CN105218782A - 一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法 - Google Patents
一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法 Download PDFInfo
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Abstract
本发明公开了一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,该方法首先配制白料:将聚酯多元醇、聚醚多元醇、结构型阻燃聚醚多元醇、匀泡剂、液态阻燃剂、起发催化剂、凝胶型催化剂、三聚催化剂和水混合均匀,再加入石墨,混合均匀后加入发泡剂组成白料;将配制得到的白料与黑料按照质量比1:1.5~1.8混合,搅拌后注入恒温模具中发泡熟化,得到聚氨酯硬泡;其中,所述的黑料为多异氰酸酯。本发明提高了聚氨酯硬泡的氧指数,燃烧性能可达到不燃级,力学强度和尺寸稳定性好,导热系数低;与市场上同类产品相比有很大的价格优势,并且易于加工成型;添加的阻燃剂不挥发,不易析出,毒性低,阻燃效果持久。
Description
技术领域
本发明属于管道、储罐保冷材料领域,具体涉及一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法。
背景技术
聚氨酯硬泡是一种性能优良的高分子合成材料,具有导热系数低、相对质量轻、尺寸稳定性好、强度高、防水、防震、耐溶剂和耐老化等诸多优点。但是,该材料的阻燃性能较差,耐高温性能也不太理想,故其在某些领域的应用受到限制。随着国家对公共场所阻燃制品及组件燃烧性能要求越来越高,聚氨酯在防火性能方面面临的挑战也越来越大,具有较高阻燃性能的聚氨酯硬泡保温材料将会得到越来越广泛的重视和应用。通常情况下,氧指数越高,阻燃效果越好。目前,市场上出售的聚氨酯泡沫的氧指数一般为26左右。国内一些企业通过添加复合阻燃剂的方法,成功研制出氧指数达到28的硬泡聚氨酯体系,可达到GB8624-2006中规定的B1难燃级标准。但是,大量阻燃剂的使用会影响聚氨酯硬泡的力学性能和发泡工艺。此外,氧指数达到28后,聚氨酯硬泡的阻燃性能很难再提高。并且氧指数每提高一个水平,费用就会增加很多,市场出售的氧指数在28以上的聚氨酯硬泡价格昂贵。
发明内容
本发明的目的在于针对现有技术问题,提供一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,采用该方法制备产品的氧指数在33左右,达到了不燃级要求。同时,该产品还具有力学性能和尺寸稳定性好,导热系数低等优点,并且添加的固态阻燃剂无毒、稳定性好、不挥发。此外,采用该方法制备的产品与市场出售的同类产品相比,在价格上有很大的优势,并且容易加工成型。
本发明为解决上述问题提供的技术方案为:
一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,它包括以下步骤:
(1)、配制白料:将聚酯多元醇、聚醚多元醇、结构型阻燃聚醚多元醇、匀泡剂、液态阻燃剂、起发催化剂、凝胶型催化剂、三聚催化剂和水混合均匀,再加入石墨,混合均匀后加入发泡剂组成白料;
所述的白料中各组分的重量份为:聚酯多元醇40~60份,聚醚多元醇20~40份,结构型阻燃聚醚多元醇20~40份,匀泡剂2~4份,液态阻燃剂10~20份,石墨16~30份,起发催化剂0.01~0.2份,凝胶型催化剂0.5~1.5份,三聚催化剂0.4~2份,发泡剂30~50份,水0.4~1.0份;
(2)、将步骤(1)配制得到的白料与黑料按照质量比1:1.5~1.8混合,搅拌后注入恒温模具中发泡熟化,得到聚氨酯硬泡;其中,所述的黑料为多异氰酸酯。
