
引发剂 3.5-4份Initiator 3.5-4 parts
去离子水 130-150份。Deionized water 130-150 parts.
作为本发明的一种优选技术方案,所述功能单体为甲基丙烯酸、马来酸、富马酸和衣康酸中的一种或多种;所述丙烯酸酯由甲基丙烯酸甲酯和季胺类丙烯酸酯按质量比10:1-1.5混合而成;所述季胺类丙烯酸酯为3-(N,N-二甲基氨基)丙烯酸乙酯。As a preferred technical solution of the present invention, the functional monomer is one or more of methacrylic acid, maleic acid, fumaric acid and itaconic acid; the acrylic ester is prepared by mixing methyl methacrylate and quaternary ammonium acrylate in a mass ratio of 10:1-1.5; the quaternary ammonium acrylate is 3-(N,N-dimethylamino)ethyl acrylate.
作为本发明的一种优选技术方案,所述乳化剂由十二烷基硫酸钠和十二烷基萘磺酸钠按质量比2.5:1-1.5混合而成;所述引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮异丁氰基甲酰胺、叔丁基过氧化氢、过氧化二苯甲酰和过氧化氢异丙苯中一种或多种。As a preferred technical solution of the present invention, the emulsifier is prepared by mixing sodium dodecyl sulfate and sodium dodecylnaphthalene sulfonate in a mass ratio of 2.5:1-1.5; the initiator is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azoisobutylcyanamide, tert-butyl hydroperoxide, dibenzoyl peroxide and cumene hydroperoxide.
作为本发明的一种优选技术方案,所述二氧化硅为纳米二氧化硅经过30%质量分数的氢氧化钠水溶液浸泡处理30-45min后,过滤取固体清洗至pH值为7进行干燥后所得。As a preferred technical solution of the present invention, the silicon dioxide is nano-silicon dioxide that is soaked in a 30% by mass sodium hydroxide aqueous solution for 30-45 minutes, filtered to obtain the solid, washed to a pH value of 7, and then dried.
作为本发明的一种优选技术方案,所述三元共聚物包覆二氧化钛的制备包括以下步骤:As a preferred technical solution of the present invention, the preparation of the terpolymer-coated titanium dioxide comprises the following steps:
S1、将二氧化钛加入溶剂中,加热搅拌,缓慢滴加偶联剂后,继续搅拌,冷却至室温后,离心分离,取固体真空干燥至恒重后,得到改性二氧化钛;S1. Add titanium dioxide to a solvent, heat and stir, slowly drop a coupling agent, continue stirring, cool to room temperature, centrifuge, and vacuum dry the solid to constant weight to obtain modified titanium dioxide;
S2、将改性二氧化钛和有机溶剂超声混合后,加入甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚和异丙醇在惰性氛围下加热搅拌后,加入引发剂继续搅拌,冷却至室温后,离心分离,取固体真空干燥至恒重后,得到三元共聚物包覆二氧化钛。S2. After ultrasonically mixing the modified titanium dioxide and the organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol and isopropanol are added, and the mixture is heated and stirred under an inert atmosphere. Then, an initiator is added and stirring is continued. After cooling to room temperature, the mixture is centrifuged and the solid is vacuum dried to a constant weight to obtain a terpolymer-coated titanium dioxide.
作为本发明的一种优选技术方案,在步骤S1中,所述加热搅拌为在35-40℃、300-400r/min下搅拌;所述继续搅拌的时间为30-45min;所述真空干燥为在70℃干燥24-30h。As a preferred technical solution of the present invention, in step S1, the heating stirring is stirring at 35-40°C and 300-400r/min; the continuous stirring time is 30-45min; and the vacuum drying is drying at 70°C for 24-30h.
作为本发明的一种优选技术方案,在步骤S1中,所述二氧化钛、溶剂和偶联剂的质量比为1-1.2:3:0.15-0.20;所述溶剂由去离子水、无水乙醇和醋酸按质量比1:9-9.5:0.01混合而成;所述偶联剂为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷或乙烯基三(β-甲氧基乙氧基)硅烷。As a preferred technical solution of the present invention, in step S1, the mass ratio of titanium dioxide, solvent and coupling agent is 1-1.2:3:0.15-0.20; the solvent is a mixture of deionized water, anhydrous ethanol and acetic acid in a mass ratio of 1:9-9.5:0.01; the coupling agent is vinyl triethoxysilane, vinyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane or vinyl tri (β-methoxyethoxy) silane.
作为本发明的一种优选技术方案,在步骤S2中,所述惰性氛围为氮气气氛;所述加热搅拌为在60-65℃、300-400r/min下搅拌;所述继续搅拌的时间为5-6h;所述真空干燥为在70℃干燥6-8h。As a preferred technical solution of the present invention, in step S2, the inert atmosphere is a nitrogen atmosphere; the heating and stirring is stirring at 60-65°C and 300-400r/min; the continued stirring time is 5-6h; and the vacuum drying is drying at 70°C for 6-8h.
作为本发明的一种优选技术方案,在步骤S2中,所述改性二氧化钛、有机溶剂、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚、异丙醇和引发剂的质量比为14-16:60-65:18-20:10-11:2.0-2.4:1.5-1.6:1.5;所述有机溶剂为四氢呋喃;所述引发剂为偶氮二异丁腈。As a preferred technical solution of the present invention, in step S2, the mass ratio of the modified titanium dioxide, the organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol, isopropanol and the initiator is 14-16:60-65:18-20:10-11:2.0-2.4:1.5-1.6:1.5; the organic solvent is tetrahydrofuran; and the initiator is azobisisobutyronitrile.
