CN110951029A - 一种有机硅改性植物油基多元醇及其制备方法和应用 - Google Patents

一种有机硅改性植物油基多元醇及其制备方法和应用 Download PDF

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CN110951029A
CN110951029A CN201911185881.8A CN201911185881A CN110951029A CN 110951029 A CN110951029 A CN 110951029A CN 201911185881 A CN201911185881 A CN 201911185881A CN 110951029 A CN110951029 A CN 110951029A
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张猛
周威
周永红
郝树杰
贾普友
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Abstract

一种有机硅改性植物油基多元醇及其制备方法和应用，步骤为：将N‑（β‑氨乙基）‑γ‑氨丙基甲基二甲氧基硅烷和环氧值为3%的环氧桐油酸甘油单酯按其环氧基团和N‑（β‑氨乙基）‑γ‑氨丙基甲基二甲氧基硅烷的摩尔比例2:1~3:1混合，进行开环反应得到有机硅改性植物油基多元醇。由该多元醇替代部分聚醚多元醇与二氧化硅微胶囊阻燃剂搅拌均匀制得的复配多元醇用于制备聚氨酯泡沫，制得的聚氨酯泡沫具有良好的力学性能、热稳定性和阻燃性能，极限氧指数可达23.5%。

Description

一种有机硅改性植物油基多元醇及其制备方法和应用
技术领域
本发明属于聚氨酯泡沫技术领域，具体涉及一种有机硅改性植物油基多元醇及其制备方法和应用。
背景技术
聚氨酯(PU)是由多元醇和多异氰酸酯为主要原料制备得到的一类具有聚氨基甲酸酯结构的化合物，广泛应用于涂料、胶粘剂、弹性体、泡沫等材料中。传统聚氨酯的生产原料主要来源于不可再生的石化资源，同时由于原油价格的不断上涨以及温室效应，环境污染等全球性问题的日趋严重，用可再生资源替代石化资源用于制备聚氨酯材料已引起科研人员的关注，这也是未来的发展趋势之一。
植物油作为一种可再生资源，因具有来源丰富，生物降解性能稳定，价格低廉，低毒性和可再生等特点，成为聚氨酯合成中的多功能单体及低聚物的重要来源。合成植物油多元醇的原理是利用植物油中不饱和双键及羧基酯等基团，经过水解、酯交换、皂化、加氢、环氧化以及胺化等反应转化为多元醇。用植物油多元醇制备的聚氨酯泡沫具有良好的化学和物理性能，特别是有较好的耐水解和热稳定性。
聚氨酯密度较小且比表面积较大，其结构中存在较多的碳氢链，导致聚氨酯泡沫极易燃烧。因含磷、氮、硅等阻燃元素的反应型阻燃剂和无机阻燃剂具有低毒和环境友好等特点，被广泛应用在阻燃聚氨酯泡沫的制备领域。但添加高剂量的无机阻燃剂不仅增加生产成本，还会降低聚氨酯泡沫的物理性能。
发明内容
解决的技术问题：为了提高聚氨酯泡沫的阻燃性能、力学性能及热稳定性，本发明提供一种有机硅改性植物油基多元醇及其制备方法和应用。本发明以可再生的桐油作为原料经过一系列反应后与N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷(KH-602)发生开环反应得到阻燃型桐油基多元醇(PTOK)。由于直接将纳米二氧化硅作为聚氨酯泡沫的增强成分，通常造成最初的纳米尺度分散相的团聚。采用钼酸铵作材料的壳而纳米二氧化硅作芯材，形成钼酸铵包覆二氧化硅。二氧化硅微胶囊阻燃剂与桐油基阻燃型多元醇及市售的聚醚多元醇(PPG4110)复配得到复配多元醇，利用复配多元醇与异氰酸酯反应得到聚氨酯泡沫，该聚氨酯泡沫的极限氧指数可达23.5％，压缩强度可达613.7KPa，泡沫初始热降解温度随着二氧化硅微胶囊阻燃剂用量的增加出现降低的趋势。
技术方案：一种有机硅改性植物油基多元醇，结构式如下：
Figure BDA0002292380360000021
其中，
Figure BDA0002292380360000022
有机硅改性植物油基多元醇的制备方法，步骤为：将N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷和环氧值为3％的环氧桐油酸甘油单酯按其环氧基团和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷的摩尔比例2:1～3:1混合，进行开环反应得到有机硅改性植物油基多元醇。
上述机硅改性植物油基多元醇在制备聚氨酯泡沫中的应用。
应用具体方法为，先将组合多元醇、二氧化硅微胶囊阻燃剂及助剂搅拌均匀形成复配多元醇，然后再与异氰酸酯搅拌20-30s，转速2000-2500r/min；倒入模具中，熟化12小时；各原料以质量份计为：组合多元醇100份；二氧化硅微胶囊阻燃剂0～20份；异氰酸酯118份；助剂：聚氨酯泡沫稳定剂3.0～4.0份；水0.4～0.6份；发泡剂15～25份；催化剂0～0.20份；所述组合多元醇的有效成分为有机硅改性植物油基多元醇。
上述二氧化硅微胶囊阻燃剂为钼酸铵包覆二氧化硅所形成，取二氧化硅和钼酸铵溶于磷酸溶液中，混合均匀；滴加硝酸并调节体系pH值至1.0，溶液静置后过滤，并对固体产物进行洗涤、干燥等操作，最后得到固体为二氧化硅微胶囊阻燃剂，二氧化硅微胶囊阻燃剂的体积平均粒径为19μm。
