阅读说明：本技术 一种从松香制备马来松香甲基丙烯酸羟乙酯聚合物的方法 (Method for preparing maleic rosin hydroxyethyl methacrylate polymer from rosin ) 是由 朱冰 舒航 张佳阳 王平 赵扬 余记乐 于 2019-10-29 设计创作，主要内容包括：本发明涉及一种从松香制备马来松香甲基丙烯酸羟乙酯聚合物的方法,其包括以下操作步骤：1)在反应釜中加入松香,升温至其完全熔化,并加入马来酸和催化剂,热反应生成马来松香；2)马来松香在醋酸丁酯中与甲基丙烯酸羟乙酯反应制得马来松香甲基丙烯酸羟乙酯；3)马来松香甲基丙烯酸羟乙酯发生聚合反应,制得马来松香甲基丙烯酸羟乙酯聚合物。本发明所提供方法能够在不破坏松香结构的前提下,利用D-A反应,将共轭双键消除,形成结构相对稳定的六元环内双键结构,同时有效减少副反应的发生,有利于后续加工,并利用甲基丙烯酸羟乙酯的双键结构进行聚合,反应活性高,有效提高了产率,符合工业化大规模生产应用的需求。(The invention relates to a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin, which comprises the following operation steps: 1) adding rosin into a reaction kettle, heating until the rosin is completely melted, adding maleic acid and a catalyst, and carrying out thermal reaction to generate maleic rosin; 2) reacting maleated rosin with hydroxyethyl methacrylate in butyl acetate to obtain maleated rosin hydroxyethyl methacrylate; 3) and carrying out polymerization reaction on the maleic rosin hydroxyethyl methacrylate to obtain the maleic rosin hydroxyethyl methacrylate polymer. The method provided by the invention can eliminate conjugated double bonds by utilizing the D-A reaction on the premise of not damaging the rosin structure, so that a six-membered ring internal double bond structure with a relatively stable structure is formed, the occurrence of side reactions is effectively reduced, the subsequent processing is facilitated, the double bond structure of hydroxyethyl methacrylate is utilized for polymerization, the reaction activity is high, the yield is effectively improved, and the requirements of industrial large-scale production and application are met.)

1. A method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin is characterized by comprising the following operation steps:

1) synthesis of maleated rosin: adding rosin into a reaction kettle, heating to 145-185 ℃, adding maleic acid and a catalyst under the stirring state until the rosin is completely melted, heating the maleic acid and the rosin to 185-225 ℃, reacting for 3-9 h, and then cooling to 60-90 ℃ to obtain maleated rosin;

2) synthesis of maleated rosin hydroxyethyl methacrylate: adding butyl acetate and the maleated rosin prepared in the step 1) into a reaction kettle, heating to 60-90 ℃ under the conditions of sealing, reflux condensation and stirring, adding hydroxyethyl methacrylate, a catalyst and a polymerization inhibitor, heating to 105-150 ℃, reacting for 3-8 h, and separating water by an oil-water separator to obtain a butyl acetate solution of maleated rosin hydroxyethyl methacrylate;

3) synthesis of maleated rosin hydroxyethyl methacrylate polymer: adding an initiator into the butyl acetate solution of the maleic rosin hydroxyethyl methacrylate obtained in the step 2), heating to 60-100 ℃ under the conditions of reflux condensation and stirring, reacting for 4-10 h, adding a polymerization product into petroleum ether for precipitation and separation, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.

2. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the molar ratio of the maleic acid to the rosin in the step 1) is 1: 1.

3. the process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the catalyst in the step 1) is AlCl₃、TiCl₄、SnCl₂、ZrCl₄、AlEt₂Cl、ZnCl₂、BF₃·Et₂One or more of O, the addition amount of which is 0.1-2.0% of the weight of the rosin.

4. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: in the step 2), the molar ratio of the hydroxyethyl methacrylate to the maleated rosin is 2: 1.

5. the process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the catalyst in the step 2) is concentrated H₂SO₄、H₃PO₄、FeCl₃One or more of p-toluenesulfonic acid, ion exchange resin, solid acid and rare earth metal oxide.

6. The process of claim 5 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the addition amount of the catalyst in the step 2) is 3.0-8.0% of the weight of the maleated rosin.

7. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the polymerization inhibitor in the step 2) is one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, phenothiazine, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.

8. The process of claim 7 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the addition amount of the polymerization inhibitor in the step 2) is 0.1-0.2% of the weight of the maleated rosin.

9. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the initiator in the step 3) is AlCl₃One or more of BPO, AIBN and ABVN.

10. The process of claim 9 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the addition amount of the initiator in the step 3) is 0.5-4% of the weight of the maleic rosin hydroxyethyl methacrylate.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin.

