WO2023060738A1 - 无溶剂的聚丙烯酸水性分散体的制备方法及其应用 - Google Patents
无溶剂的聚丙烯酸水性分散体的制备方法及其应用 Download PDFInfo
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- WO2023060738A1 WO2023060738A1 PCT/CN2021/137107 CN2021137107W WO2023060738A1 WO 2023060738 A1 WO2023060738 A1 WO 2023060738A1 CN 2021137107 W CN2021137107 W CN 2021137107W WO 2023060738 A1 WO2023060738 A1 WO 2023060738A1
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- polyacrylic acid
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- 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
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Definitions
- the invention belongs to the field of coatings, and relates to a preparation method of a solvent-free polyacrylic acid aqueous dispersion containing hydroxyl functional groups, the obtained polyacrylic acid aqueous dispersion and an application thereof.
- One of the most commonly used resins for the preparation of water-based coatings is an aqueous dispersion of hydroxyl-containing polyacrylic acid.
- aqueous dispersion of hydroxyl-containing polyacrylic acid.
- this type of preparation process usually includes providing a certain amount of organic solvent (such as propylene glycol butyl ether, etc.), adding to the reaction kettle, stirring and heating to the required temperature, adding acrylic monomers and part of the initiator Mix the solution, and finally add organic amine for neutralization. Due to the needs of the synthesis and dispersion process, and in order to reduce the viscosity, these systems need to add certain organic solvents, thus generating VOC, which is harmful to the environment and human body.
- organic solvent such as propylene glycol butyl ether, etc.
- the solvent in the subsequent process of removing the organic solvent in the dispersion, the solvent can be removed by heating and vacuum distillation. Although this can recover the solvent to a certain extent, it needs to consume a lot of energy, and the recovered solvent has complex components and cannot be reused.
- U.S. Patent No. US5750613 discloses that a polyether containing hydroxyl functional groups can be used to replace organic solvents in whole or in part during polymerization. During the subsequent cross-linking process, the hydroxyl-functional polyether can react with the blocked isocyanate curing agent to form urethane, which has no effect on VOC reduction. And the product prepared with hydroxyl-containing polyether as a diluent often has poor stability.
- the Chinese patent application with the patent publication number CN1898280A discloses a method for preparing copolymer dispersions.
- the combination of lactone and low-molecular-weight polyols as reactive diluents can produce hydroxyl-based functional diluents with low solvent content.
- Aqueous copolymer dispersions of copolymers In this method, a small amount of other organic solvents will still be used as needed, and zero solvents cannot be achieved.
- the Chinese patent application with the patent publication number CN1914237A discloses an aqueous copolymer dispersion based on a hydroxyl-functional copolymer with a low solvent content and a high level of stability of the paint film.
- This method uses a compound represented by the following formula I as the reaction medium with a small amount of additional organic solvent.
- the compound of formula I has a hydroxyl functional group and a tertiary carbon group, and n ranges from 1 to 4, i.e. it has 1 to 4 hydroxyl groups.
- the compound exists as a diluent, and the tertiary carbon group can play a role in reducing viscosity, and finally can participate in the reaction when used in conjunction with a curing agent.
- n 1 in formula I, it can only participate in the reaction, and cannot form crosslinking, which will affect the performance of the final paint film.
- an additional organic solvent will be used as needed, and zero solvent cannot be achieved.
- the Chinese patent application whose patent publication number is CN103998472A discloses that glycidyl esters of aliphatic carboxylic acids are introduced into the reaction system as a reactive diluent, and simultaneously in the process of free radical polymerization, epoxy groups and carboxyl-containing monomers The body reaction is involved in the polymer chain. However, as the reaction proceeds, the content of glycidyl esters of free aliphatic carboxylic acids gradually decreases, and the effect of the diluent gradually weakens.
- the methods for reducing the molecular weight include increasing the amount of the initiator, using a chain transfer agent, or increasing the reaction temperature. Take the method of increasing the reaction temperature as an example. The highest reaction temperature usually depends on the boiling point of the organic solvent. Although it can be pressurized, this method has higher requirements for hardware and will further increase the cost.
- the present invention provides a method for preparing a solvent-free aqueous dispersion of polyacrylic acid containing hydroxyl functional groups and its application.
- a first aspect of the present invention provides a process for the preparation of a solvent-free aqueous dispersion of polyacrylic acid containing hydroxyl functional groups, comprising the steps of: allowing a monomer or a mixture of monomers a in the presence of a reactive oligomer b Polyacrylic acid copolymer A is obtained by initiating polymerization with initiator c, neutralized by adding neutralizing agent d, and dispersed in water;
- the monomer mixture a comprises one or more of the following:
- the reactive oligomer b includes one or more of the following features:
- Reactive oligomer b does not include free radically polymerizable unsaturated bonds
- the reactive oligomer b can react with the curing agent.
- component a1 is selected from one or more of acrylates or methacrylates, wherein the alcohol residue has 1 to 18 carbon atoms; preferably, the alcohol residue
- the base moiety is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, octyl, dimethylaminoethyl, cyclohexyl, glycidyl, lauryl , dodecyl, ethylene glycol dimethyl or isobornyl in one or more.
- component a1 comprises vinylaromatics; preferably styrene.
- component a2 is a vinyl monomer containing a hydroxyl functional group; preferably an alkyl ester of an unsaturated carboxylic acid; more preferably selected from hydroxyalkyl acrylate and/or methacrylic acid One or more of hydroxyalkyl esters.
- component a2 comprises one of the reaction products of alkyl groups containing epoxy groups and acrylic acid and/or the reaction products of alkyl groups containing epoxy groups and methacrylic acid or Various.
