阅读说明：本技术 一种松香基环氧单体及其制备方法和应用 (Rosin-based epoxy monomer and preparation method and application thereof ) 是由 张海波 李婉冰 许嘉琍 商士斌 沈明贵 王丹 宋湛谦 于 2020-05-20 设计创作，主要内容包括：本发明公开了一种松香基环氧单体及其制备方法和应用,所述松香基环氧单体,包括原料：丙烯海松酸6～8份；环氧氯丙烷15～22份。所述松香基环氧单体的制备方法,包括：将丙烯海松酸和环氧丙烷在110～130℃下反应2～5h；将反应降温至70～90℃后,加入氢氧化钠,继续反应2～5h得到所需化合物。所述的松香基环氧单体在制备环氧固化树脂中的应用方法,包括：将桐油、甲醇在碱性条件下反应得到桐酸甲酯；将桐酸甲酯、马来酸酐、催化剂、阻聚剂反应得到TMA；将松香基环氧单体、TMA、2-乙基-4-甲基咪唑混合均匀后固化。通过松香基环氧单体与TMA的反应,得到了全生物基环氧固化树脂,在满足绿色、安全以及可持续性的同时,还扩宽环氧树脂的可应用领域。(The invention discloses a rosin-based epoxy monomer and a preparation method and application thereof, wherein the rosin-based epoxy monomer comprises the following raw materials: 6-8 parts of acrylpimaric acid; 15-22 parts of epoxy chloropropane. The preparation method of the rosin-based epoxy monomer comprises the following steps: reacting propylene pimaric acid with propylene oxide at 110-130 ℃ for 2-5 h; and cooling the reaction to 70-90 ℃, adding sodium hydroxide, and continuously reacting for 2-5 hours to obtain the required compound. The application method of the rosin-based epoxy monomer in preparing epoxy curing resin comprises the following steps: reacting tung oil and methanol under an alkaline condition to obtain methyl eleostearate; reacting methyl eleostearate, maleic anhydride, a catalyst and a polymerization inhibitor to obtain TMA; uniformly mixing the rosin-based epoxy monomer, TMA and 2-ethyl-4-methylimidazole and curing. Through the reaction of the rosin-based epoxy monomer and TMA, the full-biological epoxy curing resin is obtained, and the applicable field of the epoxy resin is widened while the requirements on green, safety and sustainability are met.)

1. The rosin-based epoxy monomer is characterized by comprising the following raw materials in parts by weight:

6-8 parts of acrylpimaric acid;

15-22 parts of epoxy chloropropane.

2. The method of claim 1, comprising the steps of:

(1) reacting propylene pimaric acid with propylene oxide at 110-130 ℃ for 2-5 h;

(2) and cooling the reaction to 70-90 ℃, adding sodium hydroxide, and continuously reacting for 2-5 hours to obtain the required compound.

3. The method for preparing a rosin-based epoxy monomer according to claim 2, wherein the reaction temperature in the step (1) is 117 ℃ and the reaction time is 3 hours; the reaction temperature in the step (2) is 80 ℃, and the reaction time is 3 h.

4. Use of a rosin-based epoxy monomer according to claim 1 or a rosin-based epoxy monomer prepared by the method of claim 2 or 3 for preparing an epoxy-cured resin.

5. The method of using rosin-based epoxy monomer according to claim 4 for preparing epoxy-curable resin, comprising the steps of:

(1) reacting tung oil and methanol under an alkaline condition to obtain methyl eleostearate;

(2) reacting methyl eleostearate, maleic anhydride, a catalyst and a polymerization inhibitor at 70-100 ℃ for 0.5-2 h, heating to 130-160 ℃, and continuing to react for 3-5 h to obtain TMA;

(3) uniformly mixing the rosin-based epoxy monomer, TMA and 2-ethyl-4-methylimidazole and curing.

6. The method for preparing epoxy resin according to claim 5, wherein the curing process of step (3) is as follows: curing at 130-140 ℃ for 1-3 h, and curing at 160-180 ℃ for 2-6 h.

7. The method for using the rosin-based epoxy monomer in the preparation of epoxy cured resin according to claim 5 or 6, wherein the molar ratio of the rosin-based epoxy monomer to TMA in the step (3) is 1:0.8 to 1: 1.

8. The method for using rosin-based epoxy monomer according to any one of claims 5 to 7, wherein the molar ratio of the tung oil to methanol in the step (1) is 1: 3-1: 10, the reaction temperature is 65-80 ℃, and the reaction time is 0.5-4 h.

9. The method for preparing epoxy resin according to any one of claims 5 to 8, wherein the molar ratio of methyl eleostearate to maleic anhydride in step (2) is 1: 1-1: 1.5, the reaction temperature is 80-140 ℃, and the reaction time is 3-10 h.

10. The method for using rosin-based epoxy monomer according to any one of claims 5 to 9, wherein the catalyst in step (2) is acetic acid and the polymerization inhibitor is hydroquinone.

Technical Field

The invention relates to a rosin-based epoxy monomer and a preparation method and application thereof, belonging to the technical field of natural resource modification and utilization.

