CN105793633A - 用于管道或设备的耐火性绝热涂层材料 - Google Patents
用于管道或设备的耐火性绝热涂层材料 Download PDFInfo
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- CN105793633A CN105793633A CN201580002820.7A CN201580002820A CN105793633A CN 105793633 A CN105793633 A CN 105793633A CN 201580002820 A CN201580002820 A CN 201580002820A CN 105793633 A CN105793633 A CN 105793633A
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- 239000000203 mixture Substances 0.000 claims abstract description 52
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- 239000010452 phosphate Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 35
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 34
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical compound C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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Abstract
用于管道(2)的耐火性绝热涂层材料(3)包括含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物含有多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂、及添加剂,所述添加剂含有红磷与选自磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物、及针状填料中的至少一种。
Description
技术领域
相关领域的交叉参考
本申请要求2014年2月27日提交的JP2014-036905A的优先权,其公开以其整体在此引入作为参考。
技术领域
本发明涉及用于管道或设备的耐火性绝热涂层材料、由所述涂层材料涂覆的管道或设备、及所述涂层材料的施用方法。
背景技术
为了提高一般建筑物的管道或设备等的绝热性与耐火性,先前一直进行各种施用。例如专利文献(PTL)1中公开了一种用于管道的耐火性绝热材料,其特征在于:管道外周用包括热膨胀性绝热材料的耐火层与泡沫体层的叠层体涂覆。专利文献(PTL)2中公开了一种用于低温流体管道或设备的耐火冷藏装置,其特征在于由如下4层构成:包括有机泡沫树脂且覆盖管道或设备的外部的绝热材料;包含氢氧化铝作为主要成分的耐火材料(其通过将氢氧化铝与有机树脂和起泡剂进行泡沫成形而得到,且覆盖上述绝热材料的外侧);覆盖所述耐火材料的外侧的防水、防湿材料;及覆盖所述防水、防湿材料的外侧的金属外部材料。
专利文献(PTL)3中公开了一种制备具有低热导率和优异阻燃性的氨酯(urethane)泡沫板的方法。所述氨酯泡沫板在内部不会产生焦化(scorch)。专利文献4中公开了一种在专利文献3的特征基础上进而也赋予尺寸稳定性的氨酯泡沫板的制造方法。
引用列表
专利文献
PTL1:JPH11-201374A
PTL2:JPH06-032899U
PTL3:JP4457305B
PTL4:JP2008-074880A
发明内容
技术问题
