技术领域technical field
本发明属于皮革涂饰高分子材料生产技术领域，具体涉及一种侧链为重复乙氧基结构的非离子型水性聚氨酯-聚丙烯酸酯复合乳液的制备方法。The invention belongs to the technical field of production of leather finishing polymer materials, and in particular relates to a preparation method of a nonionic water-based polyurethane-polyacrylate composite emulsion whose side chain is a repeating ethoxyl structure.
背景技术Background technique
水性聚氨酯以其低VOC含量和优异的性能在涂料、粘合剂、皮革涂饰及油墨等领域得到广泛应用。聚氨酯在水中的分散是通过外乳化法或者内乳化法实现的。外乳化法由于工艺控制严格、乳液稳定性较差、易沉淀、涂膜耐水性很差而很少使用。内乳化法制备的聚氨酯乳液根据亲水单体的种类又可分为离子型和非离子型。离子型水性聚氨酯乳液，由于在分子结构上引入离子基团，因此乳液对酸碱、电解质和低温相对敏感，而且中和剂三乙胺常常使得乳液带有氨味，而正是由于树脂的离子性，使树脂只能与非离子或与自身相同离子性的树脂或颜料色浆复配，限制了离子型树脂的使用范围。而非离子型树脂由于本身无离子倾向，既可以和阴离子材料复配，也可以和阳离子材料复配，在复配树脂时，具有广泛的适用性，能够弥补离子型树脂的缺点。非离子聚氨酯往往通过在主链或者侧链上引入重复的氧化乙烯单元而达到亲水的目的。中国专利CN200910144800.X提出一种制备侧链非离子型水性聚氨酯乳液的方法，是在干燥氮气保护下，将低聚物多元醇，异氰酸酯加入反应容器中，在机械搅拌下控制温度在80℃-100℃下进行反应2-3小时后，降低体系温度至40℃-60℃，加入扩链剂、带有重复乙氧基的亲水性扩链剂、交联剂、溶剂及催化剂，继续反应，待反应生成的预聚体中异氰酸酯基-NCO含量不再变化，再降温至室温，在高速分散下加水进行乳化，并将其减压蒸馏脱去溶剂，即得侧链非离子型水性聚氨酯乳液。制备的侧链非离子型水性聚氨酯乳液具有高固含量和低粘度，优异的乳液稳定性，较好的耐水解性，优异的耐电解质、耐酸、耐碱性，可用于织物整理用涂层剂及皮革涂饰剂。Waterborne polyurethane has been widely used in the fields of coatings, adhesives, leather finishing and inks due to its low VOC content and excellent performance. The dispersion of polyurethane in water is achieved by external emulsification or internal emulsification. The external emulsification method is rarely used due to strict process control, poor emulsion stability, easy precipitation, and poor water resistance of the coating film. The polyurethane emulsion prepared by internal emulsification can be divided into ionic type and nonionic type according to the type of hydrophilic monomer. Ionic water-based polyurethane emulsion, due to the introduction of ionic groups in the molecular structure, the emulsion is relatively sensitive to acid, alkali, electrolyte and low temperature, and the neutralizer triethylamine often makes the emulsion smell of ammonia, and it is precisely because of the resin's ionic So that the resin can only be compounded with non-ionic or the same ionic resin or pigment paste as itself, which limits the scope of use of ionic resins. Since the non-ionic resin itself has no ionic tendency, it can be compounded with anionic materials or cationic materials. When compounding resins, it has wide applicability and can make up for the shortcomings of ionic resins. Nonionic polyurethanes often achieve hydrophilicity by introducing repeating oxyethylene units into the main chain or side chains. Chinese patent CN200910144800.X proposes a method for preparing side-chain non-ionic water-based polyurethane emulsion, which is to add oligomer polyol and isocyanate into the reaction vessel under the protection of dry nitrogen, and control the temperature at 80°C- After reacting at 100°C for 2-3 hours, lower the system temperature to 40°C-60°C, add chain extender, hydrophilic chain extender with repeated ethoxy groups, crosslinking agent, solvent and catalyst, and continue the reaction , the content of isocyanate group-NCO in the prepolymer produced by the reaction will not change, then cool down to room temperature, add water to emulsify under high-speed dispersion, and distill it under reduced pressure to remove the solvent, that is, the side chain non-ionic water-based polyurethane lotion. The prepared side chain non-ionic water-based polyurethane emulsion has high solid content and low viscosity, excellent emulsion stability, good hydrolysis resistance, excellent resistance to electrolyte, acid and alkali, and can be used as a coating agent for fabric finishing and leather finishes.
但由于该方法制备的树脂是单纯的聚氨酯树脂，因此无法避免水性聚氨酯固有的耐水耐候性、压花定型性等缺点。However, since the resin prepared by this method is a pure polyurethane resin, the inherent water-resistant and weather-resistant properties of water-based polyurethane, embossing and other shortcomings cannot be avoided.
