CN115304762A - 反应型无卤阻燃聚醚多元醇的制备方法及应用 - Google Patents
反应型无卤阻燃聚醚多元醇的制备方法及应用 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 80
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- 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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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
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- 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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Abstract
本发明属于无卤阻燃聚氨酯的制备技术领域,具体涉及一种反应型无卤阻燃聚醚多元醇的制备方法及应用。所述的反应型无卤阻燃聚醚多元醇的制备方法:以含氮聚醚多元醇和三羟甲基氧化磷作为复合起始剂,在双金属氰化络合物催化剂的作用下,与环氧化合物开环聚合,得到反应型无卤阻燃聚醚多元醇;所述含氮聚醚多元醇的制备方法为:以三(2‑羟乙基)异氰脲酸酯为起始剂,在碱金属催化剂的作用下,与环氧化合物聚合得到粗聚醚;粗聚醚后处理,得到含氮聚醚多元醇。本发明提供一种反应型无卤阻燃聚醚多元醇的制备方法,其操作简单,易于工业化生产;制备的无卤阻燃聚氨酯泡沫不含卤素,且具有优异的阻燃性能、耐水解和耐热稳定性。
Description
技术领域
本发明属于无卤阻燃聚氨酯的制备技术领域,具体涉及一种反应型无卤阻燃聚醚多元醇的制备方法及应用。
背景技术
适用于聚氨酯泡沫材料的阻燃剂可以分为添加型和反应型两大类。其中,添加型阻燃剂为含一定的氯、溴、磷或氮等阻燃元素但不含任何具有反应活性基团的化合物,其添加量大,与发泡剂的相容性较差,随着材料的老化过程会发生迁出问题;而反应型阻燃剂同时包含阻燃元素及反应活性基团,它可以直接作为原料,参与聚氨酯化学反应,以化学键形式被固定于材料本体中,具有持久阻燃效果。环保型阻燃聚醚多元醇成为近年来研究的热点,但市售的反应型阻燃聚醚多元醇多为含卤结构,普遍价格较高且色值较深,影响聚氨酯材料的外观和使用性能。且含卤化合物在火灾发生时会产生大量的烟雾和有毒的腐蚀性卤化氢气体,造成二次危害。因此,将无卤阻燃元素(磷、氮等)引入其中制备反应型无卤阻燃聚醚多元醇,成为聚氨酯材料亟待解决的问题。
CN112646165A公开了一种无卤阻燃聚醚多元醇的制备方法,以三(2-羟乙基)异氰脲酸酯与端羟基低聚磷酸酯(二元醇改性的2-羧乙基苯基次磷酸缩聚形成)为复合起始剂,在磷腈催化剂作用下,与环氧烯烃进行聚合反应形成;采用二元醇改性的2-羧乙基苯基次磷酸缩聚而成的端羟基低聚磷酸酯作起始剂,其中的二元醇会优先与环氧丙烷反应,导致接在低聚磷酸酯上环氧丙烷减少,不利于提升性能。
CN104004175B公开了一种阻燃聚醚多元醇、组合聚醚、聚氨酯泡沫,采用二乙醇胺和亚磷酸三乙酯在溶剂作用下,减压蒸馏得到含氮和磷元素的起始剂,再与多官能度的羟基化合物一起合成阻燃聚醚,其操作过程复杂,且由于二乙醇胺性质不稳定导致反应条件苛刻。
CN113956425A公开了一种反应型含磷酸酯结构的阻燃聚氨酯泡沫及其制备方法,其配方中添加了由三羟甲基氧化磷和磷酸制成的反应型含磷酸酯结构的阻燃剂,其绿色环保,阻燃效果优异,但存在耐热性能较差的问题。CN105801833A公开了一种反应型无卤阻燃聚醚多元醇的制备方法,用四羟甲基磷化物在催化氧化作用下制备得到三羟甲基氧化磷,纯化后与环氧烷烃发生加成反应制得,但是其工艺路线中需要使用大量有机溶剂如四氢呋喃,二氧六环等,风险较高。CN112759753A公开了一种磷氮协同阻燃聚醚多元醇的制备方法,具有优良的阻燃性能和戊烷互溶性,但其耐水解性和耐热稳定性较差。