Background

With the increasing environmental pressure and depletion of petroleum resources, bio-based polymer materials have gained widespread attention (Schneiderman, D.K.; Hillmyer, M.A.50th and university permanent; heat is a great variety of polymers in superstatinable polymers 2017,50(10),3733 and 3749.). Epoxy resin is one of the most widely used high molecular materials in various industries, however, the raw material source of epoxy resin mainly depends on petrochemical resources, and the most used bisphenol A type epoxy resin is harmful to human bodies, which limits the application of epoxy resin in the health field (Huang, K.; Zhang, P.; Zhang, J.; Li, S.; Li, M.; Xia, J.; Zhou, Y.preparation of bisphenol used oil fat fatty acid-derived C21 diacid and C22 ternary polymerization of epoxy properties, Green Chemistry 2013,15(9), 2466.). The biomass-based material has wide sources, safety, no toxicity and sustainability, so the development of epoxy resin by using biomass becomes one of the ways of replacing petrochemical epoxy resin.

Rosin is one of main forest products in China, the annual output is between 40 and 80 ten thousand tons, and the rosin is the first in the world. The hydrogenated phenanthrene ring structure of rosin endows the molecular hardness of its aliphatic ring and benzene ring, so that the rosin is widely used as a substitute of petrochemical products in the field of high polymer materials. Rosin derivatives (fumaropimaric acid, acrylpimaric acid, maleopimaric acid, and the like) are used as epoxy curing agents, and can significantly improve the thermal stability, mechanical properties, and the like of materials (Liu, x.; Xin, w.; Zhang, j.rosin-based anhydrides as additives to polymers. green chemistry 2009,11(7), 1018.). However, the use of rosin to prepare epoxy monomers instead of bisphenol a type epoxy resins has been rarely reported. Therefore, the rosin is green, safe and sustainable in developing the bio-based epoxy resin, and the application field of the epoxy resin can be widened.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a rosin-based epoxy monomer and a preparation method and application thereof.

In order to solve the technical problems, the invention provides a rosin-based epoxy monomer which comprises the following raw materials in parts by weight:

6-8 parts of acrylpimaric acid;

15-22 parts of epoxy chloropropane.

Meanwhile, the invention also provides a preparation method of the rosin-based epoxy monomer, which comprises the following steps:

(1) reacting propylene pimaric acid with propylene oxide at 110-130 ℃ for 2-5 h;

(2) and cooling the reaction to 70-90 ℃, adding sodium hydroxide, and continuously reacting for 2-5 hours to obtain the required compound.

Further, the reaction temperature in the step (1) is 117 ℃, and the reaction time is 3 hours; the reaction temperature in the step (2) is 80 ℃, and the reaction time is 3 h.

The invention also provides an application of the rosin-based epoxy monomer in preparation of epoxy cured resin.

The application method of the rosin-based epoxy monomer in the preparation of epoxy cured resin comprises the following steps:

(1) reacting tung oil and methanol under an alkaline condition to obtain methyl eleostearate;

(2) reacting methyl eleostearate, maleic anhydride, a catalyst and a polymerization inhibitor at 70-100 ℃ for 0.5-2 h, heating to 130-160 ℃, and continuing to react for 3-5 h to obtain an addition product (TMA) of methyl eleostearate and maleic anhydride;

(3) uniformly mixing the rosin-based epoxy monomer, TMA and 2-ethyl-4-methylimidazole and curing.

Further, the curing process of the step (3) is as follows: curing at 130-140 ℃ for 1-3 h, and curing at 160-180 ℃ for 2-6 h.

Further, the molar ratio of the rosin-based epoxy monomer to TMA in the step (3) is 1: 0.8-1: 1.

Further, the mole ratio of the tung oil to the methanol in the step (1) is 1: (3-10), the reaction temperature is 65-80 ℃, and the reaction time is 0.5-4 h.

Further, the reaction temperature in the step (1) is 65-80 ℃, and the reaction time is 0.5-4 h.

Further, the molar ratio of methyl eleostearate to maleic anhydride in the step (2) is 1: (1-1.5), the reaction temperature is 80-140 ℃, and the reaction time is 3-10 h.

Further, the catalyst in the step (2) is acetic acid, and the polymerization inhibitor is hydroquinone.

The invention achieves the following beneficial effects:

(1) according to the rosin-based epoxy monomer, the acrylpimaric acid and the epoxy chloropropane are used as raw materials, and the natural derivatives are used as the raw materials, so that the application and use fields of natural products are expanded;

(2) the preparation method of the rosin-based epoxy monomer has the advantages that the reaction is easy to realize, the rosin-based epoxy monomer with high yield is obtained through simple reaction steps, and the preparation method is suitable for industrial production;

(3) according to the application of the rosin-based epoxy monomer, the rosin-based epoxy monomer is reacted with methyl eleostearate and maleic anhydride adduct (TMA), so that the all-biological epoxy cured resin with higher Young modulus, tensile strength and glass transition temperature than commercial DER332 cured resin is obtained, and the applicable field of the epoxy resin is widened while the requirements on green, safety and sustainability are met.

Drawings

FIG. 1 is a DMA curve of a rosin-based epoxy cured resin obtained according to the present invention;

FIG. 2 is a stress-strain curve of the rosin-based epoxy cured resin obtained according to the present invention.

Detailed Description

The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

DMA was detected using us TA Q800 using a double cantilever mode, temperature range: -60 to 200 ℃.

Tensile testing Using a SANS tensile tester, the tensile properties of resin cast bodies were tested at room temperature according to GB/T2568-.