WO2019120036A1 - 一种改性松香树脂及其制备方法和应用 - Google Patents

一种改性松香树脂及其制备方法和应用 Download PDF

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WO2019120036A1
WO2019120036A1 PCT/CN2018/117104 CN2018117104W WO2019120036A1 WO 2019120036 A1 WO2019120036 A1 WO 2019120036A1 CN 2018117104 W CN2018117104 W CN 2018117104W WO 2019120036 A1 WO2019120036 A1 WO 2019120036A1
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rosin resin
modified rosin
rosin
benzene ring
hydroxyl group
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PCT/CN2018/117104
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English (en)
French (fr)
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林剑雄
陈传文
郑学飞
刘强
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惠州市华泓新材料股份有限公司
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Publication of WO2019120036A1 publication Critical patent/WO2019120036A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04—Chemical modification, e.g. esterification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/08—Printing inks based on natural resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin

Definitions

  • the invention relates to the field of rosin modification, in particular to a modified rosin resin and a preparation method and application thereof.
  • Rosin has many excellent properties such as anti-corrosion, moisture-proof, insulation, adhesion, emulsification, softening, etc., and is widely used in various industrial sectors. Among them, one of the main applications of rosin is used as a binder in the ink printing industry.
  • the binder is the binder of the ground toner in the ink manufacturing, the main mobile phase and the film-forming substance after the ink is dried, which directly determines the performance of the ink and the printing effects such as viscosity, adhesion, gloss and dryness.
  • the technological innovation of the binder determines the technological innovation of the ink, which directly affects the performance of the ink and the printing effect.
  • rosin the structural characteristics of rosin lead to some defects in its properties, such as large crystallization tendency, low softening point and high acid value, which limit its application in ink. Therefore, it is of great significance to select the best process conditions for the chemical modification of the two active centers of rosin.
  • the chemical modification of rosin is generally based on the monocarboxylic acid and carbon-carbon double bonds in its structure, and the two reactive groups are used to introduce other functional groups for the purpose of modification.
  • the object of the present invention is to overcome the deficiencies in the prior art, and to provide a modified rosin resin, which has excellent water resistance and good ultraviolet curing property, and a preparation method and application thereof. In the preparation process, no additional organic solvent is needed, and it is environmentally friendly.
  • the present invention provides a modified rosin resin obtained by reacting rosin, a benzene ring-containing carboxylic acid, an epoxy compound, maleic acid and its derivatives, and a hydroxyl group-containing ether compound.
  • the modified rosin resin is obtained by reacting rosin, a benzene ring-containing carboxylic acid, an epoxy compound, maleic acid and a derivative thereof, and a hydroxyl group-containing ether compound under the action of a catalyst.
  • the catalyst comprises one or more of triphenylphosphine and triethylamine.
  • the mass ratio of the total mass of the rosin, the benzene ring-containing carboxylic acid, and the epoxy compound to the catalyst is from 1:0.001 to 0.02 (more preferably from 1:0.002 to 0.008).
  • the rosin comprises one or more of gum rosin, polymerized rosin, and disproportionated rosin.
  • the benzene ring-containing carboxylic acid comprises one or more of benzoic acid, isophthalic acid, and phthalic acid.
  • the epoxy compound comprises one or more of epoxy resin DER331, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and butanediol diglycidyl ether.
  • the derivative of the maleic acid and its derivative is maleic anhydride.
  • the hydroxyl group-containing ether compound comprises one or more of p-hydroxyanisole, butylhydroxyanisole, 4-hydroxybutyl vinyl ether, trimethylolpropane diallyl ether.
  • p-hydroxyanisole butylhydroxyanisole
  • 4-hydroxybutyl vinyl ether trimethylolpropane diallyl ether.
  • the molar ratio of the rosin to the epoxy compound is from 0.5 to 1.5:1.
  • the molar ratio of the rosin to the epoxy compound is 1:1.
  • the molar ratio of the benzene ring-containing carboxylic acid to the epoxy compound is from 0.5 to 1.5:1.
  • the molar ratio of the benzene ring-containing carboxylic acid to the epoxy compound is 1:1.
