CN104927022B - 一种无卤本质阻燃型硬质聚氨酯泡沫塑料及其制备方法 - Google Patents
一种无卤本质阻燃型硬质聚氨酯泡沫塑料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种无卤本质阻燃型硬质聚氨酯泡沫塑料及其制备方法,包括以下步骤:首先将磷氮阻燃多元醇、聚醚多元醇、聚酯多元醇、胺类催化剂、有机锡类催化剂、泡沫稳定剂、水和发泡剂混合均匀,得到聚氨酯组合物;然后将异氰酸酯加入该聚氨酯组合物中,搅拌均匀,再倒入模具,进行发泡,再熟化,最后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。本发明成型工艺简单,采用一步法浇注成型工艺,成本较低,并且所制备出的无卤本质阻燃型硬质聚氨酯泡沫塑料具有优良的阻燃防火性能,其氧指数最高可达32。
Description
技术领域
本发明涉及一种泡沫塑料,尤其是涉及一种无卤本质阻燃型硬质聚氨酯泡沫塑料及其制备方法。
背景技术
硬质聚氨酯泡沫(RPUF)因其重量轻、比强度高、导热系数小、隔声抗震等众多优点因而广泛应用于建筑、交通运输、石油化工管道、航海航空、军事等领域。RPUF分子链中含有比例较高的可燃烧的碳氢分子链段,而且泡沫为孔状结构,密度小,比表面积大,燃烧时会加快燃烧速度,故普通硬泡氧指数只有17%左右,属于易燃材料,也不能达到理想的阻燃效果;同时,RPUF本身无毒,但是其燃烧产生大量有毒气体,给灭火和火场逃生造成很大困难。震惊全国的上海11·15特大火灾事故就是由于违规焊接引燃了楼房外墙的RPUF保温材料引起的,RPUF燃烧产生大量有毒气体和烟雾,造成了重大的人员伤亡和财产损失。因此随着RPUF的广泛应用,其防火阻燃性能亟待提高。
中国专利公开号102585140 A的专利介绍了一种阻燃聚氨酯组合物、阻燃聚氨酯材料及其制备方法,该聚氨酯材料具有良好的阻燃性能,所使用的四溴醚通过化学键连接在交联网络上,发挥了反应型阻燃剂的作用,并且在泡沫材料中均匀分散,对基体本身的力学性能影响较少。但是由于该阻燃剂含有卤素,在燃烧中会产生有毒有害、有强烈刺激性的卤化氢气体,由此带来的二次污染问题使其难以满足环保要求。
中国专利公开号102276977 A的专利通过添加大量的阻燃剂聚磷酸铵、硼酸锌和氢氧化铝,并添加膨胀石墨作为无机填料,制备出一种高阻燃型硬质聚氨酯泡沫塑料,其阻燃性能达到B1级。但该制备方法所使用的阻燃剂属于无机添加型阻燃剂,与泡沫基体相容性很差,生产聚氨酯泡沫制品时易产生“烧芯”现象,并且会对硬质聚氨酯泡沫塑料的力学性能、保温性能产生较大影响。
发明内容
本发明的目的是提供一种可克服上述现有技术的不足,具有良好的防火阻燃、力学和保温性能,而且成本较低的无卤本质阻燃型硬质聚氨酯泡沫塑料及其制备方法。
本发明解决其技术问题所采用的技术方案之一是:
一种无卤本质阻燃型硬质聚氨酯泡沫塑料的制备方法,包括以下步骤:
1)按下述质量份数称取各组分,将称取的磷氮阻燃多元醇、聚醚多元醇、聚酯多元醇、胺类催化剂、有机锡类催化剂、泡沫稳定剂、水和发泡剂混合均匀,得到聚氨酯组合物;
2)将称取的异氰酸酯加入到步骤1)所得的聚氨酯组合物中,2500r/min搅拌混合均匀,再倒入模具,在温度25℃,相对湿度25%~50%下发泡,再熟化2~7天,然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。
一实施例中,所述磷氮阻燃多元醇的化学结构式如(I)式所示,是一种反应型的阻燃剂,平均官能度为2~12,羟值为250~600mg KOH/g;
其中R基团可以相同也可以不同,可以是下列基团之一或者其组合:-H、-OCH3、-O(CH2)nCH3其中n=2-9或所述的磷氮阻燃多元醇制备方法参考中国专利CN103980313A制备所得。
一实施例中,所述聚醚多元醇的羟值为250~450mg KOH/g;优选聚醚多元醇635、聚醚多元醇450或聚醚多元醇4110。