然而,在专利文献1中,为了赋予保热性与防火性,必须对管道分别进行耐火层与泡沫体层的施加。在专利文献2中,绝热材料与耐火材料也为分别的层。在专利文献2中,另外还提供了用以防止结露与吸水的金属外部材料。
虽然专利文献3和4致力于消除内部焦化,但这些文献并未着眼于提升耐火性能。
本发明的一个目的在于提供一种用于管道或设备的耐火性绝热涂层材料,所述涂层材料包括具备优异耐火性的泡沫聚氨酯绝热层。
解决问题的方案
本发明人发现通过对管道或设备施加包括含有多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂、及添加剂的阻燃性氨酯组合物的泡沫聚氨酯绝热层,可赋予管道或设备绝热性及耐火性两者。从而完成了本发明。
更具体地,本发明如下所述:
项1.一种用于管道或设备的耐火性绝热涂层材料,所述涂层材料包括含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物含有多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂、及添加剂,所述添加剂含有红磷与选自磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物、及针状填料中的至少一种。
项2.根据项1的用于管道或设备的耐火性绝热涂层材料,其中所述阻燃性氨酯组合物包含,基于100重量份包含多异氰酸酯及多元醇的聚氨酯树脂组合物,三聚催化剂的量在0.1至10重量份的范围内,起泡剂的量在0.1至30重量份的范围内,泡沫稳定剂的量在0.1至10重量份的范围内,且添加剂的量在4.5至70重量份的范围内,且其中所述添加剂包含含量在3至18重量份范围内的红磷,和含量在1.5至52重量份的范围内的除红磷以外的至少一种添加剂。
项3.一种管道或设备,其由项1或2的用于管道或设备的耐火性绝热涂层材料所涂覆。
项4.一种用于管道或设备的耐火性绝热涂层材料的施加方法,所述方法包括:利用用于管道或设备的耐火性绝热涂层材料涂覆管道或设备的外周,所述涂层材料包括含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物含有多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂、及添加剂,所述添加剂含有红磷与选自磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物、及针状填料中的至少一种。
发明的有利效果
根据本发明,通过施加耐火性优异的泡沫聚氨酯绝热层,可对管道或设备赋予优异的绝热性及耐火性。
附图简述
图1表示施加有本发明的用于管道或设备的耐火性绝热涂层材料的管道结构的实例的横截面示意图。
图2表示管道结构的另一实例的横截面示意图。
实施方式
如说明书所用,单数形式(“一个”、“一种”和“所述”)包括复数,除了另有单独指示,或除非上下文清楚地指示。
图1显示了横截面示意图,其阐明施加本发明的用于管道或设备的耐火性绝热涂层材料的管道结构的一个实例。所述管道结构1包括中空的、通常为圆柱形的管2,且在管2上,耐火性绝热涂层材料3施加至管2的整个外周。
管2可由任何材料形成,如金属和树脂。
耐火性绝热涂层材料3为对管2赋予耐火性和绝热性的层,且为包括阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物包含多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂和添加剂。以下详细描述了阻燃性氨酯组合物的各组分。
耐火性绝热涂层材料3具有的厚度通常为0.2至300mm,且优选10至150mm。厚度为0.2mm或更少不能实现足够的耐火性或防火性,而厚度超过300mm增加重量,使得材料难以处理。