  • the molar ratio of the maleic acid and its derivative to the epoxy compound is from 1 to 2:1.
  • the molar ratio of the maleic acid and its derivative to the epoxy compound is 2:1.
  • the molar ratio of the hydroxyl group-containing ether compound to the maleic acid and its derivative is from 0.5 to 1:1.
  • the molar ratio of the hydroxyl group-containing ether compound to the maleic acid and its derivative is 1:1.
  • the present invention provides a method for preparing a modified rosin resin, comprising the steps of:
  • reaction intermediate (1) mixing rosin, a benzene ring-containing carboxylic acid, an epoxy compound and a catalyst uniformly, and reacting at 90 to 110 ° C for 2 to 4 hours to obtain a reaction intermediate;
  • the method of mixing the rosin, the epoxy compound and the catalyst described in the step (1) of the present invention is not particularly limited, and a mixed technical solution well known to those skilled in the art may be employed.
  • the rosin comprises one or more of gum rosin, polymerized rosin, and disproportionated rosin.
  • the benzene ring-containing carboxylic acid comprises one or more of benzoic acid, isophthalic acid, and phthalic acid.
  • the epoxy compound comprises one or more of epoxy resin DER331, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and butanediol diglycidyl ether.
  • epoxy resin DER331 ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and butanediol diglycidyl ether.
  • the catalyst comprises one or more of triphenylphosphine and triethylamine.
  • the molar ratio of the rosin to the epoxy compound is 0.5 to 1.5:1.
  • the molar ratio of the rosin to the epoxy compound is 1:1.
  • the molar ratio of the benzene ring-containing carboxylic acid to the epoxy compound is from 0.5 to 1.5:1.
  • the molar ratio of the benzene ring-containing carboxylic acid to the epoxy compound is 1:1.
  • the mass ratio of the total mass of the rosin, the benzene ring-containing carboxylic acid and the epoxy compound to the catalyst is 1:0.001 to 0.02 (more preferably 1:0.002 to 0.008) ).
  • the reaction temperature is 100 °C.
  • the reaction time is 3 h.
  • the hydroxyl group-containing ether compound comprises p-hydroxyanisole, butylhydroxyanisole, 4-hydroxybutyl vinyl ether, trimethylolpropane diallyl One or more of the ethers.
  • the derivative of the maleic acid and its derivative is maleic anhydride.
  • the molar ratio of the maleic acid and its derivative to the epoxy compound described in the step (1) is from 1 to 2:1.
  • the molar ratio of the maleic acid and its derivative to the epoxy compound described in the step (1) is 2:1.
  • the molar ratio of the hydroxyl group-containing ether compound to the maleic acid and the derivative thereof is 0.5 to 1:1.
  • the molar ratio of the hydroxyl group-containing ether compound to the maleic acid and the derivative thereof is 1:1.
  • the reaction temperature is 150 °C.
  • the reaction time is 3 h.
  • the modified rosin resin according to the first aspect of the present invention is produced by the method for producing a modified rosin resin according to the second aspect of the present invention.
  • the present invention provides a modified rosin resin, which first reacts with a carboxyl group on a rosin and a benzene ring-containing carboxylic acid and an epoxy group on an epoxy compound under the action of a catalyst to obtain a An intermediate of a hydroxyl group; an ether compound having a hydroxyl group, maleic acid and a derivative thereof, maleic acid and a derivative thereof are directly reacted with a hydroxyl group on the intermediate and the ether compound to obtain a modified rosin resin.
  • the hydrophobic group benzene ring is introduced into the molecule of the modified rosin resin, and the carboxyl group in the system completely reacts with the hydroxyl group to form a hydrophilic group having a low hydrophilicity, the water resistance of the modified rosin resin is greatly improved.
  • the invention provides the use of a modified rosin resin as described in the first aspect in the preparation of an ink, paint or adhesive.