本发明公开了一种改性丁苯胶乳粘结剂的制备方法,所述制备方法包括以下步骤:将功能单体、丙烯酸酯、丁二烯、甲基苯乙烯、丙烯酸羟乙酯、三元共聚物包覆二氧化钛、二氧化硅、乳化剂和去离子水搅拌混合后,加入引发剂加热乳化共聚后,调节pH值,过筛后,即得改性丁苯胶乳粘结剂;The invention discloses a method for preparing a modified styrene butadiene latex binder. The method comprises the following steps: stirring and mixing functional monomers, acrylate, butadiene, methyl styrene, hydroxyethyl acrylate, terpolymer-coated titanium dioxide, silicon dioxide, an emulsifier and deionized water, adding an initiator, heating and emulsifying copolymerization, adjusting the pH value, and sieving to obtain the modified styrene butadiene latex binder;
作为本发明的一种优选技术方案,在所述制备方法中,所述搅拌混合为在80℃下、搅拌2-3h;所述加热乳化共聚为在80-90℃下、反应5-8h;所述调节pH值为采用氢氧化钠调节pH值至6-7;所述过筛为过100目筛。As a preferred technical solution of the present invention, in the preparation method, the stirring and mixing is carried out at 80°C for 2-3 hours; the heating emulsification copolymerization is carried out at 80-90°C for 5-8 hours; the pH value is adjusted to 6-7 using sodium hydroxide; and the screening is carried out through a 100-mesh sieve.
本发明的有益效果:Beneficial effects of the present invention:
(1)本发明制得的三元共聚物包覆二氧化钛,二氧化钛作为粒子核和包覆于粒子核外层的腰果酚-甲基丙烯酸酯-丙烯酸缩水甘油酯的聚合物层,增加了二氧化钛在丁苯胶乳体系的分散性和相容性的同时,其所含环氧基团与不但能和丁苯胶乳体系中的羧基高效反应,还可与二氧化硅表面的羟基反应,形成化学键连接,另外,三元共聚物包覆二氧化钛含有极性的环氧基团、羟基基团以及非极性的苯环结构,可以作为相容剂,增加二氧化硅与丁苯胶乳界面粘合力,进而显著提高二氧化硅在体系中的分散性和相容性。(1) The terpolymer coated titanium dioxide prepared by the present invention has titanium dioxide as a particle core and a polymer layer of cardanol-methacrylate-glycidyl acrylate coated on the outer layer of the particle core. While increasing the dispersibility and compatibility of titanium dioxide in the styrene-butadiene latex system, the epoxy groups contained in the terpolymer can not only react efficiently with the carboxyl groups in the styrene-butadiene latex system, but also react with the hydroxyl groups on the surface of silicon dioxide to form a chemical bond connection. In addition, the terpolymer coated titanium dioxide contains polar epoxy groups, hydroxyl groups and non-polar benzene ring structures, which can be used as a compatibilizer to increase the interfacial adhesion between silicon dioxide and styrene-butadiene latex, thereby significantly improving the dispersibility and compatibility of silicon dioxide in the system.
(2)三元共聚物包覆二氧化钛的环氧基团的加入可提高粘结剂的拉伸强度和附着力,腰果酚的化学名称为间十五碳烯基苯酚,作为增塑剂和扩链剂加入二氧化硅/丁苯胶乳体系中,增强增韧,提高其拉断伸长率;另外,脂肪族长侧链有利于分子链之间的滑动,结合经氢氧化钠处理过的二氧化硅羟基数量的增加,利于二氧化硅在丁苯胶乳体系的流动,二氧化硅与丁苯胶乳粒子接触面积增大,形成较多的交联网络结构,使网络结构致密化,显著增加其力学性能和粘结性能。(2) The addition of epoxy groups to the terpolymer-coated titanium dioxide can improve the tensile strength and adhesion of the adhesive. The chemical name of cardanol is pentadecene phenol. It is added to the silica/styrene-butadiene latex system as a plasticizer and chain extender to enhance toughness and improve its elongation at break. In addition, the long aliphatic side chains are conducive to the sliding between molecular chains. Combined with the increase in the number of hydroxyl groups of silica treated with sodium hydroxide, it is conducive to the flow of silica in the styrene-butadiene latex system. The contact area between silica and styrene-butadiene latex particles is increased, forming a larger cross-linked network structure, making the network structure denser, and significantly improving its mechanical properties and bonding properties.
(3)本发明通过季胺类丙烯酸酯的加入,利用氨基与丁苯胶乳体系中含羟基、羧基组分的分子间的氢键、离子键相互作用力,来提高粘结剂的力学性能,有助于提高丁苯胶乳粘结剂在纸张或其他材料表面的附着力。(3) The present invention improves the mechanical properties of the binder by adding quaternary ammonium acrylate and utilizing the hydrogen bonding and ionic bonding interactions between amino groups and the molecules containing hydroxyl and carboxyl groups in the styrene-butadiene latex system, thereby helping to improve the adhesion of the styrene-butadiene latex binder to the surface of paper or other materials.
具体实施方式Detailed ways
为更进一步阐述本发明为实现预定发明目的所采取的技术手段及功效,以下结合实施例,对依据本发明的具体实施方式、结构、特征及其功效,详细说明如下。In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.