Background

Rosin is a rich and cheap renewable resource, the yield of gum rosin in China is the top of the world, and how to replace disposable resources such as petroleum by the renewable natural resource of rosin becomes an increasingly important research subject. The rosin has the characteristics of easy oxidation, high acid value, poor thermal stability and the like, so that the direct application is limited to a certain extent, and the modification of the rosin by utilizing two active centers of carboxyl and double bond contained in the rosin becomes a hot point of domestic and foreign research. The rosin polymer is prepared from rosin and is mainly used for preparing high-grade printing ink, paint, adhesive and other fields.

Disclosure of Invention

Based on the above, the invention aims to provide a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin, which has the advantages of simple process flow, mild and controllable reaction conditions, environment-friendly and easily-obtained and renewable raw materials and high product conversion rate.

The invention realizes the purpose through the following technical scheme:

a method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin comprises the following operation steps:

1) synthesis of maleated rosin: adding rosin into a reaction kettle, heating to 145-185 ℃, adding maleic acid and a catalyst under the stirring state until the rosin is completely melted, heating the maleic acid and the rosin to 185-225 ℃, reacting for 3-9 h, and then cooling to 60-90 ℃ to obtain maleated rosin;

2) synthesis of maleated rosin hydroxyethyl methacrylate: adding butyl acetate and the maleated rosin prepared in the step 1) into a reaction kettle, heating to 60-90 ℃ under the conditions of sealing, reflux condensation and stirring, adding hydroxyethyl methacrylate, a catalyst and a polymerization inhibitor, heating to 105-150 ℃, reacting for 3-8 h, and separating water by an oil-water separator to obtain a butyl acetate solution of maleated rosin hydroxyethyl methacrylate;

3) synthesis of maleated rosin hydroxyethyl methacrylate polymer: adding an initiator into the butyl acetate solution of the maleic rosin hydroxyethyl methacrylate obtained in the step 2), heating to 60-100 ℃ under the conditions of reflux condensation and stirring, reacting for 4-10 h, adding a polymerization product into petroleum ether for precipitation and separation, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.

Compared with the prior art, the method for preparing the maleic rosin hydroxyethyl methacrylate polymer from the rosin eliminates conjugated double bonds by utilizing the D-A reaction (Diels-Alder reaction translated into Diels-Alder reaction) on the premise of not damaging the rosin structure to form a six-membered ring internal double bond structure with relatively stable structure, effectively reduces the occurrence of side reactions simultaneously, is beneficial to subsequent processing, utilizes the double bond structure of the hydroxyethyl methacrylate to carry out polymerization, has high reaction activity, effectively improves the yield, has simple preparation method flow, mild and controllable reaction conditions, environment-friendly and easily-obtained and renewable raw materials and higher product conversion rate, and meets the requirements of industrial large-scale production and application.

Further, the molar ratio of maleic acid to rosin in step 1) is 1: 1.

further, the catalyst in the step 1) is AlCl₃、TiCl₄、SnCl₂、ZrCl₄、AlEt₂Cl、ZnCl₂、BF₃·Et₂One or more of O, the addition amount of which is 0.1-2.0% of the weight of the rosin.

Further, the molar ratio of the hydroxyethyl methacrylate to the maleated rosin in the step 2) is 2: 1.

further, the catalyst in the step 2) is concentrated H₂SO₄、H₃PO₄、FeCl₃One or more of p-toluenesulfonic acid, ion exchange resin, solid acid and rare earth metal oxide.

Further, the adding amount of the catalyst in the step 2) is 3.0-8.0% of the weight of the maleated rosin.

Further, the polymerization inhibitor in the step 2) is one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, phenothiazine, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone.

Further, the addition amount of the polymerization inhibitor in the step 2) is 0.1-0.2% of the weight of the maleated rosin.

Further, the initiator in the step 3) is AlCl₃One or more of BPO, AIBN and ABVN.

Further, the addition amount of the initiator in the step 3) is 0.5-4% of the weight of the maleated rosin hydroxyethyl methacrylate.

Compared with the prior art, the method for preparing the maleic rosin hydroxyethyl methacrylate polymer from the rosin has the advantages that the conjugated double bonds are eliminated by utilizing the D-A reaction on the premise of not damaging the rosin structure, the double bond structure in the six-membered ring with relatively stable structure is formed, the side reaction is effectively reduced, the subsequent processing is facilitated, the double bond structure of the hydroxyethyl methacrylate is utilized for polymerization, the reaction activity is high, the yield is effectively improved, the number average molecular weight of the product is high, the preparation method is simple in flow, the reaction conditions are mild and controllable, the raw materials are environment-friendly and easy to obtain and regenerate, the product conversion rate is higher, and the requirements of industrial large-scale production and application are met.

Detailed Description