  • the present invention provides a modified rosin resin which reacts by introducing a hydrophobic group (benzene ring) into a molecular chain of a rosin resin, and reacting a hydrophilic group (carboxyl group) with a hydroxyl group-containing ether compound to form a pro a low water-soluble ester group which improves the water resistance of the rosin resin;
  • the rosin resin modification method provided by the invention does not use an organic solvent as a reaction medium in the reaction process, avoids environmental pollution and solvent residue defects of the product, and no other by-products are formed outside the product, so no additional product is required. After the treatment process, the preparation process has low energy consumption and no pollution, and realizes green environmental synthesis.
  • FIG. 1 is a table showing an ink emulsification rate process according to an embodiment of the present invention.
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the embodiment of the invention provides a preparation method of a modified rosin resin, comprising the following steps:
  • the modified rosin resins prepared in Examples 1-7 were respectively formulated into inks and tested for curing effects and emulsifying properties of the inks.
  • the specific method for disposing the modified rosin resin into an ink is as follows: 27.5 g of modified rosin resin, 47.5 g of propoxyglycerol triacrylate, stirred and dissolved, and then added 4 g of 2-methyl-1-[4-methylthiobenzene 2-ylmorpholinyl-1-propanone, 1 g 2-isopropylthioxanthone and 20 g of BASF 57:1 pigment red L4BH, stirred at 300 rpm for 20 min, then passed through a three-roller Grinding is formulated into a UV curable ink sample.
  • the curing speed test method is as follows: the configured ink sample is coated on a blank paper by a printability tester with a thickness of about 15 ⁇ m, and an ultraviolet lamp with a tunable filter of 50 W/CM line power at a wavelength of 320-420. Under the range, curing was performed at a speed of 100 m/min, and the number of passes under the lamp required to obtain a good surface and complete curing was recorded, and the results are shown in Table 1 below.