实施例1Example 1
一种改性丁苯胶乳粘结剂,按重量份数包括以下组分:A modified styrene-butadiene latex binder comprises the following components in parts by weight:
甲基丙烯酸 3份Methacrylic acid 3 parts
丙烯酸酯 70份Acrylate 70 parts
丁二烯 45份Butadiene 45 parts
甲基苯乙烯 90份Methyl styrene 90 parts
丙烯酸羟乙酯 3份3 parts of Hydroxyethyl Acrylate
三元共聚物包覆二氧化钛 15份15 parts of terpolymer coated titanium dioxide
二氧化硅 5份Silicon dioxide 5 parts
乳化剂 4份Emulsifier 4 parts
引发剂 3.5份Initiator 3.5 parts
去离子水 130份。Deionized water 130 parts.
所述丙烯酸酯由甲基丙烯酸甲酯和3-(N,N-二甲基氨基)丙烯酸乙酯按质量比10:1混合而成;The acrylic acid ester is prepared by mixing methyl methacrylate and 3-(N,N-dimethylamino)ethyl acrylate in a mass ratio of 10:1;
所述乳化剂由十二烷基硫酸钠和十二烷基萘磺酸钠按质量比2.5:1混合而成;所述引发剂为偶氮二异丁腈;The emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecylnaphthalene sulfonate in a mass ratio of 2.5:1; the initiator is azobisisobutyronitrile;
所述二氧化硅为纳米二氧化硅经过30%质量分数的氢氧化钠水溶液浸泡处理30min后,过滤取固体清洗至pH值为7进行干燥后所得。The silicon dioxide is obtained by soaking nano silicon dioxide in a 30% by mass sodium hydroxide aqueous solution for 30 minutes, filtering out solids, washing until the pH value is 7, and then drying.
所述三元共聚物包覆二氧化钛的制备包括以下步骤:The preparation of the terpolymer coated titanium dioxide comprises the following steps:
S1、将二氧化钛加入溶剂中,在35℃、300r/min下搅拌30min,缓慢滴加乙烯基三乙氧基硅烷后,继续搅拌30min,冷却至室温后,离心分离,取固体70℃真空干燥24h后,得到改性二氧化钛;其中,所述二氧化钛、溶剂和偶联剂的质量比为1:3:0.15;所述溶剂由去离子水、无水乙醇和醋酸按质量比1:9:0.01混合而成;S1. Add titanium dioxide to the solvent, stir at 35°C and 300r/min for 30min, slowly drop vinyltriethoxysilane, continue stirring for 30min, cool to room temperature, centrifuge, take the solid and vacuum dry it at 70°C for 24h to obtain modified titanium dioxide; wherein the mass ratio of the titanium dioxide, the solvent and the coupling agent is 1:3:0.15; the solvent is a mixture of deionized water, anhydrous ethanol and acetic acid in a mass ratio of 1:9:0.01;
S2、将改性二氧化钛和四氢呋喃超声混合后,加入甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚和异丙醇在氮气气氛下,60℃、300r/min下搅拌30min后,加入偶氮二异丁腈继续搅拌5h,冷却至室温后,离心分离,取固体在70℃真空干燥6h后,得到三元共聚物包覆二氧化钛;其中,所述改性二氧化钛、有机溶剂、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚、异丙醇和引发剂的质量比为14:60:18:10:2.0:1.5:1.5。S2. After ultrasonically mixing the modified titanium dioxide and tetrahydrofuran, glycidyl methacrylate, methyl methacrylate, cardanol and isopropanol are added, and the mixture is stirred at 60°C and 300 r/min for 30 min under a nitrogen atmosphere. Then, azobisisobutyronitrile is added and stirring is continued for 5 h. After cooling to room temperature, the mixture is centrifuged and the solid is vacuum dried at 70°C for 6 h to obtain a terpolymer-coated titanium dioxide; wherein the mass ratio of the modified titanium dioxide, organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol, isopropanol and initiator is 14:60:18:10:2.0:1.5:1.5.
一种改性丁苯胶乳粘结剂的制备方法包括以下步骤:A method for preparing a modified styrene-butadiene latex binder comprises the following steps:
将功能单体、丙烯酸酯、丁二烯、甲基苯乙烯、丙烯酸羟乙酯、三元共聚物包覆二氧化钛、二氧化硅、乳化剂和去离子水搅拌混合后,加入引发剂加热乳化共聚后,调节pH值,过筛后,即得改性丁苯胶乳粘结剂;The functional monomer, acrylate, butadiene, methyl styrene, hydroxyethyl acrylate, terpolymer-coated titanium dioxide, silicon dioxide, emulsifier and deionized water are stirred and mixed, an initiator is added, heated and emulsified for copolymerization, the pH value is adjusted, and the modified styrene-butadiene latex binder is obtained after sieving;
其中,所述搅拌混合为在80℃下、搅拌2h;所述加热乳化共聚为在80℃下、反应5h;所述调节pH值为采用氢氧化钠调节pH值至6;所述过筛为过100目筛。The stirring and mixing is carried out at 80° C. for 2 hours; the heating emulsification copolymerization is carried out at 80° C. for 5 hours; the pH value is adjusted to 6 using sodium hydroxide; and the screening is carried out through a 100-mesh sieve.