一实施例中,所述聚酯多元醇选自脂肪族聚酯多元醇、芳香族聚酯多元醇、脂环族聚酯多元醇中的至少一种;优选苯酐聚酯多元醇(PS-3152)。
一实施例中,所述胺类催化剂为叔胺类催化剂,选自三乙醇胺、二乙醇胺、三乙烯二胺、三亚乙基三胺、三亚乙基二胺、N,N-二甲基环己胺中的一种。
一实施例中,所述有机锡类催化剂选自辛酸亚锡、二月桂酸二丁基锡中的一种。
一实施例中,所述泡沫稳定剂选自聚二甲基硅油、聚硅氧烷、硅油L-580、泡沫稳定剂AL-5309、泡沫稳定剂L-5333中的一种。
一实施例中,所述发泡剂选自三氯氟甲烷(F11)、二氯二氟甲烷(F12)、二氟一氯乙烷(HCFC-141B)、环戊烷、异戊烷中的至少一种。
一实施例中,所述异氰酸酯为多亚甲基多苯基异氰酸酯(PAPI)、甲苯二异氰酸酯(TDI)、二苯基甲烷-4,4’-二异氰酸酯(MDI)中的至少一种。
本发明解决其技术问题所采用的技术方案之二是:
一种无卤本质阻燃型硬质聚氨酯泡沫塑料,其按质量份数计的原料组成如下:
一实施例中,所述磷氮阻燃多元醇的化学结构式如(I)式所示;该磷氮阻燃多元醇平均官能度为2~12,羟值为250~600mg KOH/g;
其中R基团可以相同也可以不同,可以是下列基团之一或者其组合:-H、-OCH3、-O(CH2)nCH3其中n=2-9或所述聚醚多元醇的羟值为250~450mg KOH/g;所述聚酯多元醇选自脂肪族聚酯多元醇、芳香族聚酯多元醇、脂环族聚酯多元醇中的至少一种;所述胺类催化剂选自三乙醇胺、二乙醇胺、三乙烯二胺、三亚乙基三胺、三亚乙基二胺、N,N-二甲基环己胺中的一种;所述有机锡类催化剂选自辛酸亚锡、二月桂酸二丁基锡中的一种;所述泡沫稳定剂选自聚二甲基硅油、聚硅氧烷、硅油L-580、泡沫稳定剂AL-5309、泡沫稳定剂L-5333中的一种;所述发泡剂选自三氯氟甲烷、二氯二氟甲烷、二氟一氯乙烷、环戊烷、异戊烷中的至少一种;所述异氰酸酯为多亚甲基多苯基多异氰酸酯、甲苯二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯中的至少一种。
本技术方案与背景技术相比,它具有如下优点:
1)成型工艺简单,采用一步法浇注成型工艺,制备方法十分简单,成本低。
2)采用含磷氮元素的磷氮阻燃多元醇来提高硬质聚氨酯泡沫塑料的阻燃性能,不含卤素,安全无污染;该磷氮阻燃多元醇为反应型阻燃剂,可部分代替聚醚多元醇作为制备聚氨酯泡沫的原料,能够使泡沫塑料产生优良的阻燃防火特性;且磷氮阻燃多元醇、聚醚多元醇、聚酯多元醇相互配合,三者的比例基于整个体系中磷氮含量、羟值等多方面因素来综合确定,实现了聚氨酯泡沫的力学性能、保温性能、阻燃防火性能、成本等多方面的均衡优化,制得的聚氨酯泡沫塑料综合性能优异,其氧指数最高可达32,阻燃性能级别达到B1级。
3)应用范围广,本发明所述无卤本质阻燃型硬质聚氨酯泡沫塑料可以应用于建筑外墙保温、室内装饰、门窗框架保温材料以及冰箱等冷藏保温的许多行业。
具体实施方式
下面通过实施例对本发明进行具体描述。
实施例1:
1)称取50g磷氮阻燃多元醇、20g聚醚多元醇4110、30g苯酐聚酯多元醇PS-3152、1.0g N,N-二甲基环己胺、0.02g二月桂酸二丁基锡、1.0g泡沫稳定剂AL-5309、0.1g水和25g二氟一氯乙烷(HCFC-141B),混合均匀,得到聚氨酯组合物;
2)将130g多亚甲基多苯基异氰酸酯(PAPI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化48h(即2天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为25.5。
本实施例之中,所述磷氮阻燃多元醇是一种反应型的阻燃剂,平均官能度为2~12,羟值为250~600mg KOH/g;化学结构式如(I)式所示:
其中R基团可以相同也可以不同,可以是下列基团之一或者其组合:-H、-OCG3、-O(CH2)nCH3其中n=2-9或其制备方法参考中国专利CN103980313A。
实施例2:
