WO2022174555A1 - 一种高粘度自交联丙烯酸酯乳液及其制备方法 - Google Patents

一种高粘度自交联丙烯酸酯乳液及其制备方法 Download PDF

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WO2022174555A1
WO2022174555A1 PCT/CN2021/108885 CN2021108885W WO2022174555A1 WO 2022174555 A1 WO2022174555 A1 WO 2022174555A1 CN 2021108885 W CN2021108885 W CN 2021108885W WO 2022174555 A1 WO2022174555 A1 WO 2022174555A1
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initiator
sodium
methacrylate
mass ratio
preparation
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French (fr)
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朱清梅
袁业兴
黄宏存
陈招强
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海南必凯水性新材料有限公司
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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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • 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
    • C09D133/24—Homopolymers or copolymers of amides or imides

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  • the invention belongs to the technical field of acrylic emulsions, and in particular relates to a high-viscosity self-crosslinking acrylate emulsion and a preparation method thereof.
  • Acrylate polymer emulsions are widely used in the coating of PE/PP films due to their good barrier properties and environmental protection features, and there are many modified products on the market. There are very few acrylic products.
  • Chinese invention patent CN201310526726.4 discloses a low-temperature self-crosslinking acrylate emulsion with a core-shell structure, which has the characteristics of high adhesion, good water resistance, and excellent anti-blocking properties, and can be widely used in PE, PP, BOPP and other substrates.
  • Chinese invention patent CN201611159516.6 discloses a self-crosslinking acrylic emulsion for water-based metallic paint by adding diacetone acrylamide and a large amount of long-chain functional monomers to the crosslinking monomers to improve the overall performance of the emulsion, but the emulsion viscosity is low, Poor adaptability to substrates limits the scope of application.
  • the purpose of the present invention is to provide a high-viscosity self-crosslinking acrylate emulsion and a preparation method thereof.
  • the acrylate emulsion prepared by the method has higher viscosity.
  • the invention provides a kind of preparation method of high viscosity self-crosslinking acrylate emulsion, comprises the following steps:
  • the compound emulsifier is a reactive emulsifier and sodium lauryl sulfate in a mass ratio of 5-8:2-5; the reactive emulsifier is selected from the group consisting of sodium allyloxy hydroxypropyl sulfonate, 3- One or more of allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt, sodium allyl hydroxypropyl sulfonate and sodium allyl sulfonate;
  • the methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl mercaptan , the mass ratio of initiator, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 1 ⁇ 2:15 ⁇ 25:2 ⁇ 6:2 ⁇ 6:0.5 ⁇ 1:0.2 ⁇ 0.5:1 ⁇ 3:0.2 ⁇ 0.3: 0.1 to 0.2: 0.2 to 0.5: 0.02 to 0.1: 1 to 4: 50 to 80.
  • the methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl mercaptan , the mass ratio of initiator, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 1 ⁇ 2:15 ⁇ 25:2 ⁇ 6:2 ⁇ 6:0.5 ⁇ 1:0.2 ⁇ 0.5:1 ⁇ 3:0.2 ⁇ 0.3: 0.1 to 0.2: 0.2 to 0.5: 0.02 to 0.1: 1 to 4: 50 to 80.
  • the compound emulsifier is selected from the mixture of sodium allyl hydroxypropyl sulfonate and sodium lauryl sulfate with a mass ratio of 4:1;
  • the temperature is raised to 85-90°C.
  • methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl mercaptan, initiator The mass ratio of agent, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 2:25:6:6:1:0.5:3:0.3:0.2:0.5:0.1:4:51.4;
  • methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl mercaptan, initiator The mass ratio of agent, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 1.5:20:4:4:0.8:0.4:2:0.2:0.15:0.35:0.06:2.5:64.04.
  • the temperature of the heat preservation is 82-90° C., and the time of the heat preservation is 1 to 2 hours;
  • the present invention provides a high-viscosity self-crosslinking acrylate emulsion, which is prepared by the preparation method described in the above technical solution.
