CN108517024A - Pickering fine emulsion polymerizations prepare polyacrylate/nano-ZnO composite leather coating agent and preparation method - Google Patents
Pickering fine emulsion polymerizations prepare polyacrylate/nano-ZnO composite leather coating agent and preparation method Download PDFInfo
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 32
- 239000010985 leather Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 title abstract description 11
- 239000011248 coating agent Substances 0.000 title abstract description 5
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010556 emulsion polymerization method Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000006210 lotion Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- -1 acrylic ester Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
Description
技术领域technical field
本发明属于皮革涂饰剂技术领域,涉及一种Pickering细乳液聚合法制备聚丙烯酸酯/纳米ZnO复合皮革涂饰剂及制备方法。The invention belongs to the technical field of leather finishing agents, and relates to a polyacrylate/nanometer ZnO composite leather finishing agent prepared by a Pickering mini-emulsion polymerization method and a preparation method.
背景技术Background technique
聚丙烯酸酯类乳液具有优异的耐热稳定性、耐候性、耐酸碱性、保光性、机械性、粘接性等特性,同时具有成膜性好、原料易得和成本相对较低等优点,是目前最常用的皮革涂饰材料之一。传统的聚丙烯酸酯涂饰剂应用虽然较为普遍,但聚丙烯酸酯乳液成膜耐水性较差,严重影响涂饰后革样的耐湿擦牢度;同时其成膜相对较为致密,透气、透水汽性较差,不利于革样卫生性能的保持。这些缺陷导致了聚丙烯酸酯涂饰剂难以应用于高端的皮革市场。近年来,许多研究者将无机纳米粒子引入到聚丙烯酸酯乳液中,结果发现不仅能够显著提升聚丙烯酸酯乳液成膜的耐水性、力学性能、透气性及透水汽性等,此外,还可以赋予聚丙烯酸酯乳液薄膜诸多特性,如抗菌性、抗紫外性、导电性等。其中纳米ZnO粒子价廉易得,且具有优异的抗菌、光催化及紫外线吸收等性能,是目前聚合物基质中引入较多的一种无机纳米粒子。Polyacrylate emulsion has excellent heat resistance stability, weather resistance, acid and alkali resistance, gloss retention, mechanical properties, adhesive properties, etc., and also has good film-forming properties, easy to obtain raw materials and relatively low cost, etc. The advantage is that it is one of the most commonly used leather finishing materials at present. Although the application of traditional polyacrylate finishing agents is relatively common, the water resistance of polyacrylate emulsion film formation is poor, which seriously affects the wet rubbing fastness of leather samples after coating; at the same time, its film formation is relatively dense, and its air permeability and water vapor permeability are relatively low. Poor, not conducive to the maintenance of leather-like hygienic performance. These defects have caused polyacrylate finishes to be difficult to apply to the high-end leather market. In recent years, many researchers have introduced inorganic nanoparticles into polyacrylate emulsions, and found that it can not only significantly improve the water resistance, mechanical properties, air permeability and water vapor permeability of polyacrylate emulsion films, but also impart Polyacrylate emulsion film has many properties, such as antibacterial, UV resistance, electrical conductivity, etc. Among them, nano-ZnO particles are cheap and easy to obtain, and have excellent antibacterial, photocatalytic and ultraviolet absorption properties, and are currently a kind of inorganic nanoparticles introduced into polymer matrices.