实施例2Example 2
一种改性丁苯胶乳粘结剂,按重量份数包括以下组分:A modified styrene-butadiene latex binder comprises the following components in parts by weight:
甲基丙烯酸 4份Methacrylic acid 4 parts
丙烯酸酯 73份Acrylate 73 parts
丁二烯 50份Butadiene 50 parts
甲基苯乙烯 93份Methylstyrene 93 parts
丙烯酸羟乙酯 3.7份Hydroxyethyl acrylate 3.7 parts
三元共聚物包覆二氧化钛 17份17 parts of terpolymer coated titanium dioxide
二氧化硅 6份Silicon dioxide 6 parts
乳化剂 4.7份Emulsifier 4.7 parts
引发剂 3.7份Initiator 3.7 parts
去离子水 135份。Deionized water 135 parts.
所述丙烯酸酯由甲基丙烯酸甲酯和3-(N,N-二甲基氨基)丙烯酸乙酯按质量比10:1.2混合而成;The acrylic acid ester is prepared by mixing methyl methacrylate and 3-(N,N-dimethylamino)ethyl acrylate in a mass ratio of 10:1.2;
所述乳化剂由十二烷基硫酸钠和十二烷基萘磺酸钠按质量比2.5:1.2混合而成;所述引发剂为偶氮二异丁腈;The emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecylnaphthalene sulfonate in a mass ratio of 2.5:1.2; the initiator is azobisisobutyronitrile;
所述二氧化硅为纳米二氧化硅经过30%质量分数的氢氧化钠水溶液浸泡处理35min后,过滤取固体清洗至pH值为7进行干燥后所得。The silicon dioxide is obtained by soaking nano silicon dioxide in a 30% by mass sodium hydroxide aqueous solution for 35 minutes, filtering out solids, washing until the pH value is 7, and then drying.
所述三元共聚物包覆二氧化钛的制备包括以下步骤:The preparation of the terpolymer coated titanium dioxide comprises the following steps:
S1、将二氧化钛加入溶剂中,在37℃、330r/min下搅拌30min,缓慢滴加乙烯基三乙氧基硅烷后,继续搅拌35min,冷却至室温后,离心分离,取固体70℃真空干燥25h后,得到改性二氧化钛;其中,所述二氧化钛、溶剂和偶联剂的质量比为1.1:3:0.17;所述溶剂由去离子水、无水乙醇和醋酸按质量比1:9.2:0.01混合而成;S1. Add titanium dioxide to the solvent, stir at 37°C and 330r/min for 30min, slowly drop vinyltriethoxysilane, continue stirring for 35min, cool to room temperature, centrifuge, take the solid and vacuum dry it at 70°C for 25h to obtain modified titanium dioxide; wherein the mass ratio of the titanium dioxide, the solvent and the coupling agent is 1.1:3:0.17; the solvent is a mixture of deionized water, anhydrous ethanol and acetic acid in a mass ratio of 1:9.2:0.01;
S2、将改性二氧化钛和四氢呋喃超声混合后,加入甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚和异丙醇在氮气气氛下,62℃、330r/min下搅拌30min后,加入偶氮二异丁腈继续搅拌5.5h,冷却至室温后,离心分离,取固体在70℃真空干燥6.5h后,得到三元共聚物包覆二氧化钛;其中,所述改性二氧化钛、有机溶剂、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚、异丙醇和引发剂的质量比为14.7:62:18.7:10.5:2.1:1.55:1.5。S2. After ultrasonically mixing the modified titanium dioxide and tetrahydrofuran, glycidyl methacrylate, methyl methacrylate, cardanol and isopropanol are added, and the mixture is stirred at 62°C and 330 r/min for 30 min under a nitrogen atmosphere. Then, azobisisobutyronitrile is added and stirring is continued for 5.5 h. After cooling to room temperature, the mixture is centrifuged and the solid is vacuum dried at 70°C for 6.5 h to obtain a terpolymer-coated titanium dioxide; wherein the mass ratio of the modified titanium dioxide, organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol, isopropanol and initiator is 14.7:62:18.7:10.5:2.1:1.55:1.5.
一种改性丁苯胶乳粘结剂的制备方法包括以下步骤:A method for preparing a modified styrene-butadiene latex binder comprises the following steps:
将功能单体、丙烯酸酯、丁二烯、甲基苯乙烯、丙烯酸羟乙酯、三元共聚物包覆二氧化钛、二氧化硅、乳化剂和去离子水搅拌混合后,加入引发剂加热乳化共聚后,调节pH值,过筛后,即得改性丁苯胶乳粘结剂;The functional monomer, acrylate, butadiene, methyl styrene, hydroxyethyl acrylate, terpolymer-coated titanium dioxide, silicon dioxide, emulsifier and deionized water are stirred and mixed, an initiator is added, heated and emulsified for copolymerization, the pH value is adjusted, and the modified styrene-butadiene latex binder is obtained after sieving;
其中,所述搅拌混合为在80℃下、搅拌2.5h;所述加热乳化共聚为在83℃下、反应6h;所述调节pH值为采用氢氧化钠调节pH值至6.5;所述过筛为过100目筛。The stirring and mixing is carried out at 80° C. for 2.5 hours; the heating emulsification copolymerization is carried out at 83° C. for 6 hours; the pH value is adjusted to 6.5 using sodium hydroxide; and the screening is carried out through a 100-mesh sieve.