  • the invention provides a method for preparing a viscosity self-crosslinking acrylate emulsion, comprising the following steps: a) mixing butyl acrylate, methacrylic acid, hydroxyethyl methacrylate, lauryl methacrylate, diacetone acrylamide and Dodecyl mercaptan is mixed, 69-71 wt % of the total amount of the compound emulsifier is added, and stirring is uniform to obtain a mixed solution a; 79-81 wt % of the total initiator is dissolved with 17-19 wt % of the total amount of soft water to obtain an initiator solution; the compound emulsifier is a reactive emulsifier and sodium lauryl sulfate with a mass ratio of 5-8:2-5; the reactive emulsifier is selected from allyloxy hydroxypropyl One or more of sodium sulfonate, sodium 3-allyloxy-1-hydroxy-1-propane sulfonate
  • the emulsion prepared by the above process of the present invention has higher viscosity and better cohesion.
  • the emulsion provided by the invention can be coated on the non-woven fabric and will not penetrate into the back of the cloth; the coating has good adhesion to the cloth after coating and completely covers the pores of the cloth; the coating is soft and does not affect the Softness of non-woven fabrics.
  • the experimental results show that the viscosity of the acrylate emulsion prepared in the embodiment of the present invention is 8-900 Pa ⁇ S; the coating will not be removed by boiling at 80°C for 2 hours.
  • the invention provides a kind of preparation method of high viscosity self-crosslinking acrylate emulsion, comprises the following steps:
  • the compound emulsifier is a reactive emulsifier and sodium lauryl sulfate in a mass ratio of 5-8:2-5; the reactive emulsifier is selected from the group consisting of sodium allyloxy hydroxypropyl sulfonate, 3- One or more of allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt, sodium allyl hydroxypropyl sulfonate and sodium allyl sulfonate;
  • the methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl The mass ratio of mercaptan, initiator, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 1 ⁇ 2:15 ⁇ 25:2 ⁇ 6:2 ⁇ 6:0.5 ⁇ 1:0.2 ⁇ 0.5:1 ⁇ 3: 0.2 ⁇ 0.3: 0.1 ⁇ 0.2: 0.2 ⁇ 0.5: 0.02 ⁇ 0.1: 1 ⁇ 4: 50 ⁇ 80.
  • the methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl The mass ratio of mercaptan, initiator, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 1:15:2:2:0.5:0.2:1:0.2:0.1:0.2:0.02:1:76.78;
  • methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl mercaptan, initiator The mass ratio of agent, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 2:25:6:6:1:0.5:3:0.3:0.2:0.5:0.1:4:51.4;
  • methyl methacrylate, butyl acrylate, methacrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, lauryl methacrylate, adipic acid dihydrazide, dodecyl mercaptan, initiator The mass ratio of agent, compound emulsifier, sodium bicarbonate, ammonia water and soft water is 1.5:20:4:4:0.8:0.4:2:0.2:0.15:0.35:0.06:2.5:64.04.
  • the functional monomer methacrylic acid used in the present invention is a hydrophilic monomer, which can enhance the water solubility of the polymer. Adding an appropriate amount of methacrylic acid can introduce carboxyl groups, and in the pH value adjustment stage, the alkali thickening effect greatly improves the Viscosity and cohesion of emulsions.
  • the functional monomers hydroxyethyl methacrylate and lauryl methacrylate used in the present invention are both long-chain functional monomers, which can effectively extend the branched chain length of the polymer, increase the reaction node, and help the polymer in the formation of When the film is formed, a three-dimensional network-like three-dimensional structure is formed, thereby effectively improving the film-forming performance.
  • the invention adopts dodecyl mercaptan as the molecular weight regulator, which can control the molecular weight of the polymer and effectively prevent the gel phenomenon from occurring during the polymerization reaction; At the same time no gelling occurred. At the same time, adjusting the dosage of dodecyl mercaptan and methacrylic acid can improve the viscosity of the emulsion on the premise of ensuring the stability of the emulsion.
  • the present invention adopts the initiator as thermal initiator, preferably potassium persulfate.
  • the present invention adopts compound emulsifier as reactive emulsifier and sodium lauryl sulfate in mass ratio of 5-8:2-5; - One or more of allyloxy-1-hydroxy-1-propanesulfonic acid sodium salt, sodium allylhydroxypropylsulfonate and sodium allylsulfonate.