上述异氰酸酯为多次甲基多异氰酸酯PAPI。
上述聚氨酯泡沫稳定剂为硅型泡沫稳定剂5501。
上述发泡剂为HFC-365mfc。
上述催化剂为：二月桂酸二丁基锡。
有益结果：以桐油为原料得到环氧桐油酸甘油单酯与N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷按一定配比反应得到的多元醇是一种反应型结构阻燃多元醇，具有热稳定性高、反应活性强及高羟值等特点。由该多元醇替代部分聚醚多元醇与二氧化硅微胶囊阻燃剂搅拌均匀制得的复配多元醇用于制备聚氨酯泡沫，制得的聚氨酯泡沫具有良好的力学性能、热稳定性和阻燃性能，极限氧指数可达23.5％。所制得的有机硅改性桐油基多元醇的羟值为344.71mgKOH/g，硅含量为1.00％，氮含量1.00％，酸值低于1.30mgKOH/g，水分低于0.10％，适合用于制备聚氨酯泡沫。
附图说明
图1为环氧桐油酸甘油单酯的红外谱图。3400cm-1为—OH的振动吸收峰，2920cm-1和2860cm-1处分别为甲基、亚甲基的伸缩振动吸收峰，1730cm-1是C＝O的伸缩振动吸收峰，1460cm-1和1370cm-1是甲基的弯曲振动吸收峰，1240cm-1、1170cm-1、1100cm-1这三处甘油单酯中C—O伸缩振动吸收峰，1050cm-1是C—O—C醚键特征吸收峰，908cm-1是环氧基团的特征吸收峰。
图2为N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的桐油基多元醇的红外谱图。3440cm-1处是—OH和—NH的特征吸收峰，2920cm-1和2850cm-1处吸收峰分别对应甲基、亚甲基的伸缩振动，1740cm-1处为桐油酸甘油单酯骨架上的酯键特征吸收峰。1460cm-1和1370cm-1为甲基的弯曲振动吸收峰，1240cm-1、1170cm-1、1040cm-1处C—O伸缩振动吸收峰。其中987cm-1、823cm-1、731cm-1、693cm-1为Si—C和Si—C的特征吸收峰，说明N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷成功接入环氧化桐油酸甘油单酯结构上。
图3为二氧化硅微胶囊阻燃剂的红外谱图。3226cm-1处N—H的氢键吸收峰，1632cm-1附近的峰是水的H—O—H弯曲振动峰，795cm-1、584cm-1、570cm-1和547cm-1是Si—O键对称伸缩振动吸收峰。
具体实施方式：
下面结合实施例对本发明作进一步说明，本发明中％都代表质量分数。
本发明对桐油进行一系列改性得到N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的桐油基多元醇。所制得的结构阻燃型桐油基多元醇与市售聚聚醚多元醇、二氧化硅微胶囊阻燃剂、助剂及多聚异氰酸酯，通过一步法发泡制得二氧化硅微胶囊阻燃剂增强有机硅改性桐油基聚氨酯泡沫。
主要方案包括以下两方面的内容：
一：制备上述的N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的桐油基多元醇的方法
通过对桐油酯键和双键的改性得到含有环氧基团的桐油酸甘油单酯，利用N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷的结构中的伯氨基具有活泼的反应活性可与环氧基团发生开环反应，反应方程式为：
Figure BDA0002292380360000041
方程式二：环氧桐油酸甘油单酯与N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷的开环反应
更具体的制法为，以质量份计：取100质量份环氧化桐油酸甘油单酯，7.94质量份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷，升温至60-70℃，在氮气保护下反应2～3小时得到棕褐色液体即为有机硅改性的桐油基多元醇。
本发明所制备的有机硅改性的桐油基多元醇的羟值按GB/T 12008.3-2009中的邻苯二甲酸酐酯化法测定，酸值按照GB/T 12008.5-2010方法测定，黏度按照GB/T 12008.7-2010中的旋转粘度计方法测定。
二：二氧化硅微胶囊阻燃剂增强有机硅改性桐油基聚氨酯泡沫：
1、复配多元醇的组成，按质量份计：
(1)N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的桐油基多元醇的质量为25份，聚醚多元醇(PPG4110)的质量份为75份。
(2)二氧化硅微胶囊阻燃剂的质量份为0～20份。
2、助剂的组成，按质量份计：
(1)水：质量份为0.30～0.70份。
(2)发泡剂：质量份为25份。
(3)泡沫稳定剂：硅型泡沫稳定剂5501，质量份为3.75份。
(4)催化剂：二月桂酸二丁基锡，质量份为0～0.20份。
3、二氧化硅微胶囊阻燃剂增强有机硅改性桐油基聚氨酯泡沫：
聚氨酯泡沫的制备配方、性能测试结果见表1，表2。以复配多元醇和异氰酸酯为主要原料。
具体操作如下：把复配多元醇和助剂在快速搅拌的条件下使其混合均匀，然后再与异氰酸酯在快速搅拌的条件下搅拌20～30s，转速2000～2500r/min，倒入模具中，熟化12h。
异氰酸酯为多次甲基多苯基多异氰酸酯(PAPI)，商品牌号为烟台万华聚氨酯股份有限公司的PM-200。
本发明中以钼酸铵包覆二氧化硅形成二氧化硅微胶囊阻燃剂，组成硅-氮-钼阻燃体系。同时利用桐油为原料经过酯交换反应、环氧化反应及开环反应得到有机硅改性的反应型桐油基阻燃多元醇(PTOK)，该多元醇替代部分石油基多元醇(PPG4110)并与二氧化硅微胶囊阻燃剂复配形成复配多元醇作为制备聚氨酯泡沫的原料之一。将二氧化硅微胶囊阻燃剂加入聚氨酯泡沫制得的阻燃聚氨酯泡沫具有优异的力学性能和阻燃效果，适量的二氧化硅微胶囊能够促进聚氨酯泡沫在燃烧过程中脱水成炭且稀释易燃气体，同时由于炭层的包覆与阻隔作用，可表现出优异的气相和固相的阻燃效果。
本发明公开制备一系列二氧化硅微胶囊阻燃剂增强的有机硅改性植物油基聚氨酯泡沫的方法，与由市售聚醚多元醇制备的聚氨酯泡沫的性能相比，由二氧化硅微胶囊增强的有机硅改性植物油基聚氨酯泡沫具有较优异的阻燃性能及力学性能，但泡沫初始分解温度降低。
实施例1
将环氧桐油酸甘油单酯和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷按摩尔比n环氧基团：nN-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷＝7:3混合，升温至70℃，在氮气保护下反应2h后得有机硅改性桐油基多元醇。根据表1所示的配方，100质量份的聚醚多元醇PPG4110及助剂混合均匀，再与118质量份的异氰酸酯搅拌20～30s，转速2000～2500r/min，倒入模具中，于60℃的鼓风干燥箱中熟化12h。
实施例2
将环氧桐油酸甘油单酯和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷按摩尔比n环氧基团：nN-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷＝7:3混合，升温至70℃，在氮气保护下反应2h得有机硅改性桐油基多元醇。根据表1所示的配方，先把25质量份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的桐油基多元醇与75质量份的聚醚多元醇PPG4110及助剂混合均匀，再与118质量份的异氰酸酯搅拌20～30s，转速2000～2500r/min，倒入模具中，于60℃的鼓风干燥箱中熟化12h。
实施例3
将环氧桐油酸甘油单酯和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷按摩尔比n环氧基团：nN-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷＝7:3混合，升温至70℃，在氮气保护下反应2h得有机硅改性桐油基多元醇。根据表1所示的配方，先把25质量份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的多元醇与75质量份的聚醚多元醇PPG4110、7.50质量份二氧化硅微胶囊阻燃剂及助剂混合均匀，再与118质量份的异氰酸酯搅拌20～30s，转速2000～2500r/min，倒入模具中，于60℃的鼓风干燥箱中熟化12h。
实施例4
将环氧桐油酸甘油单酯和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷按摩尔比n环氧基团：nN-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷＝7:3混合，升温至70℃，在氮气保护下反应2h得有机硅改性桐油基多元醇。根据表1所示的配方，先把25质量份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的多元醇与75质量份的聚醚多元醇PPG4110、10.90质量份二氧化硅微胶囊及助剂混合均匀，再与118质量份的异氰酸酯搅拌20～30s，转速2000～2500r/min，倒入模具中，于60℃的鼓风干燥箱中熟化12h。
实施例5
将环氧桐油酸甘油单酯和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷按摩尔比n环氧基团：nN-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷＝7:3混合，升温至70℃，在氮气保护下得有机硅改性桐油基多元醇。根据表1所示的配方，先把25质量份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷改性的多元醇与75质量份的聚醚多元醇PPG4110、17.50质量份二氧化硅微胶囊阻燃剂及助剂混合均匀，再与118质量份的异氰酸酯搅拌20～30s，转速2000～2500r/min，倒入模具中，于60℃的鼓风干燥箱中熟化12h。
表1二氧化硅微胶囊增强有机硅改性桐油基聚氨酯泡沫(质量份)
Figure BDA0002292380360000071
表2二氧化硅微胶囊阻燃剂增强有机硅改性桐油基聚氨酯泡沫(测试方法参照国家标准)
Figure BDA0002292380360000072
利用可再生的桐油为原料合成的植物油基多元醇，可以部分取代石油基多元醇PPG4110用于生产聚氨酯泡沫，这可以缓解聚氨酯行业对石油基多元醇的依赖。添加适量的二氧化硅微胶囊阻燃剂可以提高聚氨酯泡沫的力学强度及阻燃性能，同时对聚氨酯泡沫的抑烟也有一定的效果。