耐火性绝热涂层材料3可通过使用之前已知的方法施加至管2,如通过雾化、涂覆(包括刷涂),印刷,或喷雾(包括使用喷雾罐或喷雾装置,如喷雾枪进行喷雾)构成所述耐火性绝热涂层材料3的阻燃性氨酯组合物,或通过将管2浸渍在阻燃性氨酯组合物中。或者,所述耐火性绝热涂层材料3可通过将阻燃性氨酯树脂组合物挤出成形在管2上而直接施加至管2。还可将阻燃性氨酯树脂组合物置于容器如模子或框架中,以预先得到片形式的耐火性绝热涂层材料3,然后将所得的涂层材料片缠绕在管2的外周。在图3中,管2设置有两个半圆形元件,即,预先制备以适合外部管直径的所述耐火性绝热涂层材料3。
以下描述了构成耐火性绝热涂层材料3的阻燃性氨酯组合物。所述阻燃性氨酯组合物包含多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂和添加剂。
多异氰酸酯
作为氨酯树脂的主要成分的多异氰酸酯的实例包括芳族多异氰酸酯、脂环族多异氰酸酯、脂族多异氰酸酯,等。
芳族多异氰酸酯的实例包括苯二异氰酸酯、甲苯二异氰酸酯、苯二甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二甲基二苯基甲烷二异氰酸酯、三苯基甲烷三异氰酸酯、萘二异氰酸酯、聚亚甲基聚苯基多异氰酸酯,等。
脂环族多异氰酸酯的实例包括亚环己基二异氰酸酯、甲基亚环己基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、二甲基二环己基甲烷二异氰酸酯,等。
脂族多异氰酸酯的实例包括亚甲基二异氰酸酯、亚乙基二异氰酸酯、亚丙基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯,等。
所述多异氰酸酯可单独使用或以两种或更多种组合使用。氨酯树脂的主要成分优选为聚亚甲基聚苯基多异氰酸酯,因为其例如,易于使用且容易获得。
多元醇
作为氨酯树脂的固化剂的多元醇的实例,包括聚内酯多元醇、聚碳酸酯多元醇、芳族多元醇、脂环族多元醇、脂族多元醇、聚酯多元醇、聚合多元醇、聚醚多元醇,等。
聚内酯多元醇的实例包括聚丙内酯二醇、聚己内酯二醇、聚戊内酯二醇,等。
聚碳酸酯多元醇的实例包括通过含羟基的化合物,如乙二醇、丙二醇、丁二醇、戊二醇、己二醇、辛二醇和壬二醇,与二乙烯碳酸酯、二丙烯碳酸酯等的脱醇反应而得到的多元醇。
芳族多元醇的实例包括双酚A、双酚F、酚醛树脂、甲酚醛树脂,等。
脂环族多元醇的实例包括环己烷二醇、甲基环己烷二醇、异佛尔酮二醇、二环己基甲烷二醇、二甲基二环己基甲烷二醇,等。
脂族多元醇的实例包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇,等。
聚酯多元醇的实例包括多元酸与多元醇脱水缩合得到的聚合物;内酯,如ε-己内酯或α-甲基-ε-己内酯开环聚合得到的聚合物;和羟基羧酸与上述多元醇的缩合产物等。
本文使用的多元酸的具体实例包括己二酸、壬二酸、癸二酸、对苯二甲酸、间苯二甲酸、琥珀酸,等。多元醇的具体实例包括双酚A、乙二醇、1,2-丙二醇、1,4-丁二醇、二甘醇、1,6-己烷二醇、新戊二醇,等。
羟基羧酸的具体实例包括蓖麻油;蓖麻油与乙二醇的反应产物;等。
聚合多元醇的实例包括通过芳族多元醇、脂环族多元醇、脂族多元醇和聚酯多元醇与烯属不饱和化合物,如丙烯腈、苯乙烯、丙烯酸甲酯和甲基丙烯酸酯的接枝聚合得到的聚合物;聚丁二烯多元醇;多元醇的改性多元醇;它们的氢化产物;等。
多元醇的改性多元醇的实例包括,例如,通过将用作起始材料的多元醇与环氧烷反应来修饰而得到的那些。
多元醇的实例包括三元醇,如甘油和三羟甲基丙烷;四至八元醇,如季戊四醇、山梨醇、甘露醇、脱水山梨醇、二甘油、二季戊四醇等、蔗糖、葡萄糖、甘露糖、果糖、甲基葡糖苷,及其衍生物;酚类如苯酚、间苯三酚、甲酚、邻苯三酚、儿茶酚、氢醌、双酚A、双酚F、双酚S、1-羟基萘、1,3,6,8-四羟基萘、蒽酚、1,4,5,8-四羟基蒽、和1-羟基芘;聚丁二烯多元醇;蓖麻油多元醇;多官能多元醇(例如,2至100个官能团),如羟基烷基(甲基)丙烯酸酯和聚乙烯醇的(共)聚合物;和苯酚与甲醛的缩合产物(novolak)。
修饰多元醇的方法没有特别限制。优选使用将环氧烷(“AO”)添加至多元醇的方法。