  • Described compound emulsifier is selected from the mixture of sodium allyl hydroxypropyl sulfonate and sodium lauryl sulfate of mass ratio 4:1; Or the allyloxy hydroxypropyl sulfonic acid that mass ratio is 7:3 A mixture of sodium and sodium dodecyl sulfonate; or a mixture of 3-allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt and sodium dodecyl sulfate in a mass ratio of 3:2.
  • the present invention adopts sodium bicarbonate as the pH value stabilizer in the reaction process, which can stabilize the pH value of the reaction system in the polymerization process, so that the reaction system is always maintained between weakly alkaline and weakly acidic.
  • the present invention adopts diacetone acrylamide and adipic acid dihydrazide as the cross-linking system, and the two react and dehydrate under weak acid conditions to form hydrazone.
  • the carbonyl reaction of diacetone acrylamide on different molecular chains closely links the two molecular chains together. Controlling the addition amount of ketohydrazine can make the molecular chains of the emulsion form a close connection during film formation, forming a dense coating with an orderly structure.
  • Floor is controlled by controlling the addition amount of ketohydrazine.
  • the present invention uses ammonia water as a pH value regulator, adjusts the pH of the emulsion from weak acid to alkaline after the emulsion reaction is completed, and increases the viscosity of the emulsion through the action of alkali thickening.
  • the emulsion system is transformed into weak acid during the film-forming process, which is beneficial to the occurrence of the keto-hydrazine cross-linking reaction.
  • the prepared mixed solution a is used as the shell layer raw material liquid, wherein the butyl acrylate used has a lower glass transition temperature T g , and is used as the main monomer of the shell layer; the mixed solution b is used as the core layer raw material liquid, which adopts Methyl methacrylate with a higher glass transition temperature T g is used as the main monomer of the core layer to prepare a core-shell acrylate polymer emulsion with a soft shell and a hard core to improve the overall performance of the film.
  • the temperature of the heat preservation is 82-90° C., and the time of heat preservation is 1-2 hours; and then ammonia water is added at 82-85° C.
  • the present invention provides a high-viscosity self-crosslinking acrylate emulsion, which is prepared by the preparation method described in the above technical solution.
  • the high-viscosity self-crosslinking acrylate emulsion provided by the present invention does not need to add a thickener, and has better viscosity than the self-crosslinking acrylic emulsion with low viscosity currently on the market needs to add a thickener.
  • step (a) Slowly add the prepared monomer and initiator solution in the step (a) dropwise into the reaction kettle, after 3-5h dripping, keep a uniform speed during the dripping; after the dripping is completed, keep the temperature for 1h, and the temperature during the insulation is 88 °C;
  • the present invention carries out performance test to the emulsion prepared by above-mentioned embodiment and comparative example, and the results are shown in Table 3:
  • the present invention provides a method for preparing a high-viscosity self-crosslinking acrylate emulsion, comprising the following steps: a) mixing butyl acrylate, methacrylic acid, hydroxyethyl methacrylate, and lauryl methacrylate Mix the ester, diacetone acrylamide and dodecyl mercaptan, add 69-71 wt % of the total amount of the compound emulsifier, stir evenly, and obtain a mixed solution a; use 17-19 wt % of the total amount of soft water to make the total initiator 79-81wt% of the amount of emulsifier is dissolved to obtain an initiator solution; the compound emulsifier is a reactive emulsifier and sodium lauryl sulfate in a mass ratio of 5-8:2-5; the reactive emulsifier is selected from One of sodium allyloxy hydroxypropyl sulfonate, sodium
  • the adipic acid dihydrazide solution was added and stirred to obtain a self-crosslinking acrylate emulsion.
  • the emulsion prepared by the above process of the present invention has higher viscosity and better cohesion.
  • the emulsion provided by the present invention can be coated on the non-woven fabric and will not penetrate into the back of the cloth; the coating has good adhesion to the cloth after coating and completely covers the pores of the cloth; the coating is soft and does not affect the Softness of non-woven fabrics.
  • the experimental results show that the viscosity of the acrylate emulsion prepared in the embodiment of the present invention is 8-900 Pa ⁇ S; the coating will not be removed by boiling at 80°C for 2 hours.

