CN112759753A - 磷氮协同阻燃聚醚多元醇的制备方法 - Google Patents
磷氮协同阻燃聚醚多元醇的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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Abstract
本发明涉及一种磷氮协同阻燃聚醚多元醇的制备方法,属于硬泡聚醚多元醇改性技术领域。本发明所述的磷氮协同阻燃聚醚多元醇的制备方法,以含氮磷的化合物和多元醇为复合起始剂,在催化剂作用下,与环氧丙烷进行聚合反应,得到所述的磷氮协同阻燃聚醚多元醇;所述含氮磷的化合物由芳香族磷酸酯、醛、胺在溶剂中反应得到。本发明设计科学合理,将制备的产品可以应用在聚氨酯材料阻燃领域,同时制备的产品具有优良的戊烷互溶性能和储存稳定性。
Description
技术领域
本发明涉及一种磷氮协同阻燃聚醚多元醇的制备方法,属于硬泡聚醚多元醇改性技术领域。
背景技术
聚氨酯材料是分子结构中含有氨基甲酸酯连段的聚合物,由于其具有耐磨性强、吸震性能优良、机械加工性能优异等特点,被广泛应用于服装鞋帽、建筑外墙、管道、航天航空、家具、汽车、医疗等领域。但普通聚氨酯材料在空气中易燃烧,且燃烧过程中会产生大量的有毒气体和烟尘,会造成很大的经济损失和人员伤亡,因此国内外对于聚氨酯材料的阻燃性能也提出了一定的要求,各地都纷纷颁布了相应的标准文件,限制和禁止非阻燃聚氨酯材料的应用。
目前,提高聚氨酯材料阻燃性能的主要途径是添加含磷、氯、溴及其它阻燃元素的阻燃剂。根据使用方法的不同可分为添加型阻燃和结构性阻燃两大类。
添加型阻燃是在聚氨酯材料的制备过程中直接将不和反应物发生理或者化学反应的阻燃剂添加到塑料里面,使得具材料具有一定阻燃性能的方法。但该方法添加的阻燃剂会使得材料的强度机加工性能降低,且在材料的使用过程中阻燃剂会逐渐地迁移出来导致阻燃效果下降并对环境造成一定的危害。
由于聚醚多元醇是生产聚氨酯材料的一个最普遍的原料,而且其生产过程相对较简单、环保,反应条件较温和。近年来,通过对聚醚多元醇进行改性以达到聚氨酯材料的结构阻燃的研究层出不穷。目前市面上也存在较多此类的阻燃聚醚多元醇,但市面上流通的阻燃聚醚多元醇,大多是通过引入卤素达到阻燃的效果。含卤阻燃聚醚多元醇制备的聚氨酯材料,在燃烧时会产生大量的烟雾及多种有毒有害气体,在发生火灾时容易导致人员窒息死亡,致使火灾的程度增加。
磷氮协同阻燃聚醚是一种新型较环保阻燃聚醚,用该类聚醚生产的聚氨酯材料结构中同时可以含有磷元素和氮元素,且二者是通过一定的化学结构进行连接。一般认为在高温或聚氨酯材料燃烧过程中,磷化物和氮化物在高温下形成膨胀性焦炭层,它起着隔热阻氧保护层的作用,含氮化合物起着发泡剂和焦炭增强剂的作用,且磷-氮阻燃体系能有机化合物在较低温度下分解形成焦炭和水,并增加焦炭残留物生产量,从而提高阻燃效果。但目前市售的磷氮协同阻燃聚醚种类较少,且合成方法较繁琐。因此,磷氮协同阻燃聚醚的开发和应用意义重大。
发明内容
本发明的目的是提供一种磷氮协同阻燃聚醚多元醇的制备方法,其设计科学合理,将制备的产品可以应用在聚氨酯材料阻燃领域,同时制备的产品具有优良的戊烷互溶性能和储存稳定性。
本发明所述的磷氮协同阻燃聚醚多元醇的制备方法,以含氮磷的化合物和多元醇为复合起始剂,在催化剂作用下,与环氧丙烷进行聚合反应,得到所述的磷氮协同阻燃聚醚多元醇;
所述含氮磷的化合物由芳香族磷酸酯、醛、胺在溶剂中反应得到。
优选的,芳香族磷酸酯为磷酸甲基二苯酯、磷酸二苯酯或磷酸三苯酯中的一种或多种。
优选的,醛为甲醛。
优选的,胺为一乙醇胺、二乙醇胺或二异丙醇胺中的一种或多种。
优选的,溶剂为乙醚、甲醇、乙醇、乙二醇或水中的一种或多种。
优选的,芳香族磷酸酯、醛和胺的摩尔比为0.1-1:0.1-4:0.1-4.5。
优选的,制备含氮磷的化合物时,反应温度为80-105℃,反应时间为2-4h。
优选的,多元醇为丙二醇、二乙二醇、水、甘油、山梨醇或蔗糖中的两种以上的混合物;催化剂为有机胺类催化剂,进一步优选为N,N-二甲基环己胺、N,N-二甲基苄胺、五甲基二乙烯三胺、N,N,N',N'-四甲基亚烷基二胺、三乙胺、三乙烯二胺、N,N’-二乙基哌嗪、DMEA、DBU或N,N’-二甲基吡啶;环氧烷烃为环氧乙烷或环氧丙烷。
优选的,所用原料的用量如下:
以四种物质的总质量为100%计。
优选的,聚合反应温度为80-120℃,聚合反应时间为2-8h。
本发明所述的磷氮协同阻燃聚醚多元醇的制备方法,具体包括以下步骤:
(1)将芳香族磷酸酯、醛、胺以及溶剂按照以一定比例依次加入反应容器中,在一定条件下搅拌反应一段时间,将溶剂脱除并回收,得到结构中含磷氮的起始剂;
(2)按照理论设计的官能度以及羟值的不同,将步骤(1)合成的结构中含磷氮的起始剂、多元醇、催化剂按照设定的比例,在一定条件下与环氧烷烃发生聚合反应生成磷氮协同阻燃聚醚多元醇。
步骤(1)中,搅拌速度优选为10-25r/min,其中醛类物质需要滴加、分批次加或直接全部加入。
步骤(2)中,复合起始剂的类型选择对聚醚指标的影响也不尽相同,可以根据需求合成不同指标范围的聚醚多元醇。
本发明通过芳香族磷酸酯与胺类化合物发生反应生成结构中含有磷氮的起始剂,将化合物复配一定量的硬泡聚醚多元醇起始剂,以改善泡沫的强度、韧性等指标,在催化剂作用下引发环氧烷烃聚合反应,最终得到不同指标的聚醚多元醇;本发明还可以引入含有羟基、氨基等可引发环氧烷烃聚合反应的基团合成聚醚多元醇,进一步参与聚氨酯反应以达到结构阻燃的目的。经过此方法合成的聚醚多元醇具有良好的阻燃性能,较高的强度以及尺寸稳定性,且由于体系中苯环的存在会使得产品的戊烷互溶性得到较大改观。
与现有技术相比,本发明具有以下有益效果:
(1)本发明通过芳香族磷酸酯与胺类化合物发生反应生成结构中同时含有磷、氮元素以及羟基或胺基的化合物,不仅提高了体系的官能度,使得阻燃成分可以进入到聚氨酯的结构中;同时也使得其生产的聚氨酯材料在高温或燃烧时,结构中的磷元素和氮元素可以起到协同作用,提高阻燃效率;
(2)本发明合成的聚醚多元醇具有一定的自催化活性,与阻燃聚酯、添加型阻燃剂相比,其保存稳定性好,戊烷互溶性好;
(3)本发明设计科学合理,简单易行,采用本发明制得的聚醚多元醇制备的聚氨酯泡沫塑料,具有良好的阻燃效果,尺寸稳定性,较高的强度。
具体实施方式
下面结合实施例对本发明作进一步的说明,但其并不限制本发明的实施。
实施例中所用原料均为市售产品。
实施例1
(1)在装配有温度计、回流冷凝管和氮气保护装置的三口烧瓶内,加入磷酸甲基二苯酯249g,二乙醇胺220g,37%甲醛水溶液164g,乙醚溶剂50g。放在磁力加热搅拌器上,搅拌速度22r/min,在80℃下反应2h。
(2)溶剂通过旋转蒸发回收,可重复利用,得到结构中含磷氮的起始剂。
(3)准确称量结构中含磷氮的起始剂315g、二乙二醇27.5g,蔗糖40g,有机胺类催化剂5g,加入反应釜内,将210g环氧丙烷通过压力容器缓慢滴加至反应釜,搅拌速度18r/min,在100℃下进行聚合反应,得磷氮协同阻燃聚醚多元醇,外观为黄色透明液体。
实施例2
(1)在装配有温度计、回流冷凝管和氮气保护装置的三口烧瓶内,加入磷酸二苯酯250g,二异丙醇醇胺267g,37%甲醛水溶液164g,乙醇溶剂50g。放在磁力加热搅拌器上,搅拌速度22r/min,在80℃下反应2h。
(2)溶剂通过旋转蒸发回收,可重复利用,得到结构中含磷氮的起始剂。
(3)准确称量结构中含磷氮的起始剂270g、甘油20g,山梨醇30g,有机胺类催化剂5g,加入反应釜内,将260g环氧丙烷通过压力容器缓慢滴加至反应釜,搅拌速度18r/min,在100℃下进行聚合反应,得磷氮协同阻燃聚醚多元醇,外观为黄色透明液体。
实施例3
(1)在装配有温度计、回流冷凝管和氮气保护装置的三口烧瓶内,加入磷酸三苯酯327g,一乙醇胺122g,37%甲醛水溶液164,80g水作为溶剂。放在磁力加热搅拌器上,搅拌速度22r/min,在80℃下反应2h。
(2)溶剂通过旋转蒸发回收,可重复利用,得到结构中含磷氮的起始剂。
(3)准确称量结构中含磷氮的起始剂241g、丙二醇20g,蔗糖35g,有机胺类催化剂5g,加入反应釜内,将230g环氧丙烷通过压力容器缓慢滴加至反应釜,搅拌速度18r/min,在100℃下进行聚合反应,得磷氮协同阻燃聚醚多元醇,外观为黄色透明液体。
对比例1
在反应釜中加入磷酸三苯酯327g,甲醇溶剂50g,丙二醇40g,蔗糖70g,有机胺类催化剂5g,将230g环氧丙烷通过压力容器缓慢滴加至反应釜,搅拌速度18r/min,在100℃下进行聚合反应,反应完毕放料,溶剂通过旋转蒸发回收除去,得到的聚醚多元醇为外观为浅黄色浑浊,且存在大量白色悬浮物。
常规聚醚多元醇为浅黄至棕黄色的透明均一溶液,对比例1制得的聚醚多元醇的外观为浅黄色浑浊,且存在大量白色悬浮物,无法进行下一步使用。
对比例1中未提前制得结构中含磷氮的起始剂,而是直接向聚合体系中加入磷酸三苯酯,与实施例3比较,无法将阻燃结构引入聚醚多元醇中,且由于磷酸三苯酯无法在体系中稳定存在使得体系变浑浊且有白色固体析出,无法进一步检测和使用。
对比例2
在反应釜中加入蔗糖265g,二乙二醇140g,有机胺类催化剂11g,将690g环氧丙烷通过压力容器缓慢滴加至反应釜,搅拌速度18r/min,在100℃下进行聚合反应,反应完毕放料,得到的聚醚多元醇为外观为浅黄色透明液体。
将实施例1、实施例2、实施例3以及对比例2制得的聚醚多元醇的分别进行羟值、粘度及戊烷互溶性测试,其测试结果见表1。
表1实施例1-3以及对比例2制得的聚醚多元醇的羟值、粘度及戊烷互溶性结果
将上述4个聚醚分别按照一定比例复配成组合料,并分别与PM200按照1:1.2混合发泡制得聚氨酯泡沫,测试泡沫性能,组合料配比及泡沫性能结果如表2所示。
表2实施例1-3以及对比例2对应的组合料配比及泡沫性能结果
由表1及表2可知,本发明制得的磷氮协同阻燃聚醚多元醇具有较好的戊烷互溶性,且用该类聚醚多元醇制备的聚氨酯泡沫塑料具有较高的强度和良好的阻燃效果。
Claims (10)
1.一种磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:以含氮磷的化合物和多元醇为复合起始剂,在催化剂作用下,与环氧丙烷进行聚合反应,得到所述的磷氮协同阻燃聚醚多元醇;
所述含氮磷的化合物由芳香族磷酸酯、醛、胺在溶剂中反应得到。
2.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:芳香族磷酸酯为磷酸甲基二苯酯、磷酸二苯酯或磷酸三苯酯中的一种或多种。
3.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:醛为甲醛。
4.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:胺为一乙醇胺、二乙醇胺或二异丙醇胺中的一种或多种。
5.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:溶剂为乙醚、甲醇、乙醇、乙二醇或水中的一种或多种。
6.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:芳香族磷酸酯、醛和胺的摩尔比为0.1-1:0.1-4:0.1-4.5。
7.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:制备含氮磷的化合物时,反应温度为80-105℃,反应时间为2-4h。
8.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:多元醇为丙二醇、二乙二醇、水、甘油、山梨醇或蔗糖中的两种以上的混合物,催化剂为有机胺类催化剂,环氧烷烃为环氧乙烷或环氧丙烷。
10.根据权利要求1所述的磷氮协同阻燃聚醚多元醇的制备方法,其特征在于:聚合反应温度为80-120℃,聚合反应时间为2-8h。
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