AO的实例包括具有2至6个碳原子的AO,如环氧乙烷(“EO”)、1,2-环氧丙烷(“PO”)、1,3-环氧丙烷、1,2-环氧丁烷和1,4-环氧丁烷。在这些之中,从其特征和反应性的观点看,PO、EO和1,2-环氧丁烷是优选的,且PO和EO是更优选的。当使用两种或更多种类型的AO(例如,PO和EO)时,它们可以以嵌段和/或随机聚合物形式来添加。
聚醚多元醇的实例包括通过以下获得的聚合物,在至少一种例如具有两个或更多个活性氢原子的低分子量活性氢化合物存在的情况下,将环氧烷如环氧乙烷、环氧丙烷、四氢呋喃中的至少一种进行开环聚合。
具有两个或更多个活性氢原子的低分子量活性氢化合物的实例包括二醇,如双酚A、乙二醇、丙二醇、丁二醇和1,6-己二醇;三元醇,如甘油和三羟甲基丙烷;胺,如乙二胺和丁烯二胺;等。
本发明使用的多元醇优选为聚酯多元醇或聚醚多元醇,因为它们极大地有助于减少燃烧时的总热值。
在这些之中,更优选使用分子量为200至800的聚酯多元醇,且还更优选使用分子量为300至500的聚酯多元醇。
异氰酸酯指数是多异氰酸酯的异氰酸酯基与多元醇羟基的当量比的百分数。值超过100表示异氰酸酯基的量大于羟基的量。
异氰酸酯指数使用以下公式计算。OHV是指羟基值。
异氰酸酯指数=(添加的异氰酸酯的份数/NCO当量)/(多元醇的当量数+水的当量数)x100
NCO当量=NCO的化学式量/NCO%x100
多元醇的当量数=(添加的多元醇的份数x平均OHV)/(KOH的化学式量)x1000
水的当量数=每100份树脂总共添加的水的份数/(H2O的化学式量/2)
本发明使用的氨酯树脂的异氰酸酯指数优选在120至1000的范围,更优选200至800,且还更优选300至600。
三聚催化剂
三聚催化剂与多异氰酸酯(即,聚氨酯树脂的主要成分)的异氰酸酯基反应,以实现异氰酸酯的三聚,导致形成异氰尿酸酯环。
用于促进异氰尿酸酯环形成的三聚催化剂的实例包括含氮芳族化合物,如三(二甲基氨基甲基)苯酚,2,4-二(二甲基氨基甲基)苯酚和2,4,6-三(二烷基氨基烷基)六氢-S-三嗪;
羧酸碱金属盐,如乙酸钾和辛酸钾;
叔铵盐,如三甲基铵盐,三乙基铵盐和三苯基铵盐;
季铵盐,如四甲基铵盐,四乙基铵盐和四苯基铵盐;等。
阻燃性氨酯组合物中使用的三聚催化剂的量的优选范围在0.1至10重量份,更优选0.6至8重量份,还更优选0.6至6重量份,且最优选0.6至3.0重量份,基于100重量份的氨酯树脂。0.6重量份或更多的量排除了阻碍异氰酸酯三聚化的失败,而10重量份或更少的量维持合适的起泡率,使得容易处理。
起泡剂
阻燃性氨酯组合物中使用的起泡剂促进氨酯树脂的起泡。
起泡剂的具体实例包括:
水;
低沸点烃,如丙烷、丁烷、戊烷、己烷、庚烷、环丙烷、环丁烷、环戊烷、环己烷和环庚烷;
氯化脂族烃化合物,如二氯乙烷、丙基氯、异丙基氯、丁基氯、异丁基氯、戊基氯和异戊基氯;
氟化合物,如三氯单氟甲烷、三氯三氟乙烷、CHF3、CH2F2、CH3F、和氢氟烯烃(HFO),例如,反-1-氯-3,3,3-三氟丙烯;
含氯氟烃化合物,如二氯单氟乙烷(例如,HCFC141b(1,1-二氯-1-氟乙烷)),HCFC22(氯二氟甲烷),和HCFC142b(1-氯-1,1-二氟乙烷);
含氯氟烃化合物,如HFC-245fa(1,1,1,3,3-五氟丙烷)和HFC-365mfc(1,1,1,3,3-五氟丁烷);
醚化合物,如二异丙基醚;
有机物理起泡剂,如这些化合物的混合物;
无机物理起泡剂,如氮气、氧气、氩气和二氧化碳气体;
等。
起泡剂的量优选在0.1至30重量份的范围,基于100重量份的氨酯树脂。起泡剂的量更优选在0.1至18重量份的范围,还更优选0.5至18重量份,且最优选1至15重量份,基于100重量份的氨酯树脂。
当起泡剂的范围为0.1重量份或更多时,促进了起泡,其降低了所得模制产品的密度。当所述范围为30重量份或更少时,避免了无法形成泡沫。
泡沫稳定剂
泡沫稳定剂的实例包括表面活性剂,如聚氧化烯泡沫稳定剂如聚氧化烯烷基醚,和聚硅氧烷泡沫稳定剂如有机聚硅氧烷。