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Abstract

本发明提供了一种高粘度自交联丙烯酸酯乳液的制备方法，包括：a)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂，搅拌均匀，得到混合溶液a；用软水将引发剂溶解，得到引发剂溶液；b)将软水、甲基丙烯酸甲酯、引发剂、复配乳化剂和碳酸氢钠混合，搅拌条件下升温，保温，得到混合溶液b；c)将混合溶液a和引发剂溶液滴加到所述混合溶液b中，滴加完毕后保温，然后加入氨水，搅拌均匀，降温再加入己二酸二酰肼溶液，搅拌，得到自交联丙烯酸酯乳液。本发明通过上述工艺制备的乳液具有较高的粘度，内聚力较好；涂布后涂层对布的附着力很好且完全覆盖住布的孔隙。

Description

一种高粘度自交联丙烯酸酯乳液及其制备方法
本申请要求于2021年02月22日提交中国专利局、申请号为202110196438.1、发明名称为“一种高粘度自交联丙烯酸酯乳液及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于丙烯酸乳液技术领域，尤其涉及一种高粘度自交联丙烯酸酯乳液及其制备方法。
背景技术
丙烯酸酯聚合乳液因具有良好的阻隔性和其环保的特点，广泛应用于PE/PP薄膜的涂布且市场上多有改性产品，但是目前市场上关于应用于无纺布上直接进行涂布的丙烯酸产品非常少。
中国发明专利CN201310526726.4公开的一种核壳结构的低温自交联丙烯酸酯乳液具有附着力高、耐水性好、抗粘连性优异等特点，可广泛适用于PE、PP、BOPP等基材，但是由于乳液粘度低、乳液内聚力较差的原因，无法适用于无纺布上进行涂布。中国发明专利CN201611159516.6公开的一种水性金属漆用自交联丙烯酸乳液在交联单体中加入双丙酮丙烯酰胺和大量长链功能性单体，提高乳液的综合性能，但是乳液粘度低，对基材适应性差限制了应用范围。
发明内容
有鉴于此，本发明的目的在于提供一种高粘度自交联丙烯酸酯乳液及其制备方法，该方法制备的丙烯酸酯乳液具有较高的粘度。
本发明提供了一种高粘度自交联丙烯酸酯乳液的制备方法，包括以下步骤:
a)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂总量的69～71wt％，搅拌均匀，得到混合溶液a；用软水总量的17～19wt％将引发剂总量的79～81wt％溶解，得到引发剂溶液；
所述复配乳化剂为质量比5～8:2～5的反应性乳化剂和十二烷基硫酸钠；所述反应性乳化剂选自烯丙氧基羟丙基磺酸钠、3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐、烯丙基羟丙基磺酸钠和烯丙基磺酸钠中的一种或多种；
b)将软水总量的79～81wt％、甲基丙烯酸甲酯、引发剂总量的19～21％、复配乳化剂总量的29～31wt％和碳酸氢钠混合，搅拌条件下升温，保温，得到混合溶液b；
c)将混合溶液a和引发剂溶液滴加到所述混合溶液b中，滴加完毕后保温，然后加入氨水，搅拌均匀，降温至50℃以下再加入乙二酸二酰肼溶液，搅拌，得到自交联丙烯酸酯乳液。
优选地，所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1～2：15～25：2～6：2～6：0.5～1：0.2～0.5：1～3：0.2～0.3：0.1～0.2：0.2～0.5：0.02～0.1：1～4：50～80。
优选地，所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1～2：15～25：2～6：2～6：0.5～1：0.2～0.5：1～3：0.2～0.3：0.1～0.2：0.2～0.5：0.02～0.1：1～4：50～80。
优选地，所述复配乳化剂选自质量比4:1的烯丙基羟丙基磺酸钠和十二烷基硫酸钠的混合物；
或质量比为7:3的烯丙氧基羟丙基磺酸钠和十二烷基磺酸钠的混合物；
或质量比为3:2的3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐和十二烷基硫酸钠的混合物。
优选地，所述步骤b)中升温至85～90℃。
优选地，所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1:15:2:2:0.5:0.2:1:0.2:0.1:0.2:0.02:1:76.78；