然而,聚合方法的选择对纳米粒子引入的性能具有较大影响。传统乳液聚合方法制备聚丙烯酸酯乳液需要使用大量的传统小分子表面活性剂,严重影响聚丙烯酸酯乳液成膜耐水性,同时表面活性剂附着于乳胶粒表面,极易受环境因素影响而发生迁移,使乳液稳定性降低。随着聚合理论和技术的不断完善,新型的乳液聚合方法受到了研究者的广泛关注,如:无皂乳液聚合、种子乳液聚合、核壳乳液聚合、细乳液聚合、Pickering乳液聚合等。细乳液聚合法基于液滴成核的特点,非常易于高疏水性单体的聚合,易于有机/无机复合乳液的制备,能够降低表面活性剂的用量。Pickering乳液聚合法是以无机纳米粒子代替传统表面活性剂稳定乳液的一种聚合方法,能够避免传统表面活性剂带来的缺陷,赋予复合乳液一些纳米特性,但是其存在所制备的乳液稳定性差、固含量低等缺点。However, the choice of polymerization method has a large impact on the performance of nanoparticle incorporation. The preparation of polyacrylate emulsion by traditional emulsion polymerization requires the use of a large amount of traditional small-molecule surfactants, which seriously affects the water resistance of polyacrylate emulsion film formation. At the same time, surfactants are attached to the surface of latex particles and are easily migrated due to environmental factors. , reducing the stability of the emulsion. With the continuous improvement of polymerization theory and technology, new emulsion polymerization methods have attracted extensive attention from researchers, such as: soap-free emulsion polymerization, seed emulsion polymerization, core-shell emulsion polymerization, miniemulsion polymerization, Pickering emulsion polymerization, etc. The miniemulsion polymerization method is based on the characteristics of droplet nucleation, which is very easy to polymerize highly hydrophobic monomers, easy to prepare organic/inorganic composite emulsions, and can reduce the amount of surfactants. The Pickering emulsion polymerization method is a kind of polymerization method that replaces the traditional surfactant stable emulsion with inorganic nanoparticles, which can avoid the defects caused by traditional surfactants and endow the composite emulsion with some nanometer characteristics, but it has poor stability of the prepared emulsion, Disadvantages such as low solid content.
发明内容Contents of the invention
有鉴于此,本发明的主要目的在于提供一种Pickering细乳液聚合法制备聚丙烯酸酯/纳米ZnO复合皮革涂饰剂及制备方法,提高成革的卫生性能和机械性能。In view of this, the main purpose of the present invention is to provide a kind of Pickering miniemulsion polymerization method to prepare polyacrylate/nanometer ZnO composite leather finishing agent and preparation method, improve the hygienic performance and mechanical performance of finished leather.
为达到上述目的,本发明的技术方案是这样实现的:In order to achieve the above object, technical solution of the present invention is achieved in that way:
Pickering细乳液聚合法制备聚丙烯酸酯/纳米ZnO复合皮革涂饰剂的制备方法,其特征在于:The preparation method of polyacrylate/nanometer ZnO composite leather finishing agent prepared by Pickering mini-emulsion polymerization is characterized in that:
具体包括以下步骤:以下未另外说明均为质量份,Concretely comprise the following steps: the following are parts by mass unless otherwise stated,
将0.24~1.44份三乙氧基乙烯基硅烷溶于100份去离子水中,再加入1.44~2.88份纳米ZnO粒子,混合后超声10~15 min;将24份甲基丙烯酸酯、24份丙烯酸丁酯、1.44份甲基丙烯酸六氟丁酯、1.44份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 0.24-1.44 parts of triethoxyvinylsilane in 100 parts of deionized water, then add 1.44-2.88 parts of nano-ZnO particles, mix and sonicate for 10-15 minutes; mix 24 parts of methacrylate, 24 parts of butyl acrylate Ester, 1.44 parts of hexafluorobutyl methacrylate, and 1.44 parts of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10-15 minutes to obtain a fine emulsion;
将1.44份过硫酸铵溶于100份去离子水中配制引发剂水溶液;1.44 parts of ammonium persulfate are dissolved in 100 parts of deionized water to prepare aqueous initiator solution;
将温度升至75~85 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 75-85 °C and rotate at 300 r/min. First, add 1/3 volume part of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, 1.5-2 After adding dropwise for h, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
所述的Pickering细乳液聚合法制备聚丙烯酸酯/纳米ZnO复合皮革涂饰剂的制备方法制得的聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。The polyacrylate/nanometer ZnO composite leather finishing agent prepared by the method for preparing the polyacrylate/nanometer ZnO composite leather finishing agent by the Pickering miniemulsion polymerization method.