实施例3Example 3
一种改性丁苯胶乳粘结剂,按重量份数包括以下组分:A modified styrene-butadiene latex binder comprises the following components in parts by weight:
甲基丙烯酸 5份Methacrylic acid 5 parts
丙烯酸酯 77份Acrylate 77 parts
丁二烯 55份Butadiene 55 parts
甲基苯乙烯 97份Methylstyrene 97 parts
丙烯酸羟乙酯 4.3份Hydroxyethyl acrylate 4.3 parts
三元共聚物包覆二氧化钛 18份18 parts of terpolymer coated titanium dioxide
二氧化硅 7份Silicon dioxide 7 parts
乳化剂 5.3份Emulsifier 5.3 parts
引发剂 3.8份Initiator 3.8 parts
去离子水 145份。Deionized water 145 parts.
所述丙烯酸酯由甲基丙烯酸甲酯和3-(N,N-二甲基氨基)丙烯酸乙酯按质量比10:1.3混合而成;The acrylic acid ester is prepared by mixing methyl methacrylate and 3-(N,N-dimethylamino)ethyl acrylate in a mass ratio of 10:1.3;
所述乳化剂由十二烷基硫酸钠和十二烷基萘磺酸钠按质量比2.5:1.3混合而成;所述引发剂为偶氮二异丁腈;The emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecylnaphthalene sulfonate in a mass ratio of 2.5:1.3; the initiator is azobisisobutyronitrile;
所述二氧化硅为纳米二氧化硅经过30%质量分数的氢氧化钠水溶液浸泡处理40min后,过滤取固体清洗至pH值为7进行干燥后所得。The silicon dioxide is obtained by soaking nano silicon dioxide in a 30% by mass sodium hydroxide aqueous solution for 40 minutes, filtering out solids, washing until the pH value is 7, and then drying.
所述三元共聚物包覆二氧化钛的制备包括以下步骤:The preparation of the terpolymer coated titanium dioxide comprises the following steps:
S1、将二氧化钛加入溶剂中,在38℃、365r/min下搅拌30min,缓慢滴加乙烯基三乙氧基硅烷后,继续搅拌40min,冷却至室温后,离心分离,取固体70℃真空干燥25h后,得到改性二氧化钛;其中,所述二氧化钛、溶剂和偶联剂的质量比为1.1:3:0.18;所述溶剂由去离子水、无水乙醇和醋酸按质量比1:9.3:0.01混合而成;S1. Add titanium dioxide to the solvent, stir at 38°C and 365r/min for 30min, slowly drop vinyltriethoxysilane, continue stirring for 40min, cool to room temperature, centrifuge, take the solid and vacuum dry it at 70°C for 25h to obtain modified titanium dioxide; wherein the mass ratio of the titanium dioxide, the solvent and the coupling agent is 1.1:3:0.18; the solvent is a mixture of deionized water, anhydrous ethanol and acetic acid in a mass ratio of 1:9.3:0.01;
S2、将改性二氧化钛和四氢呋喃超声混合后,加入甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚和异丙醇在氮气气氛下,63℃、367r/min下搅拌30min后,加入偶氮二异丁腈继续搅拌5.7h,冷却至室温后,离心分离,取固体在70℃真空干燥7.3h后,得到三元共聚物包覆二氧化钛;其中,所述改性二氧化钛、有机溶剂、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚、异丙醇和引发剂的质量比为15.5:63:19.5:10.7:2.5:1.55:1.5。S2. After ultrasonically mixing the modified titanium dioxide and tetrahydrofuran, glycidyl methacrylate, methyl methacrylate, cardanol and isopropanol are added, and the mixture is stirred at 63°C and 367 r/min for 30 min under a nitrogen atmosphere. Then, azobisisobutyronitrile is added and stirring is continued for 5.7 h. After cooling to room temperature, the mixture is centrifuged and the solid is vacuum dried at 70°C for 7.3 h to obtain a terpolymer-coated titanium dioxide; wherein the mass ratio of the modified titanium dioxide, organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol, isopropanol and initiator is 15.5:63:19.5:10.7:2.5:1.55:1.5.
一种改性丁苯胶乳粘结剂的制备方法包括以下步骤:A method for preparing a modified styrene-butadiene latex binder comprises the following steps:
将功能单体、丙烯酸酯、丁二烯、甲基苯乙烯、丙烯酸羟乙酯、三元共聚物包覆二氧化钛、二氧化硅、乳化剂和去离子水搅拌混合后,加入引发剂加热乳化共聚后,调节pH值,过筛后,即得改性丁苯胶乳粘结剂;The functional monomer, acrylate, butadiene, methyl styrene, hydroxyethyl acrylate, terpolymer-coated titanium dioxide, silicon dioxide, emulsifier and deionized water are stirred and mixed, an initiator is added, heated and emulsified for copolymerization, the pH value is adjusted, and the modified styrene-butadiene latex binder is obtained after sieving;
其中,所述搅拌混合为在80℃下、搅拌2.5h;所述加热乳化共聚为在85℃下、反应7h;所述调节pH值为采用氢氧化钠调节pH值至6.5;所述过筛为过100目筛。The stirring and mixing is carried out at 80° C. for 2.5 hours; the heating emulsification copolymerization is carried out at 85° C. for 7 hours; the pH value is adjusted to 6.5 using sodium hydroxide; and the screening is carried out through a 100-mesh sieve.