步骤(1)中,在20~30℃,优选在25℃条件下配制白料。石墨容易沉淀,发泡剂容易挥发,等到其他组分都加完混合均匀后,发泡前加入计量的石墨和发泡剂混合均匀组成白料。
优选的,所述的白料中各组分的重量份为:聚酯多元醇45~60份,聚醚多元醇20~30份,结构型阻燃聚醚多元醇20~40份,匀泡剂2~4份,液态阻燃剂10~20份,石墨20~30份,起发催化剂0.01~0.2份,凝胶型催化剂0.5~1.0份,三聚催化剂1.5~2份,发泡剂30~50份,水0.4~1.0份;
步骤(2)中,在20~30℃条件下将白料与黑料混合,2500~3000r/min高速搅拌8~12s后注入40~50℃恒温模具中发泡熟化,得到聚氨酯硬泡。
所述的黑料优选为聚合MDI。
所述的聚酯多元醇为脂肪族聚酯多元醇、脂环族聚酯多元醇或含芳香环结构的芳香族聚酯多元醇中的一种或几种,优选含芳香环结构的芳香族聚酯多元醇PS-3152、PS-2412、PS-2352。
所述的聚醚多元醇为聚氧化丙烯多元醇或聚四氢呋喃多元醇中的一种或几种。优选为聚醚多元醇380、635C、N450、N210、NJ410HN或ED-5083中的一种或几种。
所述的结构型阻燃聚醚多元醇为含磷系阻燃元素和杂环结构的聚醚多元醇、或含磷氮系阻燃聚醚多元醇中的一种或几种;优选为结构型阻燃聚醚多元醇F-7190或Y-501F、Y-502F,结构型阻燃聚醚多元醇F-7190为含磷系阻燃元素和杂环结构的聚醚多元醇,结构型阻燃聚醚多元醇Y-501F、Y-502F为含磷氮系阻燃聚醚多元醇。
所述的匀泡剂为聚醚改性聚硅氧烷、聚硅氧烷或聚醚硅氧烷的一种或几种,优选为匀泡剂B8525、B8462(高斯米特公司)、L-6863(迈图)、SD624或SD622(苏州思德新材料科技有限公司)中的一种或几种。
所述的液态阻燃剂为三乙基磷酸酯(简写:TEP)、磷酸三(2-氯丙基)酯(TCPP)、磷酸三氯乙酯(TCEP)或甲基膦酸二甲酯(DMMP)中的一种或几种。
所述的石墨的粒径小于80目,膨胀系数为210~300ml/g。
所述的起发催化剂为五甲基二乙烯三胺(起发催化剂PC-5)或N,N-二甲基环己胺(起发催化剂PC-8)中的一种或几种。
所述的凝胶型催化剂为三乙烯二胺类催化剂,优选为三乙烯二胺类催化剂DabcoJXP-508、DabcoJXP-509或A-33中的一种或几种。
所述的三聚催化剂为异辛酸钾或季铵盐类催化剂中的一种或几种;所述的异辛酸钾优选为DabcoK-15催化剂,所述的季铵盐类催化剂优选为季铵盐类催化剂JD-18或DabcoTMR-2催化剂。
所述的发泡剂为一氟二氯乙烷141b。
所述的水为蒸馏水。
本发明从影响聚氨酯硬泡阻燃效果的两个方面入手,一方面加入结构型阻燃聚醚多元醇,与异氰酸酯发生凝胶反应,并且结构型阻燃聚醚多元醇本身含有刚性结构,增强了泡沫的力学性能;同时,分子中含有磷氮类阻燃元素,泡沫的阻燃性能也有所提高。另一方面加入高效阻燃剂石墨,经过调研和实验发现石墨的阻燃效果最好,而且其稳定性好,不容易析出。石墨的粒径和膨胀系数也影响聚氨酯泡沫的阻燃效果,粒径和膨胀系数越大阻燃效果越好。
黑料与白料之比为1.5~1.8:1,聚合反应中除了生成氨基甲酸酯基外,多余的-NCO基团三聚反应生成异氰脲酸酯基,在聚氨酯结构中引入异氰脲酸酯基团,提高了所制备的聚氨酯泡沫的耐热性和耐火焰贯穿性,同时也具有燃烧发烟量低的特点。
本发明的有益效果:
本发明明显的提高了聚氨酯硬泡的氧指数,燃烧性能可达到不燃级,力学强度和尺寸稳定性好,导热系数低;与市场上同类产品相比有很大的价格优势,并且易于加工成型;添加的阻燃剂不挥发,不易析出,毒性低,阻燃效果持久。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行完整地描述,显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例,凡采用等同替换或者等效变换方式所获得的技术方案,均应落在本发明的保护范围之内。
