可自由基聚合的松香基苯并环丁烯单体的制备及其聚合性能研究

doi:10.3969/j.issn.0253-2417.2019.06.003

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (6): 21-28.doi: 10.3969/j.issn.0253-2417.2019.06.003

可自由基聚合的松香基苯并环丁烯单体的制备及其聚合性能研究

付飞^1,²,王丹^1,²,沈明贵^2,*(),商士斌²,宋湛谦²,宋杰³

1. 中国林业科学研究院林业新技术研究所, 北京 100091
2. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
3. Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI 48502, USA

收稿日期:2019-07-09 出版日期:2019-12-28 发布日期:2019-12-21
通讯作者: 沈明贵 E-mail:mingguishen@163.com
作者简介:付飞(1994-),男,河南新乡人,硕士生,研究方向为天然资源化学与利用
基金资助:
中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2017SY035);江苏省自然科学基金青年基金(BK20150071);国家自然科学基金青年基金(31500487)

Preparation of Free-radical Polymerizable Rosin-based Benzocyclobutene Monomer and Its Polymerization Performance

Fei FU^1,²,Dan WANG^1,²,Minggui SHEN^2,*(),Shibin SHANG²,Zhanqian SONG²,Jie SONG³

1. Research Institute of Forestry New Technology, CAF, Beijing 100091, China
2. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
3. Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI 48502, USA

Received:2019-07-09 Online:2019-12-28 Published:2019-12-21
Contact: Minggui SHEN E-mail:mingguishen@163.com
Supported by:
中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2017SY035);江苏省自然科学基金青年基金(BK20150071);国家自然科学基金青年基金(31500487)

摘要/Abstract

摘要：

以脱氢枞酸为原料，经溴化、Suzuki偶联、酰氯化和酯化反应制备出一种具有苯并环丁烯基团和可自由基聚合的丙烯酸酯基团的可聚合单体（12位苯并环丁烯脱氢枞酸（β-甲基丙烯酰氧基乙基）酯），通过FT-IR、NMR、MS等手段对单体结构进行表征；进一步分析了单体的固化行为及其交联固化树脂的性能。结果表明：该单体在引发剂（AIBN）存在的条件下，可以自由基聚合形成预聚体（P1）；之后在加热（>200℃）的条件下，苯并环丁烯基团开环，预聚体进行开环聚合，最终形成不溶不融的交联固化树脂。该树脂具有优良的表面平整性（平均表面粗糙度为0.434 nm）和介电性能（30℃下1 MHz时的介电常数为2.40），还具有良好的疏水性（水接触角为93°）、热稳定性（T_5%=400℃）和机械性能（硬度和杨氏模量分别为0.600、18.36 GPa）。

关键词: 松香, 苯并环丁烯, 树脂, 介电性能

Abstract:

A polymerizable monomer (12-benzocyclobutene dehydroabietic acid (β-methacryloxyethyl) ester) with benzocyclobutene group and free radical polymerizable acrylate group was prepared by bromination, Suzuki coupling, acyl chlorination and esterification with dehydroabietic acid as raw material. The monomer structure was characterized by FT-IR, NMR and MS. Additionally, the curing behavior of the monomer and the properties of the crosslinked cured resin were further analyzed. The results showed that the monomer could be polymerized by free radical polymerization in the presence of initiator (AIBN). Then, under the condition of heating (>200℃), the ring of benzocyclobutene group opened and the prepolymer (P1) was polymerized to form an insoluble and non meltingcrosslinked curing resin. The resin possessed good surface smoothness with average surface roughness of 0.434 nm, and excellent dielectric properties with dielectric constant of 2.40 at 1 MHz under 30℃. It also has good hydrophobicity with water contact angle of 93°, thermal stability with T_5%=400℃ and mechanical properties with hardness and Young's modulus of 0.600 and 18.36 GPa, respectively.

Key words: rosin, benzocyclobutene, resin, dielectric property

中图分类号:

TQ351

付飞,王丹,沈明贵,商士斌,宋湛谦,宋杰. 可自由基聚合的松香基苯并环丁烯单体的制备及其聚合性能研究[J]. 林产化学与工业, 2019, 39(6): 21-28.

Fei FU,Dan WANG,Minggui SHEN,Shibin SHANG,Zhanqian SONG,Jie SONG. Preparation of Free-radical Polymerizable Rosin-based Benzocyclobutene Monomer and Its Polymerization Performance[J]. Chemistry and Industry of Forest Products, 2019, 39(6): 21-28.

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可自由基聚合的松香基苯并环丁烯单体的制备及其聚合性能研究

Preparation of Free-radical Polymerizable Rosin-based Benzocyclobutene Monomer and Its Polymerization Performance

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