聚丙烯酸酯易溶于丙酮、乙酸乙酯、苯及二氯甲烷，而不溶于水。聚丙烯酸酯能形成光泽好而耐水的膜，具有优异的耐候性、耐化学品性及高的硬度和光泽，但耐磨性、耐寒性和粘附性较差，抗拉强度不高，可用作压敏性粘结剂和热敏性粘结剂。可以看出，聚氨酯和丙烯酸酯各有优缺点，聚氨酯具有优异的弹性、耐磨性、韧性、附着力和出众的耐低温曲挠性，但在耐候性、耐水性、耐碱性和压花定型性方面存在不足；而聚丙烯酸酯具有优良的耐候性、耐水性、耐碱性和压花定型性，但弹性和耐磨性差、热粘冷脆。因此，为了弥补两种树脂的缺点，人们将这两种树脂加以复合，以发挥两者的优点。目前与聚氨酯-聚丙烯酸酯复合乳液相关的专利申请主要有：Polyacrylate is easily soluble in acetone, ethyl acetate, benzene and methylene chloride, but insoluble in water. Polyacrylate can form a glossy and water-resistant film with excellent weather resistance, chemical resistance, high hardness and gloss, but poor wear resistance, cold resistance and adhesion, and low tensile strength. Used as pressure sensitive adhesive and heat sensitive adhesive. It can be seen that polyurethane and acrylic have their own advantages and disadvantages. Polyurethane has excellent elasticity, abrasion resistance, toughness, adhesion and outstanding low-temperature flexibility, but it is not good in weather resistance, water resistance, alkali resistance and embossing. There are deficiencies in setting performance; while polyacrylate has excellent weather resistance, water resistance, alkali resistance and embossing setting performance, but has poor elasticity and wear resistance, and is hot-sticky and brittle. Therefore, in order to make up for the shortcomings of the two resins, people compound the two resins to take advantage of both. At present, the patent applications related to polyurethane-polyacrylate composite emulsion mainly include:
1、申请号200480020225.8，发明名称“水性自交联聚氨酯分散体和聚氨酯：丙烯酸类混杂分散体”，涉及一种包含作为单独颗粒或作为复合颗粒的官能化聚氨酯聚合物(A)和官能化乙烯基聚合物(B)的混杂聚合物分散体，其中聚氨酯聚合物在高沸点氧化的聚结溶剂中制备，所述溶剂不含有与异氰酸酯反应的官能团并且在水分散之后仍保留。其丙烯酸类混杂分散体通过共混的方式将聚氨酯和聚丙烯酸酯复合，但该方法制得的复合乳液中聚氨酯和聚丙烯酸酯相互增强的协同效应不够，且共混的稳定性差。1. Application No. 200480020225.8, title of invention "waterborne self-crosslinking polyurethane dispersion and polyurethane:acrylic hybrid dispersion", relates to a functionalized polyurethane polymer (A) and functionalized ethylene as separate particles or as composite particles A hybrid polymer dispersion of the base polymer (B), wherein the polyurethane polymer is prepared in a high-boiling oxygenated coalescing solvent that does not contain isocyanate-reactive functional groups and remains after aqueous dispersion. Its acrylic hybrid dispersion composites polyurethane and polyacrylate by blending, but the synergistic effect of mutual reinforcement between polyurethane and polyacrylate in the composite emulsion prepared by this method is not enough, and the stability of blending is poor.
2、中国专利CN200310112355.1，涉及一种丙烯酸酯化聚氨酯为核主体的核壳粒子及其制法和应用。该核壳粒子，以丙烯酸酯化聚氨酯单体与丙烯酸酯类软单体的共聚物为核，再往外接枝上丙烯酸酯类硬单体为壳。其制法包括如下步骤：1)、制备丙烯酸酯化聚氨酯；2)、再乳化，得到水性的丙烯酸酯化聚氨酯乳液；3)、A：在上述乳液中加入丙烯酸酯类软单体，反应得种子乳液；B：在上述种子乳液中加入丙烯酸酯类硬单体反应得核壳乳液；4)、用氯化钠饱和溶液破乳，冷冻，抽滤，洗涤，干燥，研磨，得丙烯酸酯化聚氨酯为核主体的核壳粒子。核壳粒子可用作环氧树脂中增韧剂不会导致玻璃化转变温度较大幅度降低，与环氧树脂具有良好的界面相容性，且制法具环保性。即通过种子乳液聚合法制备水性聚氨酯-丙烯酸酯乳液，以用于环氧树脂的改性。该方法主要是用于制备阴离子聚氨酯-丙烯酸酯复合乳液。2. Chinese patent CN200310112355.1, which relates to a core-shell particle with acrylated polyurethane as the main core and its preparation method and application. The core-shell particle uses the copolymer of acrylated polyurethane monomer and acrylate soft monomer as the core, and then grafts the acrylate hard monomer as the shell. The preparation method includes the following steps: 1), preparing acrylated polyurethane; 2), re-emulsifying to obtain water-based acrylated polyurethane emulsion; 3), A: adding acrylate soft monomer to the above emulsion, and reacting to obtain Seed emulsion; B: add acrylate hard monomer to the above seed emulsion to react to obtain core-shell emulsion; 4), use saturated sodium chloride solution to demulsify, freeze, filter with suction, wash, dry, and grind to obtain acrylated Polyurethane is a core-shell particle with the core host. The core-shell particle can be used as a toughening agent in epoxy resin without causing a large decrease in glass transition temperature, has good interfacial compatibility with epoxy resin, and the preparation method is environmentally friendly. That is, the aqueous polyurethane-acrylate emulsion was prepared by seed emulsion polymerization for the modification of epoxy resin. The method is mainly used to prepare anionic polyurethane-acrylate composite emulsion.
以上专利信息显示，上述两种方法制备的树脂都为离子型乳液，且主要为阴离子体系，在皮革特别是鞋面革封底所用的阳离子体系中的复配稳定性较差。因此有必要合成一种与离子型树脂、助剂等复配性好，同时具有非离子性和复合特性，且兼具聚氨酯和丙烯酸酯优点的皮革用非离子性聚氨酯-丙烯酸酯复合乳液。The above patent information shows that the resins prepared by the above two methods are both ionic emulsions, which are mainly anionic systems, and have poor compounding stability in cationic systems used in leather, especially shoe leather back covers. Therefore, it is necessary to synthesize a nonionic polyurethane-acrylate composite emulsion for leather that has good compatibility with ionic resins, auxiliary agents, etc., has nonionic and composite properties, and has the advantages of both polyurethane and acrylate.