Claims (9)

1.一种有机硅改性植物油基多元醇，其特征在于结构式如下：
Figure FDA0002292380350000011
其中，
Figure FDA0002292380350000012
2.权利要求1所述有机硅改性植物油基多元醇的制备方法，其特征在于步骤为：将N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷和环氧值为3％的环氧桐油酸甘油单酯按其环氧基团和N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷的摩尔比例2:1～3:1混合，进行开环反应得到有机硅改性植物油基多元醇。
3.权利要求1所述有机硅改性植物油基多元醇在制备聚氨酯泡沫中的应用。
4.根据权利要求3所述的应用，其特征在于先将组合多元醇、二氧化硅微胶囊阻燃剂及助剂搅拌均匀形成复配多元醇，然后再与异氰酸酯搅拌20-30s，转速2000-2500r/min；倒入模具中，熟化12小时；各原料以质量份计为：组合多元醇100份；二氧化硅微胶囊阻燃剂0～20份；异氰酸酯118份；助剂：聚氨酯泡沫稳定剂3.0～4.0份；水0.4～0.6份；发泡剂15～25份；催化剂0～0.20份；所述组合多元醇的有效成分为有机硅改性植物油基多元醇。
5.根据权利要求4所述的应用，其特征在于所述二氧化硅微胶囊阻燃剂为钼酸铵包覆二氧化硅所形成，取二氧化硅和钼酸铵溶于磷酸溶液中，混合均匀；滴加硝酸并调节体系pH值至1.0，溶液静置后过滤，并对固体产物进行洗涤、干燥等操作，最后得到固体为二氧化硅微胶囊阻燃剂，二氧化硅微胶囊阻燃剂的体积平均粒径为19μm。
6.根据权利要求4所述的应用，其特征在于所述催化剂为：二月桂酸二丁基锡。
7.根据权利要求4所述的应用，其特征在于所述聚氨酯泡沫稳定剂为硅型泡沫稳定剂5501。
8.根据权利要求4所述的应用，其特征在于所述异氰酸酯为多次甲基多异氰酸酯PAPI。
9.根据权利要求4所述的应用，其特征在于所述发泡剂为HFC-365mfc。
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CN114716640A (zh) * 2021-03-12 2022-07-08 深圳飞扬兴业科技有限公司 一种水性聚氨酯-聚脲分散体及其制备方法
CN113943320A (zh) * 2021-11-17 2022-01-18 广州航海学院 一种有机硅植物油基多元醇及其制备方法和应用
CN113943320B (zh) * 2021-11-17 2024-01-23 广州航海学院 一种有机硅植物油基多元醇及其制备方法和应用
CN114409869A (zh) * 2022-01-12 2022-04-29 万华化学集团股份有限公司 一种多重固化异氰酸酯预聚体及其制备方法和其应用
CN114409869B (zh) * 2022-01-12 2023-07-11 万华化学集团股份有限公司 一种多重固化异氰酸酯预聚体及其制备方法和其应用

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