实施例4Example 4
一种改性丁苯胶乳粘结剂,按重量份数包括以下组分:A modified styrene-butadiene latex binder comprises the following components in parts by weight:
甲基丙烯酸 6份Methacrylic acid 6 parts
丙烯酸酯 80份Acrylate 80 parts
丁二烯 60份Butadiene 60 parts
甲基苯乙烯 100份Methyl styrene 100 parts
丙烯酸羟乙酯 5份Hydroxyethyl acrylate 5 parts
三元共聚物包覆二氧化钛 20份20 parts of terpolymer coated titanium dioxide
二氧化硅 8份Silicon dioxide 8 parts
乳化剂 6份Emulsifier 6 parts
引发剂 4份Initiator 4 parts
去离子水 150份。Deionized water 150 parts.
所述丙烯酸酯由甲基丙烯酸甲酯和3-(N,N-二甲基氨基)丙烯酸乙酯按质量比10:1.5混合而成;The acrylic acid ester is prepared by mixing methyl methacrylate and 3-(N,N-dimethylamino)ethyl acrylate in a mass ratio of 10:1.5;
所述乳化剂由十二烷基硫酸钠和十二烷基萘磺酸钠按质量比2.5:1.5混合而成;所述引发剂为偶氮二异丁腈;The emulsifier is a mixture of sodium dodecyl sulfate and sodium dodecylnaphthalene sulfonate in a mass ratio of 2.5:1.5; the initiator is azobisisobutyronitrile;
所述二氧化硅为纳米二氧化硅经过30%质量分数的氢氧化钠水溶液浸泡处理45min后,过滤取固体清洗至pH值为7进行干燥后所得。The silicon dioxide is obtained by soaking nano silicon dioxide in a 30% by mass sodium hydroxide aqueous solution for 45 minutes, filtering out solids, washing until the pH value is 7, and then drying.
所述三元共聚物包覆二氧化钛的制备包括以下步骤:The preparation of the terpolymer coated titanium dioxide comprises the following steps:
S1、将二氧化钛加入溶剂中,在40℃、400r/min下搅拌30min,缓慢滴加乙烯基三乙氧基硅烷后,继续搅拌45min,冷却至室温后,离心分离,取固体70℃真空干燥30h后,得到改性二氧化钛;其中,所述二氧化钛、溶剂和偶联剂的质量比为1.2:3:0.20;所述溶剂由去离子水、无水乙醇和醋酸按质量比1:9.5:0.01混合而成;S1. Add titanium dioxide to a solvent, stir at 40°C and 400 r/min for 30 min, slowly drop vinyltriethoxysilane, continue stirring for 45 min, cool to room temperature, centrifuge, take the solid and vacuum dry it at 70°C for 30 h to obtain modified titanium dioxide; wherein the mass ratio of the titanium dioxide, the solvent and the coupling agent is 1.2:3:0.20; the solvent is a mixture of deionized water, anhydrous ethanol and acetic acid in a mass ratio of 1:9.5:0.01;
S2、将改性二氧化钛和四氢呋喃超声混合后,加入甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚和异丙醇在氮气气氛下,65℃、400r/min下搅拌30min后,加入偶氮二异丁腈继续搅拌6h,冷却至室温后,离心分离,取固体在70℃真空干燥8h后,得到三元共聚物包覆二氧化钛;其中,所述改性二氧化钛、有机溶剂、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚、异丙醇和引发剂的质量比为16:65:20:11:2.4:1.6:1.5。S2. After ultrasonically mixing the modified titanium dioxide and tetrahydrofuran, glycidyl methacrylate, methyl methacrylate, cardanol and isopropanol are added, and the mixture is stirred at 65°C and 400 r/min for 30 min under a nitrogen atmosphere. Then, azobisisobutyronitrile is added and stirring is continued for 6 h. After cooling to room temperature, the mixture is centrifuged and the solid is vacuum dried at 70°C for 8 h to obtain a terpolymer-coated titanium dioxide; wherein the mass ratio of the modified titanium dioxide, organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol, isopropanol and initiator is 16:65:20:11:2.4:1.6:1.5.
一种改性丁苯胶乳粘结剂的制备方法包括以下步骤:A method for preparing a modified styrene-butadiene latex binder comprises the following steps:
将功能单体、丙烯酸酯、丁二烯、甲基苯乙烯、丙烯酸羟乙酯、三元共聚物包覆二氧化钛、二氧化硅、乳化剂和去离子水搅拌混合后,加入引发剂加热乳化共聚后,调节pH值,过筛后,即得改性丁苯胶乳粘结剂;The functional monomer, acrylate, butadiene, methyl styrene, hydroxyethyl acrylate, terpolymer-coated titanium dioxide, silicon dioxide, emulsifier and deionized water are stirred and mixed, an initiator is added, heated and emulsified for copolymerization, the pH value is adjusted, and the modified styrene-butadiene latex binder is obtained after sieving;
其中,所述搅拌混合为在80℃下、搅拌3h;所述加热乳化共聚为在90℃下、反应8h;所述调节pH值为采用氢氧化钠调节pH值至7;所述过筛为过100目筛。The stirring and mixing is carried out at 80° C. for 3 hours; the heating emulsification copolymerization is carried out at 90° C. for 8 hours; the pH value is adjusted to 7 using sodium hydroxide; and the screening is carried out through a 100-mesh sieve.