发明内容
本发明要解决的技术问题是提供一种反应型无卤阻燃聚醚多元醇的制备方法,其操作简单,易于工业化生产;制备的无卤阻燃聚醚多元醇泡沫不含卤素,且具有优异的阻燃性能、耐水解和耐热稳定性。
本发明所述的反应型无卤阻燃聚醚多元醇的制备方法,以含氮聚醚多元醇和三羟甲基氧化磷作为复合起始剂,在双金属氰化络合物催化剂的作用下,与环氧化合物开环聚合,得到反应型无卤阻燃聚醚多元醇;
所述含氮聚醚多元醇的制备方法为:以三(2-羟乙基)异氰脲酸酯为起始剂,在碱金属催化剂的作用下,与环氧化合物聚合得到粗聚醚;粗聚醚后处理,得到含氮聚醚多元醇。
含氮聚醚多元醇的羟值为168-420mgKOH/g,粘度为200-2800mPa·s。
反应型无卤阻燃聚醚多元醇的羟值为170-525mgKOH/g,粘度为400-15000mPa·s。
双金属氰化络合物催化剂为DMC催化剂,是新型高性能催化氧化烯烃开环聚合催化剂,适用于合成起始剂含1~6官能团的氧化烯烃聚醚。
双金属氰化络合物催化剂加入量为20-200ppm。
环氧化合物为环氧乙烷、环氧丙烷、或环氧丁烷中的一种或多种;优选为环氧丙烷,环氧化合物用量是根据目标产品分子量要求,配方计算而得,限定了产品羟值范围便确定了其用量。
碱金属催化剂为氢氧化钾、氢氧化钠、甲醇钾或甲醇钠的一种或多种;碱金属催化剂加入量为含氮聚醚多元醇质量的0.2%-1%。碱金属催化剂优选为氢氧化钾KOH。
含氮聚醚多元醇与三羟甲基氧化磷的质量比为1:1-1:12。
含氮聚醚多元醇和三羟甲基氧化磷聚合反应温度为130-140℃,反应时间为12h。
含氮聚醚多元醇的制备中反应温度为100-115℃,反应时间为2-4h。
采用上述的制备方法制得的反应型无卤阻燃聚醚多元醇,用于各类无卤阻燃聚氨酯泡沫材料的制备。
具体地,所述的反应型无卤阻燃聚醚多元醇的制备方法,包括以下步骤:
(1)制备含氮聚醚多元醇:以三(2-羟乙基)异氰脲酸酯为起始剂,碱金属为催化剂,氮气置换,升温至105-115℃,-0.098MPa至-0.093MPa真空条件下脱水1.5-3h,控制水分含量≤0.05%,然后加入环氧化合物进行聚合反应,反应完毕内压反应2-4h,脱除未反应单体,得到粗聚醚多元醇;向所得粗制含氮聚醚多元醇中加入磷酸,80-90℃下搅拌反应1h后加入水,继续搅拌0.5h,然后再加入吸附剂,80-90℃下搅拌0.5-1h进行吸附处理,吸附完毕后脱水干燥,减压抽滤即得到含氮聚醚多元醇;含氮聚醚多元醇的羟值为168-420mgKOH/g,粘度为200-2800mPa·s;
(2)以含氮聚醚多元醇和三羟甲基氧化磷作为复合起始剂,加入双金属氰化络合物催化剂,按照配方量加入耐压反应釜,氮气置换,在110-130℃真空度低于-0.09MPa条件下氮气鼓泡计时1-2h,计时结束后在130-140℃下加入少量环氧丙烷进行引发反应,然后继续加入剩余的环氧化合物进行聚合反应,反应完毕内压0.5-1h,脱除未反应单体,得到反应型无卤阻燃聚醚多元醇;反应型无卤阻燃聚醚多元醇的羟值为170-525mgKOH/g,粘度为400-15000mPa·s;
(3)采用上述的制备方法制得的反应型无卤阻燃聚醚多元醇,用于各类无卤阻燃聚氨酯泡沫材料的制备。
与现有技术相比,本发明具有的有益效果是:
(1)采用本发明的的制备方法,得到的反应型具有阻燃性能的聚醚多元醇,不含卤素元素,符合绿色环保阻燃的需求;
(2)采用本发明的反应型无卤阻燃聚醚多元醇采用磷氮协同阻燃,阻燃效果优异,在聚氨酯材料中分散均匀、相容性好,且具有持久阻燃性,无迁移;
(3)采用本发明的反应型无卤阻燃聚醚多元醇制备的阻燃聚氨酯材料中不含磷酸酯键,而以P-C键连接,热稳定性好、耐水解性能优异,不影响原料的储存性能,同时在生产中对模具没有腐蚀性。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例中采用的原料,除特殊说明外均为市购。
实施例1
所述的反应型无卤阻燃聚醚多元醇的制备方法,包括以下步骤:
(1)制备含氮聚醚多元醇:将524g三(2-羟乙基)异氰脲酸酯、3g氢氧化钾加入反应釜中,开启搅拌,充压试漏、氮气置换后,将反应釜温度升高至100℃,真空脱水,氮气鼓泡1.5h,缓慢通入476g环氧丙烷,进料结束后内压反应2h,脱除未反应的单体,降温后转移至后处理釜中,85℃下加入7.14g磷酸,搅拌1h,加入35g水搅拌反应0.5h,加入1g硅酸镁、0.5g硅酸铝吸附剂,搅拌30min后进行脱水干燥4h,干燥后抽滤即得含氮聚醚多元醇;其羟值为336mgKOH/g,粘度为2200mPa·s;
(2)将84g含氮聚醚多元醇、116g三羟甲基氧化磷和0.045g双金属催化剂依次加入反应釜中,开启搅拌,充压试漏、氮气置换后,将反应釜温度升高至110℃,-0.098MPa至-0.093MPa真空脱水、氮气鼓泡计时1h,结束后130-140℃下通入20g环氧丙烷进行引发反应,待压力降至-0.06MPa以下,继续通入剩余的280g环氧丙烷,进料结束后内压反应1h,脱除未反应的单体,即制得反应型无卤阻燃聚醚多元醇。
测试其反应型无卤阻燃聚醚多元醇的羟值为337.1mg KOH/g,粘度为11000mPa·s。
实施例2
所述的反应型无卤阻燃聚醚多元醇的制备方法,包括以下步骤:
(1)制备含氮聚醚多元醇:将437g三(2-羟乙基)异氰脲酸酯、4g氢氧化钠加入反应釜中,开启搅拌,充压试漏、氮气置换后,将反应釜温度升高至110℃,真空脱水,氮气鼓泡2h,缓慢通入563g环氧丙烷,进料结束后内压反应3h,脱除未反应的单体,降温后转移至后处理釜中,85℃下加入9.52g磷酸,搅拌1h,加入38g水搅拌反应0.5h,加入1.2g硅酸镁、0.6g硅酸铝吸附剂,搅拌30min后进行脱水干燥4h,干燥后抽滤即得含氮聚醚多元醇;其羟值为270mgKOH/g,粘度为2400mPa·s;
(2)将60g含氮聚醚多元醇、126g三羟甲基氧化磷和0.048g双金属催化剂依次加入反应釜中,开启搅拌,充压试漏、氮气置换后,将反应釜温度升高至110℃,-0.098MPa至-0.093MPa真空脱水、氮气鼓泡计时1h,结束后130℃下通入20g环氧丙烷进行引发反应,待压力降至-0.06MPa以下,继续通入剩余的280g环氧丙烷和104g环氧乙烷,进料结束后内压反应0.5h,脱除未反应的单体,即制得反应型无卤阻燃聚醚多元醇。
测试其反应型无卤阻燃聚醚多元醇的羟值为285.4mg KOH/g,粘度13000mPa·s。
实施例3
所述的反应型无卤阻燃聚醚多元醇的制备方法,包括以下步骤:
(1)制备含氮聚醚多元醇:将628g三(2-羟乙基)异氰脲酸酯、4.8g甲醇甲加入反应釜中,开启搅拌,充压试漏、氮气置换后,将反应釜温度升高至100-110℃,真空脱水,氮气鼓泡2h,缓慢通入572g环氧丙烷,进料结束后内压反应4h,脱除未反应的单体,降温后转移至后处理釜中,85℃下加入11.4g磷酸,搅拌1h,加入42g水搅拌反应0.5h,加入1.5g硅酸镁、0.75g硅酸铝吸附剂,搅拌30min后进行脱水干燥4h,干燥后抽滤即得含氮聚醚多元醇;其羟值为310mgKOH/g,粘度为1500mPa·s;
(2)将62.5g含氮聚醚多元醇、122.5g三羟甲基氧化磷和0.055g双金属催化剂依次加入反应釜中,开启搅拌,充压试漏、氮气置换后,将反应釜温度升高至110℃,-0.098MPa至-0.093MPa真空脱水、氮气鼓泡计时1.5h,结束后130-140℃下通入20g环氧丙烷进行引发反应,待压力降至-0.06MPa以下,继续通入剩余的265g环氧丙烷和80g环氧丁烷,进料结束后内压反应1h,脱除未反应的单体,即制得反应型无卤阻燃聚醚多元醇。
测试其反应型无卤阻燃聚醚多元醇的羟值为308.6mg KOH/g,粘度为9200mPa·s。
将实施例1至实施例3制备的聚醚多元醇,应用于:与其他助剂配方制备聚氨酯泡沫,其配方如表1所示;
其中C305为山东一诺威新材料有限公司生产聚醚产品,A-33,T-9,L580,PM200,三羟甲基氧化磷阻燃剂,添加型TCPP阻燃剂,添加型TEP阻燃剂,以上物质均为常规市售产品。
并设置对比例1、对比例2、对比例3分别采用的添加型阻燃剂为三羟甲基氧化磷阻燃剂(THPO)、添加型TCPP阻燃剂,添加型TEP阻燃剂。