用于氨酯树脂(其通过化学反应固化)的泡沫稳定剂的量,适当地根据使用的氨酯树脂设定。作为一个实例,所述范围优选为,例如,0.1至10重量份,基于100重量份的氨酯树脂。
所述三聚催化剂、起泡剂和泡沫稳定剂可各自单独使用或以两种或更多种组合使用。
添加剂
所述添加剂包括红磷和选自磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物和针状填料的至少一种。
在所述情况下,可用添加剂的优选组合的实例包括以下(a)至(n)。
(a)红磷和磷酸酯
(b)红磷和含磷酸盐的阻燃剂
(c)红磷和含溴的阻燃剂
(d)红磷和含硼的阻燃剂
(e)红磷和含锑的阻燃剂
(f)红磷和金属氢氧化物
(g)红磷和针状填料
(h)红磷、磷酸酯和含磷酸盐的阻燃剂
(i)红磷、磷酸酯和含溴的阻燃剂
(j)红磷、磷酸酯和含硼的阻燃剂
(k)红磷、磷酸酯和针状填料
(l)红磷、含磷酸盐的阻燃剂和含溴的阻燃剂
(m)红磷、含磷酸盐的阻燃剂和含硼的阻燃剂
(n)红磷、含溴的阻燃剂和含硼的阻燃剂
(n)红磷、含溴的阻燃剂和含硼的阻燃剂
(o)红磷、磷酸酯、含磷酸盐的阻燃剂和含溴的阻燃剂
(p)红磷、磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂和含硼的阻燃剂
(q)进一步添加针状填料的(l)-(p)
(r)红磷;磷酸酯和含磷酸盐的阻燃剂;和选自含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物和针状填料的至少一种
(s)红磷;选自磷酸酯、含磷酸盐的阻燃剂和含溴的阻燃剂的一种或两种;选自含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物和针状填料的至少一种
(t)红磷;磷酸酯、含磷酸盐的阻燃剂和含溴的阻燃剂;选自含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物和针状填料的至少一种
本发明使用的红磷没有限制,且可适当选用商购产品。
阻燃性氨酯组合物中使用的红磷的量优选在3.0至18重量份的范围,基于100重量份的氨酯树脂。
范围为3.0重量份或更多的红磷保持阻燃性氨酯树脂组合物的自熄性质,而18重量份或更少的范围不会防止阻燃性氨酯树脂组合物的起泡。
本发明使用的磷酸酯没有特别限制。优选使用单磷酸酯、缩合磷酸酯,等。
单磷酸酯的实例包括,但不具体限于,三甲基磷酸酯、三乙基磷酸酯、三丁基磷酸酯、三(2-乙基己基)磷酸酯、三丁氧基乙基磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、三(二甲苯基)磷酸酯、三(异丙基苯基)磷酸酯、三(苯基苯基)磷酸酯、三萘基磷酸酯、甲苯基二苯基磷酸酯、二甲苯基二苯基磷酸酯、二苯基(2-乙基己基)磷酸酯、二(异丙基苯基)苯基磷酸酯、单异癸基磷酸酯、酸式磷酸2-丙烯酰基氧基乙基酯、酸式磷酸2-甲基丙烯酰基氧基乙基酯、二苯基-2-丙烯酰基氧基乙基磷酸酯、二苯基-2-甲基丙烯酰基氧基乙基磷酸酯、三聚氰胺磷酸酯、二(三聚氰胺)磷酸酯、三聚氰胺焦磷酸酯、三苯基氧化膦、三甲苯基氧化膦、二苯基甲烷膦酸酯、二乙基苯基膦酸酯、间苯二酚二(二苯基磷酸酯)、双酚A二(二苯基磷酸酯)、磷杂菲、三(β-氯丙基)磷酸酯,等。
缩合磷酸酯的实例包括,但不具体限于,三烷基聚磷酸酯、间苯二酚聚苯基磷酸酯、间苯二酚聚(二-2,6-二甲苯基)磷酸酯(DaihachiChemicalIndustryCo.,Ltd.生产,商品名:PX-200)、氢醌聚(2,6-二甲苯基)磷酸酯,其缩合产物,以及类似缩合磷酸酯。
可商购的缩合磷酸酯的实例包括间苯二酚聚苯基磷酸酯(商品名:CR-733S)、双酚A聚甲苯基磷酸酯(商品名:CR-741)、芳族缩合磷酸酯(商品名:CR747)、间苯二酚聚苯基磷酸酯(AdekaCo.Ltd.生产,商品名:ADKStabPFR)、双酚A聚甲苯基磷酸酯(商品名:FP-600,FP-700),等。