- component a2 comprises the product after the reaction of glycidyl tertiary carbonic acid ester and acrylic acid, and the general formula of this product is shown in the following formula II, wherein R 1 group and R 2 carbon atoms in the group The total is 7:
- the glycidyl tertiary carbonic acid ester is selected from the glycidyl tertiary carbonic acid ester of the product model Cardura E10P provided by Momentive Corporation of the United States.
- component a2 comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate; preferably methacrylic acid One or both of hydroxyethyl ester or hydroxypropyl methacrylate.
- component a3 is an ionic and/or potential ionic monomer that can be free radically polymerized; preferably a3 is a vinyl monomer containing a carboxylic acid group; preferably the carboxylic acid group
- the vinyl monomer is selected from vinyl monomers containing acrylic acid, methacrylic acid or dibasic acid, and the preferred dibasic acid is selected from one or more of itaconic acid, fumaric acid or maleic acid, more
- the vinyl monomers containing carboxylic acid groups are selected from vinyl monomers containing acrylic acid or methacrylic acid.
- component a3 is a vinyl monomer containing phosphate groups, preferably 2-hydroxyethyl methacrylate phosphate.
- the weight ratio of components a1 to a3 ranges from 55 to 90 parts by weight for a1, 10 to 40 parts by weight for a2, and 0.5 to 5 parts by weight for a3, where a1, a2, The sum of a3 is 100 parts by weight.
- the reactive oligomer b contains a group that can react with a curing agent, and the group includes a hydroxyl group, an amino group, a carboxyl group and/or an amide group; preferably, the group The group is a hydroxyl group; more preferably low, the average number of hydroxyl groups per 1 mol of reactive oligomer b is not less than 1.5 mol; more preferably per 1 mol of reactive oligomer b contains 2 mol of hydroxyl groups.
- Aqueous polyacrylic acid dispersions can be prepared by using monohydroxyl b, which is beneficial to reduce product viscosity, but such aqueous dispersions will produce a large number of oligomers when they are subsequently cured with curing agents, which will affect the final performance of the paint film. Therefore, considering the convenience of production and the application performance of the product, it is preferable that the average number of hydroxyl groups per 1 mol of reactive oligomer b is not less than 1.5 mol.
- the reactive oligomer b has a molecular weight ranging from 200 to 1000 g/mol; preferably 200 to 600 g/mol.
- the reactive oligomer b is a reaction product of aliphatic glycidyl ester b1 and carboxylic acid b2.
- the aliphatic glycidyl ester b1 is selected from glycidyl esters of alkane carboxylic acids, preferably glycidyl esters of tertiary carbonic acid, such as Cardura E10P.
- the number of carboxyl groups of the carboxylic acid b2 is 2 or more, preferably the polycarboxylic acid b2 is an aliphatic carboxylic acid with 2 carboxyl groups, more preferably adipic acid, Pimelic acid, suberic acid, or combinations thereof.
- the reactive oligomer b is the reaction product of Cardura E10P and adipic acid.
- the mass of reactive oligomer b accounts for 5-40% of the sum of the mass of components a1 to a3, preferably 10-30%, more preferably 15-25%.
- the polymerization of one or more monomer mixtures a is initiated under the action of an initiator, and the reaction temperature is in the range of 50-200°C, preferably 100-150°C.
- the initiator c is an organic peroxide and/or an azo compound, preferably di-tert-butyl peroxide and/or azobisisobutyronitrile (AIBN), more preferably Di-tert-butyl peroxide is preferred.
- AIBN azobisisobutyronitrile
- the amount of initiator added can be calculated according to the set molecular weight.
- the monomers a1-a3 are added to the polymerization in two stages in the presence of the reactive oligomer b, and kept warm for 0.5-1 hour after each stage of polymerization is completed.
- the proportion of hydrophilic monomers in the second stage is higher than that in the first stage.
- the neutralizing agent d is an organic amine, preferably triethylamine, N,N-dimethylethanolamine, triethanolamine, ethyldiisopropylamine, N,N-dimethyl isopropanolamine, N-methyldiethanolamine and/or diethylethanolamine, more preferably N,N-dimethylethanolamine and/or triethanolamine.
- the neutralizing agent can cause the polyacrylic acid copolymer to change from acid to salt form before emulsification.
- the molar ratio of the amount of neutralizing agent added should reach 50-150% of the theoretical neutralization degree, preferably 80-120%.
- the theoretical degree of neutralization refers to the ratio of the added basic groups to the acid groups in the polyacrylic acid copolymer.
- the pH range of the neutralized and emulsified polyacrylic acid aqueous dispersion is 6-10, preferably 6.5-8.5.
- the polyacrylic acid aqueous dispersion has a mass content of non-volatile matter in the range of 30-70%, preferably 40-60%, and an organic solvent content of zero.
- the second aspect of the present invention provides the polyacrylic acid aqueous dispersion prepared by the above method.
- a third aspect of the present invention also provides a water-based paint composition, comprising:
- At least one curing agent capable of reacting with hydroxyl groups At least one curing agent capable of reacting with hydroxyl groups.
- the curing agent suitable for reacting with hydroxyl group includes non-blocked polyisocyanate curing agent, blocked polyisocyanate curing agent and/or amine-based curing agent. Preference is given to non-blocked polyisocyanate curing agents and/or blocked polyisocyanate curing agents.
- the polyisocyanate curing agent has more than two -NCO groups, and the polyisocyanate curing agent after hydrophilic modification can also be used.
- the polyacrylic acid water-based dispersion containing hydroxyl functional groups of the present invention can be used in water-based coatings in combination with a curing agent.
- a curing agent is a latent curing agent
- one-component or two-component coatings can be prepared.
- the base material part and the curing agent are stored separately and mixed evenly during use, preferably by heating to promote the crosslinking reaction, while the oligomer component also participates in the reaction.
- the aqueous coating composition of the polyacrylic acid aqueous dispersion containing hydroxyl functional group of the present invention can be applied to the surface of materials such as metal, inorganic matter or wood, and can be used as a pigmented or transparent topcoat, varnish As well as high gloss paint use.
- the curing temperature range of the water-based coating composition of the present invention is 0-140°C, preferably 15-100°C.
- the organic solvent is replaced with a reactive oligomer to obtain a solvent-free polyacrylic acid aqueous dispersion
- the reactive oligomer used in the present invention only exists as a diluent in the preparation process of the polyacrylic acid aqueous dispersion, and cannot be polymerized by free radicals, and then participates in the reaction when used in conjunction with a curing agent. Therefore, the present invention realizes the solvent-free preparation process of the polyacrylic acid dispersion, that is, the organic solvent is replaced by the oligomer as the reaction medium, and the performance of the polyacrylic acid dispersion in the coating is not affected;
- the VOC content of the aqueous coating composition can be greatly reduced, and the impact on construction personnel is small.
- Fig. 1 is a graph showing the change in viscosity of a coating based on the polyacrylic acid aqueous dispersion in 6 hours.
- first and second are used for descriptive purposes only, and do not refer to limitations on chronological order, quantity, or importance, and cannot be interpreted as indicating or implying relative importance or implicitly indicating the indicated technology
- the number of features is only for the purpose of distinguishing one technical feature from another technical feature in this technical solution.
- a feature defined as “first” or “second” may explicitly or implicitly include one or more of these features.
- plural means two or more, unless otherwise specified.
- the qualifiers similar to "a” appearing in this article do not refer to a limitation on quantity, but describe technical features that have not appeared above.
- At least one (item) means one or more, and “multiple” means two or more.
- “And/or” is used to describe the association relationship of associated objects, which means that there can be three kinds of relationships, for example, “A and/or B” can mean: only A exists, only B exists, and A and B exist at the same time. Among them, A and B can be singular or plural.
- the character “/” generally indicates that the contextual objects are an “or” relationship.
- At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
- At least one item (piece) of a, b or c can mean: a, b, c, "a and b", “a and c", “b and c", or "a and b and c ", where a, b, c can be single or multiple.
- Acid value test method ISO 2114-2000.
- Non-volatile content test conditions 1g sample, dried at 120°C for 1 hour.
- the reaction product of glycidyl tertiary carbonic acid ester and acrylic acid used in Example 4 and Example 5 can be purchased from Foshan Jinjia New Material Technology Co., Ltd. with a trade name of ACE. It can also be obtained by reacting Cardura E10P with acrylic acid as described below.
- Embodiment 1 the preparation of reactive oligomer b-1
- Embodiment 2 the preparation of reactive oligomer b-2
- Example 3 Preparation of solvent-free aqueous dispersion 1 of polyacrylic acid containing hydroxyl functional groups
- Example 4 Preparation of solvent-free aqueous dispersion 2 of polyacrylic acid containing hydroxyl functional groups
- Example 5 Preparation of solvent-free aqueous dispersion 3 of polyacrylic acid containing hydroxyl functional groups
- reaction vessel of 3L add the reactive oligomer b-1 among the 91.2g embodiment 1 and the reactive oligomer b-245.6g among the embodiment 2 (b-1, b-2 mixture contains on average every 1mol 1.55mol hydroxyl group), heated to 145°C, pre-mixed 248.9g component a1 methyl methacrylate, 125.3g component a2 hydroxyethyl methacrylate, 157.5g component a1 ethylhexyl acrylate, 70.08g group Divide into a2 the reaction product of glycidyl tertiary carbonic acid ester and acrylic acid, mix well with 24.9g of initiator c di-tert-butyl peroxide (DTBP), and add it dropwise at a constant speed within 2 hours at 145°C. Due to the exothermic reaction, the reaction temperature needs to be controlled 145 ⁇ 3°C. After the dropwise addition, keep warm for 30min.
- DTBP initiator c di-tert-but
- aqueous dispersion in embodiment 4 and 268 curing agent is used together (water-dispersible isocyanate curing agent, based on hexamethylene diisocyanate, Wanhua Company) according to the -OH:-NCO ratio of 1:1.1, and the viscosity change is measured within 6 hours.
- the viscosity change is shown in Figure 1 shown.
- the polyacrylic acid aqueous dispersion of the present invention exhibits a longer pot life, and the viscosity change within 6h is less than 10KU.
- the invention realizes that no organic solvent needs to be added in the preparation process of the polyacrylic acid dispersion, and at the same time, the performance of the polyacrylic acid dispersion in the paint is not affected.
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Abstract
一种制备无溶剂的包含羟基官能团的聚丙烯酸水性分散体的方法,包括步骤:使一种单体或多种单体混合物在反应性低聚物的存在下通过引发剂引发聚合得到聚丙烯酸共聚物,加入中和剂中和,分散在水中。反应性低聚物在聚丙烯酸水性分散体的制备过程中仅作为稀释剂存在,不参与任何反应,随后与固化剂搭配使用时能够与固化剂反应。因此,实现了聚丙烯酸分散体无溶剂制备工艺(低聚物代替有机溶剂作为反应介质),同时不影响聚丙烯酸分散体在涂料中的性能。
Description
本发明属于涂料领域,涉及一种无溶剂的包含羟基官能团的聚丙烯酸水性分散体的制备方法及所得的聚丙烯酸水性分散体和其应用。
制备水性涂料最常用的树脂之一是含羟基的聚丙烯酸水性分散体。在含羟基的聚丙烯酸水性分散体的制备过程中,通常需要先制备含羟基的聚丙烯树脂。具体地说,这类制备过程通常包括提供一定量的有机溶剂(例如丙二醇丁醚等),加入到反应釜中,搅拌并加热到所需温度后,添加丙烯酸类的单体和部分引发剂的混合溶液,最后加入有机胺中和得到。由于合成和分散工艺的需要,并且为了降低粘度,这些体系需要添加一定的有机溶剂,从而产生了VOC,这对环境和人体带来危害。
此外,在随后的除去分散体中的有机溶剂的过程中,可以通过加热减压蒸馏法脱除溶剂。虽然这可以在一定程度上回收溶剂,但是需要消耗许多能量,并且回收的溶剂成分复杂,无法重复利用。
比如,专利号为US5750613的美国专利公开了一种能够在聚合时使用含有羟基官能团的聚醚全部或部分地代替有机溶剂。在随后的交联过程中,含羟基官能团的聚醚可以与封闭的异氰酸酯类固化剂反应生成氨基甲酸乙酯,对降低VOC不起作用。并且含羟基聚醚作为稀释剂制备的产物往往稳定性很差。
又如,专利公布号为CN1898280A的中国专利申请公开了一种制备共聚物分散体的方法,将内酯和小分子量的多元醇结合作为活性稀释剂,可以制得具有低溶剂含量的基于羟基官能共聚物的水性共聚物分散体。该方法中,根据需要仍然会使用少量的其它类有机溶剂,无法实现零溶剂。
再如,专利公布号为CN1914237A的中国专利申请公开了基于羟基官能共聚物的低溶剂含量并且使其漆膜具有高稳定性水平的共聚物水分散体。该方法使用以下式I所示的化合物作为反应介质,使用少量附加的有机溶剂。式I化合物具有羟基官能团以及叔碳基团,n的范 围为1至4,即其具有1至4个羟基。在制备聚丙烯酸共聚物过程中该化合物作为稀释剂存在,叔碳基团可以起到降粘的作用,最终在与固化剂搭配使用时可以参与反应。式I中当n为1时,其只能参与反应,并不能形成交联,会影响最终漆膜的性能。并且在该方法中,同时具有羟基官能团以及叔碳基团的组分作为稀释剂时,根据需要还会使用额外的有机溶剂,也无法实现零溶剂。
还如,专利公布号为CN103998472A的中国专利申请公开了在反应体系中引入脂肪族羧酸的缩水甘油酯作为反应性稀释剂,同时在自由基聚合反应的过程中环氧基团与含羧基单体反应介入到聚合物链。但是随着反应的进行,游离脂肪族羧酸的缩水甘油酯的含量逐渐下降,稀释剂作用逐渐减弱。
现有技术中还有一些方法采用降低含羟基聚丙烯酸树脂的分子量来提高树脂的固体分,以此实现接近无溶剂体系的效果。而降低分子量的方法包括增加引发剂用量、使用链转移剂、或提高反应温度。以提高反应温度这一方法为例,最高的反应温度通常取决于有机溶剂的沸点,尽管可以通过加压的方式,但该方法对硬件的要求较高,成本也会进一步提升。
有鉴于此,本领域技术人员亟待需要研发一种含羟基的聚丙烯酸分散体,在制备过程中避免使用有机溶剂,同时不影响树脂在涂料中的应用。
发明内容
为了克服上述技术问题,本发明提供了一种制备无溶剂的包含羟基官能团的聚丙烯酸水性分散体的方法及其应用。
本发明的第一方面提供了一种制备无溶剂的包含羟基官能团的聚丙烯酸水性分散体的方法,包括步骤:使一种单体或多种单体混合物a在反应性低聚物b的存在下通过引发剂c引发聚合得到聚丙烯酸共聚物A,加入中和剂d中和,分散在水中;
其中,单体混合物a包含以下一种或多种:
a1无羟基的丙烯酸酯、无羟基的甲基丙烯酸酯、和/或无羟基的乙烯基芳烃,
a2含羟基官能团的丙烯酸酯、含羟基官能团的甲基丙烯酸酯和/或乙烯基单体,
a3可以自由基聚合的离子和/或潜离子单体;
其中,反应性低聚物b包括以下的一个或多个特征:
(1)反应性低聚物b不包括可自由基聚合的不饱和键;
(2)反应性低聚物b能够与固化剂反应。
在一种较佳的实施方式中,组分a1选自丙烯酸酯或甲基丙烯酸酯中的一种或多种,其中的醇残基部分中具有1至18个碳原子;优选地,醇残基部分选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、2-乙基己基、辛基、二甲氨基乙基、环己基、缩水甘油基、月桂基、十二基、乙二醇二甲基或异冰片基中的一种或多种。
在一种较佳的实施方式中,组分a1包含乙烯基芳烃;优选包含苯乙烯。
在一种较佳的实施方式中,组分a2为含羟基官能团的乙烯基单体;优选为不饱和羧酸的烷基酯;更优选地选自丙烯酸羟烷基酯和/或甲基丙烯酸羟烷基酯中的一种或多种。
在一种较佳的实施方式中,组分a2包含含环氧基团的烷基与丙烯酸的反应产物和/或含环氧基团的烷基与甲基丙烯酸的反应产物中的一种或多种。
在一种较佳的实施方式中,组分a2包含叔碳酸缩水甘油酯与丙烯酸反应后的产物,该产物通式如下式II所示,其中R
1基团和R
2基团中的碳原子总数为7:
具体地说,所述的叔碳酸缩水甘油酯选自美国迈图公司提供的产品型号为Cardura E10P的叔碳酸缩水甘油酯。
在一种较佳的实施方式中,组分a2包含丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的一种或多种;优选包含甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的一种或两种。
在一种较佳的实施方式中,组分a3是可以自由基聚合的离子和/或潜离子单体;优选a3为含羧酸基团的乙烯基单体;优选所述含羧酸基团的乙烯基单体选自含丙烯酸、甲基丙烯酸或二元酸的乙烯基单体,优选的二元酸选自衣康酸、富马酸或马来酸中的一种或多种,更优选所述含羧酸基团的乙烯基单体选自含丙烯酸或甲基丙烯酸的乙烯基单体。
在一种较佳的实施方式中,组分a3为含有磷酸酯基团的乙烯基单体,优选为2-羟乙酯甲基丙烯酸酯磷酸酯。
在一种较佳的实施方式中,组分a1至a3的重量份比例范围为a1为55~90重量份,a2为10~40重量份,a3为0.5~5重量份,以a1,a2,a3的和为100重量份。
在一种较佳的实施方式中,所述反应性低聚物b含有可以和固化剂反应的基团,所述基团包括羟基、氨基、羧基和/或酰胺基;优选地,所述基团为羟基;更优选低,平均每1mol反应性低聚物b含有的羟基不小于1.5mol;在为更优选地每1mol反应性低聚物b含有2mol的羟基。
使用单羟基的b可以制备得到聚丙烯酸水性分散体,并且有利于降低产品粘度,但此类水性分散体在后续与固化剂反应固化时会产生大量低聚物,影响漆膜最终性能。因此综合考虑生产的便利性和产品的应用性能,优选平均每1mol反应性低聚物b含有的羟基不小于1.5mol。
在一种较佳的实施方式中,所述反应性低聚物b的分子量范围为200至1000g/mol;优选为200至600g/mol。
在一种较佳的实施方式中,所述反应性低聚物b是脂肪族缩水甘油酯b1和羧酸b2的反应产物。
在一种较佳的实施方式中,所述脂肪族缩水甘油酯b1选自烷烃羧酸的缩水甘油酯,优选为叔碳酸缩水甘油酯,例如Cardura E10P。
在一种较佳的实施方式中,所述羧酸b2的羧基数量为2个及以上,优选所述多元羧酸b2为羧基数量为2的脂防族羧酸,更优选为己二酸、庚二酸、辛二酸或其组合。
在一种较佳的实施方式中,所述反应性低聚物b是Cardura E10P和己二酸的反应产物。
在一种较佳的实施方式中,反应性低聚物b的质量占组分a1至a3质量之和的5~40%,优选为10~30%,更优选为15~25%。
在一种较佳的实施方式中,所述方法中,在引发剂的作用下引发一种或多种单体混合物a的聚合,反应温度范围在50~200℃,优选为100~150℃。
在一种较佳的实施方式中,所述引发剂c为有机过氧化物和/或偶氮化合物,优选为二叔丁基过氧化物和/或偶氮二异丁腈(AIBN),更优选为二叔丁基过氧化物。可以根据设定的分子量计算引发剂的添加量。
在一种较佳的实施方式中,单体a1~a3在反应性低聚物b的存在下分两阶段加入聚合,每段聚合结束后保温0.5~1h。优选地,第二阶段的亲水单体比例高于第一阶段的亲水单体比例。
在一种较佳的实施方式中,中和剂d为有机胺,优选为三乙胺、N,N-二甲基乙醇胺、三乙醇胺、乙基二异丙基胺、N,N-二甲基异丙醇胺、N-甲基二乙醇胺和/或二乙基乙醇胺,更优选为N,N-二甲基乙醇胺和/或三乙醇胺。所述的中和剂可以使得聚丙烯酸共聚物在乳化前从酸变为盐的形式。
在一种较佳的实施方式中,中和剂的加入量的摩尔比应达到理论中和度50~150%,优选80~120%。该理论中和度指的是加入的碱性基团与聚丙烯酸共聚物中的酸性基团之比。中和并乳化后的聚丙烯酸水性分散体的pH值范围为6~10,优选6.5~8.5。
在一种较佳的实施方式中,所述聚丙烯酸水性分散体的非挥发分的质量含量范围为30~70%,优选地为40~60%;有机溶剂含量为零。
本发明第二方面提供了由上述方法制得的聚丙烯酸水性分散体。
本发明的第三方面还提供一种水性涂料组合物,包含:
(1)一种或多种本发明第一方面的制备方法制得的聚丙烯酸水性分散体;和
(2)至少一种可以与羟基反应的固化剂。
在一种较佳的实施方式中,适合与羟基反应的固化剂包括非封闭型多异氰酸酯固化剂、封闭型多异氰酸酯固化剂和/或胺基固化剂。优选为非封闭型多异氰酸酯固化剂和/或封闭型多异氰酸酯固化剂。多异氰酸酯固化剂具有两个以上的-NCO基团,也可以使用亲水改性后的多异氰酸酯固化剂。
本发明的含包含羟基官能团的聚丙烯酸水性分散体可与固化剂配合,应用于水性涂料。按照固化剂是否为潜伏性固化剂可以制备单组份或双组分涂料。用于本发明目的的双组分涂料,其基料部分和固化剂分开储存,在使用时混合均匀,优选通过加热的方式促进交联反应,同时低聚物组分也参与反应。
在一种较佳的实施方式中,本发明的包含羟基官能团的聚丙烯酸水性分散体的水性涂料组合物可应用于金属、无机物或木材等材料表面,可作为含颜料或透明面漆,清漆以及高光泽涂料使用。
在一种较佳的实施方式中,本发明的水性涂料组合物的固化温度范围为0~140℃,优选为15~100℃。
与现有技术相比较,本发明所提供的技术方案具有以下优点:
1.在聚丙烯酸水性分散体的制备过程中,以反应性低聚物代替有机溶剂,得到无溶剂型聚丙烯酸水性分散体;
2.本发明所使用的反应性低聚物在聚丙烯酸水性分散体的制备过程中仅作为稀释剂存在,无法通过自由基聚合,随后与固化剂搭配使用时参与反应。因此,本发明实现了聚丙烯酸分散体的无溶剂制备工艺,即以低聚物代替有机溶剂作为反应介质,同时不影响聚丙烯酸分散体在涂料中的性能;
3.由于本发明的包含羟基官能团的聚丙烯酸水性分散体的故意引入的挥发性有机溶剂含量为0,因此可以极大地降低水性涂料组合物的VOC含量,对施工人员造成的影响较小。
需要说明的是:由于原料制备工艺可能导致的原料中带入少量残留的溶剂,或者原料在生产条件下发生反应而可能产生少量挥发性有机物,此二者均不计入故意引入的挥发性有机溶剂,故在本发明中,实际测定得到的VOC含量不总为0。
图1是基于本发明所述的聚丙烯酸水性分散体的涂料在6小时内的粘度变化图。
下面结合附图详细说明本发明的具体实施例。然而,应当将本发明理解成并不局限于以下描述的这种实施方式,并且本发明的技术理念可以与其他公知技术或功能与那些公知技术相同的其他技术组合实施。
在以下具体实施例的说明中,为了清楚展示本发明的结构及工作方式,将借助诸多方向性词语进行描述,但是应当将“前”、“后”、“左”、“右”、“外”、“内”、“向外”、“向内”、“轴向”、“径向”等词语理解为方便用语,而不应当理解为限定性词语。
此外,术语“第一”、“第二”仅用于描述目的,并非是指对时间顺序、数量、或者重要性的限定,不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量,而仅仅是为了将本技术方案中的一个技术特征与另一个技术特征相区分。由此,限定有“第一”、“第二”的特征可以明示或隐含地包括一个或多个该特征。在本发明的描述中,“多个”的含义是两个或两个以上,除非另有明确具体的规定。同样地,本文中出现的类似于“一”的限定语并非是指对数量的限定,而是描述在前文中未曾出现的技术特征。同样地,除非是有特定的数量量词修饰的名词,否则在本文中应当视作即包含单数形式又包含复数形式,在该技术方案中即可以包括单数个该技术特征,也可以包括复数个该技术特征。同样地,本文中在数词前出现的类似于“大约”、“近似地”的修饰语通常包含本数,并且其具体的含义应当结合上下文意理解。
应当理解,在本申请中,“至少一个(项)”是指一个或者多个,“多个”是指两个或两个以上。“和/或”用于描述关联对象的关联关系,表示可以存在三种关系,例如,“A和/或B”可以表示:只存在A,只存在B以及同时存在A和B三种情况,其中A,B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。“以下至少一项(个)”或其类似表达,是指这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,a,b或c中的至少一项(个),可以表示:a,b,c,“a和b”,“a和c”,“b和c”,或“a和b和c”,其中a,b,c可以是单个,也可以是多个。
除非清楚地指出相反的,这里限定的每个方面或实施方案可以与任何其他一个或多个方面或一个或多个实施方案组合。特别地,任何指出的作为优选的或有利的特征可以与任何其他指出的作为优选的或有利的特征组合。
术语说明以及测试方法和条件
在以下实施例中,除非特别指出,所有百分数都指重量百分数。
树脂粘度的测量在25℃下使用Brookfield粘度计测量。
涂料粘度的测量在25℃下使用斯托默粘度计测量。
酸值测试方法:ISO 2114-2000。
非挥发分含量测试条件:1g样品,120℃下烘干1小时。
实施例4、实施例5中使用的叔碳酸缩水甘油酯与丙烯酸反应后的产物可从佛山今佳新材料科技有限公司购买得到,商品名ACE。亦可以通过如下述的Cardura E10P与丙烯酸反应得到。
实施例1:反应性低聚物b-1的制备
3L的反应容器中加入1548g脂肪族缩水甘油酯b1—Cardura E10P(叔碳酸缩水甘油酯,购自美国迈图公司)和452g多元羧酸b2—己二酸,搅拌条件下升温至140℃,此时反应出现大量放热,确保温度不超过160℃。在140℃下保温2h后每小时检测酸值,当酸值小于1mg KOH/g时反应结束,降温出料得到淡黄色树脂。
实施例2:反应性低聚物b-2的制备
3L的反应容器中加入634.9g脂肪族缩水甘油酯b1—Cardura E10P(叔碳酸缩水甘油酯,购自美国迈图公司)和365.1g羧酸b2—异辛酸,搅拌条件下升温至140℃,此时反应出现大量放热,确保温度不超过160℃。在140℃下保温2h后每小时检测酸值,当酸值小于1mg KOH/g时反应结束,降温出料得到淡黄色树脂。
实施例3:无溶剂的包含羟基官能团的聚丙烯酸水性分散体1的制备
3L的反应容器中加入195.58g实施例1中所得的反应性低聚物b-1,升温加热至145℃,预先将117.3g组分a1甲基丙烯酸甲酯,128.7g组分a2甲基丙烯酸羟乙酯,189.3g组分a1丙烯酸正丁酯,组分a1 164.7g苯乙烯,33.3g引发剂c过氧化二叔丁基(DTBP)混合均匀,在145℃下4h内匀速滴加,由于反应放热,需控制反应温度145±3℃。滴加结束后保温30min。
随后,将43.35g组分a1甲基丙烯酸甲酯,61.2g组分a2甲基丙烯酸羟乙酯,34g组分a1丙烯酸正丁酯,27.15g组分a3丙烯酸,6.53g引发剂c过氧化二叔丁基混合均匀后在1h内匀速滴加完毕,并保温1h。
随后降温至100℃,并加入56.65g中和剂d三乙醇胺保温30min。然后,在30min内加入1040g水分散,并在温度80℃下保温1.5h。最后降温至45℃出料。
该聚丙烯酸水性分散体1的基本参数如下表1所示。
表1
检测项 | 数值 |
酸值(固体) | 26.6mgKOH/g |
非挥发分含量 | 45.8% |
粘度(S64 60rpm,25℃) | 2440cps |
pH | 7.4 |
实施例4:无溶剂的包含羟基官能团的聚丙烯酸水性分散体2的制备
3L的反应容器中加入182g实施例1中的反应性低聚物b-1,升温加热至145℃,预先将368.5g组分a1甲基丙烯酸甲酯,177g组分a2甲基丙烯酸羟乙酯,236.6g组分a1丙烯酸异辛酯,20.1g组分a2叔碳酸缩水甘油酯与丙烯酸反应后的产物,16.6g引发剂c过氧化二叔丁基(DTBP)混合均匀,在145℃下4h内匀速滴加,由于反应放热,需控制反应温度145±3℃。滴加结束后保温30min。
随后,将92.8g组分a1甲基丙烯酸甲酯,73.4g组分a2甲基丙烯酸羟乙酯,26.04g组分a3丙烯酸,3.3g引发剂c过氧化二叔丁基混合均匀后在1h内匀速滴加完毕,并保温1h。
随后降温至100℃,并加入50.5g中和剂d三乙醇胺保温30min。然后,在30min内加入1454.1g水分散,并在温度80℃下保温1.5h。最后降温至45℃出料。
该聚丙烯酸水性分散体2的基本参数如下表2所示。
表2
检测项 | 数值 |
酸值(固体) | 21.5mgKOH/g |
非挥发分含量 | 43.6% |
粘度(S64 60rpm,25℃) | 332cps |
pH | 7.19 |
实施例5:无溶剂的包含羟基官能团的聚丙烯酸水性分散体3的制备
3L的反应容器中加入91.2g实施例1中的反应性低聚物b-1与实施例2中的反应性低聚物b-245.6g(b-1,b-2混合物平均每1mol中含有1.55mol羟基),升温加热至145℃,预先将248.9g组分a1甲基丙烯酸甲酯,125.3g组分a2甲基丙烯酸羟乙酯,157.5g组分a1丙烯酸乙基己酯,70.08g组分a2叔碳酸缩水甘油酯与丙烯酸反应后的产物,24.9g引发剂c过氧化二叔丁基(DTBP)混合均匀,在145℃下2h内匀速滴加,由于反应放热,需控制反应温度145±3℃。滴加结束后保温30min。
随后,将69.6g组分a1甲基丙烯酸甲酯,55.05g组分a2甲基丙烯酸羟乙酯,19.53g组分a3丙烯酸,4.96g引发剂c过氧化二叔丁基混合均匀后在1h内匀速滴加完毕,并保温1h。
随后降温至100℃,并加入37.85g中和剂d三乙醇胺保温30min。然后,在30min内加入765g水分散,并在温度80℃下保温1.5h。最后降温至45℃出料。
该聚丙烯酸水性分散体的基本参数如下表3所示。
表3
检测项 | 数值 |
酸值(固体) | 21.7mgKOH/g |
非挥发分含量 | 43.2% |
粘度(S64 60rpm,25℃) | 2690cps |
pH | 7.17 |
实施例6活化期
为测定活化期,由实施例4中的聚丙烯酸水性分散体配置成涂料后与
268固化剂搭配使用(水可分散异氰酸酯固化剂,基于六亚甲基二异氰酸酯,万华公司)按照-OH:-NCO为1:1.1搭配使用,测定6h内粘度变化,其粘度变化如下图1所示。
从图中可知,本发明的聚丙烯酸水性分散体表现出较长的活化期,在6h内粘度变化小于10KU。本发明实现了在聚丙烯酸分散体的制备过程中无需添加有机溶剂,同时不影响聚丙烯酸分散体在涂料中的性能。
本说明书中所述的只是本发明的较佳具体实施例,以上实施例仅用以说明本发明的技术方案而非对本发明的限制。凡本领域技术人员依本发明的构思通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在本发明的范围之内。
Claims (19)
- 一种制备无溶剂的包含羟基官能团的聚丙烯酸水性分散体的方法,包括步骤:使一种单体或多种单体混合物a在反应性低聚物b的存在下通过引发剂c引发聚合,得到聚丙烯酸共聚物A,加入中和剂d中和,分散在水中;其中,单体混合物a包含以下一种或多种:a1无羟基的丙烯酸酯、无羟基的甲基丙烯酸酯、和/或无羟基的乙烯基芳烃,a2含羟基官能团的丙烯酸酯、含羟基官能团的甲基丙烯酸酯和/或含羟基官能团的乙烯基单体,a3可以自由基聚合的离子和/或潜离子单体;其中,反应性低聚物b包括以下的一个或多个特征:(1)反应性低聚物b不包括可自由基聚合的不饱和键;(2)反应性低聚物b能够与固化剂反应。
- 如权利要求1所述的方法,其特征在于,组分a1选自丙烯酸酯或甲基丙烯酸酯中的一种或多种,其中的醇残基部分中具有1至18个碳原子;优选地,该醇残基部分选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、2-乙基己基、辛基、二甲氨基乙基、环己基、缩水甘油基、月桂基、十二基、乙二醇二甲基或异冰片基中的一种或多种。
- 如权利要求1-2任一项所述的方法,其特征在于,组分a1包含苯乙烯。
- 如权利要求1-3任一项所述的方法,其特征在于,组分a2为含羟基官能团的乙烯基单体;优选地为不饱和羧酸的烷基酯,更优选地选自丙烯酸羟烷基酯和/或甲基丙烯酸羟烷基酯中的一种或多种。
- 如权利要求4所述的方法,其特征在于,组分a2包含丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的一种或多种;优选包含甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的一种或两种。
- 如权利要求1-6任一项所述的方法,其特征在于,组分a3为含羧酸基团的乙烯基单体;优选所述含羧酸基团的乙烯基单体选自含丙烯酸、甲基丙烯酸或二元酸的乙烯基单体;优选的二元酸选自衣康酸、富马酸或马来酸中的一种或多种;更优选地,所述含羧酸基团的乙烯基单体选自丙烯酸或甲基丙烯酸中的一种或两种。
- 如权利要求1-7任一项所述的方法,其特征在于,组分a3包括含有磷酸酯基团的乙烯基单体;优选包括2-羟乙酯甲基丙烯酸酯磷酸酯。
- 如权利要求1-8任一项所述的方法,其特征在于,组分a1至a3的重量份比例范围为:a1为55~90重量份,a2为10~40重量份,a3为0.5~5重量份,以a1,a2,a3的和为100重量份。
- 如权利要求1-9任一项所述的方法,其特征在于,所述反应性低聚物b含有可以和固化剂反应的基团,所述基团包括羟基、氨基、羧基和/或酰胺基;优选地所述基团为羟基;更优选平均每1mol反应性低聚物b含有的羟基不小于1.5mol;更优选地每1mol反应性低聚物b含有2mol的羟基。
- 如权利要求1-9任一项所述的方法,其特征在于,所述反应性低聚物b的分子量范围为200至1000g/mol,优选为200至600g/mol。
- 如权利要求1-11任一项所述的方法,其特征在于,所述反应性低聚物b是脂肪族缩水甘油酯b1和羧酸b2的反应产物;优选地,羧酸b2的羧基数量为2个及以上;更优选地,羧酸b2为羧基数量为2的脂防族羧酸,再更优选为己二酸、庚二酸、辛二酸或其组合。
- 如权利要求1-12任一项所述的方法,其特征在于,反应性低聚物b的质量为组分a1至a3质量之和的5~40%,优选为10~30%,更优选为15~25%。
- 如权利要求1-13任一项所述的方法,其特征在于,所述方法中,在引发剂的作用下引发一种单体或多种单体混合物a的聚合,反应温度范围在50~200℃,优选为100~150℃。
- 如权利要求1-14任一项所述的方法,其特征在于,所述引发剂c为有机过氧化物和/或偶氮化合物,优选为二叔丁基过氧化物和/或偶氮二异丁腈(AIBN),更优选为二叔丁基过氧化物。
- 如权利要求1-15任一项所述的方法,其特征在于,单体a1~a3在反应性低聚物b的存在下分两阶段加入聚合;优选地,第二阶段的亲水单体比例高于第一阶段的亲水单体比例。
- 如权利要求1-16任一项所述的方法,其特征在于,中和剂d为有机胺,优选选自三乙胺、N,N-二甲基乙醇胺、三乙醇胺、乙基二异丙基胺、N,N-二甲基异丙醇胺、N-甲基二乙醇胺和/或二乙基乙醇胺中的一种或多种,更优选选自N,N-二甲基乙醇胺和/或三乙醇胺中的一种或两种。
- 一种由上述权利要求1至17任一项所述方法制得的聚丙烯酸水性分散体,其特征在于,所述聚丙烯酸水性分散体的非挥发分含量范围为30~70%,挥发性有机溶剂含量为0,pH值范围为6~10,优选地所述聚丙烯酸水性分散体A的非挥发分含量范围为40~60%,pH值范围为6.5~8.5。
- 一种水性涂料组合物,包含:1)一种或多种权利要求1至18任一项所述方法制得的聚丙烯酸水性分散体;和2)至少一种可以与羟基反应的固化剂。
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CN116751334A (zh) * | 2023-08-21 | 2023-09-15 | 广州境好新材料有限公司 | 一种水性氨基烤漆用丙烯酸树脂水分散体及其制备方法 |
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US6946515B1 (en) * | 1999-04-01 | 2005-09-20 | Basf Coating Ag | Coating substance consisting of at least three components, method for producing said coating substance and use thereof |
US20060100348A1 (en) * | 2004-11-11 | 2006-05-11 | Bayer Materialscience Ag | Polyester-polyacrylate dispersions with reactive diluents based on hydroxy-functional esters |
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CN116751334B (zh) * | 2023-08-21 | 2023-11-17 | 广州境好新材料有限公司 | 一种水性氨基烤漆用丙烯酸树脂水分散体及其制备方法 |
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