或所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、 复配乳化剂、碳酸氢钠、氨水和软水的质量比为2:25:6:6:1:0.5:3:0.3:0.2:0.5:0.1:4:51.4；
或所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1.5:20:4:4:0.8:0.4:2:0.2:0.15:0.35:0.06:2.5:64.04。
优选地，所述步骤c)中滴加完毕后保温的温度为82～90℃，保温的时间为1～2h；
然后在82～85℃下加入氨水。
本发明提供了一种高粘度自交联丙烯酸酯乳液，由上述技术方案所述制备方法制得。
本发明提供了一种粘度自交联丙烯酸酯乳液的制备方法，包括以下步骤：a)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂总量的69～71wt％，搅拌均匀，得到混合溶液a；用软水总量的17～19wt％将引发剂总量的79～81wt％溶解，得到引发剂溶液；所述复配乳化剂为质量比5～8:2～5的反应性乳化剂和十二烷基硫酸钠；所述反应性乳化剂选自烯丙氧基羟丙基磺酸钠、3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐、烯丙基羟丙基磺酸钠和烯丙基磺酸钠中的一种或多种；b)将软水总量的79～81wt％、甲基丙烯酸甲酯、引发剂总量的19～21％、复配乳化剂总量的29～31wt％和碳酸氢钠混合，搅拌条件下升温，保温，得到混合溶液b；c)将混合溶液a和引发剂溶液滴加到所述混合溶液b中，滴加完毕后保温，然后加入氨水，搅拌均匀，降温至50℃以下再加入己二酸二酰肼溶液，搅拌，得到自交联丙烯酸酯乳液。本发明通过上述工艺制备的乳液具有较高的粘度，内聚力较好。本发明提供的乳液能够在无纺布上进行涂布且不会渗透到布的背面；涂布后涂层对布的附着力很好且完全覆盖住布的孔隙；涂层柔软，不会影响无纺布的柔软性。实验结果表明：本发明实施例制备的丙烯酸酯乳液的粘度为8～900Pa·S；80℃下水煮2h不脱涂层。
具体实施方式
本发明提供了一种高粘度自交联丙烯酸酯乳液的制备方法，包括以下步 骤：
a)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂总量的69～71wt％，搅拌均匀，得到混合溶液a；用软水总量的17～19wt％将引发剂总量的79～81wt％溶解，得到引发剂溶液；
所述复配乳化剂为质量比5～8:2～5的反应性乳化剂和十二烷基硫酸钠；所述反应性乳化剂选自烯丙氧基羟丙基磺酸钠、3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐、烯丙基羟丙基磺酸钠和烯丙基磺酸钠中的一种或多种；
b)将软水总量的79～81wt％、甲基丙烯酸甲酯、引发剂总量的19～21％、复配乳化剂总量的29～31wt％和碳酸氢钠混合，搅拌条件下升温，保温，得到混合溶液b；
c)将混合溶液a和引发剂溶液滴加到所述混合溶液b中，滴加完毕后保温，然后加入氨水，搅拌均匀，降温至50℃以下再加入己二酸二酰肼溶液，搅拌，得到自交联丙烯酸酯乳液。
在本发明中，所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1～2：15～25：2～6：2～6：0.5～1：0.2～0.5：1～3：0.2～0.3：0.1～0.2：0.2～0.5：0.02～0.1：1～4：50～80。具体实施例中，所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1:15:2:2:0.5:0.2:1:0.2:0.1:0.2:0.02:1:76.78；
或所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为2:25:6:6:1:0.5:3:0.3:0.2:0.5:0.1:4:51.4；
或所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为 1.5:20:4:4:0.8:0.4:2:0.2:0.15:0.35:0.06:2.5:64.04。
本发明采用的功能性单体甲基丙烯酸为亲水性单体，能够增强聚合物的水溶性，加入适量的甲基丙烯酸能够引入羧基，在pH值调节阶段通过碱增稠作用，极大地提高乳液的粘度和内聚力。
本发明采用的功能性单体甲基丙烯酸羟乙酯和甲基丙烯酸月桂酯均为长链功能性单体，其能够有效扩展聚合物的支链长度，增加反应节点，有利于聚合物在成膜时形成三维网状的立体结构，从而有效提升成膜性能。