在以上之中,优选使用单磷酸酯,且更优选使用三(β-氯丙基)磷酸酯,因为其以高度有效的方式降低固化之前组合物的粘度,以及初始热值。
所述磷酸酯可单独使用或以两种或更多种组合使用。
所用的磷酸酯的量优选范围为1.5至52重量份,更优选1.5至20重量份,还更优选2.0至15重量份,且最优选2.0至10重量份,基于100重量份的氨酯树脂。
范围为1.5重量份或更多的磷酸酯防止当使用阻燃性氨酯树脂组合物制备的模制产品用火加热时形成的致密残余物的断裂。52重量份或更少的范围不阻碍阻燃性氨酯树脂组合物的起泡。
本发明使用的含磷酸盐的阻燃剂包括磷酸。含磷酸盐的阻燃剂中使用的磷酸的实例包括,但不具体限于,各种磷酸,如单磷酸、焦磷酸、多磷酸,及其组合。
含磷酸盐的阻燃剂的实例包括多种磷酸与至少一种选自属于周期表IA族至IVB族的金属的金属或化合物、氨、脂族胺和芳族胺形成的磷酸盐。属于周期表IA族至IVB族的金属的实例包括锂、钠、钙、钡、铁(II)、铁(III)、铝,等。
脂族胺的实例包括甲基胺、乙基胺、二乙基胺、三乙胺、乙二胺、哌嗪,等。
芳族胺的实例包括吡啶、三嗪、三聚氰胺、铵,等。
为改善耐水性,所述含磷酸盐的阻燃剂可进行硅烷偶合剂处理,用三聚氰胺树脂覆盖,或其它已知处理。还可添加已知的起泡助剂,如三聚氰胺或季戊四醇。
含磷酸盐的阻燃剂的具体实例包括单磷酸盐、焦磷酸盐、聚磷酸盐,等。
单磷酸盐的实例包括,但不具体限于,铵盐,如磷酸铵、磷酸二氢铵和磷酸氢二铵;钠盐,如磷酸单钠、磷酸二钠、磷酸三钠、亚磷酸单钠、亚磷酸二钠、次磷酸钠;钾盐,如磷酸单钾、磷酸二钾、磷酸三钾、亚磷酸单钾、亚磷酸二钾、和次磷酸钾;锂盐,如磷酸单锂、磷酸二锂、磷酸三锂、亚磷酸单锂、亚磷酸二锂、和次磷酸锂;钡盐,如磷酸二氢钡、磷酸氢钡、磷酸三钡、和次磷酸钡;镁盐,如磷酸一氢镁、磷酸氢镁、磷酸三镁、和次磷酸镁;钙盐,如磷酸二氢钙、磷酸氢钙、磷酸三钙、和次磷酸钙;锌盐、如磷酸锌、亚磷酸锌、和次磷酸锌;等。
聚磷酸盐的实例包括,但不具体限于,聚磷酸铵、哌嗪聚磷酸盐、三聚氰胺聚磷酸盐、聚磷酸铵酰胺、聚磷酸铝,等。
在这些之中,优选使用单磷酸盐,且更优选使用磷酸二氢铵,以改善含磷酸盐的阻燃剂的自熄性质。
含磷酸盐的阻燃剂可单独使用或以两种或更多种组合使用。
本发明使用的含磷酸盐的阻燃剂的量优选范围为1.5至52重量份,更优选1.5至20重量份,还更优选2.0至15重量份,且最优选2.0至10重量份,基于100重量份的氨酯树脂。
范围为1.5重量份或更多的含磷酸盐的阻燃剂保持阻燃性氨酯树脂组合物的自熄性质,而52重量份或更少的范围不抑制阻燃性氨酯树脂组合物的起泡。
本发明使用的含溴的阻燃剂没有特别限制,只要其为在分子结构中包含溴的化合物。其实例包括芳族的溴化化合物等。
芳族的溴化化合物的具体实例包括单体有机溴化合物,如六溴苯、五溴甲苯、六溴联苯、十溴联苯、六溴环癸烷、十溴二苯基醚、八溴二苯基醚、六溴二苯基醚、二(五溴苯氧基)乙烷、亚乙基-二(四溴邻苯二甲酰亚胺)、和四溴双酚A;溴化聚碳酸酯,如使用溴化双酚A作为起始材料制备的聚碳酸酯寡聚物,和聚碳酸酯寡聚物与双酚A的共聚物;溴化环氧化合物,如溴化双酚A和环氧氯丙烷反应制备的二环氧化合物,和溴化苯酚和环氧氯丙烷反应得到的单环氧化合物;聚(溴化苄基丙烯酸酯);溴化聚亚苯基醚;溴化双酚A、氰尿酰氯和溴化苯酚的缩合产物;溴化聚苯乙烯,如溴化(聚苯乙烯)、聚(溴化苯乙烯)、和交联溴化聚苯乙烯;和卤化溴化合物聚合物,如交联或非交联的溴化聚(甲基苯乙烯)。
优选使用溴化聚苯乙烯、六溴苯,等,且更优选使用六溴苯,来控制在燃烧初始阶段的热值。
含溴的阻燃剂可单独使用或以两种或更多种组合使用。
本发明使用的含溴的阻燃剂的量的优选范围为1.5至52重量份,更优选1.5至20重量份,还更优选2.0至15重量份,且最优选2.0至10重量份,基于100重量份的氨酯树脂。
范围为0.1重量份或更多的含溴的阻燃剂保持阻燃性氨酯树脂组合物的自熄性质,而52重量份或更少的范围不阻碍阻燃性氨酯树脂组合物的起泡。
本发明使用的含硼的阻燃剂的实例包括硼砂、氧化硼、硼酸、硼酸盐,等。
氧化硼的实例包括三氧化二硼、三氧化硼、二氧化二硼、三氧化四硼、五氧化四硼,等。
硼酸盐的实例包括以下物质的硼酸盐:碱金属、碱土金属、周期表中4、12和13族的元素、铵,等。
具体实例包括碱金属硼酸盐,如硼酸锂、硼酸钠、硼酸钾和硼酸铯;碱土金属硼酸盐,如硼酸镁、硼酸钙和硼酸钡;硼酸锆;硼酸锌;硼酸铝;硼酸铵;等。
本发明使用的含硼的阻燃剂优选为硼酸盐,且更优选硼酸锌。
含硼的阻燃剂可单独使用或以两种或更多种组合使用。本发明使用的含硼的阻燃剂的量的优选范围为1.5至52重量份,更优选1.5至20重量份,还更优选2.0至15重量份,且最优选2.0至10重量份,基于100重量份的氨酯树脂。
范围为1.5重量份或更多的含硼的阻燃剂保持阻燃性氨酯树脂组合物的自熄性质,而52重量份或更少的范围不阻碍阻燃性氨酯树脂组合物的起泡。
本发明使用的含锑的阻燃剂的实例包括氧化锑、锑酸盐、焦锑酸盐,等。
氧化锑的实例包括三氧化锑、五氧化锑,等。
锑酸盐的实例包括锑酸钠、锑酸钾,等。
焦锑酸盐的实例包括焦锑酸钠、焦锑酸钾,等。
本发明使用的含锑的阻燃剂优选为氧化锑。
含锑的阻燃剂可单独使用或以两种或更多种组合使用。
含锑的阻燃剂的量的优选范围为1.5至52重量份,更优选1.5至20重量份,还更优选2.0至15重量份,且最优选2.0至10重量份,基于100重量份的氨酯树脂。
范围为1.5重量份或更多的含锑的阻燃剂保持阻燃性氨酯树脂组合物的自熄性质,而52重量份或更少的范围不阻碍阻燃性氨酯树脂组合物的起泡。
本发明使用的金属氢氧化物的实例包括氢氧化镁、氢氧化钙、氢氧化铝、氢氧化铁、氢氧化镍、氢氧化锆、氢氧化钛、氢氧化锌、氢氧化铜、氢氧化钒、氢氧化锡,等。
金属氢氧化物可单独使用或以两种或更多种组合使用。
使用的金属氢氧化物的量的优选范围为1.5至52重量份,更优选1.5至20重量份,还更优选2.0至15重量份,且最优选2.0至10重量份,基于100重量份的氨酯树脂。
范围为1.5重量份或更多的金属氢氧化物保持阻燃性氨酯树脂组合物的自熄性质,而52重量份或更少的范围不阻碍阻燃性氨酯树脂组合物的起泡。
本发明使用的针状填料的实例包括钛酸钾晶须(whisker)、硼酸铝晶须、含镁晶须、含硅晶须、硅灰石、海泡石、蛭石(zonolite)、硅磷灰石、勃姆石、圆柱形羟基磷灰石、玻璃纤维、石棉纤维、碳纤维、石墨纤维、金属纤维、熔渣纤维、石膏纤维、二氧化硅纤维、氧化铝纤维、二氧化硅-氧化铝纤维、氧化锆纤维、氮化硼纤维、硼纤维、不锈钢纤维,等。
本发明使用的针状填料的纵横比(长度/直径)优选范围为5至50,且更优选10至40。
针状填料可单独使用或以两种或更多种组合使用。
本发明使用的针状填料的量没有特别限制。其优选范围为3.0至30重量份,更优选3.0至20重量份,还更优选3.0至18重量份,且最优选6.0至18重量份,基于100重量份的氨酯树脂。
范围为3.0重量份或更多的针状填料保持燃烧后本发明的阻燃性绝热材料组合物的形状,而30重量份或更少的范围不阻碍本发明的阻燃性绝热材料组合物的起泡。
本发明使用的添加剂的量的优选范围为4.5至70重量份,更优选4.5至40重量份,还更优选4.5至30重量份,且最优选4.5至20重量份,基于100重量份的氨酯树脂。
范围为4.5重量份或更多的添加剂防止使用阻燃性氨酯树脂组合物制备的模制产品用火加热时形成的致密残余物的断裂。70重量份或更少的范围不阻碍阻燃性氨酯树脂组合物的起泡。
在一个优选实施方案中,所述阻燃性氨酯组合物包含0.6至100重量份的三聚催化剂、0.1至30重量份的起泡剂、4.5至70重量份的添加剂、3至18重量份的红磷、1.5至52重量份的至少一种除红磷之外的添加剂,基于100重量份的包含多异氰酸酯和多元醇的聚氨酯树脂组合物。
其它组分
所述阻燃性氨酯组合物可进一步包含除了上述三聚催化剂之外的催化剂。这些催化剂的实例包括含氮催化剂、如三乙胺、N-甲基吗啉二(2-二甲基氨基乙基)醚、N,N,N',N”,N”-五甲基二亚乙基三胺、N,N,N'-三甲基氨基乙基-乙醇胺、二(2-二甲基氨基乙基)醚、N-甲基,N'-二甲基氨基乙基哌嗪、咪唑化合物(其中咪唑环中的仲胺官能团被氰基乙基替代);等。
