CN106699941B - 一种萜烯树脂的制备方法 - Google Patents
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- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
Abstract
本发明公开了一种萜烯树脂的制备方法，具体步骤为：在催化剂负载到分子筛过程中进行超声分散，负载后的分子筛放入管式反应器中，将反应原料、溶剂、偶联剂加入管式反应器，控制反应温度70～80℃，管式反应器出口处连接水洗机对产物进行水洗，水洗后产品进入蒸馏装置，经蒸馏后得到溶剂和萜烯树脂，溶剂返回系统循环利用。本发明能够加快反应速度，提高转化率，可以进行连续生产。
Description
技术领域
本发明属于有机高分子领域，为一种萜烯树脂的制备方法。
背景技术
萜烯树脂是以蒎烯为原料，经阳离子催化聚合而得到的聚合物。萜烯树脂具有无毒、疏水、不结晶、电绝缘、粘接力强等优良的物理性能和耐酸碱、抗老化等化学性能，易溶于芳香烃及植物油，是一种优良的增粘剂和热熔材料的改良剂，广泛应用在橡胶、塑料、油墨、涂料、纺织、胶粘剂、压敏胶、电缆、油漆、包装、防锈油、食品工业等领域。
目前，萜烯树脂使用的催化剂还是以AlCl3为主的一系列催化剂，AlCl3不易溶于甲苯类非极性溶剂，而萜烯树脂合成工艺通常采用甲苯类作溶剂，所制得的萜烯树脂聚合度小、软化点低、色泽深、催化剂用量大、反应时间较长，导致反应不充分，原料转化率低。
发明内容
本发明的目的是提供一种萜烯树脂的制备方法，这种方法采用纳米CuO和纳米ZnO的混合物做催化剂，负载到分子筛过程中进行超声分散，可以加快反应速度，提高转化率。
为了达到以上目的，本发明采用如下技术方案：一种萜烯树脂的制备方法，其特征在于，包括以下步骤：在催化剂负载到分子筛过程中进行超声分散，负载后的分子筛放入管式反应器中,将反应原料、溶剂、偶联剂加入管式反应器，控制反应温度70～80℃，管式反应器出口处连接水洗机对产物进行水洗，水洗后产品进入蒸馏装置，经蒸馏后得到溶剂和萜烯树脂，溶剂返回系统循环利用；所述反应原料为α-蒎烯或β-蒎烯；所述溶剂为甲苯；所述偶联剂为硅烷偶联剂。
上述催化剂为纳米CuO和纳米ZnO重量比为1:1～2的混合物；上述催化剂在分子筛上的负载量为分子筛和催化剂总质量的29～30%。
上述反应原料为100～120份；所述溶剂为140～160份；所述偶联剂为15～20份。
上述超声过程中超声时间为10～15分钟，超声频率为25000～30000Hz。
和现有技术相比，本发明具有以下优点：
本发明采用纳米CuO和纳米ZnO的混合物做催化剂，纳米CuO作为活性物质，纳米ZnO作为分散体，二者按照1：1～2比例混合可以使催化剂活性达到最佳，加快反应速率，提高原料转化率，减少副反应发生。
本发明采用分子筛作为载体，将催化剂纳米CuO和纳米ZnO负载于分子筛的微孔道内，负载后的催化剂均匀分布在分子筛中，可以与原料充分接触，由于分子筛的选择性，二者相结合，可以促进萜烯树脂的生成，减少副反应的发生同时减少催化剂的消耗节约成本，负载量为29～30%时萜烯树脂的转化率达到最大，继续增加催化剂在分子筛上的负载量时，转化率逐渐降低。
本发明采用纳米CuO和纳米ZnO的混合物做催化剂，纳米CuO作为活性物质，纳米ZnO作为分散体，负载到分子筛过程中进行超声分散，该方法制得的催化剂可以加快反应速度，转化率增加，从而达到连续制备的目的。
具体实施例
下面结合实施例，对本发明做进一步说明。
实施例一
以纳米CuO和纳米ZnO重量比为1:1.5的混合物为催化剂，在催化剂负载到分子筛过程中进行超声分散，超声频率25000Hz超声时间为10分钟，负载量为分子筛和催化剂总质量的29%，负载后的分子筛放入管式反应器中，将β-蒎烯100份、甲苯140份、硅烷偶联剂15份加入管式反应器，控制反应温度70℃，管式反应器出口处接水洗机对产物进行水洗，水洗后进入蒸馏装置，经蒸馏后得到甲苯和萜烯树脂，甲苯返回系统循环利用。
实施例二
以纳米CuO和纳米ZnO重量比为1:2的混合物为催化剂，在催化剂负载到分子筛过程中进行超声分散，超声频率30000Hz超声时间为15分钟，负载量为分子筛和催化剂总质量的30%，负载后的分子筛放入管式反应器中，将β-蒎烯120份、甲苯160份、硅烷偶联剂20份加入管式反应器，控制反应温度80℃，管式反应器出口处接水洗机对产物进行水洗，水洗后进入蒸馏装置，经蒸馏后得到甲苯和萜烯树脂，甲苯返回系统循环利用。
对实施例一和实施例二得到的产品进行转化率计算得到实施例一和实施例二的转化率均在97%以上，说明本发明可以加快反应速度，提高转化率，进行连续生产。
上述仅是本发明较佳的实施例而已，需要指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应该为本发明的保护范围。
Claims (3)
1.一种萜烯树脂的制备方法，其特征在于，包括以下步骤：在催化剂负载到分子筛过程中进行超声分散，负载后的分子筛放入管式反应器中,将反应原料、溶剂、偶联剂加入管式反应器，控制反应温度70～80℃，管式反应器出口处连接水洗机对产物进行水洗，水洗后产品进入蒸馏装置，经蒸馏后得到溶剂和萜烯树脂，溶剂返回系统循环利用；所述反应原料为α-蒎烯或β-蒎烯；所述溶剂为甲苯；所述偶联剂为硅烷偶联剂；所述催化剂为纳米CuO和纳米ZnO重量比为1:1～2的混合物，催化剂在分子筛上的负载量为分子筛和催化剂总质量的29～30％。
2.根据权利要求1所述的一种萜烯树脂的制备方法，其特征在于：所述反应原料为100～120份；所述溶剂为140～160份；所述偶联剂为15～20份。
3.根据权利要求1所述的一种萜烯树脂的制备方法，其特征在于：超声过程中超声时间为10～15分钟，超声频率为25000～30000Hz。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709927A (zh) * | 2005-07-08 | 2005-12-21 | 广西大学 | 无色萜烯树脂的制备方法 |
| CN104119300A (zh) * | 2014-07-29 | 2014-10-29 | 浙江大学 | 一种α-蒎烯环氧化制备2,3-环氧蒎烷的方法 |
| CN104211843A (zh) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | 萜烯树脂的制备方法 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709927A (zh) * | 2005-07-08 | 2005-12-21 | 广西大学 | 无色萜烯树脂的制备方法 |
| CN104119300A (zh) * | 2014-07-29 | 2014-10-29 | 浙江大学 | 一种α-蒎烯环氧化制备2,3-环氧蒎烷的方法 |
| CN104211843A (zh) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | 萜烯树脂的制备方法 |
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