  • the emulsification performance test method is as follows: using the principle of oil-water incompatibility, 100 g of the ink sample is mixed with 100 g of dampening solution, and the mixture is stirred at a high speed to form a stable saturated state of the ink sample and the dampening solution for a certain period of time, and then try to The free dampening water in the ink sample is removed, and the weight of the dampening solution remaining in the ink sample is accurately measured, and the emulsification rate is obtained by dividing the total amount of the dampening solution.
  • the test data are shown in Table 2 and Figure 1.
  • the modified rosin resin prepared in Example 1-6 is configured by using the modified rosin resin prepared in Examples 1-6, and the number of passes required for complete curing is 3 to 4 times, and the modified rosin resin prepared in Example 7 is configured.
  • the number of passes required to completely cure the ink is 4, and the difference between the two is small. This shows that the addition of a benzene ring-containing carboxylic acid and a hydroxyl group-containing ether compound has little effect on the curing speed of the ink.
  • the inks prepared by using the modified rosin resin prepared in Examples 1-6 have an emulsification rate of less than 30% after 60 minutes, and both have high water resistance.
  • the carboxylic acid having a benzene ring and the ether compound having a hydroxy group were not added, and it was apparent that the emulsification rate was 40.6% after 60 minutes, which was much higher than that of the preparation of Examples 1-6. Rosin resin. This indicates that the hydrolysis resistance of the prepared modified rosin resin is improved after the addition of the benzene ring-containing carboxylic acid and the hydroxyl group-containing ether compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明提供了一种改性松香树脂及其制备方法和应用，其中，所述的改性松香树脂由松香、带苯环的羧酸、环氧化合物、马来酸及其衍生物、带羟基的醚类化合物反应制得。本发明提供的改性松香树脂，通过在松香分子中引入疏水基团苯环，以及采用带羟基的醚类化合物与亲水基团羧基反应生成亲水性低的酯基，大大提高了松香树脂的抗水性；且在改性松香树脂制备过程中没有使用有机溶剂作为反应介质，避免了环境污染及产物的溶剂残留缺陷，安全环保。

Description

一种改性松香树脂及其制备方法和应用 技术领域
本发明涉及松香改性领域，尤其涉及一种改性松香树脂及其制备方法和应用。
背景技术
我国是松香生产大国，脂松香年产50万吨以上，居世界首位。松香具有许多优良的特性，如防腐、防潮、绝缘、粘合、乳化、软化等，被广泛地应用于各工业部门。其中，松香的一个主要应用是作为连接料用在油墨印刷行业。
连接料是油墨制造中研磨色粉的基料、主要的流动相和油墨干燥后的成膜物质，直接决定着油墨的使用性能和印刷效果，如黏度、附着力、光泽度和干燥性。连结料的技术创新决定着油墨的技术革新，它直接影响着油墨的使用性能和印刷效果。