与现有技术相比,本发明的有益效果:Compared with prior art, the beneficial effect of the present invention:
本发明采用Pickering细乳液聚合法,以纳米ZnO代替传统表面活性剂,改善了聚丙烯酸酯乳液成膜耐水性差的缺陷,同时利用Pickering细乳液聚合法液滴成核的特点,易于含氟单体的引入,改善了单独使用Pickering乳液聚合法制备出乳液稳定性差的缺点,通过复合乳液包覆形貌的获得,提高其成膜透气性、透水汽性及力学性能等,进而提高涂饰后革样的耐湿擦牢度与卫生性能。The invention adopts the Pickering miniemulsion polymerization method, replaces the traditional surfactant with nano-ZnO, improves the defect of poor water resistance of polyacrylate emulsion film formation, and utilizes the characteristics of droplet nucleation of the Pickering miniemulsion polymerization method to facilitate fluorine-containing monomers The introduction of the Pickering emulsion polymerization method has improved the shortcomings of the poor stability of the emulsion prepared by the Pickering emulsion polymerization method alone. Through the acquisition of the composite emulsion coating morphology, the air permeability, water vapor permeability and mechanical properties of the film are improved, and the leather appearance after coating is improved. Excellent wet rubbing fastness and hygienic performance.
具体实施方式Detailed ways
下面结合具体实施方式对本发明进行详细的说明。The present invention will be described in detail below in combination with specific embodiments.
本发明提供一种Pickering细乳液聚合法制备聚丙烯酸酯/纳米ZnO复合皮革涂饰剂的制备方法,The invention provides a method for preparing polyacrylate/nano-ZnO composite leather finishing agent by Pickering mini-emulsion polymerization,
具体包括以下步骤:以下未另外说明均为质量份,Concretely comprise the following steps: the following are parts by mass unless otherwise stated,
将0.24~1.44份三乙氧基乙烯基硅烷(DNS-86)溶于100份去离子水中,再加入1.44~2.88份纳米ZnO粒子,混合后超声10~15 min;将24份甲基丙烯酸酯(MMA)、24份丙烯酸丁酯(BA)、1.44份甲基丙烯酸六氟丁酯(G02)、1.44份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 0.24-1.44 parts of triethoxyvinylsilane (DNS-86) in 100 parts of deionized water, then add 1.44-2.88 parts of nano-ZnO particles, mix and sonicate for 10-15 minutes; 24 parts of methacrylate (MMA), 24 parts of butyl acrylate (BA), 1.44 parts of hexafluorobutyl methacrylate (G02), and 1.44 parts of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10-15 minutes to obtain fine lotion;
将1.44份过硫酸铵(APS)溶于100份去离子水中配制引发剂水溶液;Dissolve 1.44 parts of ammonium persulfate (APS) in 100 parts of deionized water to prepare an aqueous initiator solution;
将温度升至75~85 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 75-85 °C and rotate at 300 r/min. First, add 1/3 volume part of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, 1.5-2 After adding dropwise for h, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
所述的Pickering细乳液聚合法制备聚丙烯酸酯/纳米ZnO复合皮革涂饰剂的制备方法制得的聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。The polyacrylate/nanometer ZnO composite leather finishing agent prepared by the method for preparing the polyacrylate/nanometer ZnO composite leather finishing agent by the Pickering miniemulsion polymerization method.
实施例1:Example 1:
将0.24质量份三乙氧基乙烯基硅烷(DNS-86)溶于100质量份去离子水中,再加入1.44~2.88质量份纳米ZnO粒子,混合后超声10~15 min;将24质量份甲基丙烯酸酯(MMA)、24质量份丙烯酸丁酯(BA)、1.44质量份甲基丙烯酸六氟丁酯(G02)、1.44质量份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 0.24 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, then add 1.44 to 2.88 parts by mass of nano-ZnO particles, mix and sonicate for 10 to 15 minutes; Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10 minutes. ~15 min to get fine emulsion;
将1.44质量份过硫酸铵(APS)溶于100质量份去离子水中配制引发剂水溶液;Dissolving 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;
将温度升至75~85 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 75-85 °C and rotate at 300 r/min. First, add 1/3 volume part of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, 1.5-2 After adding dropwise for h, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
实施例2:Example 2:
将0.24~1.44质量份三乙氧基乙烯基硅烷(DNS-86)溶于100质量份去离子水中,再加入1.44质量份纳米ZnO粒子,混合后超声10~15 min;将24质量份甲基丙烯酸酯(MMA)、24质量份丙烯酸丁酯(BA)、1.44质量份甲基丙烯酸六氟丁酯(G02)、1.44质量份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 0.24-1.44 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, then add 1.44 parts by mass of nano-ZnO particles, mix and sonicate for 10-15 minutes; 24 parts by mass of methyl Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10 minutes. ~15 min to get fine emulsion;