对比例1Comparative Example 1
与实施例2相比,对比例1不同之处在于三元共聚物和二氧化钛组成的混合物代替三元共聚物包覆二氧化钛;Compared with Example 2, the difference in Comparative Example 1 is that the mixture consisting of the terpolymer and titanium dioxide replaces the terpolymer to coat the titanium dioxide;
混合物的制备包括以下步骤:The preparation of the mixture comprises the following steps:
向四氢呋喃加入甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚和异丙醇在氮气气氛下,62℃、330r/min下搅拌30min后,加入偶氮二异丁腈继续搅拌5.5h,冷却至室温后,离心分离,取固体在70℃真空干燥6.5h后,加入二氧化钛搅拌混合,得到混合物;其中,所述二氧化钛、有机溶剂、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、腰果酚、异丙醇和引发剂的质量比为14.7:62:18.7:10.5:2.1:1.55:1.5;Add glycidyl methacrylate, methyl methacrylate, cardanol and isopropanol to tetrahydrofuran, stir for 30 min at 62° C. and 330 r/min under a nitrogen atmosphere, add azobisisobutyronitrile and continue stirring for 5.5 h, cool to room temperature, centrifuge, take the solid and dry it in vacuum at 70° C. for 6.5 h, add titanium dioxide and stir and mix to obtain a mixture; wherein the mass ratio of titanium dioxide, organic solvent, glycidyl methacrylate, methyl methacrylate, cardanol, isopropanol and initiator is 14.7:62:18.7:10.5:2.1:1.55:1.5;
其余组分、制备步骤和参数均一致。The remaining components, preparation steps and parameters were the same.
对比例2Comparative Example 2
与实施例2相比,对比例2不同之处在于,对比例2使用4-烯丙基苯酚代替腰果酚,其余组分、制备步骤和参数均一致。Compared with Example 2, the difference of Comparative Example 2 is that Comparative Example 2 uses 4-allylphenol instead of cardanol, and the other components, preparation steps and parameters are the same.
对比例3Comparative Example 3
与实施例2相比,对比例3不同之处在于,对比例3的丙烯酸酯为甲基丙烯酸甲酯,即不使用3-(N,N-二甲基氨基)丙烯酸乙酯,其余组分、制备步骤和参数均一致。Compared with Example 2, Comparative Example 3 is different in that the acrylic acid ester in Comparative Example 3 is methyl methacrylate, that is, 3-(N,N-dimethylamino)ethyl acrylate is not used, and the other components, preparation steps and parameters are the same.
对比例4Comparative Example 4
与实施例2相比,对比例4不同之处在于,对比例4的二氧化硅为纳米二氧化硅,即不经过氢氧化钠水溶液处理,其余组分、制备步骤和参数均一致。Compared with Example 2, Comparative Example 4 is different in that the silicon dioxide in Comparative Example 4 is nano silicon dioxide, that is, it is not treated with a sodium hydroxide aqueous solution, and the other components, preparation steps and parameters are the same.
将实施例1-4和对比例1-4制得的改性丁苯胶乳粘结剂进行以下测试;其测试结果如表1所示。The modified styrene-butadiene latex binders prepared in Examples 1-4 and Comparative Examples 1-4 were subjected to the following tests; the test results are shown in Table 1.
粘结强度测试:采用万能拉伸试验机,依据GB/T2791-1995T测试;Bond strength test: using a universal tensile testing machine, tested according to GB/T2791-1995T;
力学性能测试:依据GB/T8655-2019测试拉伸强度和拉断伸长率。Mechanical properties test: tensile strength and elongation at break are tested according to GB/T8655-2019.
表1Table 1
从表1测试结果可知,实施例1-4与对比例1-4相比,本发明实施例1-4制得的改性丁苯胶乳粘结剂的粘结强度、拉伸强度和拉断伸长率优于对比例1-4;其中,本发明方案制得的粘结剂的拉伸强度和拉断伸长率与对比例1-4差别显著。It can be seen from the test results in Table 1 that compared with comparative examples 1-4, the bonding strength, tensile strength and elongation at break of the modified styrene-butadiene latex binder prepared in embodiments 1-4 of the present invention are better than those in comparative examples 1-4; among them, the tensile strength and elongation at break of the binder prepared by the scheme of the present invention are significantly different from those of comparative examples 1-4.