但是松香的结构特点导致其性能存在着一些缺陷，例如结晶倾向大、软化点低及酸值较高等，这些缺点限制了它在油墨中的应用。因此，选择最佳工艺条件对松香两个活性中心综合进行化学改性，具有十分重要的意义。松香的化学改性一般是基于它结构中的一元羧酸和碳碳双键，利用这两个反应性基团引入其他官能团以达到改性的目的。
在我司前期的研究中(201710180667.8一种改性松香树脂、制备方法及采用该改性松香树脂的油墨)，采用了环氧树脂、马来酸酐对松香树脂进行改性，制备得到可紫外光固化的改性松香树脂，将它应用于紫外光固化油墨，表现出较好的混溶性、颜料润湿性和较快的干燥速度。但是，随着研究的深入，发现由松香、环氧树脂、马来酸酐制备的改性松香树脂，由于其分子链上带有亲水性的羧基，在作为油墨连接料时，具有抗水性较差的缺点。油墨连接料抗水性差，油墨接触水后，水容易进入油墨中造成油墨乳化、黏度下降，破坏了油墨的结构，改变了油墨的性能，会发生相应的印刷故障。
因此，改善松香树脂的抗水性能，研究和开发一种性能优良的改性松香树脂是本领域亟待解决的问题，也一直是科研人员关注的焦点。
发明内容
本发明的目的是克服现有技术中的不足之处，提供了一种改性松香树脂及其制备方法 和应用，所述的改性松香树脂具有优异的抗水性能，良好的紫外光固化性，制备过程中不需要额外加入有机溶剂，绿色环保。
为实现上述目的，本申请提供如下技术方案：
第一方面，本发明提供了一种改性松香树脂，由松香、带苯环的羧酸、环氧化合物、马来酸及其衍生物、带羟基的醚类化合物反应制得。
优选地，所述的改性松香树脂由松香、带苯环的羧酸、环氧化合物、马来酸及其衍生物、带羟基的醚类化合物在催化剂的作用下反应制得。
进一步优选地，所述的催化剂包括三苯基膦、三乙胺中的一种或多种。
更进一步优选地，所述的松香、带苯环的羧酸和环氧化合物总质量与所述催化剂的质量比为1：0.001～0.02(进一步优选为1:0.002～0.008)。
优选地，所述的松香包括脂松香、聚合松香、歧化松香中的一种或多种。
优选地，所述的带苯环的羧酸包括苯甲酸、间苯二甲酸、邻苯二甲酸中的一种或多种。
优选地，所述的环氧化合物包括环氧树脂DER331、乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、丁二醇二缩水甘油醚中的一种或多种。
优选地，所述的马来酸及其衍生物中的衍生物为马来酸酐。
优选地，所述的带羟基的醚类化合物包括对羟基苯甲醚、丁基羟基茴香醚、4-羟丁基乙烯基醚、三羟甲基丙烷二烯丙基醚中的一种或多种。
优选地，所述的松香与所述的环氧化合物的摩尔比为0.5～1.5:1。
进一步优选地，所述的松香与所述的环氧化合物的摩尔比为1:1。
优选地，所述的带苯环的羧酸与所述的环氧化合物的摩尔比为0.5～1.5:1。
进一步优选地，所述的带苯环的羧酸与所述的环氧化合物的摩尔比为1:1。
优选地，所述的马来酸及其衍生物与所述的环氧化合物的摩尔比为1～2:1。
进一步优选地，所述的马来酸及其衍生物与所述的环氧化合物的摩尔比为2:1。
优选地，所述的带羟基的醚类化合物与所述的马来酸及其衍生物的摩尔比为0.5～1:1。
进一步优选地，所述的带羟基的醚类化合物与所述的马来酸及其衍生物的摩尔比为1:1。
第二方面，本发明提供了一种改性松香树脂的制备方法，包括如下步骤：
(1)将松香、带苯环的羧酸、环氧化合物和催化剂混合均匀，在90～110℃下反应2～4h，得到反应中间体；
(2)将步骤(1)所得的反应中间体和带羟基的醚类化合物、马来酸及其衍生物混合， 在140～160℃下反应2～4h，得到改性松香树脂。
可以理解的是，本发明对步骤(1)所述的将松香、环氧化合物和催化剂混合的方法没有特殊限制，采用本领域技术人员熟知的混合的技术方案即可。
优选地，所述步骤(1)中，所述的松香包括脂松香、聚合松香、歧化松香中的一种或多种。
优选地，所述步骤(1)中，所述的带苯环的羧酸包括苯甲酸、间苯二甲酸、邻苯二甲酸中的一种或多种。
优选地，所述步骤(1)中，所述的环氧化合物包括环氧树脂DER331、乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、丁二醇二缩水甘油醚中的一种或多种。
优选地，所述步骤(1)中，所述的催化剂包括三苯基膦、三乙胺中的一种或多种。
优选地，所述步骤(1)中，所述的松香与所述的环氧化合物的摩尔比为0.5～1.5:1。
进一步优选地，所述步骤(1)中，所述的松香与所述的环氧化合物的摩尔比为1:1。
优选地，所述步骤(1)中，所述的带苯环的羧酸与所述的环氧化合物的摩尔比为0.5～1.5:1。
进一步优选地，所述步骤(1)中，所述的带苯环的羧酸与所述的环氧化合物的摩尔比为1:1。
优选地，所述步骤(1)中，所述的松香、带苯环的羧酸和环氧化合物总质量与所述催化剂的质量比为1：0.001～0.02(进一步优选为1:0.002～0.008)。
优选地，所述步骤(1)中，反应温度为100℃。
优选地，所述步骤(1)中，反应时间为3h。
优选地，所述步骤(2)中，所述的带羟基的醚类化合物包括对羟基苯甲醚、丁基羟基茴香醚、4-羟丁基乙烯基醚、三羟甲基丙烷二烯丙基醚中的一种或多种。
优选地，所述步骤(2)中，所述的马来酸及其衍生物中的衍生物为马来酸酐。
优选地，所述步骤(2)中，所述的马来酸及其衍生物与步骤(1)中所述的环氧化合物的摩尔比为1～2:1。
进一步优选地，所述步骤(2)中，所述的马来酸及其衍生物与步骤(1)中所述的环氧化合物的摩尔比为2:1。
优选地，所述步骤(2)中，所述的带羟基的醚类化合物与所述的马来酸及其衍生物的摩尔比为0.5～1:1。
进一步优选地，所述步骤(2)中，所述的带羟基的醚类化合物与所述的马来酸及其衍生物的摩尔比为1:1。
优选地，所述步骤(2)中，反应温度为150℃。
优选地，所述步骤(2)中，反应时间为3h。
优选地，本发明第一方面所述的改性松香树脂为采用本发明第二方面所述改性松香树脂的制备方法制得。
本发明的原理：本发明提供了一种改性松香树脂，首先在催化剂作用下，利用松香和带苯环的羧酸上的羧基与环氧化合物上的环氧基团进行反应，得到带有羟基的中间体；再加入带羟基的醚类化合物、马来酸及其衍生物，马来酸及其衍生物直接与中间体和醚类化合物上的羟基反应，得到改性松香树脂。因为改性松香树脂分子中引入了疏水基团苯环，并且体系中的羧基与羟基完全反应，生成亲水性低的酯基，所以改性松香树脂的抗水性能得到大大改善。
第三方面，本发明提供了一种如第一方面所述的改性松香树脂在制备油墨、涂料油漆或胶黏剂中的应用。
本发明的有益效果如下：
(1)本发明提供一种改性松香树脂，通过在松香树脂分子链中引入疏水性基团(苯环)，以及采用带羟基的醚类化合物将亲水性基团(羧基)反应生成亲水性低的酯基，提高了松香树脂的抗水性；
(2)本发明提供的松香树脂改性方法，反应过程没有使用有机溶剂作为反应介质，避免了环境污染及产物的溶剂残留缺陷，且产物外无其他副产物生成，所以不需要对产物进行额外后处理工序，制备过程能耗低、无污染，实现了绿色环保化的合成。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例所提供的油墨乳化率进程表。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的 附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入30.2g(0.1mol)脂松香和34g(0.1mol)环氧树脂DER331，升温至140℃，抽负压促进反应物熔融，再降温至100℃，加入三苯基膦0.76g和苯甲酸12.2g(0.1mol)，100℃下搅拌反应3小时；
(2)再加入24.80g(0.2mol)对羟基苯甲醚和23.2g(0.2mol)马来酸，在150℃下反应3h，得到改性松香树脂一。
测试结果表明，改性松香树脂一的结构式如下：
Figure PCTCN2018117104-appb-000001
实施例2
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入45.3g(0.15mol)脂松香和34g(0.1mol)环氧树脂DER331，升温至140℃，抽负压促进反应物熔融，再降温至90℃，加入三苯基膦0.76g和间苯二甲酸8.3g(0.05mol)，90℃下搅拌反应4小时；
(2)再加入27g(0.15mol)丁基羟基茴香醚和17.4g(0.15mol)马来酸，在140℃下反应4h，得到改性松香树脂二。
实施例3
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入60.5g(0.1mol)聚合松香和17.4g(0.1mol)乙二醇二缩水甘油醚，升温至140℃，抽负压促进反应物熔融，再降温至110℃，加入三苯基膦0.76g和邻苯二甲酸8.3g(0.05mol)，110℃下搅拌反应2小时；
(2)再加入11.6g(0.1mol)4-羟丁基乙烯基醚和11.6g(0.1mol)马来酸，在160℃下反应2h，得到改性松香树脂三。
实施例4
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入30.25g(0.05mol)聚合松香和18.8g(0.1mol)丙二醇二缩水甘油醚，升温至140℃，抽负压促进反应物熔融，再降温至100℃，加入三乙胺0.76g和苯甲酸18.3g(0.15mol)，100℃下搅拌反应4小时；
(2)再加入21.4g(0.1mol)三羟甲基丙烷二烯丙基醚和23.2g(0.2mol)马来酸，在150℃下反应2h，得到改性松香树脂四。
实施例5
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入30.4g(0.1mol)歧化松香和20.2g(0.1mol)丁二醇二缩水甘油醚，升温至140℃，抽负压促进反应物熔融，再降温至90℃，加入三乙胺0.76g和苯甲酸12.2g(0.1mol)，90℃下搅拌反应3小时；
(2)再加入24.8g(0.2mol)对羟基苯甲醚和19.6g(0.2mol)马来酸酐，在160℃下反应3h，得到改性松香树脂五。
实施例6
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入30.4g(0.1mol)歧化松香和34g(0.1mol)环氧树脂DER331，升温至140℃，抽负压促进反应物熔融，再降温至100℃，加入三苯基膦0.76g和苯甲酸12.2g(0.1mol)，100℃下搅拌反应3小时；
(2)再加入42.8g(0.2mol)三羟甲基丙烷二烯丙基醚和19.6g(0.2mol)马来酸酐，在150℃下反应3h，得到改性松香树脂六。
实施例7
本发明实施例提供了一种改性松香树脂的制备方法，包括以下步骤：