发明内容Contents of the invention
本发明的目的在于提供一种非离子型水性聚氨酯-聚丙烯酸酯复合乳液的制备方法，由该方法制得的复合乳液具有稳定性好，耐酸碱和电解质，压花定型性好的特点，尤其适用于做皮革涂饰剂。The object of the present invention is to provide a kind of preparation method of nonionic water-based polyurethane-polyacrylate composite emulsion, the composite emulsion prepared by the method has good stability, acid and alkali resistance and electrolyte, embossing good characteristics of setting property, Especially suitable for leather finishing agent.
为实现上述发明目的，本发明采用的技术方案如下：For realizing above-mentioned purpose of the invention, the technical scheme that the present invention adopts is as follows:
一种皮革涂饰用非离子型水性聚氨酯-聚丙烯酸酯复合乳液的制备方法，其特征在于工艺步骤如下：A kind of preparation method of nonionic water-based polyurethane-polyacrylate composite emulsion for leather finishing, it is characterized in that process steps are as follows:
1）丙烯酸酯-聚氨酯种子乳液的制备1) Preparation of acrylate-polyurethane seed emulsion
A将聚合物二元醇预先真空脱水处理，取25～42份，再取二异氰酸酯10～20份、非离子亲水扩链剂23～29份、催化剂0.06～0.2份加入反应容器中，在机械搅拌下，于70～100℃反应2～5小时；A Pre-vacuum dehydration treatment of polymer diol, take 25-42 parts, and then take 10-20 parts of diisocyanate, 23-29 parts of non-ionic hydrophilic chain extender, 0.06-0.2 parts of catalyst and add them to the reaction container. Under mechanical stirring, react at 70-100°C for 2-5 hours;
B将步骤A的反应物冷却至室温，加入丙烯酸酯单体19～29份、溶剂10～15份，搅拌15～30分钟，使预聚物溶解降粘；B Cool the reactant in step A to room temperature, add 19-29 parts of acrylate monomer, 10-15 parts of solvent, and stir for 15-30 minutes to dissolve the prepolymer and reduce the viscosity;
C在高剪切力作用下，加10℃以下的去离子水240份，乳化5～20分钟；C. Under the action of high shear force, add 240 parts of deionized water below 10°C and emulsify for 5-20 minutes;
D最后加入含小分子胺类扩链剂0.12～3份的水溶液10～25份，继续搅拌1～2小时，即得到丙烯酸酯-聚氨酯种子乳液；D Finally, add 10 to 25 parts of an aqueous solution containing 0.12 to 3 parts of a small molecule amine chain extender, and continue stirring for 1 to 2 hours to obtain an acrylate-polyurethane seed emulsion;
2）聚氨酯-聚丙烯酸酯复合乳液的制备2) Preparation of polyurethane-polyacrylate composite emulsion
取步骤1）的D步骤制备的种子乳液，通入保护氮气，升温至70～90℃，滴加由0.05～0.15份引发剂溶于48份水组成的水溶液，并在2小时内滴加完毕，继续保温2～3小时，即得到聚氨酯-聚丙烯酸酯复合乳液产品。Take the seed emulsion prepared in step D of step 1), pass through protective nitrogen, heat up to 70-90°C, add dropwise an aqueous solution consisting of 0.05-0.15 parts of initiator dissolved in 48 parts of water, and complete the dropwise addition within 2 hours , and continue to keep warm for 2 to 3 hours to obtain a polyurethane-polyacrylate composite emulsion product.
在步骤A中In step A
所述的聚合物二元醇为聚氧化丙烯二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚酯二元醇中的一种或几种，数均分子量为1000～4000。The polymer diol is one or more of polyoxypropylene diol, polycarbonate diol, polycaprolactone diol, polyester diol, and the number average molecular weight is 1000～ 4000.
所述的二异氰酸酯为异佛尔酮二异氰酸酯（IPDI）、1，6-六亚甲基二异氰酸酯（HDI）、4，4-二环己基甲烷二异氰酸酯（HMDI）、环己烷二亚甲基二异氰酸酯、甲苯二异氰酸酯（TDI）、二苯基甲烷二异氰酸酯（MDI）、1，5-萘二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二甲基二异氰酸酯中的一种或几种。The diisocyanate is isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate (HMDI), cyclohexane dimethylene One of diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate or several.
所述的非离子亲水扩链剂是指三羟甲基丙烷聚乙二醇单甲醚，数均分子量为1000～2000，结构式如下：The non-ionic hydrophilic chain extender refers to trimethylolpropane polyethylene glycol monomethyl ether, the number average molecular weight is 1000-2000, and the structural formula is as follows:
所述的催化剂选择有机锡类催化剂或有机铋类催化剂，有机锡类催化剂包括二丁基二醋酸锡、二烷基锡二马来酸酯、二月桂酸二丁基锡或辛酸亚锡等；有机铋类催化剂选自美国领先化学品公司生产的BiCAT有机铋聚氨酯系列催化剂，如BiCAT88%Bi8%Zn，BiCATZ19%Zn，BiCAT811816%Bi，BiCAT322822%Zn，BiCAT810820%Bi，BiCAT822024%Bi，BiCAT810620%Bi，BiCATH28%Bi等。The catalyst is selected from organic tin catalysts or organic bismuth catalysts, and the organic tin catalysts include dibutyltin diacetate, dialkyltin dimaleate, dibutyltin dilaurate or stannous octoate, etc.; organic bismuth The catalysts are selected from BiCAT organic bismuth polyurethane series catalysts produced by leading American chemical companies, such as BiCAT88%Bi8%Zn, BiCATZ19%Zn, BiCAT811816%Bi, BiCAT322822%Zn, BiCAT810820%Bi, BiCAT822024%Bi, BiCAT810620%Bi, BiCATH28 %Bi and so on.
在步骤B中in step B
所述的丙烯酸酯单体为甲基丙烯酸的C1～C18酯、丙烯酸的C1～C18酯、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、乙二醇二甲基丙烯酸酯或乙二醇二丙烯酸酯中的一种或其任意组合。The acrylate monomers are C1-C18 esters of methacrylic acid, C1-C18 esters of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol One or any combination of alcohol dimethacrylate or ethylene glycol diacrylate.
所述的溶剂为丙酮或丁酮。Described solvent is acetone or butanone.
步骤D中所述的小分子胺类扩链剂为水合肼、乙二胺、丁二胺、己二胺、异佛尔二胺（IPDA）、二亚甲基胺基苯（Xylenediamine）、聚醚二胺、二乙烯三胺或三乙烯四胺中的一种或几种。The small molecule amine chain extenders described in step D are hydrazine hydrate, ethylenediamine, butylenediamine, hexamethylenediamine, isophordiamine (IPDA), xylenediamine, poly One or more of ether diamine, diethylene triamine or triethylene tetramine.
步骤2）中所述的引发剂为过硫酸钾、过硫酸钠或过硫酸铵等。The initiator described in step 2) is potassium persulfate, sodium persulfate or ammonium persulfate, etc.
特别说明，本发明各组分的含量均为质量份数。In particular, the content of each component in the present invention is in parts by mass.
本发明的有益技术效果主要体现在以下几个方面：The beneficial technical effects of the present invention are mainly reflected in the following aspects:
1、本发明在皮革涂饰领域首次提出了一种利用种子乳液聚合法制备用于非离子型聚氨酯-聚丙烯酸酯复合乳液的方法。本发明通过在非离子聚氨酯乳液中引入聚丙烯酸酯进行互穿聚合，得到的乳液在力学性能上兼具聚氨酯树脂和丙烯酸树脂的双重优点，即干膜具有较好的力学性能，还具有良好的压花定型性和手感，固含量达25%，尤其适用于皮革涂饰领域。1. The present invention proposes a method for preparing nonionic polyurethane-polyacrylate composite emulsion by seed emulsion polymerization for the first time in the field of leather finishing. In the present invention, polyacrylate is introduced into nonionic polyurethane emulsion for interpenetrating polymerization, and the obtained emulsion has the dual advantages of polyurethane resin and acrylic resin in terms of mechanical properties, that is, the dry film has good mechanical properties and good mechanical properties. Embossed shape and feel, solid content up to 25%, especially suitable for the field of leather finishing.
2、本发明制备的非离子型水性聚氨酯-聚丙烯酸酯是以水作为分散介质的复合树脂，不需要外加乳化剂，提高乳液的耐水性和稳定性的同时，还提高了乳液的耐冻融性，并同时降低了成本。2. The non-ionic water-based polyurethane-polyacrylate prepared by the present invention is a composite resin with water as the dispersion medium, and does not need an emulsifier, which improves the water resistance and stability of the emulsion, and also improves the freeze-thaw resistance of the emulsion performance while reducing costs.
3、本发明制备的复合树脂为非离子型树脂，因而乳液对酸、碱和电解质等各种环境因素不敏感，且具有低粘度和较好的通透性，既可以与非离子、阴离子树脂及材料复配，也可以与阳离子树脂及材料复配，因此具有更广的复配适用性。3. The composite resin prepared by the present invention is a non-ionic resin, so the emulsion is insensitive to various environmental factors such as acid, alkali and electrolyte, and has low viscosity and good permeability. It can be mixed with non-ionic and anionic resins. It can also be compounded with cationic resins and materials, so it has wider compounding applicability.
4、本发明可以通过调节亲水单体的含量、聚氨酯/聚丙烯酸酯的相对含量，低聚物二元醇和丙烯酸酯单体以及小分子扩链剂的种类和含量等参数，获得各种不同力学性能的涂膜，以适应不同的要求。4. The present invention can obtain various parameters such as the content of hydrophilic monomers, the relative content of polyurethane/polyacrylate, the type and content of oligomer diols and acrylate monomers, and small molecule chain extenders. Coating films with mechanical properties to suit different requirements.
5、本发明各工艺步骤相互配合互为作用，并在特定配比的原料组成及相应参数条件控制下，有效实现了非离子型聚氨酯-聚丙烯酸酯复合乳液的合成，具有稳定性好，耐酸碱和电解质，压花定型性好的优越技术效果，尤其适用于做皮革涂饰剂。5. Each process step of the present invention cooperates and interacts with each other, and under the control of specific proportioning raw material composition and corresponding parameter conditions, the synthesis of nonionic polyurethane-polyacrylate composite emulsion is effectively realized, which has good stability and durability Acid-base and electrolyte, good embossing and good technical effect, especially suitable for leather finishing agent.
以下通过实施例形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下实施例，凡基于本发明上述内容所实现的技术手段均属于本发明的范围。The above-mentioned content of the present invention will be further described in detail below through specific implementation in the form of examples. However, it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples, and all technical means realized based on the above content of the present invention belong to the scope of the present invention.
具体实施方式detailed description
以下实施例所涉及的原料如下：The raw materials involved in the following examples are as follows:
异佛尔酮二异氰酸酯（IPDI）；Isophorone diisocyanate (IPDI);
1，6-六亚甲基二异氰酸酯（HDI）；1,6-Hexamethylene diisocyanate (HDI);
4，4-二环己基甲烷二异氰酸酯（HMDI)；4,4-dicyclohexylmethane diisocyanate (HMDI);
数均分子量为1000，羟值为110mgKOH/g的三羟甲基丙烷聚乙二醇单甲醚（柏斯托，YmerN120）；Trimethylolpropane polyethylene glycol monomethyl ether with a number average molecular weight of 1000 and a hydroxyl value of 110 mgKOH/g (Perstorp, YmerN120);
二月桂酸二丁基锡；有机铋BiCAT8118；Dibutyltin dilaurate; Organic bismuth BiCAT8118;
甲基丙烯酸甲酯；丙烯酸丁酯；丙烯酸乙酯；丙烯酸异辛酯；Methyl methacrylate; Butyl acrylate; Ethyl acrylate; Isooctyl acrylate;
水合肼；三乙烯四胺（TETA）；Hydrazine hydrate; Triethylenetetramine (TETA);
丙酮；acetone;
数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇，工业品；Polyoxypropylene diol with a number average molecular weight of 2000 and a hydroxyl value of 56 mgKOH/g, an industrial product;
数均分子量为1000、羟值为112mgKOH/g的聚氧化丙烯二元醇，工业品；Polyoxypropylene diol with a number average molecular weight of 1000 and a hydroxyl value of 112 mgKOH/g, an industrial product;
数均分子量为2000、羟值为53～59mgKOH/g的聚碳酸酯二元醇，工业品；聚酯二元醇：柏斯托OxymerM112、NIPPOLLAN963、柏斯托CAPA2101A；Polycarbonate diols with a number average molecular weight of 2000 and a hydroxyl value of 53-59 mgKOH/g, industrial products; polyester diols: Perstorp OxymerM112, NIPPOLLAN963, Perstorp CAPA2101A;
数均分子量为1000、羟值为104～120mgKOH/g的聚碳酸酯二元醇，工业品；Polycarbonate diol with a number average molecular weight of 1000 and a hydroxyl value of 104-120 mgKOH/g, an industrial product;
数均分子量为1000，羟值为112mgKOH/g的聚己内酯二元醇；Number average molecular weight is 1000, the polycaprolactone diol of hydroxyl value 112mgKOH/g;
硫酸钾、过硫酸钠、过硫酸铵。Potassium sulfate, sodium persulfate, ammonium persulfate.
实施例1Example 1
将真空脱水后的数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇10.0g，异佛尔酮二异氰酸酯4.0g，三羟甲基丙烷聚乙二醇单甲醚9.2g、催化剂二月桂酸二丁基锡0.024g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0076mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯3.60g，甲基丙烯酸甲酯4.00g，丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入26g去离子水，乳化2min，再加入70g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.24g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～2小时后，然后通入氮气，升温至75℃，在2小时内滴加由0.02g过硫酸钾和19.2g水组成的混合液，继续保温2～3小时，即得固含量约为20%的非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。（PU=23.416g，PA=7.6g，PUA=31.016g）The number average molecular weight after vacuum dehydration is 10.0g of polyoxypropylene glycol of 2000, hydroxyl value 56mgKOH/g, 4.0g of isophorone diisocyanate, 9.2g of trimethylolpropane polyethylene glycol monomethyl ether , Add 0.024g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0076mol) or below, put The temperature of the system is lowered to room temperature, add 3.60g of butyl acrylate, 4.00g of methyl methacrylate, and 4g of acetone, continue to stir for 15-30 minutes, add 26g of deionized water under high shear force at 950rpm, emulsify for 2min, and then add 70g Deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, dropwise add a hydrazine hydrate solution composed of 0.24g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 2 hours, then pass in nitrogen, and heat up to 75 ℃, add dropwise a mixture of 0.02g potassium persulfate and 19.2g water within 2 hours, and keep warm for 2 to 3 hours to obtain a non-ionic water-based polyurethane-polyacrylate composite emulsion product with a solid content of about 20%. . (PU=23.416g, PA=7.6g, PUA=31.016g)
比较例1Comparative example 1
将真空脱水后的数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇17.41g，异佛尔酮二异氰酸酯5.37g，三羟甲基丙烷聚乙二醇单甲醚5.82g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0194mol）或以下时，将体系温度降至室温，加入丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入27.4g去离子水，乳化2min，再加入54.8g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.61g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～2h，即得固含量约为25%的非离子水性聚氨酯乳液产品。17.41g of polyoxypropylene glycol with a number average molecular weight of 2000 and a hydroxyl value of 56mgKOH/g after vacuum dehydration, 5.37g of isophorone diisocyanate, and 5.82g of trimethylolpropane polyethylene glycol monomethyl ether , Add 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0194mol) or below, put The temperature of the system is lowered to room temperature, add 4g of acetone, continue to stir for 15 to 30 minutes, add 27.4g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 54.8g of deionized water, continue to emulsify for 13 minutes, reduce the stirring speed , add dropwise a hydrazine hydrate solution consisting of 0.61g hydrazine hydrate (mass fraction 80%) and 4g water, and react for 1-2 hours to obtain a non-ionic water-based polyurethane emulsion product with a solid content of about 25%.
比较例2Comparative example 2
将真空脱水后的数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇15.40g，异佛尔酮二异氰酸酯5.37g，二羟甲基丙酸0.91g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0194mol）或以下时，将体系温度降至室温，加入丙酮4g，搅拌15分钟，加入三乙胺0.69g，反应15分钟，在950rpm高剪切力下加入21.2g去离子水，乳化2min，再加入42.4g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.61g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～2h，即得固含量约为25%的阴离子水性聚氨酯乳液产品。The number-average molecular weight after vacuum dehydration is 2000, the polyoxypropylene glycol 15.40g of hydroxyl value 56mgKOH/g, isophorone diisocyanate 5.37g, dimethylolpropionic acid 0.91g, catalyst dilaurate di Add 0.025g of butyltin into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, then take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0194mol) or below, lower the system temperature to room temperature, Add 4g of acetone, stir for 15 minutes, add 0.69g of triethylamine, react for 15 minutes, add 21.2g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 42.4g of deionized water, continue to emulsify for 13 minutes, reduce Stirring speed, add dropwise a hydrazine hydrate solution consisting of 0.61g hydrazine hydrate (mass fraction 80%) and 4g water, and react for 1-2 hours to obtain an anionic water-based polyurethane emulsion product with a solid content of about 25%.
实施例1、比较例1、比较例2的产品性能按以下1）～5）项进行测试The product properties of Example 1, Comparative Example 1, and Comparative Example 2 are tested according to the following items 1) to 5)
1）吸水率的测定：将充分干燥的胶膜试样裁剪成20mm×20mm的正方形，称质量记为W1，置于去离子水中，浸泡24h后取出，用滤纸吸去表面水分后称量，记为W2，按下式计算：1) Determination of water absorption: Cut the fully dried film sample into a square of 20mm×20mm, weigh the mass as W1 , put it in deionized water, take it out after soaking for 24 hours, and weigh it after absorbing the surface moisture with filter paper , denoted as W2 , calculated according to the following formula:
吸水率（%）=[(W2-W1)/W1]×100%Water absorption (%)=[(W2 -W1 )/W1 ]×100%
2）乳液耐酸碱、耐盐性的测定：将一定量5wt%的盐酸，调节乳液pH=1，观察乳液稳定性；将10%的氯化钠溶液慢慢滴加到乳液中，观察乳液稳定性；2) Determination of acid and alkali resistance and salt resistance of the emulsion: adjust the pH of the emulsion to 1 with a certain amount of 5wt% hydrochloric acid, and observe the stability of the emulsion; slowly add 10% sodium chloride solution into the emulsion, and observe the emulsion stability;
3）耐冻融性的测定：将乳液置于-10℃环境中冷冻12h，在将其加热至50度融化，重复3遍，观察乳液稳定性；3) Determination of freeze-thaw resistance: freeze the emulsion at -10°C for 12 hours, heat it to 50°C to melt, repeat 3 times, and observe the stability of the emulsion;
4）拉伸强度的测定：将胶膜制成30mm×3mm的哑铃状，使用XLM-智能电子拉力试验机测试其拉伸强度，拉伸速度为150mm/min；4) Determination of tensile strength: make the film into a dumbbell shape of 30mm×3mm, and test its tensile strength with an XLM-intelligent electronic tensile testing machine at a tensile speed of 150mm/min;
5）压花定型性能的测试。5) Test of embossing setting performance.
性能测试结果见下表The performance test results are shown in the table below
由上表可以看出，本发明实施例1产品相对于比较例2（阴离子水性聚氨酯乳液产品），具有更好的耐酸碱、耐盐、耐冻融性，且稳定性好；而相对于比较例1，又表现为耐水性增加，压花定型性好，拉伸强度提高，即本发明产品具有更为优良的综合性能，尤其适合作为皮革涂饰剂使用。As can be seen from the above table, the product of Example 1 of the present invention has better acid and alkali resistance, salt resistance, freeze-thaw resistance, and good stability compared to Comparative Example 2 (anionic water-based polyurethane emulsion product); In Comparative Example 1, the water resistance is increased, the embossing setting is good, and the tensile strength is improved, that is, the product of the present invention has more excellent comprehensive properties, and is especially suitable for use as a leather finishing agent.
实施例2Example 2
将真空脱水后的数均分子量为2000、羟值为53～59mgKOH/g的聚碳酸酯二元醇PCD16.8g，异佛尔酮二异氰酸酯8.0g，三羟甲基丙烷聚乙二醇单甲醚11.6g、催化剂二月桂酸二丁基锡0.08g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0321mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯6.6g，甲基丙烯酸甲酯5.0g，丙酮6g，继续搅拌15～30分钟，在950rpm高剪切力下加入26g去离子水，乳化2min，再加入70g去离子水，继续乳化13分钟，降低搅拌速度，滴加由1.00g水合肼（质量分数80%）和10g水组成的水合肼溶液，反应1～3小时后，然后通入氮气，升温至75℃，在2小时内滴加由0.06g过硫酸钾和19.2g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。After vacuum dehydration, 16.8g of polycarbonate diol PCD with a number average molecular weight of 2000 and a hydroxyl value of 53-59mgKOH/g, 8.0g of isophorone diisocyanate, trimethylolpropane polyethylene glycol monomethyl Add 11.6g of ether and 0.08g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, then take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0321mol) or below When the temperature of the system was lowered to room temperature, 6.6 g of butyl acrylate, 5.0 g of methyl methacrylate, and 6 g of acetone were added, and the stirring was continued for 15 to 30 minutes. Then, 26 g of deionized water was added under high shear force at 950 rpm, and emulsified for 2 min. Then add 70g of deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, dropwise add a hydrazine hydrate solution consisting of 1.00g of hydrazine hydrate (80% mass fraction) and 10g of water, react for 1 to 3 hours, and then pass nitrogen, Raise the temperature to 75°C, add dropwise a mixture of 0.06g potassium persulfate and 19.2g water within 2 hours, and keep warm for 2-3 hours to obtain a non-ionic water-based polyurethane-polyacrylate composite emulsion product.
实施例3Example 3
将真空脱水后的数均分子量为1000、羟值为112mgKOH/g的聚氧化丙烯二元醇8.62g，异佛尔酮二异氰酸酯6.75g，三羟甲基丙烷聚乙二醇单甲醚9.59g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0244mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯5.24g，甲基丙烯酸甲酯1.13g，丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.76g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～3小时后，然后通入氮气，升温至75℃，在2小时内滴加含0.019g过硫酸钾和16g水的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。After vacuum dehydration, 8.62g of polyoxypropylene glycol with a number average molecular weight of 1000 and a hydroxyl value of 112mgKOH/g, 6.75g of isophorone diisocyanate, and 9.59g of trimethylolpropane polyethylene glycol monomethyl ether , Add 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0244mol) or below, put The temperature of the system is lowered to room temperature, add 5.24g of butyl acrylate, 1.13g of methyl methacrylate, 4g of acetone, continue to stir for 15-30 minutes, add 27g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 53g Deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, dropwise add a hydrazine hydrate solution composed of 0.76g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 3 hours, then pass in nitrogen, and heat up to 75 ℃, dropwise add the mixed solution containing 0.019g potassium persulfate and 16g water within 2 hours, and continue to keep warm for 2 to 3 hours to obtain the nonionic water-based polyurethane-polyacrylate composite emulsion product.
实施例4Example 4
将真空脱水后的数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇13.19g，异佛尔酮二异氰酸酯5.40g，三羟甲基丙烷聚乙二醇单甲醚8.00g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0194mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯3.95g，甲基丙烯酸甲酯0.85g，丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.61g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～3小时后，然后通入氮气，升温至75℃，在2小时内滴加由0.019g过硫酸钾和16g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。The number average molecular weight after vacuum dehydration is 2000, the polyoxypropylene diol of 56mgKOH/g hydroxyl value 13.19g, isophorone diisocyanate 5.40g, trimethylolpropane polyethylene glycol monomethyl ether 8.00g , Add 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0194mol) or below, put The temperature of the system is lowered to room temperature, add 3.95g of butyl acrylate, 0.85g of methyl methacrylate, 4g of acetone, continue stirring for 15-30 minutes, add 27g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 53g Deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, add dropwise a hydrazine hydrate solution composed of 0.61g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 3 hours, then pass nitrogen gas, and heat up to 75 ℃, within 2 hours, add dropwise a mixed solution consisting of 0.019g potassium persulfate and 16g water, and continue to keep warm for 2-3 hours to obtain a non-ionic water-based polyurethane-polyacrylate composite emulsion product.
实施例5Example 5
将真空脱水后的数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇14.31g，1，6-六亚甲基二异氰酸酯4.24g，三羟甲基丙烷聚乙二醇单甲醚7.99g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0202mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯2.40g，甲基丙烯酸甲酯2.40g，丙酮3g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.63g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～3小时后，然后通入氮气，升温至75℃，在2小时内滴加由0.014g过硫酸钾和16g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。The number average molecular weight after vacuum dehydration is 2000, the polyoxypropylene glycol 14.31g of hydroxyl value 56mgKOH/g, 1,6-hexamethylene diisocyanate 4.24g, trimethylolpropane polyethylene glycol mono Add 7.99g of methyl ether and 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, then take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0202mol) or When the temperature is below, lower the system temperature to room temperature, add 2.40g butyl acrylate, 2.40g methyl methacrylate, 3g acetone, continue stirring for 15-30 minutes, add 27g deionized water under high shear force at 950rpm, and emulsify for 2min , then add 53g deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, add dropwise a hydrazine hydrate solution composed of 0.63g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 3 hours, and then pass nitrogen , heated up to 75°C, added dropwise a mixture of 0.014g potassium persulfate and 16g water within 2 hours, and continued to keep warm for 2-3 hours to obtain a non-ionic water-based polyurethane-polyacrylate composite emulsion product.
实施例6Example 6
将真空脱水后的数均分子量为2000、羟值为56mgKOH/g的聚氧化丙烯二元醇15.09g，1，6-六亚甲基二异氰酸酯3.67g，三羟甲基丙烷聚乙二醇单甲醚8.04g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在85℃下反应3小时后，取样测定NCO含量，当NCO含量达到预定值（0.0161mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯2.40g，甲基丙烯酸甲酯2.40g，丙酮3g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.39g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～3小时后，然后通入氮气，升温至75℃，在2小时内滴加由0.014g过硫酸钾和16g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。The number average molecular weight after vacuum dehydration is 2000, the polyoxypropylene glycol 15.09g of hydroxyl value 56mgKOH/g, 1,6-hexamethylene diisocyanate 3.67g, trimethylolpropane polyethylene glycol mono Add 8.04g of methyl ether and 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 85°C for 3 hours, then take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0161mol) or When the temperature is below, lower the system temperature to room temperature, add 2.40g butyl acrylate, 2.40g methyl methacrylate, 3g acetone, continue stirring for 15-30 minutes, add 27g deionized water under high shear force at 950rpm, and emulsify for 2min , then add 53g deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, add dropwise a hydrazine hydrate solution composed of 0.39g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 3 hours, and then pass nitrogen , heated up to 75°C, added dropwise a mixture of 0.014g potassium persulfate and 16g water within 2 hours, and continued to keep warm for 2-3 hours to obtain a non-ionic water-based polyurethane-polyacrylate composite emulsion product.