1)称取55g磷氮阻燃多元醇、15g聚醚多元醇4110、30g苯酐聚酯多元醇PS-3152、1.0g N,N-二甲基环己胺、0.02g二月桂酸二丁基锡、1.0g泡沫稳定剂AL-5309、0.1g水和25g二氟一氯乙烷(HCFC-141B),混合均匀,得到聚氨酯组合物;
2)将130g多亚甲基多苯基异氰酸酯(PAPI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化48h(即2天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为27。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
实施例3:
1)称取60g磷氮阻燃多元醇、10g聚醚多元醇4110、30g聚酯多元醇PS-3152、1.0gN,N-二甲基环己胺、0.02g二月桂酸二丁基锡、1.0g泡沫稳定剂AL-5309、0.1g水和25g二氟一氯乙烷(HCFC-141B),混合均匀,得到聚氨酯组合物;
2)将130g多亚甲基多苯基异氰酸酯(PAPI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化48h(即2天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为29。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
实施例4:
1)称取65g磷氮阻燃多元醇、10g聚醚多元醇4110、25g聚酯多元醇PS-3152、1.0gN,N-二甲基环己胺、0.02g二月桂酸二丁基锡、1.0g泡沫稳定剂AL-5309、0.1g水和25g二氟一氯乙烷(HCFC-141B),混合均匀,得到聚氨酯组合物;
2)将130g多亚甲基多苯基异氰酸酯(PAPI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化48h(即2天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为31。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
实施例5:
1)称取70g磷氮阻燃多元醇、10g聚醚多元醇4110、20g聚酯多元醇PS-3152、1.0gN,N-二甲基环己胺、0.02g二月桂酸二丁基锡、1.0g泡沫稳定剂AL-5309、0.1g水和25g二氟一氯乙烷(HCFC-141B),混合均匀,得到聚氨酯组合物;
2)将130g多亚甲基多苯基异氰酸酯(PAPI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化48h(即2天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为32。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
实施例6:
1)称取75g磷氮阻燃多元醇、10g聚醚多元醇635、35g苯酐聚酯多元醇PS-3152、1.5g三乙醇胺或二乙醇胺、0.5g辛酸亚锡、1.5g泡沫稳定剂L-5333、0.5g去离子水和30g三氯氟甲烷(F11),混合均匀,得到聚氨酯组合物;
2)将120g甲苯二异氰酸酯(TDI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化72h(即3天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T 2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为26。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
实施例7:
1)称取70g磷氮阻燃多元醇、10g聚醚多元醇450、40g苯酐聚酯多元醇PS-3152、2g三乙烯二胺、1g辛酸亚锡、2g硅油L-580、1g去离子水和20g二氯二氟甲烷(F12),混合均匀,得到聚氨酯组合物;
2)将140g二苯基甲烷-4,4’-二异氰酸酯(MDI)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化120h(即5天),然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T 2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为28。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
实施例8:
1)称取65g磷氮阻燃多元醇、15g聚醚多元醇450、20g苯酐聚酯多元醇PS-3152、2.5g三亚乙基三胺或三亚乙基二胺、2g二月桂酸二丁基锡、1.0g聚二甲基硅油或聚硅氧烷、1.5g去离子水和25g环戊烷和/或异戊烷,混合均匀,得到聚氨酯组合物;
2)将150g异氰酸酯(多亚甲基多苯基异氰酸酯(PAPI)和二苯基甲烷-4,4’-二异氰酸酯(MDI)各75g)快速加入到该聚氨酯组合物中,室温2500r/min下高速搅拌混合均匀,观察到混合料发白时,即倒入自制模具中自由发泡,发泡温度25℃,相对湿度25%~50%,发泡完后熟化7天,脱模即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。将所得产品按照按GB-T2406-93《塑料燃烧性能试验方法氧指数法》测得氧指数为28.5。
本实施例之中,所述磷氮阻燃多元醇同实施例1。
以上所述,仅为本发明较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (5)
1.一种无卤阻燃型硬质聚氨酯泡沫塑料的制备方法,其特征在于:包括以下步骤:
1)按下述质量份数称取各组分,将称取的磷氮阻燃多元醇、聚醚多元醇、聚酯多元醇、胺类催化剂、有机锡类催化剂、泡沫稳定剂、水和发泡剂混合均匀,得到组合物;
所述磷氮阻燃多元醇的化学结构式如(I)式所示;该磷氮阻燃多元醇平均官能度为2~12,羟值为250~600mg KOH/g;
其中R基团可以相同也可以不同,可以是下列基团之一或者其组合:-H、-CH3、-(CH2)nCH3其中n=2-9或
所述聚酯多元醇为苯酐聚酯多元醇PS-3152;
2)将称取的异氰酸酯加入到步骤1)所得的组合物中,2400~2600r/mi n搅拌混合均匀,再倒入模具,在温度22~28℃,相对湿度20%~55%下发泡,再熟化1~8天,然后脱模,即得到无卤本质阻燃型硬质聚氨酯泡沫塑料。
2.根据权利要求1所述的一种无卤阻燃型硬质聚氨酯泡沫塑料的制备方法,其特征在于:所述聚醚多元醇的羟值为250~450mg KOH/g。
3.根据权利要求2所述的一种无卤阻燃型硬质聚氨酯泡沫塑料的制备方法,其特征在于:所述聚醚多元醇选自聚醚多元醇635、聚醚多元醇450或聚醚多元醇4110。
4.根据权利要求1所述的一种无卤阻燃型硬质聚氨酯泡沫塑料的制备方法,其特征在于:
所述胺类催化剂选自三乙醇胺、二乙醇胺、三乙烯二胺、N,N-二甲基环己胺中的一种;所述有机锡类催化剂选自辛酸亚锡、二月桂酸二丁基锡中的一种;所述泡沫稳定剂选自聚二甲基硅油、硅油L-580、泡沫稳定剂AL-5309、泡沫稳定剂L-5333中的一种;所述发泡剂选自三氯氟甲烷、二氯二氟甲烷、二氟一氯乙烷、环戊烷、异戊烷中的至少一种。
5.根据权利要求1所述的一种无卤阻燃型硬质聚氨酯泡沫塑料的制备方法,其特征在于:
所述异氰酸酯为多亚甲基多苯基多异氰酸酯、甲苯二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯中的至少一种。
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