(1)在带有机械搅拌的500mL三颈瓶中，加入60.5g(0.2mol)脂松香和34g(0.1mol)环氧树脂DER331，升温至140℃，抽负压促进反应物熔融，再降温至100℃，加入三苯基膦0.76g，100℃下搅拌反应3小时；
(2)再加入23.2g(0.2mol)马来酸，在150℃下反应3h，得到改性松香树脂七。
测试结果表明，改性松香树脂七的结构式如下：
Figure PCTCN2018117104-appb-000002
实施例8
为了进一步说明本发明的有益效果，分别将实施例1-7制备得到的改性松香树脂配置成油墨并测试油墨的固化效果和乳化性能。
将改性松香树脂配置成油墨的具体方法如下：将27.5g改性松香树脂，47.5g丙氧化甘油三丙烯酸酯，搅拌溶解后，加入4g 2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮、1g 2-异丙基硫杂蒽酮以及20g巴斯夫57：1颜料红L4BH，在300转/分钟的转速下，搅拌20min，再经过三辊机研磨配制成紫外光固化油墨样品。
固化速度测试方法如下：将配置的油墨样品用印刷适性仪涂布约15微米厚度于空白纸张上，用功率为50W/CM线功率的带可调过滤器的紫外灯，在320-420波长范围下，以100米/分速度进行固化，记录获得良好的表面及彻底固化所需要的灯下通过次数，结果如下表1所示。
表1紫外线照射固化效果测定结果
Figure PCTCN2018117104-appb-000003
乳化性能测试方法如下：利用油水不相容原理，将100g的所述油墨样品与100g润版液混合，高速搅拌混合物，在一定时间内，形成油墨样品与润版液的稳定饱和状态，然后尽量去除油墨样品中游离的润版水，准确衡量残留在油墨样品中的润版液重量，再与润版液的总量相除即得出乳化率数值，测试数据如表2和图1。
表2油墨的乳化率测试数据
Figure PCTCN2018117104-appb-000004
Figure PCTCN2018117104-appb-000005
从固化效果测试数据可以看出，采用实施例1-6制备的改性松香树脂配置成的油墨，完全固化所需通过次数为3～4次，实施例7制备的改性松香树脂配置成的油墨完全固化所需通过次数为4次，二者差异不大。这说明，添加带苯环的羧酸和带羟基的醚类化合物后，对油墨的固化速度影响不大。
从乳化性能测试数据可以看出，采用实施例1-6制备的改性松香树脂配置成的油墨，60min后乳化率均低于30％，均具有较高的抗水性。实施例7制备的改性松香树脂中，未加入带苯环的羧酸和带羟基的醚类化合物，可以明显看到60min后乳化率为40.6％，远高于实施例1-6制备的改性松香树脂。这说明，加入带苯环的羧酸和带羟基的醚类化合物后，制备得到的改性松香树脂抗水性得到提高。
最后应说明的是：显然，上述实施例仅仅是为清楚地说明本申请所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变动或变化。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本申请的保护范围之中。

Claims (10)

  1. 一种改性松香树脂，其特征在于，由松香、带苯环的羧酸、环氧化合物、马来酸及其衍生物、带羟基的醚类化合物反应制得。
  2. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的松香包括脂松香、聚合松香、歧化松香中的一种或多种。
  3. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的带苯环的羧酸包括苯甲酸、间苯二甲酸、邻苯二甲酸中的一种或多种。
  4. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的环氧化合物包括环氧树脂DER331、乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、丁二醇二缩水甘油醚中的一种或多种。
  5. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的带羟基的醚类化合物包括对羟基苯甲醚、丁基羟基茴香醚、4-羟丁基乙烯基醚、三羟甲基丙烷二烯丙基醚中的一种或多种。
  6. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的松香与所述的环氧化合物的摩尔比为0.5～1.5:1。
  7. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的带苯环的羧酸与所述的环氧化合物的摩尔比为0.5～1.5:1。
  8. 如权利要求1所述的一种改性松香树脂，其特征在于，所述的带羟基的醚类化合物与所述的马来酸及其衍生物的摩尔比为0.5～1:1。
  9. 一种改性松香树脂的制备方法，包括如下步骤：
    (1)将松香、带苯环的羧酸、环氧化合物和催化剂混合均匀，在90～110℃下反应2～4h，得到反应中间体；
    (2)将步骤(1)所得的反应中间体和带羟基的醚类化合物、马来酸及其衍生物混合，在140～160℃下反应2～4h，得到改性松香树脂。
  10. 一种如权利要求1所述的改性松香树脂在制备油墨、涂料油漆或胶黏剂中的应用。
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