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭示如上,然而并非用以限定本发明,任何本领域技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简介修改、等同变化与修饰,均仍属于本发明技术方案的范围内。The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410833088.9A CN118421221B (en) | 2024-06-26 | 2024-06-26 | Modified styrene-butadiene latex binder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410833088.9A CN118421221B (en) | 2024-06-26 | 2024-06-26 | Modified styrene-butadiene latex binder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118421221A true CN118421221A (en) | 2024-08-02 |
| CN118421221B CN118421221B (en) | 2024-12-10 |
Family
ID=92323523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410833088.9A Active CN118421221B (en) | 2024-06-26 | 2024-06-26 | Modified styrene-butadiene latex binder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118421221B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120173498A (en) * | 2025-05-21 | 2025-06-20 | 铜陵兢强电子科技股份有限公司 | A high-adhesion enameled wire primer and preparation method thereof |
| CN120966390A (en) * | 2025-08-22 | 2025-11-18 | 珠海金鸡化工有限公司 | A styrene-butadiene latex composite adhesive and its preparation process |
| CN121108520A (en) * | 2025-11-13 | 2025-12-12 | 淄博奥固特科技有限公司 | A carboxylated styrene-butadiene latex and its preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0228269A (en) * | 1988-07-16 | 1990-01-30 | Aisin Chem Co Ltd | Coating composition for freeze-resistant and chipping-resistant treatment |
| CN112552452A (en) * | 2020-12-09 | 2021-03-26 | 珠海金鸡化工有限公司 | Modified styrene-butadiene latex and preparation method thereof |
| CN115505078A (en) * | 2022-10-10 | 2022-12-23 | 上海东升新材料有限公司 | A kind of preparation method of styrene-butadiene latex adhesive for metal surface printing |
| CN117551234A (en) * | 2023-12-30 | 2024-02-13 | 珠海金鸡化工有限公司 | Low-odor carboxyl styrene-butadiene latex and preparation method thereof |
| CN117924623A (en) * | 2024-02-01 | 2024-04-26 | 广西腾龙化工科技有限公司 | Modified styrene-butadiene copolymer composite latex for paper coating |
-
2024
- 2024-06-26 CN CN202410833088.9A patent/CN118421221B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0228269A (en) * | 1988-07-16 | 1990-01-30 | Aisin Chem Co Ltd | Coating composition for freeze-resistant and chipping-resistant treatment |
| CN112552452A (en) * | 2020-12-09 | 2021-03-26 | 珠海金鸡化工有限公司 | Modified styrene-butadiene latex and preparation method thereof |
| CN115505078A (en) * | 2022-10-10 | 2022-12-23 | 上海东升新材料有限公司 | A kind of preparation method of styrene-butadiene latex adhesive for metal surface printing |
| CN117551234A (en) * | 2023-12-30 | 2024-02-13 | 珠海金鸡化工有限公司 | Low-odor carboxyl styrene-butadiene latex and preparation method thereof |
| CN117924623A (en) * | 2024-02-01 | 2024-04-26 | 广西腾龙化工科技有限公司 | Modified styrene-butadiene copolymer composite latex for paper coating |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120173498A (en) * | 2025-05-21 | 2025-06-20 | 铜陵兢强电子科技股份有限公司 | A high-adhesion enameled wire primer and preparation method thereof |
| CN120173498B (en) * | 2025-05-21 | 2025-08-05 | 铜陵兢强电子科技股份有限公司 | High-adhesion enameled wire priming paint and preparation method thereof |
| CN120966390A (en) * | 2025-08-22 | 2025-11-18 | 珠海金鸡化工有限公司 | A styrene-butadiene latex composite adhesive and its preparation process |
| CN120966390B (en) * | 2025-08-22 | 2026-03-06 | 珠海金鸡化工有限公司 | A styrene-butadiene latex composite adhesive and its preparation process |
| CN121108520A (en) * | 2025-11-13 | 2025-12-12 | 淄博奥固特科技有限公司 | A carboxylated styrene-butadiene latex and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118421221B (en) | 2024-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN118421221A (en) | A modified styrene-butadiene latex binder and preparation method thereof | |
| CN103289010B (en) | Method for preparing core-shell nano SiO2/fluorine-containing polyacrylate soap-free emulsion | |
| CN102585111B (en) | Modified epoxy emulsion and preparation method thereof | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN102516904B (en) | One-component water-based adhesive for evaporative cooling wet curtain and preparation method thereof | |
| CN104311716B (en) | Organic silicon modified styrene-acrylate microemulsion reinforcing agent as well as preparation method and application thereof | |
| CN105440310B (en) | Aqueous epoxy resins are impact-resistant modified to use core-shell nano lotion preparation process | |
| CN105440228B (en) | Aqueous epoxy resins are impact-resistant modified to use core-shell nano lotion preparation process | |
| CN114230723B (en) | Graphene oxide modified styrene-acrylic pickering emulsion, composite emulsion, and preparation method and application thereof | |
| CN115386123B (en) | A kind of silicon-coated release film and its preparation method and application | |
| CN108329417A (en) | Nano-meter SiO_22/ organic-silicon-modified core-shell acrylic-resin emulsion and preparation method | |
| CN112159494B (en) | Water-based road marking paint emulsion and preparation method thereof | |
| CN114369202B (en) | Preparation method and coating material of nanocellulose hollow microspheres | |
| CN108084376A (en) | Core-shell type nano silica/fluorine-containing polyacrylate soap-free emulsion preparation method | |
| CN100387653C (en) | A kind of single-component self-crosslinking epoxy acrylic compound emulsion and its preparation method and application | |
| CN111825860B (en) | Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof | |
| CN118290674A (en) | Nanocellulose fiber modified core-shell polymer particles and preparation method thereof | |
| CN113105588B (en) | Method for preparing fluorine-containing polyacrylate emulsion using photoresponsive nanocellulose | |
| CN109575735B (en) | A kind of nano-ZnO/organofluorine modified polyacrylate emulsion leather finishing agent and its preparation method and application | |
| CN112142927B (en) | An organic-inorganic nanoparticle composite water-repellent agent and its preparation and application methods | |
| CN109293834A (en) | A kind of preparation method of styrene-butadiene latex and products thereof and application | |
| CN118668522A (en) | Composite styrene-acrylic emulsion surface sizing agent and preparation method thereof | |
| CN115490810B (en) | A core polymer BDDA cross-linked PVAc/PS core-shell emulsion and preparation method thereof | |
| CN108794705B (en) | A kind of preparation method and application of modified carboxylated styrene-butadiene latex | |
| CN109400791A (en) | Silicone acrylic emulsion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |