CN102993424B - Novel acrylic acid modified alkyd resin and method for preparing same - Google Patents

Novel acrylic acid modified alkyd resin and method for preparing same Download PDF

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CN102993424B
CN102993424B CN201210489242.2A CN201210489242A CN102993424B CN 102993424 B CN102993424 B CN 102993424B CN 201210489242 A CN201210489242 A CN 201210489242A CN 102993424 B CN102993424 B CN 102993424B
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acrylic
modified alkyd
alkyd resin
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acid
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CN102993424A (en
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周法华
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上海振华重工(集团)常州油漆有限公司
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Abstract

本发明的任务是提供一种丙烯酸改性的醇酸树脂,它提高了醇酸树脂的硬度、干性、耐磨擦性以及耐老化性能,同时又保留了醇酸树脂特有的柔韧性、颜料润湿性等特征;同时本发明的丙烯酸改性醇酸树脂解决了市场上普通丙烯酸改性醇酸树脂耐酸碱性不良的问题。 Object of the invention is to provide an acrylic-modified alkyd resin, it improves the rigidity of the alkyd resin, dry, abrasion resistance and aging resistance, while retaining the unique flexibility alkyd resin, a pigment wettability characteristics; while acrylic modified alkyd resin of the present invention solves the poor market ordinary acrylic acid modified alkyd resins problem. 本发明产品按照GB/T 9274-1988经耐液体介质实验测定,48h漆膜不气泡、不生锈、不开裂、不脱落,明显优于传统的大豆油醇酸树脂和普通丙烯酸改性醇酸树脂。 The liquid product of the present invention, the experimentally determined dielectric GB / T 9274-1988 via resistance, 48h film no bubbles, no rust, no cracking, no loss, significantly better than conventional soybean oil alkyd and acrylic modified alkyd Normal resin.

Description

一种丙烯酸改性醇酸树脂及其制备方法 Preparing a modified alkyd resin and acrylic acid

技术领域 FIELD

[0001] 本发明属于树脂领域,尤其是丙烯酸改性醇酸树脂及其制备方法。 [0001] The present invention belongs to the field of resins, especially acrylic acid modified alkyd resin and preparation method.

背景技术 Background technique

[0002] 醇酸树脂系涂膜丰满、光亮,以其易于施工和与氧气交联的特性,它的颜料分散性、涂料的施工性较好,涂膜柔韧坚牢、合成技术成熟、原料易得、树脂涂膜的综合性能良好,而且基本上不依赖于石油产品,具有独一无二的价格优势,是涂料用合成树脂中用量最大、用途最广的品种之一。 [0002] alkyd resin-based coating fullness, bright, easy construction and its properties and oxygen crosslinking, pigment dispersibility its construction better coating, film flexibility fastness, synthesis technology is mature, easy to feed too, good overall performance of the resin coating film, and substantially independent of petroleum products, with a unique price advantage, the amount of coating is one of the largest, most widely used variety of synthetic resins. 但醇酸树脂涂膜干燥缓慢、硬度低、耐水性、耐腐蚀性差,不佳等限制了醇酸树脂的使用范围。 But slow drying alkyd resin coating film, low hardness, water resistance and poor corrosion resistance, such as poor limit the scope of the alkyd resin. 然而,丙烯酸树脂色浅、耐光、耐候、户外暴晒耐久性好,使用的温度范围宽,刚好能在一些性能上能弥补醇酸树脂性能的不足。 However, an acrylic resin light color, light resistance, weatherability, durability outdoor exposure, using a wide range of temperatures, just to be able to compensate for the lack of performance in an alkyd resin some properties. 但是,丙烯酸树脂的颜料分散性、涂料施工性以及涂膜的柔韧性和耐寒性都不理想,价格也比较昂贵。 However, a pigment dispersible acrylic resins, coatings and coating workability and cold flexibility is not over, the price is more expensive. 这些欠缺也限制了丙烯酸树脂的使用范围。 These also limit the use of the lack of an acrylic resin.

[0003] 丙烯酸改性醇酸树脂广泛应用于户外大型钢结构及轮船等的装饰与保护,在经常受到紫外光、高湿度及海水等的侵蚀条件下,传统醇酸树脂涂料在这些条件下使用会出现粉化、退色和失光等不良现象。 [0003] The acrylic-modified alkyd resins are widely used in large-scale outdoor decoration and protection of steel structures and ships, etc., conventional alkyd coatings used under these conditions often subjected to ultraviolet light under aggressive conditions, such as high humidity and water It will exhibit chalking, fading and loss of light and other undesirable phenomena. 丙烯酸改性醇酸树脂弥补了醇酸树脂涂膜的耐候性及耐久性不足的缺陷,延长其使用寿命。 Acrylic modified alkyd resin an alkyd resin coating film to make up for deficiencies of weather resistance and insufficient durability, extending its life. 丙烯酸改性醇酸树脂涂料还可应用于火车车厢涂料、纺织机构涂料及中高档溶剂型外墙涂料等。 Acrylic modified alkyd resin coatings may also be applied to the railcar coatings, textile coatings and bodies of high-grade solvent-based exterior paint.

[0004] 丙烯酸改性醇酸树脂涂料的发展趋势为高性能、高固体分含量、功能化、水性化。 [0004] Trend acrylic modified alkyd resin paint for high-performance, high solids content, functional, water-based. 高性能指改性树脂在克服醇酸树脂缺陷的基础上,解决现有丙烯酸改性醇酸树脂的外观、耐溶剂性、抗冲击性、重涂性及超强的耐侯性等方面的不足,扩大其应用领域。 It refers to high performance on the basis of modified resin to overcome the defects on the alkyd resin, to solve the deficiencies of conventional appearance acrylic modified alkyd resin, solvent resistance, impact resistance, and recoatability superior weather resistance and the like, expand its application areas. 高固体分含量和水性化是涂料发展的趋势,是环保法对涂料VOC含量严格限制的结果。 High solid content and water-based paint is the development trend is the result of environmental laws strictly limit the VOC content of paint. 提高改性树脂的固体含量,可以从分子结构入手,设计低分子量、具有高反应活性的官能化丙烯酸低聚物,同时结合使用部分高效溶剂;改性树脂的水性化一方面可采用乳液聚合方法合成丙烯酸醇酸树脂乳液,另一方面可采用脂肪酸法合成改性水溶性醇酸树脂,提高水性醇酸涂料的耐黄变性及干燥速度。 Increase the solids content of the modified resin, available from the molecular structure, the design of low molecular weight oligomer having a functional acrylic highly reactive, while efficiently using solvent bonding portion; modified resin of the aqueous emulsion polymerization process may be used on the one hand synthesis of acrylic alkyd emulsions, fatty acid-modified synthetic methods may be employed on the other hand a water-soluble alkyd resin, resistance to yellowing and improved the drying speed of the aqueous alkyd paint. 功能化改性树脂的制造可在丙烯酸预聚物中引入官能基团(如引入卤素、磷等),将官能基团引入醇酸树脂分子上,合成阻燃、防水、防油和防霉杀菌等功能树脂。 Producing a functional modification can be introduced in the acrylic resin prepolymer functional groups (e.g., introduction of halogen, phosphorus, etc.), the functional groups introduced into the alkyd resin molecule, synthetic flame retardant, water, oil, and of sterilization and other functional resins.

[0005]目前,市场上的丙烯酸改性醇酸树脂普遍存在耐酸碱性不良的弊端,因此研发一款新的具有优良耐酸碱性的丙烯酸改性醇酸树脂是一个急待解决的问题。 [0005] Currently, acrylic modified alkyd resin on the prevailing adverse market disadvantages of acid and alkali resistance, thus developing a new acrylic modified alkyd resin has excellent acid and alkali resistance is a pressing problem .

发明内容 SUMMARY

[0006] 本发明的任务是提供一种丙烯酸改性的醇酸树脂,解决市场上普通丙烯酸改性醇酸树脂耐酸碱性不良的问题。 Task [0006] The present invention is to provide an acrylic-modified alkyd resins, ordinary market solve the acrylic modified alkyd resins problem of poor acid.

[0007] 为解决上述技术问题本发明的新型丙烯酸改性醇酸树脂采用的技术方案为:本发明的丙烯酸改性醇酸树脂具有优良的酸碱性能。 [0007] In order to solve the above problems novel aspect of the present invention, acrylic modified alkyd resins employed are: acrylic modified alkyd resin of the present invention has excellent acid-base properties.

[0008] 其具体制备方法如下: [0008] Specific preparation methods are as follows:

[0009] (I)将二甲苯和乙酸乙酯的混合溶液搅拌升温,待温度达到100-110°c时保温O. 5-1小时,然后开始滴加引发剂、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸正丁酯(n-BA)以及甲基丙烯酸(MA)的混合物进行共聚合反应,滴加时间控制在2-3小时,制备出丙烯酸预聚物; [0009] (I) mixed solution of xylene and warmed ethyl acetate was stirred until the temperature reached 100-110 ° c incubation O. 5-1 hours, then dropwise addition of initiator, methyl methacrylate (MMA ), styrene (St), n-butyl acrylate (n-BA) and methacrylic acid (MA) in the copolymerization reaction, the dropwise addition time control in 2-3 hours, to prepare an acrylic prepolymer;

[0010] 所述丙烯酸预聚物的配方组份含量以重量百分比计为:二甲苯48. 76-52. 17%,乙酸乙酯7. 51-11. 23%,甲基丙烯酸甲酯19. 38-24. 26%,丙烯酸正丁酯7. 32-9. 88%,甲基丙烯酸O. 91-1. 73%,苯乙烯5. 11-9. 27%,引发剂O. 50-1. 97%。 [0010] Formulation parts of the acrylic prepolymer component content in percent by weight: 48. Xylene 76-5217% ethyl acetate 7 51-1123%, methyl methacrylate 19. 38-24. 26% n-butyl acrylate, 7. 32-9. 88% methacrylic O. 91-1. 73%, styrene 5. 11-9. 27%, initiator O. 50-1 97%.

[0011] (2)将大豆油和季戊四醇加入反应釜升温到140°C〜150°C后加入催化剂继续升温到240°C〜250°C,待醇清后降温到140°C〜150°C加入步骤(I)的丙烯酸预聚物以及邻苯二甲酸酐和苯甲酸;待温度升到170-180°C时以10-12°C /h的升温速率缓慢升温至240-250°C进行酯化缩合反应,待树脂酸值降到6-10mgK0H/g后停止加热,最后用二甲苯兑稀,制备出丙烯酸改性醇酸树脂; After [0011] (2) Add soybean oil and pentaerythritol kettle was heated to 140 ° C~150 ° C catalyst was added to continue to heat up 240 ° C~250 ° C, until clear alcohol cooled to 140 ° C~150 ° C added in step (I) the acrylate oligomer and benzoic acid and phthalic anhydride; time until the temperature rose to 170-180 ° C to 10-12 ° C / h ramp rate was slowly warmed to 240-250 ° C for esterification condensation reaction, until the resin acid value dropped 6-10mgK0H / g the heating was stopped, and finally xylene letdown, acrylic modified alkyd resins prepared;

[0012] 所述丙烯酸改性醇酸树脂的配方组份含量以重量百分比计为:大豆油20. 20-26. 18 %,季戊四醇7. 81-12. 46 %,催化剂O. 08-0. 12 %,丙烯酸预聚物20. 49-26. 84 %,苯甲酸2. 05-4. 48 %,邻苯二甲酸酐7. 90-11. 24 %,二甲苯27. 25-33. 45%。 [0012] The formulations parts acrylic modified alkyd resin component content in percent by weight: 20. A soybean 20-2618% pentaerythritol 7. 81-1246% catalyst O. 08-0... 12% acrylate oligomer 20. 49-26. 84%, benzoic 2. 05-4. 48%, phthalic anhydride, 7. 90-11 24% 25-33 27 xylenes. 45 %.

[0013] 本发明步骤(I)的丙烯酸预聚物采用“饥饿法”滴加合成。 [0013] Step acrylate present invention (I) using prepolymer "starvation" Synthesis dropwise. “饥饿法”滴加合成是首先将溶液加入反应釜升温到适合温度,然后通过高位槽滴加甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸正丁酯(n-BA)、甲基丙烯酸(MA)以及引发剂的混合物,这样可以通过改变混合物的滴加速率来调节共聚合反应的速率,以达到控制丙烯酸预聚物分子质量的目的; "Starvation" Synthesis was dropwise added to the kettle and the solution was first heated to a suitable temperature, followed by dropwise addition of methyl methacrylate (MMA), styrene (St), n-butyl acrylate (n-BA) by the high slot, methacrylic acid (MA), and mixtures of such initiators, so that the rate may be adjusted by changing the copolymerization reaction mixture during the dropwise rate, in order to control the molecular weight of acrylate oligomer;

[0014] 同时还可以通过改变混合物的滴加速率来调节反应釜内温度的变化,以达到使引发剂效率最大化的目的。 [0014] can also be adjusted while the kettle temperature changes by changing the addition rate of the mixture, in order to achieve the purpose of maximizing the efficiency of initiator agent.

[0015] 丙烯酸(酯)单体的共聚反应有本体聚合、乳液聚合、溶液聚合、悬浮聚合等多种方法。 [0015] The copolymerization reaction of acrylic acid (acrylate) monomers include bulk polymerization, emulsion polymerization, various methods, solution polymerization, suspension polymerization and the like. 本发明步骤(I)中丙烯酸预聚物的合成采用溶液法,它是丙烯酸(酯)单体在溶液状态下通过自由基聚合反应合成而成。 Invention, step (I) of this acrylic Prepolymer solution method, which is an acrylic (ester) monomer in a solution state obtained by synthesizing by radical polymerization reaction. 其优点是体系粘度低而避免了凝胶效应;受热均匀,聚合温度容易控制;易于调节产品的相对分子质量及其分布。 The advantage is a low viscosity system avoids gel effect; uniformly heated, the polymerization temperature is easily controlled; easy to adjust the molecular weight of the product and its distribution. 其缺点是聚合速率低,相对分子质量小,在这里我们就是利用其合成的预聚物相对分子质量低的缺点,如果预聚物的分子质量过大,后面合成改性醇酸树脂时树脂粘度会过大,容易胶化。 The disadvantage is the low rate of polymerization, a small molecular weight, here we are using the synthesis low molecular weight prepolymer disadvantage if prepolymer molecular weight is too large, the back viscosity synthetic resin-modified alkyd resin It will be too large, easy to gel.

[0016] 本发明步骤(I)以引发剂、甲基丙烯酸甲酯(MMA)和苯乙烯(St)作为硬单体来提供树脂需要的硬度;丙烯酸正丁酯(n-BA)作为软单体来调节预聚物的玻璃化温度;甲基丙烯酸(MA)作为功能单体来提供后续反应需要的官能团。 [0016] The steps of the present invention (I) to initiate the polymerization of methyl methacrylate (MMA) and styrene (St) as a hard monomer providing desired hardness of the resin; n-butyl acrylate (n-BA) as a soft single body to regulate the glass transition temperature of the prepolymer; methacrylic acid (MA) as the functional monomer provides a functional group for subsequent reaction required. 甲基丙烯酸甲酯(MMA)和苯乙烯(St)具有很高的玻璃化温度,可以提供树脂需要的硬度,使得制备出的改性醇酸树脂具有优良的硬度。 Methyl methacrylate (MMA) and styrene (St) having a high glass transition temperature, hardness of the resin needs to be provided so that the modified alkyd resins prepared having excellent hardness. 同时大量使用甲基丙烯酸甲酯(MMA)和苯乙烯(St)也极大的提高了该丙烯酸改性醇酸树脂的耐酸碱性。 While a large number of methyl methacrylate (MMA) and styrene (St) also greatly improves the acid resistance of the acrylic-modified alkyd resin.

[0017] 本发明步骤(I)所述的引发剂有两大类:有机过氧化物和偶氮化合物,不同的引发剂引发效率和半衰期有很大差别,通常要根据实验的目的及方法来选择合适的引发剂。 [0017] invention, step (I) of the initiator in two categories: organic peroxides and azo compounds, various initiators efficiency and half-life are very different, depending on the purpose and is usually added to the experimental method suitable initiators selected.

[0018] 上述适用于丙烯酸溶液聚合的引发剂多为苯甲酰类和腈类偶氮化合物,如过氧化苯甲酰(BPO)、偶氮二异丁腈(AIBN)、2,2-偶氮二(甲基丁腈)、2,2-偶氮(2,4- 二甲基戊腈)等。 [0018] The acrylic acid solution suitable polymerization initiator benzoyl mostly azo compounds and nitriles, such as benzoyl peroxide (the BPO), azobisisobutyronitrile (AIBN), 2,2- Even azobis (methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile) and the like.

[0019] 本发明步骤(I)的丙烯酸预聚物原材料要求严格不能含有水份,同时要保证单体的纯度。 [0019] Step acrylate present invention (I) a prepolymer containing raw water not critical, while ensuring the purity of the monomers. 原材料中的水份会降低引发剂的效率;单体不纯会使合成的预聚物不透明,影响产品质量。 The raw water will reduce the efficiency of the initiator; impure monomer prepolymer synthesis opaque will affect product quality.

[0020] 本发明步骤(I)的丙烯酸预聚物的丙烯酸(酯)单体要求纯度彡99. 5%,以避免合成的预聚物出现浑浊现象。 [0020] Step acrylate present invention (I) a prepolymer of acrylic acid (ester) monomer in claim San purity 99.5%, in order to avoid the synthesis of prepolymers turbidity phenomenon.

[0021] 本发明步骤⑴的丙烯酸预聚物的合成温度要求较为严格,应当控制在100-110°c,温度过低,引发剂的引发效率不高,制得的预聚物分子质量相对较大,对后面树脂合成影响较大;温度过高,引发剂半衰期短,利用率低,合成的预聚物分子质量相对较低,残余单体量较大。 [0021] Step invention ⑴ acrylic prepolymer synthesis temperature more stringent requirements, should be controlled at 100-110 ° c, the temperature is too low, the efficiency of initiator initiator agent is not high, the resulting molecular weight of the prepolymer relatively large influence on the synthetic resin larger rear; high temperature, initiator half-life is short, the use of low molecular weight prepolymer synthesis is relatively low, a large amount of residual monomer.

[0022] 本发明步骤(2)中丙烯酸改性醇酸树脂的合成采用单甘油酯法,以季戊四醇、大豆油、邻苯二甲酸酐、苯甲酸、丙烯酸单体预聚物为主要合成原料。 [0022] Step (2) Synthesis of acrylic acid-modified alkyd resin using method monoglyceride, pentaerythritol, soya oil, phthalic anhydride, benzoic acid, acrylic monomer prepolymer synthesis the main raw material of the present invention. 采用支化程度最高的季戊四醇作为主要合成原料丰富了醇酸树脂的结构,同时它还能提供硬度。 With the highest degree of branching rich pentaerythritol alkyd resin structure as a main raw material for synthesis, while it can also provide stiffness.

[0023] 本发明步骤(2)中所述的大豆油、季戊四醇、邻苯二甲酸酐、苯甲酸、溶剂二甲苯均为工业级。 [0023] The (2) in the present invention, the step of soybean oil, pentaerythritol, phthalic anhydride, benzoic acid, are industrial grade xylene solvent. 其中季戊四醇纯度> 95%、羟基含量为45-49%。 Wherein pentaerythritol purity> 95%, hydroxyl content of 45-49%.

[0024] 本发明步骤(2)中没有催化剂时,油与醇的反应即使在高温下也进行的非常慢,而且程度低,因此需要加入催化剂。 [0024] The present invention step (2) in the absence of catalyst, reaction of the oil with an alcohol at high temperature even for very slow and low level, thus requiring addition of a catalyst.

[0025] 上述步骤(2)常用的醇解催化剂有氧化钙、氢氧化钙、环烷酸钴、氧化铅、环烷酸铅、氢氧化锂或环烷酸锂。 [0025] The above step (2) commonly used alcoholysis catalysts are calcium oxide, calcium hydroxide, cobalt naphthenate, lead oxide, lead naphthenate, lithium hydroxide or lithium naphthenate. 催化剂可使醇解速率与深度大为提高,但催化剂的用量应控制在一个限度之内,钙和铅催化剂的过多使用会使树脂发浑。 Alcoholysis catalyst can greatly enhance the rate and depth, but the amount of the catalyst should be controlled within a limit, the excessive use of calcium and lead will resin catalyst muddy.

[0026] 本发明步骤⑵中的醇清测试采用乙醇容忍度法。 Step invention ⑵ [0026] the alcohol present is ethanol tolerance clearance test method. 醇清终点的测试方法有甲醇容忍度试验法、乙醇容忍度试验法、发浑点法、电导率法。 Test Method alcohols are methanol clear endpoint tolerance test, ethanol tolerance test, muddy point method, electrical conductivity method. 具体测试步骤为取Iml醇解物,在250C以95%乙醇滴定至浑浊不消失为终点。 Specific steps taken Iml test alcoholysis was 250C in 95% ethanol was titrated to end point turbidity does not disappear. 我们采用乙醇容忍度法是因为甲醇毒性比乙醇大,发浑点法操作较为复杂,电导率法对仪器设备要求较高。 Ethanol tolerance method we used is methanol because toxic than ethanol, muddy-point method is more complex, higher conductivity methods equipment requirements.

[0027] 本发明的有益效果是:本发明的新型丙烯酸改性醇酸树脂具有优良的干性、耐候性、耐摩擦性、耐老化性、耐酸碱性,具体优点和使用效果如下: [0027] Advantageous effects of the present invention are: novel acrylic-modified alkyd resin according to the present invention has excellent dry, weather resistance, abrasion resistance, aging resistance, acid and alkali resistance, and the effect of the following particular advantages:

[0028] I、优良的干性:该树脂清漆能达到5-8小时实干,比普通大豆油醇酸树脂干性缩短2/3的时间。 [0028] I, excellent dry: The resin varnish can reach 5-8 hours of hard work, 2/3 times shorter than normal soybean oil alkyd resin dry.

[0029] 2、优良的机械性能:附着力、抗冲击、硬度、柔韧性等均佳。 [0029] 2, excellent mechanical properties: adhesion, impact resistance, hardness, flexibility, etc. is good.

[0030] 3、优异的施工性能:该树脂成漆后和其他溶剂型涂料一样,可采用刷、喷、浸、辊等各种方法施工。 [0030] 3, good workability: the lacquer resin and other solvent-based coatings, as employed brushing, spraying, dipping a variety of methods, roll construction.

[0031] 4、较强的耐候性:按照GB/T9276-1996经自然气候曝露实验方法,漆膜不气泡、不生锈、不开裂、不脱落,耐久寿命达3-5年,比传统的大豆油醇酸树脂长。 [0031] 4, strong weather resistance: according to GB / T9276-1996 experimentally by exposure to natural weathering, the film no bubbles, no rust, no cracking, no loss, the durability life of 3--5 years, than conventional soybean oil length alkyd resin.

[0032] 5、超强的耐酸碱性:按照GB/T9274-1988经耐液体介质实验测定,48h漆膜不气泡、不生锈、不开裂、不脱落,明显优于传统的大豆油醇酸树脂和普通丙烯酸改性醇酸树脂。 [0032] 5, the super acid and alkali resistance: according to GB / T9274-1988 liquid measured by resistance to experimental medium, 48h film no bubbles, no rust, no cracking, no loss, significantly better than conventional soybean oil alcohol acid resin and ordinary acrylic modified alkyd resin. 我们通过实验验证得出,市场上存在的丙烯酸改性醇酸树脂普遍耐酸碱性不良,按照GB/T9274-1988经耐液体介质实验测定,48h后漆膜出现气泡、生锈、以及部分脱落,限制了丙烯酸改性醇酸树脂的使用范围。 We verified by experiment results, the present market acrylic modified alkyd resin generally poor acid resistance, measured in accordance with GB / T9274-1988 via a liquid medium resistance test, film air bubbles after 48h, rust, and some off , limit the use of acrylic-modified alkyd resin.

[0033] 6、自干型的丙烯酸改性的醇酸树脂,它成漆后不需要加入固化剂即可固化成膜,易于施工。 [0033] 6, from acrylic-modified alkyd resins drying, after which the lacquer can be cured without adding a curing agent deposition, easy construction.

具体实施方式 Detailed ways

[0034] 实施例I [0034] Example I

[0035] (I)将二甲苯和乙酸乙酯的混合溶液搅拌升温,待温度达到1001:时保温0.5小时,然后开始滴加引发剂过氧化苯甲酰(BPO)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸正丁酯(n-BA)以及甲基丙烯酸(MA)是混合物进行共聚合反应,滴加时间控制在2小时,最后制备出丙烯酸预聚物; [0035] (I) mixed solution of xylene and warmed ethyl acetate was stirred until the temperature reached 1001: for 0.5 hours, then dropwise addition of benzoyl peroxide initiator (the BPO), methyl methacrylate ( MMA), styrene (St), n-butyl acrylate (n-BA) and methacrylic acid (MA) is a copolymerization reaction mixture was added dropwise in 2 hours time control, the final prepared acrylic prepolymer;

[0036] 所述丙烯酸预聚物的配方组份含量以重量百分比计为:二甲苯51. 69%,乙酸乙酯7. 67%,甲基丙烯酸甲酯23. 55%,丙烯酸正丁酯7. 84%,甲基丙烯酸I. 62%,苯乙烯 [0036] The parts of acrylic acid component content of the prepolymer formulation in percent by weight: 51.69% of xylene, ethyl acetate 7.67%, 23.55% methyl methacrylate, n-butyl acrylate 7 84% methacrylic acid I. 62%, styrene

6. 13%,引发剂I. 50%。 6.13%, initiator I. 50%.

[0037] (2)将大豆油和季戊四醇加入反应釜升温到140°C后加入催化剂LiOH继续升温到240°C,待醇清后降温到150°C以下加入步骤(I)的预聚物以及邻苯二甲酸酐和苯甲酸;待温度升到170°C时再以10°C /h的升温速率缓慢升温至240°C进行酯化缩合反应,待树脂酸值降到10mgK0H/g后停止加热,最后用二甲苯兑稀,制备出丙烯酸改性醇酸树脂; After [0037] (2) Add soybean oil and pentaerythritol kettle was heated to 140 ° C was added LiOH continue to heat the catalyst to 240 ° C, until clear alcohol cooled to below 150 ° C is added in step (I) a prepolymer and benzoic acid and phthalic anhydride; the time until the temperature rose to 170 ° C and then at 10 ° C / h ramp rate was slowly warmed to 240 ° C for esterification condensation reaction, until the resin acid value decreased 10mgK0H / g stop heating, and finally xylene letdown, acrylic modified alkyd resins prepared;

[0038] 所述丙烯酸改性醇酸树脂的配方组份含量以重量百分比计为:大豆油22. 16%,季戊四醇10. 33%,催化剂LiOHO. 10%,预聚物25. 17%,苯甲酸3. 06%,邻苯二甲酸酐9. 87%,二甲苯29. 31%。 [0038] The formulations parts acrylic modified alkyd resin component content in percent by weight: 22.16% soybean oil, pentaerythritol 10.33%, catalyst LiOHO 10%, 25.17% prepolymer, benzene. 3.06% formic acid, phthalic anhydride, 9.87% xylene 29.31%.

[0039] 实施例2 [0039] Example 2

[0040] (I)将二甲苯和乙酸乙酯的混合溶液加入反应釜搅拌升温,待温度达到110°C时保温I小时,然后开始滴加引发剂偶氮二异丁腈(AIBN)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸正丁酯(n-BA)以及甲基丙烯酸(MA)是混合物进行共聚合反应,滴加时间控制在3小时,制备出丙烯酸预聚物; [0040] (I) the mixed solution of xylene and ethyl acetate added to the reaction kettle heated with stirring, incubated I hour until the temperature reaches 110 ° C, and then dropwise addition of initiator azobisisobutyronitrile (AIBN), A methacrylate (MMA), styrene (St), n-butyl acrylate (n-BA) and methacrylic acid (MA) is a copolymerization reaction mixture dropwise over at 3 hours to prepare a prepolymerized acrylate thing;

[0041] 所述丙烯酸预聚物的配方组份含量以重量百分比计为:二甲苯50. 04%,乙酸乙酯9. 82%,甲基丙烯酸甲酯20. 06%,丙烯酸正丁酯8. 90%,甲基丙烯酸I. 87%,苯乙烯 [0041] The parts of acrylic acid component content of the prepolymer formulation in percent by weight: 50.04% of xylene, ethyl acetate 9.82%, 20.06% methyl methacrylate, n-butyl acrylate, 8 90% methacrylic acid I. 87%, styrene

7. 51%,引发剂I. 80%。 7.51%, initiator I. 80%.

[0042] (2)将大豆油和季戊四醇加入反应釜升温到150°C后加入催化剂氧化钙继续升温到250°C,待醇清后降温到140°C以下加入步骤(I)的预聚物以及邻苯二甲酸酐和苯甲酸;待温度升到180°C时再以12°C /h的升温速率缓慢升温至250°C进行酯化缩合反应,待树脂酸值降到6mgK0H/g后停止加热,最后用二甲苯兑稀,制备出丙烯酸改性醇酸树脂; [0042] (2) Add soybean oil and pentaerythritol The autoclave is heated to 150 ° C was added calcium oxide catalysts continue to heat up to 250 ° C, until clear alcohol cooled to 140 ° C was added the following step (I) a prepolymer when the temperature was raised until 180 ° C and then to 12 ° C / h ramp rate of 250 ° C was slowly warmed to esterification condensation reaction, until the resin acid value decreased 6mgK0H / g; and benzoic acid, and phthalic anhydride heating was stopped, and finally xylene letdown, acrylic modified alkyd resins prepared;

[0043] 所述丙烯酸改性醇酸树脂的配方组份含量以重量百分比计为:大豆油24. 87%,季戊四醇9. 16%,催化剂O. 10%,预聚物22. 44%,苯甲酸3. 14%,邻苯二甲酸酐10. 09%,二甲苯30. 20%。 [0043] The formulations parts acrylic modified alkyd resin component content in percent by weight: 24.87% soybean oil, 9.16% of pentaerythritol, a catalyst O. 10%, 22.44% prepolymer, benzene 3.14% formic acid, phthalic anhydride, 10.09%, xylene, 30.20%.

[0044] 实施例3 [0044] Example 3

[0045] (I)将二甲苯和乙酸乙酯的混合溶液加入反应釜搅拌升温,待温度达到110°C时保温I小时,然后开始滴加引发剂2,2-偶氮二(甲基丁腈)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸正丁酯(n-BA)以及甲基丙烯酸(MA)是混合物进行共聚合反应,滴加时间控制在2. 5小时,最后制备出丙稀酸预聚物; I hour incubation [0045] (I) the mixed solution of xylene and ethyl acetate added to the reaction kettle heated with stirring until the temperature reached 110 ° C, and then dropwise addition of 2,2-azobis (methylbut carbonitrile), methyl methacrylate (MMA), styrene (St), n-butyl acrylate (n-BA) and methacrylic acid (MA) is a copolymerization reaction mixture was added dropwise in 2.5 hours time control Finally, acrylic acid was prepared prepolymer;

[0046] 所述丙烯酸预聚物的配方组份含量以重量百分比计为:二甲苯52. 17%,乙酸乙酯11.23%,甲基丙烯酸甲酯19. 38%,丙烯酸正丁酯9. 88%,甲基丙烯酸I. 73%,苯乙烯5. 11%,引发剂O. 50%o [0046] The parts of acrylic acid component content of the prepolymer formulation in percent by weight: 52.17% of xylene, ethyl acetate 11.23%, 19.38% methyl methacrylate, n-butyl acrylate 9.88 %, methacrylic acid I. 73%, 5.11% styrene, initiator O. 50% o

[0047] (2)将大豆油和季戊四醇加入反应釜升温到150°C后加入催化剂氧化铅继续升温到240°C,待醇清后降温到140°C以下加入步骤(I)的预聚物以及邻苯二甲酸酐和苯甲酸;待温度升到180°C时再以10°C /h的升温速率缓慢升温至240°C进行酯化缩合反应,待树脂酸值降到10mgK0H/g后停止加热,最后用二甲苯兑稀,制备出丙烯酸改性醇酸树脂; [0047] (2) Add soybean oil and pentaerythritol The autoclave is heated to 150 ° C was added lead oxide catalysts continue to heat up to 240 ° C, until clear alcohol cooled to 140 ° C was added the following step (I) a prepolymer when the temperature was raised until 180 ° C and then at 10 ° C / h ramp rate was slowly warmed to 240 ° C for esterification condensation reaction, until the resin acid value decreased 10mgK0H / g; and benzoic acid, and phthalic anhydride heating was stopped, and finally xylene letdown, acrylic modified alkyd resins prepared;

[0048] 所述丙烯酸改性醇酸树脂的配方组份含量以重量百分比计为:大豆油20. 20%,季戊四醇12. 46%,催化剂O. 12%,预聚物26. 84%,苯甲酸2. 05%,邻苯二甲酸酐7. 90%,二甲苯30. 43%。 [0048] The formulations parts acrylic modified alkyd resin component content in percent by weight: 20.20% soybean oil, pentaerythritol 12.46%, catalyst O. 12%, 26.84% prepolymer, benzene 2.05% formic acid, phthalic anhydride, 7.90% xylene 30.43%.

[0049] 实施例4 [0049] Example 4

[0050] (I)将二甲苯和乙酸乙酯的混合溶液加入反应釜搅拌升温,待温度达到110°C时保温I小时,然后开始滴加引发剂2,2-偶氮(2,4-二甲基戊腈)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸正丁酯(n-BA)以及甲基丙烯酸(MA)是混合物进行共聚合反应,滴加时间控制在3小时,最后制备出丙稀酸预聚物; [0050] (I) the mixed solution of xylene and ethyl acetate added to the reaction kettle heated with stirring, incubated I hour until the temperature reaches 110 ° C, and then dropwise addition of 2,2-azobis (2,4- dimethylvaleronitrile), methyl methacrylate (MMA), styrene (St), n-butyl acrylate (n-BA) and methacrylic acid (MA) is a copolymerization reaction mixture dropwise over control for 3 hours to prepare a final acrylic prepolymer;

[0051] 所述丙烯酸预聚物的配方组份含量以重量百分比计为:二甲苯48. 76%,乙酸乙酯7. 51%,甲基丙烯酸甲酯24. 26%,丙烯酸正丁酯7. 32%,甲基丙烯酸O. 91%,苯乙烯 [0051] The parts of acrylic acid component content of the prepolymer formulation in percent by weight: 48.76% of xylene, ethyl acetate 7.51%, 24.26% methyl methacrylate, n-butyl acrylate 7 32% methacrylic acid O. 91%, styrene

9. 27%,引发剂I. 97%。 9.27%, initiator I. 97%.

[0052] (2)将大豆油和季戊四醇加入反应釜升温到140°C后加入催化剂环烷酸锂继续升温到250°C,待醇清后降温到150°C以下加入步骤(I)的预聚物以及邻苯二甲酸酐和苯甲酸;待温度升到180°C时再以10°C /h的升温速率缓慢升温至240°C进行酯化缩合反应,待树脂酸值降到8mgK0H/g后停止加热,最后用二甲苯兑稀,制备出丙烯酸改性醇酸树脂; After the precatalyst lithium naphthenate [0052] (2) Add soybean oil and pentaerythritol kettle was heated to 140 ° C was added to continue to heat up 250 ° C, until clear alcohol cooled to below 150 ° C is added in step (I) is terpolymers and benzoic acid and phthalic anhydride; time until the temperature rose to 180 ° C and then at 10 ° C / h ramp rate was slowly warmed to 240 ° C for esterification condensation reaction, until the resin acid value decreased 8mgK0H / g stopped heating, the final letdown xylene, acrylic modified alkyd resins prepared;

[0053] 所述丙烯酸改性醇酸树脂的配方组份含量以重量百分比计为:大豆油22. 45%,季戊四醇7.81%,催化剂O. 08%,预聚物20. 49 %,苯甲酸4. 48 %,邻苯二甲酸酐11. 24%,二甲苯33. 45%。 [0053] The formulations parts acrylic modified alkyd resin component content in percent by weight: 22.45% soybean oil, 7.81% of pentaerythritol, a catalyst O. 08%, 20.49% prepolymer, benzoic acid 4 48% phthalic anhydride, 11.24%, xylene, 33.45%.

Claims (7)

1.一种丙烯酸改性醇酸树脂的制备方法,其特征在于:其具有优良的耐酸碱性能;制备方法包括步骤如下: (1)将二甲苯和乙酸乙酯的混合溶液搅拌升温,待温度达到100-110°c时保温0.5-1小时,然后开始滴加引发剂、甲基丙烯酸甲酯、苯乙烯、丙烯酸正丁酯以及甲基丙烯酸的混合物进行共聚合反应,滴加时间控制在2-3小时,制备出丙烯酸预聚物; 所述丙烯酸预聚物的配方组份含量以重量百分比计为:二甲苯48.76-52.17%,乙酸乙酯7.51-11.23%,甲基丙烯酸甲酯19.38-24.26%,丙烯酸正丁酯7.32-9.88%,甲基丙烯酸0.91-1.87%,苯乙烯5.11-9.27%,引发剂0.50-1.97% ; (2)将大豆油和季戊四醇加入反应釜升温到140°C〜150°C后加入催化剂继续升温到240°C〜250°C,待醇清后降温到140°C〜150°C加入步骤(I)的丙烯酸预聚物以及邻苯二甲酸酐和苯甲酸;待温度升到170-180°C时以10-12°C /h的升温速率缓 CLAIMS 1. A method for preparing an acrylic-modified alkyd resin, characterized in that: it has excellent chemical resistance properties; preparation method comprising the steps of: (1) A mixed solution of xylene and ethyl acetate was stirred warming to be holding the temperature reached 100-110 ° c 0.5-1 h before dropwise addition of initiator, methyl methacrylate, styrene, n-butyl acrylate, methacrylic acid and mixtures of the co-polymerization reaction, the dropwise addition time control 2-3 hours to prepare an acrylate oligomer; parts by formula group content of the acrylic prepolymer by weight percentage: 48.76-52.17% xylene, ethyl acetate 7.51-11.23%, methyl methacrylate 19.38 -24.26%, 7.32-9.88% n-butyl acrylate, methacrylic acid, 0.91-1.87%, 5.11-9.27% ​​of styrene, initiator 0.50-1.97%; (2) Add soybean oil and pentaerythritol kettle was heated to 140 ° after addition of the catalyst C~150 ° C continue to heat up to 240 ° C~250 ° C, until clear alcohol cooled to 140 ° C~150 ° C is added in step (I) the acrylate oligomer and phthalic anhydride and benzene acid; until when the temperature rose to 170-180 ° C at a heating rate of 10-12 ° C / h slow 升温至240_250°C进行酯化缩合反应,待树脂酸值降到6-10mgK0H/g后停止加热,最后用二甲苯兑稀,制备出丙烯酸改性醇酸树脂; 所述丙烯酸改性醇酸树脂的配方组份含量以重量百分比计为:大豆油20.20-26.18%,季戊四醇7.81-12.46%,催化剂0.08-0.12%,丙烯酸预聚物20.49-26.84 %,苯甲酸2.05-4.48%,邻苯二甲酸酐7.90-11.24%,二甲苯27.25-33.45%。 240_250 ° C warmed to esterification condensation reaction, until the resin acid value decreased 6-10mgK0H / heating was stopped after g, and finally xylene letdown, acrylic modified alkyd resins prepared; said acrylic-modified alkyd resin fractions formula groups content in percentage by weight: 20.20-26.18% soybean oil, pentaerythritol 7.81-12.46%, 0.08-0.12% of the catalyst, the acrylic prepolymer 20.49-26.84%, 2.05-4.48% of benzoic acid, phthalic anhydride 7.90-11.24%, 27.25-33.45% xylene.
2.根据权利要求1所述的丙烯酸改性醇酸树脂的制备方法,其特征在于:步骤(I)所述的原料中不含水分。 The method for preparing an acrylic-modified alkyd resin according to claim 1, wherein: said step (I) starting material does not contain water.
3.根据权利要求1所述的丙烯酸改性醇酸树脂的制备方法,其特征在于:步骤⑴所述的引发剂为苯甲酰类和腈类偶氮化合物。 The method for preparing an acrylic-modified alkyd resin according to claim 1, wherein: said step of ⑴ initiator benzoyl azo compounds and nitriles.
4.根据权利要求3所述的丙烯酸改性醇酸树脂的制备方法,其特征在于:所述的引发剂为过氧化苯甲酰(BPO)、偶氮二异丁腈(AIBN)、2,2-偶氮二(甲基丁腈)或2,2-偶氮(2, 4- 二甲基戍臆)。 4. A method for preparing an acrylic-modified alkyd resin according to claim 3, wherein: said initiator is benzoyl peroxide (the BPO), azobisisobutyronitrile (AIBN), 2, 2- azobis (methylbutyronitrile) or 2,2-azobis (2, 4-dimethyl Shu chest).
5.根据权利要求1所述的丙烯酸改性醇酸树脂的制备方法,其特征在于:步骤(2)中所述的大豆油、季戊四醇、邻苯二甲酸酐、苯甲酸、溶剂二甲苯均为工业级。 The method for preparing an acrylic-modified alkyd resin according to claim 1, wherein: said step of soybean oil (2), pentaerythritol, phthalic anhydride, benzoic acid, solvents are xylene industrial grade.
6.根据权利要求1所述的丙烯酸改性醇酸树脂的制备方法,其特征在于:步骤(2)中所述季戊四醇纯度> 95%、羟基含量为45-49%。 6. A method for preparing an acrylic-modified alkyd resin according to claim 1, wherein: step (2) in the pentaerythritol purity> 95%, hydroxyl content of 45-49%.
7.根据权利要求1所述的丙烯酸改性醇酸树脂的制备方法,其特征在于:步骤(2)中所述的催化剂为氧化钙、氢氧化钙、环烷酸钴、氧化铅、环烷酸铅、氢氧化锂或环烷酸锂。 The method for preparing an acrylic-modified alkyd resin according to claim 1, wherein: step (2) in the catalyst is calcium oxide, calcium hydroxide, cobalt naphthenate, lead oxide, cycloalkoxy lead acid, lithium hydroxide or lithium naphthenate.
CN201210489242.2A 2012-11-27 2012-11-27 Novel acrylic acid modified alkyd resin and method for preparing same CN102993424B (en)

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CN103554379B (en) * 2013-10-29 2015-07-01 西北永新涂料有限公司 Aqueous acrylic acid-modified alkyd resin and preparation method thereof
CN103555164B (en) * 2013-11-04 2016-01-27 安徽菱湖漆股份有限公司 Salt spray resistance of a fast-drying acrylic modified alkyd excellent automotive paint and preparation method
CN103709885B (en) * 2013-12-27 2015-11-04 青岛乐化科技有限公司 An aqueous environment-friendly modified alkyd Wood
CN104073132A (en) * 2014-06-04 2014-10-01 乐凯特科技铜陵有限公司 Three-proofing (water-proof, moisture-proof and dust-proof) paint for scratch-resistant printed circuit board
CN104403564A (en) * 2014-11-24 2015-03-11 青岛市市南区隆德中医药研究所 Paint not easy to crack
CN104945567B (en) * 2015-05-20 2019-02-15 安徽省金盾涂料有限责任公司 A kind of modified water-based alkyd resin and preparation method thereof
CN105136532B (en) * 2015-07-24 2018-09-25 东莞市诚标检测科技有限公司 One kind of standard material and the coat of paint preparation leaded
CN105044803B (en) * 2015-08-13 2017-05-31 宁波雅歌新材料科技有限公司 A high-transmittance optical film preventing interference fringes and preparation method
CN105237751A (en) * 2015-11-17 2016-01-13 刘斌 Novel self-drying waterborne alkyd resin
CN106188381A (en) * 2016-08-09 2016-12-07 王建周 Flame-retardant thermoplastic acrylic resin combination and preparation method thereof
CN107325232A (en) * 2017-06-08 2017-11-07 华伦纳路新材料有限公司 Acrylic acid modified alkyd resin with water resistance, quick-drying performance and corrosion resistance and preparation method of acrylic acid modified alkyd resin
CN107793899A (en) * 2017-11-02 2018-03-13 中车青岛四方机车车辆股份有限公司 Wear-resistant and anti-fouling acrylic modified alkyd coating and preparation method thereof

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CN101831234B (en) * 2010-05-25 2012-05-09 北京化工大学 Method for preparing aqueous acrylic acid modified alkyd resin coating
CN101955721A (en) * 2010-09-17 2011-01-26 天津灯塔涂料工业发展有限公司 Quick-dry type acrylic modified alkyd paint and preparation method thereof
CN102127213B (en) * 2011-01-17 2013-05-22 华中科技大学 Waterborne acrylic alkyd resin and preparation method and application thereof
CN102675653B (en) * 2011-03-18 2014-08-20 上海涂料有限公司技术中心 Method for preparing waterborne acrylic modified alkyd emulsion
CN102660005A (en) * 2012-05-08 2012-09-12 新疆红山涂料有限公司 Preparation method of acrylic modified alkyd resin

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