CN106633623B - 一种海松酸改性酚醛发泡树脂 - Google Patents
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Abstract
一种海松酸改性酚醛发泡树脂，涉及一种发泡树脂，该发泡树脂是由以下原料按重量份配比制成的：酚醛树脂100份；海松酸80‑95份；催化剂3‑5份；表面活性剂2‑6份；发泡剂8‑10份；固化剂12‑15份。选用了一种海松酸来改性酚醛树脂，所利用的海松酸是从植物中直接提取的无毒物质，直接添加入酚醛树脂中，降低了树脂中有害物质的比例，使产品更加环保。这种新型树脂机械强度较高，吸水性较低，且残炭率也有所提高，产品的综合性能得到了提升，具有广阔的发展和应用前景。
Description
技术领域
本发明涉及一种发泡树脂，特别是涉及一种海松酸改性酚醛发泡树脂。
背景技术
纯酚醛树脂的酚羟基和亚甲基容易氧化，使耐热性和耐氧化性受到影响，固化后的酚醛树脂因芳核间仅由亚甲基相连而显脆性。故利用各种方法对酚醛树脂进行改性，已经成为了酚醛树脂研究的核心内容。随着常规化石资源的不断利用，它们的储量也在逐渐地减少，鉴于此，人类开始寻找这些资源的替代性能源。近年来，天然植物资源的开发利用愈来愈受到人们的重视，环境保护成为重点话题，而对化工材料的应用更是以环保为重中之重，所以从植物中提取的化合物多被应用于改性化工产品。
我国是松香生产大国，松香年产量75万吨左右，传统生产的脂松香主要是马尾松松香。我国脂松香中存在的海松酸型树脂酸主要包括海松酸、异海松酸、山达海松酸等几种同分异构体，是松香的重要组分。海松酸型树脂酸作为一类特殊结构的二萜树脂酸，其生物活性值得期待和进行深入研究。我国脂松香中存在的海松酸型树脂酸主要包括海松酸、异海松酸、山达海松酸等几种同分异构体，是松香的重要组分。迄今为止，松香的化学利用实际上主要针对枞酸型树脂酸成分的化学特性而展开的，基本上没有将海松酸型树脂酸进行单独考虑并加以有效的工业化利用的深入研究。
公开专利号为CN 104140510 A的发明专利申请，其公开了一种松香改性酚醛树脂的制备方法，其松香改性酚醛树脂粘度好，油溶性佳，软化点高，适用于平板或凹版印刷油墨。
近30年来，国内外学者对海松酸型树脂酸的生物活性及应用做了大量的研究工作，就其研究应用领域，主要集中在生物农药和医药方面，本发明则将海松酸应用于改性酚醛树脂发泡板上，生成一种新型热固性酚醛树脂。
发明内容
本发明的目的在于提供一种海松酸改性酚醛发泡树脂，该树脂在酚醛树脂结构中引入芳环，因其键能较高，结构稳定，故所制得的酚醛泡沫韧性大大提高，且吸水率下降明显，同时改善了酚醛泡沫的残炭率等综合性能。
本发明的目的是通过以下技术方案实现的：
一种海松酸改性酚醛发泡树脂，该发泡树脂是由以下原料按重量份配比制成的：
酚醛树脂 100份；
海松酸 80-95份；
催化剂 3-5份；
表面活性剂 2-6份；
发泡剂 8-10份；
固化剂 12-15份。
所述的一种海松酸改性酚醛发泡树脂，该发泡树脂
反应过程如下：
。
所述的海松酸改性酚醛发泡树脂，所述催化剂为三氧化二铝。。
所述的海松酸改性酚醛发泡树脂，所述表面活性剂为吐温-80、硅油中的至少一种。
所述的海松酸改性酚醛发泡树脂，所述发泡剂为正戊烷、异戊烷中的至少一种。
所述的海松酸改性酚醛发泡树脂，所述固化剂为对甲基苯磺酸、二甲苯磺酸、苯酚磺酸、苯磺酸中的一种或几种硫酸中的一种或多种。
本发明的优点与效果是：
本发明通过引入海松酸改性酚醛树脂，增加了芳基的含量，使改性泡沫的耐热性、韧性均得到了提高，同时燃烧后的残炭率及吸水率也得到了改善。所使用的海松酸为从植物中提取的无毒物质，降低了树脂中有害物质的比例，更加环保。
具体实施方式
下面结合实施例对本发明进行详细说明。
实施例 1
将苯酚与多聚甲醛100：55的质量份数比加入到反应釜中，混合均匀后加入1质量份数氢氧化钠，在恒温水浴90℃下反应90min，得到可发性酚醛树脂。将酚醛树脂、海松酸、三氧化二铝按照100：80：3的质量份数比加入到三口烧瓶，充分搅拌均匀并升温至140℃，继续搅拌反应三小时后加入3质量份数的吐温-80和8质量份数的正戊烷，经机械搅拌均匀后，得到海松酸改性后的酚醛树脂。将烘箱调制60℃预热30min，在所制得的改性酚醛树脂中加入12质量份数的甲基苯磺酸搅拌均匀，然后所制得的改性后的酚醛树脂放入烘箱内发泡45min～60min。冷却后脱模得到海松酸改性酚醛泡沫。
实施例 2
将苯酚与多聚甲醛100：55的质量份数比加入到反应釜中，混合均匀后加入1质量份数氢氧化钠，在恒温水浴90℃下反应90min，得到可发性酚醛树脂。将酚醛树脂、海松酸、三氧化二铝按照100：85：3的质量份数比加入到三口烧瓶，充分搅拌均匀并升温至140℃，继续搅拌反应三小时后加入3质量份数的吐温-80和8质量份数的正戊烷，经机械搅拌均匀后，得到海松酸改性后的酚醛树脂。将烘箱调制60℃预热30min，在所制得的改性酚醛树脂中加入12质量份数的甲基苯磺酸搅拌均匀，然后所制得的改性后的酚醛树脂放入烘箱内发泡45min～60min。冷却后脱模得到海松酸改性酚醛泡沫。
实施例 3
将苯酚与多聚甲醛100：55的质量份数比加入到反应釜中，混合均匀后加入1质量份数氢氧化钠，在恒温水浴90℃下反应90min，得到可发性酚醛树脂。将酚醛树脂、海松酸、三氧化二铝按照100：90：4的质量份数比加入到三口烧瓶，充分搅拌均匀并升温至140℃，继续搅拌反应三小时后加入3质量份数的吐温-80和8质量份数的正戊烷，经机械搅拌均匀后，得到海松酸改性后的酚醛树脂。将烘箱调制60℃预热30min，在所制得的改性酚醛树脂中加入12质量份数的甲基苯磺酸搅拌均匀，然后所制得的改性后的酚醛树脂放入烘箱内发泡45min～60min。冷却后脱模得到海松酸改性酚醛泡沫。
实施例 4
将苯酚与多聚甲醛100：55的质量份数比加入到反应釜中，混合均匀后加入1质量份数氢氧化钠，在恒温水浴90℃下反应90min，得到可发性酚醛树脂。将酚醛树脂、海松酸、三氧化二铝按照100：95：5的质量份数比加入到三口烧瓶，充分搅拌均匀并升温至140℃，继续搅拌反应三小时后加入3质量份数的吐温-80和8质量份数的正戊烷，经机械搅拌均匀后，得到海松酸改性后的酚醛树脂。将烘箱调制60℃预热30min，在所制得的改性酚醛树脂中加入12质量份数的甲基苯磺酸搅拌均匀，然后所制得的改性后的酚醛树脂放入烘箱内发泡45min～60min。冷却后脱模得到海松酸改性酚醛泡沫。
本发明实施例1至 4所制备的酚醛泡沫与普通酚醛泡沫的性能对比如下表：
由上表可见，海松酸改性后的酚醛泡沫的弯曲形变程度也大幅度增加，泡沫的弯曲形变比基础泡沫提高了接近4倍，海松酸的引入不但提高了材料的韧性，同时也改善了泡沫质脆、易粉化的缺点。
海松酸改性的酚醛泡沫与普通酚醛泡沫的残炭率结果比较可看出，引入海松酸使得改性后的酚醛泡沫比普通酚醛泡沫残炭率提升了大约10个百分点。体积吸水率减少约5个百分点，且极限氧指数略有增加。
综上所述，本发明由海松酸改性的酚醛树脂，使酚醛泡沫韧性有很大改善，体积吸水率下降明显，残炭率、极限氧指数均有提高，产品的综合性能得到了提升。
以上通过具体实施方式的描述对本发明作进一步说明，但这并非是对本发明的限制，本领域技术人员根据本发明的基本思想，可以做出各种修改或改进，但是只要不脱离本发明的基本思想，均在本发明的范围之内。
Claims (5)
1.一种海松酸改性酚醛发泡树脂，其特征在于，该发泡树脂是由以下原料按重量份配比制成的：
酚醛树脂 100份；
海松酸 80-95份；
催化剂 3-5份；
表面活性剂 2-6份；
发泡剂 8-10份；
固化剂 12-15份；
所述催化剂为三氧化二铝。
2.如权利要求1所述的一种海松酸改性酚醛发泡树脂，其特征在于，该发泡树脂反应过程如下：
。
3.如权利要求1所述的海松酸改性酚醛发泡树脂，其特征在于，所述表面活性剂为吐温-80、硅油中的至少一种。
4.如权利要求1所述的海松酸改性酚醛发泡树脂，其特征在于，所述发泡剂为正戊烷、异戊烷中的至少一种。
5.如权利要求1所述的海松酸改性酚醛发泡树脂，其特征在于，所述固化剂为对甲基苯磺酸、二甲苯磺酸、苯酚磺酸、苯磺酸、硫酸中的一种或多种。
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| JPS62143918A (ja) * | 1985-12-19 | 1987-06-27 | Toyo Ink Mfg Co Ltd | 印刷インキ用樹脂およびその製造方法 |
| EP1323776A2 (de) * | 2001-12-20 | 2003-07-02 | Surface Specialties Germany GmbH & Co. KG | Verwendung von plastifizierten Novolaken als Zusatz zu Kautschukmischungen |
| CN102131858A (zh) * | 2008-06-26 | 2011-07-20 | 华奇（张家港）化工有限公司 | 橡胶配合应用的改性酚醛增粘树脂 |
| CN104140510B (zh) * | 2014-07-25 | 2016-08-24 | 广西众昌树脂有限公司 | 松香改性酚醛树脂的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS62143918A (ja) * | 1985-12-19 | 1987-06-27 | Toyo Ink Mfg Co Ltd | 印刷インキ用樹脂およびその製造方法 |
| EP1323776A2 (de) * | 2001-12-20 | 2003-07-02 | Surface Specialties Germany GmbH & Co. KG | Verwendung von plastifizierten Novolaken als Zusatz zu Kautschukmischungen |
| CN102131858A (zh) * | 2008-06-26 | 2011-07-20 | 华奇（张家港）化工有限公司 | 橡胶配合应用的改性酚醛增粘树脂 |
| CN104140510B (zh) * | 2014-07-25 | 2016-08-24 | 广西众昌树脂有限公司 | 松香改性酚醛树脂的制备方法 |
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