表1中的配方量均已原料的质量份数为基准。
聚氨酯泡沫的制备方法包括:
将表1中的聚醚多元醇与其他配方助剂,除PM200以外的成分按质量配比依次加入容器中,混合均匀后,再加入配方量的PM200,用高速搅拌机(转速3000r/min)搅拌5s后,迅速将开始发泡的聚氨酯泡沫倒入模具中进行发泡成型,常温下固化2-4h后脱模,最后在40-60℃的鼓风烘箱中熟化24h。
表1实施例1-实施例3和对比例1-对比例3的聚氨酯泡沫的原料配方
将以上表格中的常规聚醚、实施例1至实施例3、对比例1至对比例3对应制备出的聚氨酯泡沫,根据GB/T10807-2006塑料用氧指数法测定燃烧行为,测其氧指数;根据GB/T8811-2008/ISO2796:GB/T1986硬质泡沫塑料尺寸稳定性试验方法,测其稳定性能,其尺寸稳定性实验条件为:温度70℃,时间为48h;其测试结果如表2所示;
表2测试结果
通过本发明的制备方法得到的反应型无卤阻燃聚醚多元醇,采用其制备聚氨酯泡沫,由以上表格的数据可以看出,本发明应用于制备的聚氨酯泡沫不仅产品无卤,绿色环保,其阻燃性和耐水解性也即耐热稳定性均优于现有的市购添加型市售阻燃剂产品。对比例1制备聚氨酯泡沫会直接收缩,阻燃剂的添加比例,严重影响泡沫的收缩率,难以直接进行应用。
当然,上述内容仅为本发明的较佳实施例,不能被认为用于限定对本发明的实施例范围。本发明也并不仅限于上述举例,本技术领域的普通技术人员在本发明的实质范围内所做出的均等变化与改进等,均应归属于本发明的专利涵盖范围内。
Claims (10)
1.一种反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:以含氮聚醚多元醇和三羟甲基氧化磷作为复合起始剂,在双金属氰化络合物催化剂的作用下,与环氧化合物开环聚合,得到反应型无卤阻燃聚醚多元醇;
所述含氮聚醚多元醇的制备方法为:以三(2-羟乙基)异氰脲酸酯为起始剂,在碱金属催化剂的作用下,与环氧化合物聚合得到粗聚醚;粗聚醚后处理,得到含氮聚醚多元醇。
2.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:含氮聚醚多元醇的羟值为168-420mgKOH/g,粘度为200-2800mPa·s。
3.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:反应型无卤阻燃聚醚多元醇的羟值为170-525mgKOH/g,粘度为400-15000mPa·s。
4.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:双金属氰化络合物催化剂为DMC,双金属氰化络合物催化剂加入量为20-200ppm。
5.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:环氧化合物为环氧乙烷、环氧丙烷、或环氧丁烷中的一种或多种。
6.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:碱金属催化剂为氢氧化钾、氢氧化钠、甲醇钾或甲醇钠的一种或多种;碱金属催化剂加入量为含氮聚醚多元醇质量的0.2%-1%。
7.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:含氮聚醚多元醇与三羟甲基氧化磷的质量比为1:1-1:12。
8.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:含氮聚醚多元醇和三羟甲基氧化磷聚合反应温度为130-140℃,反应时间为1-2h。
9.根据权利要求1所述的反应型无卤阻燃聚醚多元醇的制备方法,其特征在于:含氮聚醚多元醇的制备中反应温度为100-115℃,反应时间为2-4h。
10.一种采用权利要求1-9任一项所述的制备方法制得的反应型无卤阻燃聚醚多元醇,其特征在于:用于各类无卤阻燃聚氨酯泡沫材料的制备。
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