本发明采用十二烷基硫醇作为分子量调节剂，能够控制聚合物分子量，有效防止聚合反应时发生凝胶现象；特别地，在制备高粘度产品时能够使乳液具有超高粘度和强内聚力的同时不发生凝胶。同时调整十二烷基硫醇和甲基丙烯酸的用量能够实现在保证乳液稳定性的前提下提高乳液粘度。
本发明采用引发剂为热引发剂，优选为过硫酸钾。
本发明采用复配乳化剂为质量比5～8:2～5的反应型乳化剂和十二烷基硫酸钠；所述反应型乳化剂选自烯丙氧基羟丙基磺酸钠、3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐、烯丙基羟丙基磺酸钠和烯丙基磺酸钠中的一种或多种。所述复配乳化剂选自质量比4:1的烯丙基羟丙基磺酸钠和十二烷基硫酸钠的混合物；或质量比为7:3的烯丙氧基羟丙基磺酸钠和十二烷基磺酸钠的混合物；或质量比为3:2的3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐和十二烷基硫酸钠的混合物。
本发明采用碳酸氢钠作为反应过程的pH值稳定剂，能够稳定聚合过程中反应体系的pH值，使得反应体系始终维持在弱碱性到弱酸性之间。
本发明采用双丙酮丙烯酰胺和己二酸二酰肼作为交联体系，二者在弱酸性条件下反应脱水生成腙，特别的，一个己二酸二酰肼分子在乳液成膜时会和两个不同分子链上的双丙酮丙烯酰胺的羰基反应，从而将两个分子链紧密联系在一起，控制酮肼的添加量能够使乳液成膜时各个分子链间紧密连接，形成结构有序的致密涂层。
本发明采用氨水作为pH值调节剂，在乳液反应完成后将乳液pH由弱酸性调节至碱性，通过碱增稠作用使得乳液粘度变大，特别的，在乳液成膜时氨水会快速挥发，使得成膜过程中乳液体系转变为弱酸性，有利于酮肼交联反应的发生。
本发明将制备的混合溶液a作为壳层原料液，其中采用的丙烯酸丁酯的玻璃化转变温度T g较低，作为壳层的主单体；混合溶液b中作为核层原料液，其中采用玻璃化转变温度T g较高的甲基丙烯酸甲酯，作为核层的主单体，制备软壳硬核的核壳丙烯酸酯聚合乳液，提高成膜的综合性能。
在本发明中，所述步骤c)中滴加完毕后保温的温度为82～90℃，保温的时间为1～2h；然后在82～85℃下加入氨水。
本发明提供了一种高粘度自交联丙烯酸酯乳液，由上述技术方案所述制备方法制得。
本发明提供的高粘度自交联丙烯酸酯乳液无需外加增稠剂，与目前市场上粘度低的自交联丙烯酸乳液需要额外增加增稠剂相比，粘度更优异。
为了进一步说明本发明，下面结合实施例对本发明提供的一种高粘度自交联丙烯酸酯乳液及其制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1～3和对比例1～3
按照表1中物料的种类和用量采用下述工艺制备丙烯酸酯乳液：
a)先将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂的70％，搅拌均匀后备用；用软水总量的18％，将引发剂总量的80％溶解，备用；
b)将软水总量的80％、甲基丙烯酸甲酯、引发剂和复配乳化剂的30％和碳酸氢钠加入反应釜内，搅拌速度为300r/min，待温度升至88℃，保温30min；
c)将步骤(a)中已配置好的单体和引发剂溶液缓慢滴加入反应釜内，3-5h滴完，滴加时保持匀速；滴加完毕后，保温1h，保温时温度为88℃；
d)保温结束后，控制温度在82℃，加入氨水，搅拌10min；
e)降温至50℃以下，用软水总量的2％溶解己二酸二酰肼并加入反应釜中，搅拌10min，过滤出料，得到自交联丙烯酸酯乳液。
表1 实施例1～3和对比例1～3采用的物料种类和用量
Figure PCTCN2021108885-appb-000001
Figure PCTCN2021108885-appb-000002
表2 实施例1～3和对比例1～3采用的复配乳化剂
Figure PCTCN2021108885-appb-000003
本发明对上述实施例和对比例制备的乳液进行性能测试，结果见表3：
表3 实施例和对比例制备的乳液的性能测试结果
Figure PCTCN2021108885-appb-000004