将1.44质量份过硫酸铵(APS)溶于100质量份去离子水中配制引发剂水溶液;Dissolving 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;
将温度升至75~85 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 75-85 °C and rotate at 300 r/min. First, add 1/3 volume part of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, 1.5-2 After adding dropwise for h, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
实施例3:Example 3:
将1质量份三乙氧基乙烯基硅烷(DNS-86)溶于100质量份去离子水中,再加入2质量份纳米ZnO粒子,混合后超声10~15 min;将24质量份甲基丙烯酸酯(MMA)、24质量份丙烯酸丁酯(BA)、1.44质量份甲基丙烯酸六氟丁酯(G02)、1.44质量份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 1 part by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, then add 2 parts by mass of nano-ZnO particles, mix and sonicate for 10-15 min; mix 24 parts by mass of methacrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10-15 minutes. min to get a fine emulsion;
将1.44质量份过硫酸铵(APS)溶于100质量份去离子水中配制引发剂水溶液;Dissolving 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;
将温度升至75~85 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 75-85 °C and rotate at 300 r/min. First, add 1/3 volume part of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, 1.5-2 After adding dropwise for h, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
实施例4:Example 4:
将0.24~1.44质量份三乙氧基乙烯基硅烷(DNS-86)溶于100质量份去离子水中,再加入2.5质量份纳米ZnO粒子,混合后超声10~15 min;将24质量份甲基丙烯酸酯(MMA)、24质量份丙烯酸丁酯(BA)、1.44质量份甲基丙烯酸六氟丁酯(G02)、1.44质量份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 0.24-1.44 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, then add 2.5 parts by mass of nano-ZnO particles, mix and sonicate for 10-15 min; Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10 minutes. ~15 min to get fine emulsion;
将1.44质量份过硫酸铵(APS)溶于100质量份去离子水中配制引发剂水溶液;Dissolving 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;
将温度升至75 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 75°C and rotate at 300 r/min, first add 1/3 volume of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, drop for 1.5 to 2 hours After adding, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
实施例5:Example 5:
将0.56质量份三乙氧基乙烯基硅烷(DNS-86)溶于100质量份去离子水中,再加入1.44~2.88质量份纳米ZnO粒子,混合后超声10~15 min;将24质量份甲基丙烯酸酯(MMA)、24质量份丙烯酸丁酯(BA)、1.44质量份甲基丙烯酸六氟丁酯(G02)、1.44质量份正丁醇混合,高速剪切乳化10~15 min,再超声10~15 min得到细乳液;Dissolve 0.56 parts by mass of triethoxyvinylsilane (DNS-86) in 100 parts by mass of deionized water, then add 1.44 to 2.88 parts by mass of nano ZnO particles, mix and sonicate for 10 to 15 minutes; add 24 parts by mass of methyl Acrylate (MMA), 24 parts by mass of butyl acrylate (BA), 1.44 parts by mass of hexafluorobutyl methacrylate (G02), and 1.44 parts by mass of n-butanol were mixed, emulsified at high speed for 10-15 minutes, and then ultrasonicated for 10 minutes. ~15 min to get fine emulsion;
将1.44质量份过硫酸铵(APS)溶于100质量份去离子水中配制引发剂水溶液;Dissolving 1.44 parts by mass of ammonium persulfate (APS) in 100 parts by mass of deionized water to prepare an aqueous initiator solution;
将温度升至80 ℃,转速300 r/min,先将1/3体积份的引发剂水溶液加入三口烧瓶中保温10 min,后再滴加剩余的引发剂水溶液和细乳液,1.5~2 h滴加完,然后保温2 h,冷却后用纱布过滤出料,即得聚丙烯酸酯/纳米ZnO复合皮革涂饰剂。Raise the temperature to 80°C and rotate at 300 r/min, first add 1/3 volume part of the initiator aqueous solution into the three-necked flask and keep it warm for 10 minutes, then add the remaining initiator aqueous solution and fine emulsion dropwise, drop for 1.5-2 hours After adding, keep warm for 2 h, filter the material with gauze after cooling, and obtain the polyacrylate/nano-ZnO composite leather finishing agent.
本发明的内容不限于实施例所列举,本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换,均为本发明的权利要求所涵盖。The content of the present invention is not limited to the examples listed, and any equivalent transformation of the technical solution of the present invention adopted by those of ordinary skill in the art by reading the description of the present invention is covered by the claims of the present invention.
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