实施例1
一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,包括以下步骤:
(1)、配制白料:分别称取60g聚酯多元醇PS-3152(南京金陵斯泰潘化学有限公司,下同)、10g聚醚多元醇635C(句容市宁武化工有限公司,下同)、10g聚醚多元醇380(句容市宁武化工有限公司,下同)、20g结构型阻燃聚醚多元醇F-7190(上海蓝星化工新材料有限公司,下同)、2.0g匀泡剂B8525(高斯米特公司,下同)、1.0g匀泡剂L6863(迈图,下同)、10g三乙基磷酸酯TEP、0.1g起发催化剂PC-5(空气化工有限公司,下同)、0.1g起发催化剂PC-8(空气化工有限公司,下同)、1.0g三乙烯二胺类催化剂DabcoJXP-508(空气化工有限公司,下同)、1.0gDabcoK-15催化剂(蓝星化工新材料有限公司,下同)、0.5gDabcoTMR-2催化剂(空气化工有限公司,下同)和1.0g蒸馏水,搅拌均匀后加入30g石墨,混合均匀后加入30g发泡剂141b组成白料,在白料配制过程中,确保操作在25℃下进行;
(2)、温度调整到在25℃下时将白料与聚合MDI以质量比1:1.6的比例混合,高速(3000r/min)搅拌10s后注入45℃的恒温模具中发泡熟化,制得聚氨酯硬泡。
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实施例2
一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,包括以下步骤:
(1)、配制白料:分别称取40g聚酯多元醇PS-3152、10g聚酯多元醇PS-2412(南京金陵斯泰潘化学有限公司,下同)、10g聚醚多元醇635C、10g聚醚多元醇N450(句容市宁武化工有限公司,下同)、10g聚醚多元醇380、30g结构型阻燃聚醚多元醇F-7190、10g结构型阻燃聚醚多元醇Y-501F(山东一诺威聚氨酯股份有限公司,下同)、2.0g匀泡剂SD624(苏州思德新材料科技有限公司,下同)、1.0g匀泡剂B8525、10g三乙基磷酸酯TEP、10g磷酸三(2-氯丙基)酯TCPP、0.1g起发催化剂PC-5、0.1g起发催化剂PC-8、1.0g三乙烯二胺类催化剂DabcoJXP-508、1.0gDabcoK-15催化剂、1.0gDabcoTMR-2催化剂和1.0g蒸馏水水,搅拌均匀后加入20g石墨,混合均匀后加入40g发泡剂141b组成白料,在白料配制过程中,确保操作在25℃下进行;
(2)、温度调整到在20℃下时将白料与聚合MDI以质量比1:1.7的比例混合,高速(2800r/min)搅拌12s后注入50℃的恒温模具中发泡熟化,制得聚氨酯硬泡。
产品技术指标:
实施例3
一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,包括以下步骤:
(1)、配制白料:分别称取45g聚酯多元醇PS-2352(南京金陵斯泰潘化学有限公司,下同)、5g聚醚多元醇635C、5g聚醚多元醇N210(句容市宁武化工有限公司,下同)、20g聚醚多元醇NJ-410HN(句容市宁武化工有限公司,下同)、20g结构型阻燃聚醚多元醇F-7190、5g结构型阻燃聚醚多元醇Y-502F(山东一诺威聚氨酯股份有限公司,下同)、2.0g匀泡剂SD622(苏州思德新材料科技有限公司,下同)、1.0g匀泡剂B8525、8g三乙基磷酸酯TEP、8g磷酸三氯乙酯TCEP、0.1g起发催化剂PC-5、0.1g起发催化剂PC-8、0.9g三乙烯二胺类催化剂A-33(蓝星化新材料工有限公司,下同)、0.9gDabcoK-15催化剂、0.6g季铵盐类催化剂JD-18(大江化工有限公司,下同)和0.7g蒸馏水,搅拌均匀后加入30g石墨,混合均匀后加入50g发泡剂141b组成白料,在白料配制过程中,确保操作在25℃下进行;
(2)、温度调整到在30℃下时将白料与聚合MDI以质量比1:1.75的比例混合,高速(2500r/min)搅拌8s后注入40℃的恒温模具中发泡熟化,制得聚氨酯硬泡。
产品技术指标:
Claims (10)
1.一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于它包括以下步骤:
(1)、配制白料:将聚酯多元醇、聚醚多元醇、结构型阻燃聚醚多元醇、匀泡剂、液态阻燃剂、起发催化剂、凝胶型催化剂、三聚催化剂和水混合均匀,再加入石墨,混合均匀后加入发泡剂组成白料;
所述的白料中各组分的重量份为:聚酯多元醇40~60份,聚醚多元醇20~40份,结构型阻燃聚醚多元醇20~40份,匀泡剂2~4份,液态阻燃剂10~20份,石墨16~30份,起发催化剂0.01~0.2份,凝胶型催化剂0.5~1.5份,三聚催化剂0.4~2份,发泡剂30~50份,水0.4~1.0份;
(2)、将步骤(1)配制得到的白料与黑料按照质量比1:1.5~1.8混合,搅拌后注入恒温模具中发泡熟化,得到聚氨酯硬泡;其中,所述的黑料为多异氰酸酯。
2.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于步骤(1)中,在20~30℃条件下配制白料;
步骤(2)中,在20~30℃条件下将白料与黑料混合,2500~3000r/min高速搅拌8~12s后注入40~50℃恒温模具中发泡熟化,得到聚氨酯硬泡。
3.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的白料中各组分的重量份为:聚酯多元醇45~60份,聚醚多元醇20~30份,结构型阻燃聚醚多元醇20~40份,匀泡剂2~4份,液态阻燃剂10~20份,石墨20~30份,起发催化剂0.01~0.2份,凝胶型催化剂0.5~1.0份,三聚催化剂1.5~2份,发泡剂30~50份,水0.4~1.0份;
所述的黑料为聚合MDI。
4.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的聚酯多元醇为脂肪族聚酯多元醇、脂环族聚酯多元醇或芳香族聚酯多元醇中的一种或几种;
所述的聚醚多元醇为聚氧化丙烯多元醇或聚四氢呋喃多元醇中的一种或几种。
5.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的结构型阻燃聚醚多元醇为含磷系阻燃元素和杂环结构的聚醚多元醇、或含磷氮系阻燃聚醚多元醇中的一种或几种。
6.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的匀泡剂为聚醚改性聚硅氧烷、聚硅氧烷或聚醚硅氧烷中的一种或几种。
7.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的液态阻燃剂为三乙基磷酸酯、磷酸三(2-氯丙基)酯、磷酸三氯乙酯或甲基膦酸二甲酯中的一种或几种。
8.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的石墨的粒径小于80目,膨胀系数为210~300ml/g。
9.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的起发催化剂为五甲基二乙烯三胺或N,N-二甲基环己胺中的一种或几种;
所述的凝胶型催化剂为三乙烯二胺类催化剂;
所述的三聚催化剂为异辛酸钾或季铵盐类催化剂中的一种或几种。
10.根据权利要求1所述的一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法,其特征在于所述的发泡剂为一氟二氯乙烷;
所述的水为蒸馏水。
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