实施例7Example 7
将真空脱水后的数均分子量为为1000、羟值为104～120mgKOH/g的聚碳酸酯二元醇4.97g，4，4-二环己基甲烷二异氰酸酯6.34g，三羟甲基丙烷聚乙二醇单甲醚9.55g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在70℃下反应5小时后，取样测定NCO含量，当NCO含量达到预定值（0.0194mol）或以下时，将体系温度降至室温，加入丙烯酸乙酯6.37g，丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.61g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～2小时后，然后通入氮气，升温至80℃，在2小时内滴加由0.019g过硫酸钾和16g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。After vacuum dehydration, 4.97g of polycarbonate diol with a number-average molecular weight of 1000 and a hydroxyl value of 104-120mgKOH/g, 6.34g of 4,4-dicyclohexylmethane diisocyanate, trimethylolpropane polyethylene Add 9.55g of glycol monomethyl ether and 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 70°C for 5 hours, then take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0194 mol) or below, lower the system temperature to room temperature, add 6.37g of ethyl acrylate, 4g of acetone, continue stirring for 15-30 minutes, add 27g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 53g to Ionized water, continue to emulsify for 13 minutes, reduce the stirring speed, add dropwise a hydrazine hydrate solution consisting of 0.61g hydrazine hydrate (80% mass fraction) and 4g water, react for 1-2 hours, then pass nitrogen gas, and heat up to 80°C , add dropwise a mixed solution consisting of 0.019g of potassium persulfate and 16g of water within 2 hours, and continue to keep warm for 2 to 3 hours to obtain a nonionic water-based polyurethane-polyacrylate composite emulsion product.
实施例8Example 8
将真空脱水后的数均分子量为1000、羟值为112mgKOH/g的聚己内酯二元醇4.97g，异佛尔酮二异氰酸酯5.37g，三羟甲基丙烷聚乙二醇单甲醚9.55g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在90℃下反应2小时后，取样测定NCO含量，当NCO含量达到预定值（0.0194mol）或以下时，将体系温度降至室温，加入丙烯酸异辛酯6.37g，丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.61g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～2小时后，然后通入氮气，升温至90℃，在2小时内滴加由0.019g过硫酸胺和16g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。The number average molecular weight after vacuum dehydration is 4.97g of polycaprolactone diol with a hydroxyl value of 112mgKOH/g, 5.37g of isophorone diisocyanate, and 9.55g of trimethylolpropane polyethylene glycol monomethyl ether. g. Add 0.025g of catalyst dibutyltin dilaurate into a 250mL reaction vessel, control the temperature under mechanical stirring and react at 90°C for 2 hours, then take a sample to measure the NCO content. When the NCO content reaches the predetermined value (0.0194mol) or below, Lower the temperature of the system to room temperature, add 6.37g of isooctyl acrylate and 4g of acetone, continue to stir for 15-30 minutes, add 27g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 53g of deionized water, and continue to emulsify For 13 minutes, reduce the stirring speed, add dropwise a hydrazine hydrate solution consisting of 0.61g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 2 hours, then pass in nitrogen, raise the temperature to 90°C, within 2 hours Add dropwise a mixed solution consisting of 0.019 g of ammonium persulfate and 16 g of water, and continue to keep warm for 2 to 3 hours to obtain a nonionic water-based polyurethane-polyacrylate composite emulsion product.
实施例9Example 9
将真空脱水后的数均分子量为1000的M1124.97g，异佛尔酮二异氰酸酯5.37g，三羟甲基丙烷聚乙二醇单甲醚9.55g、催化剂二月桂酸二丁基锡0.025g加入250mL反应容器中，在机械搅拌下控制温度在80℃下反应3.5小时后，取样测定NCO含量，当NCO含量达到预定值（0.0194mol）或以下时，将体系温度降至室温，加入丙烯酸丁酯3.37g，丙烯酸乙酯3.00g，丙酮4g，继续搅拌15～30分钟，在950rpm高剪切力下加入27g去离子水，乳化2min，再加入53g去离子水，继续乳化13分钟，降低搅拌速度，滴加由0.61g水合肼（质量分数80%）和4g水组成的水合肼溶液，反应1～2小时后，然后通入氮气，升温至70℃，在2小时内滴加由0.019g过硫酸钠和16g水组成的混合液，继续保温2～3小时，即得非离子水性聚氨酯-聚丙烯酸酯复合乳液产品。Add 24.97g of M1124.97g with a number average molecular weight of 1000 after vacuum dehydration, 5.37g of isophorone diisocyanate, 9.55g of trimethylolpropane polyethylene glycol monomethyl ether, and 0.025g of catalyst dibutyltin dilaurate into 250mL of reaction In the container, control the temperature under mechanical stirring and react at 80°C for 3.5 hours, then take a sample to measure the NCO content, when the NCO content reaches the predetermined value (0.0194mol) or below, lower the system temperature to room temperature, and add 3.37g of butyl acrylate , ethyl acrylate 3.00g, acetone 4g, continue to stir for 15-30 minutes, add 27g of deionized water under high shear force at 950rpm, emulsify for 2min, then add 53g of deionized water, continue to emulsify for 13 minutes, reduce the stirring speed, drop Add a hydrazine hydrate solution consisting of 0.61g hydrazine hydrate (mass fraction 80%) and 4g water, react for 1 to 2 hours, then pass in nitrogen, raise the temperature to 70°C, and add 0.019g sodium persulfate dropwise within 2 hours and 16g of water to form a mixed solution, and continue to keep warm for 2 to 3 hours to obtain a nonionic water-based polyurethane-polyacrylate composite emulsion product.
| Application Number | Priority Date | Filing Date | Title |
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| CN201310652019.XACN103724574B (en) | 2013-12-06 | 2013-12-06 | A kind of preparation method of leather finish non-ion aqueous polyurethane-poly acrylate composite emulsion |
| Application Number | Priority Date | Filing Date | Title |
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| CN201310652019.XACN103724574B (en) | 2013-12-06 | 2013-12-06 | A kind of preparation method of leather finish non-ion aqueous polyurethane-poly acrylate composite emulsion |
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| CN103724574Btrue CN103724574B (en) | 2016-01-20 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201310652019.XAActiveCN103724574B (en) | 2013-12-06 | 2013-12-06 | A kind of preparation method of leather finish non-ion aqueous polyurethane-poly acrylate composite emulsion |
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