由以上实施例可知，本发明提供了一种高粘度自交联丙烯酸酯乳液的制备 方法，包括以下步骤：a)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂总量的69～71wt％，搅拌均匀，得到混合溶液a；用软水总量的17～19wt％将引发剂总量的79～81wt％溶解，得到引发剂溶液；所述复配乳化剂为质量比5～8:2～5的反应性乳化剂和十二烷基硫酸钠；所述反应性乳化剂选自烯丙氧基羟丙基磺酸钠、3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐、烯丙基羟丙基磺酸钠和烯丙基磺酸钠中的一种或多种；b)将软水总量的79～81wt％、甲基丙烯酸甲酯、引发剂总量的19～21％、复配乳化剂总量的29～31wt％和碳酸氢钠混合，搅拌条件下升温，保温，得到混合溶液b；c)将混合溶液a和引发剂溶液滴加到所述混合溶液b中，滴加完毕后保温，然后加入氨水，搅拌均匀，降温至50℃以下再加入己二酸二酰肼溶液，搅拌，得到自交联丙烯酸酯乳液。本发明通过上述工艺制备的乳液具有较高的粘度，内聚力较好。本发明提供的乳液能够在无纺布上进行涂布且不会渗透到布的背面；涂布后涂层对布的附着力很好且完全覆盖住布的孔隙；涂层柔软，不会影响无纺布的柔软性。实验结果表明：本发明实施例制备的丙烯酸酯乳液的粘度为8～900Pa·S；80℃下水煮2h不脱涂层。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (7)

  1. 一种高粘度自交联丙烯酸酯乳液的制备方法，包括以下步骤:
    a)将丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、双丙酮丙烯酰胺和十二烷基硫醇进行混合，加入复配乳化剂总量的69～71wt％，搅拌均匀，得到混合溶液a；用软水总量的17～19wt％将引发剂总量的79～81wt％溶解，得到引发剂溶液；
    所述复配乳化剂为质量比5～8:2～5的反应性乳化剂和十二烷基硫酸钠；所述反应性乳化剂选自烯丙氧基羟丙基磺酸钠、3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐、烯丙基羟丙基磺酸钠和烯丙基磺酸钠中的一种或多种；
    b)将软水总量的79～81wt％、甲基丙烯酸甲酯、引发剂总量的19～21％、复配乳化剂总量的29～31wt％和碳酸氢钠混合，搅拌条件下升温，保温，得到混合溶液b；
    c)将混合溶液a和引发剂溶液滴加到所述混合溶液b中，滴加完毕后保温，然后加入氨水，搅拌均匀，降温至50℃以下再加入己二酸二酰肼溶液，搅拌，得到自交联丙烯酸酯乳液。
  2. 根据权利要求1所述的制备方法，其特征在于，所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1～2：15～25：2～6：2～6：0.5～1：0.2～0.5：1～3：0.2～0.3：0.1～0.2：0.2～0.5：0.02～0.1：1～4：50～80。
  3. 根据权利要求1所述的制备方法，其特征在于，所述复配乳化剂选自质量比4:1的烯丙基羟丙基磺酸钠和十二烷基硫酸钠的混合物；
    或质量比为7:3的烯丙氧基羟丙基磺酸钠和十二烷基磺酸钠的混合物；
    或质量比为3:2的3-烯丙氧基-1-羟基-1-丙烷磺酸钠盐和十二烷基硫酸钠的混合物。
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤b)中升温至85～90℃。
  5. 根据权利要求1所述的制备方法，其特征在于，所述甲基丙烯酸甲酯、 丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1:15:2:2:0.5:0.2:1:0.2:0.1:0.2:0.02:1:76.78；
    或所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为2:25:6:6:1:0.5:3:0.3:0.2:0.5:0.1:4:51.4；
    或所述甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、双丙酮丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸月桂酯、己二酸二酰肼、十二烷基硫醇、引发剂、复配乳化剂、碳酸氢钠、氨水和软水的质量比为1.5:20:4:4:0.8:0.4:2:0.2:0.15:0.35:0.06:2.5:64.04。
  6. 根据权利要求1所述的制备方法，其特征在于，所述步骤c)中滴加完毕后保温的温度为82～90℃，保温的时间为1～2h；
    然后在82～85℃下加入氨水。
  7. 一种高粘度自交联丙烯酸酯乳液，由权利要求1～6任一项所述制备方法制得。
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