催化剂的量(作为三聚催化剂和除了三聚催化剂之外的催化剂的总量),优选范围为0.6至10重量份,更优选0.6至8重量份,还更优选0.6至6重量份,且最优选0.6至3.0重量份,基于100重量份的氨酯树脂。
0.6重量份或更多的范围不抑制氨酯键形成,而10重量份或更少的范围保持合适的起泡率,使得容易处理。
所述阻燃性氨酯组合物可进一步包含防沉淀剂。防沉淀剂的实例包括,但不具体限于,炭黑,二氧化硅细粉末,氢化蓖麻油蜡状物,脂肪酸酰胺蜡状物,有机粘土,聚氧化乙烯,等。
所述阻燃性氨酯组合物可进一步包含无机填料。无机填料的实例包括,但不具体限于,二氧化硅、硅藻土、氧化铝、氧化钛、氧化钙、氧化镁、氧化铁、氧化锡、氧化锑、铁素体、碱式碳酸镁、碳酸钙、碳酸镁、碳酸锌、碳酸钡、碳钠铝石、水滑石、硫酸钙、硫酸钡、石膏纤维、硅酸钙以及类似钾盐、滑石、粘土、云母、蒙脱石、膨润土、活性白土、海泡石、伊毛缟石、绢云母、玻璃纤维、玻璃珠、二氧化硅中空球、氮化铝、氮化硼、氮化硅、炭黑、石墨、碳纤维、碳中空球、炭粉末、多种金属粉末、钛酸钾、硫酸镁、锆钛酸铅、硼酸铝、硫化钼、碳化硅、不锈钢纤维、各种磁性粉末、熔渣纤维、飞灰、二氧化硅氧化铝纤维、氧化铝纤维、二氧化硅纤维、氧化锆纤维,等。
无机填料可单独使用或以两种或更多种组合使用。特别是,无机填料优选为针状。例如,所述无机填料具有的纵横比(最小厚度(相对最长长度的垂直方向)与无机填料的最长长度的比例,使用扫描电子显微镜观察无机填料得到的图像证实(或直径/厚度比))为5至50。
只要可实现本发明的目的,所述阻燃性氨酯组合物可进一步任选包含抗氧化剂(基于酚、胺、硫等)、热稳定剂、金属劣化抑制剂、抗静电剂、稳定剂、交联剂、润滑剂、柔软剂、颜料、增粘剂树脂、以及类似辅助成分;聚丁烯、石油树脂以及类似增粘剂。
阻燃性氨酯树脂组合物和阻燃性聚氨酯泡沫
当混合上述成分,所述阻燃性氨酯树脂组合物通过反应固化;因此,其粘度随时间变化。因此,所述阻燃性氨酯树脂组合物在使用前分为两个或更多部分以防止阻燃性氨酯树脂组合物通过反应固化。在使用阻燃性氨酯树脂组合物时,将所述分为两个或更多部分的阻燃性氨酯树脂组合物聚在一起。以这种方式,得到阻燃性氨酯树脂组合物。
所述阻燃性氨酯树脂组合物可以以下方式分为两个或更多部分,即各部分的组分不会独立开始固化,且固化反应在阻燃性氨酯树脂组合物独立的成分混合在一起之后开始。
以下描述了制备阻燃性氨酯树脂组合物的方法。上述制备阻燃性氨酯树脂组合物的方法没有特别限制。例如,所述阻燃性氨酯树脂组合物通过以下方法获得:
包括将阻燃性氨酯树脂组合物的各成分混合的方法;包括将阻燃性氨酯树脂组合物悬浮于有机溶剂中,或加热以熔化所述阻燃性氨酯树脂组合物,以得到涂料形式的阻燃性氨酯树脂组合物的方法;包括通过分散于溶剂而制备例如浆液的方法;等。而且,当阻燃性氨酯树脂组合物中包含的反应性固化树脂成分包括在常温(25℃)是固态的成分时,还可使用包括通过加热熔化所述阻燃性氨酯树脂组合物的方法。
所述阻燃性氨酯树脂组合物可通过使用已知的装置,如Banbury混合器、捏合混合器、捏和轧辊、Raikai混合器或行星式搅拌机,将阻燃性氨酯树脂组合物的各成分混合和捏和而获得。
或者,氨酯树脂的主要成分和固化剂可预先各自与填料等单独混合和捏和,且即将注入前,可使用静态混合器、动态混合器等将所得成分的每一种混合和捏和以得到阻燃性氨酯树脂组合物。
即将注入前,还可通过以与以上类似的方式将所述催化剂与除了所述催化剂之外的阻燃性氨酯树脂组合物的组分混合和捏和来得到所述阻燃性氨酯树脂组合物。
所述阻燃性氨酯树脂组合物通过上述方法得到。
以下描述了将阻燃性氨酯树脂组合物固化的方法。
当阻燃性氨酯树脂组合物的各组分混合时,开始反应,且粘度随时间增加,失去流动性。例如,所述阻燃性氨酯树脂组合物可直接雾化、涂覆(包括刷涂)、印刷或喷雾至管道,或可将管道浸渍在阻燃性氨酯树脂组合物中。或者,所述阻燃性氨酯树脂组合物可注入容器,如模子或框架。这使得阻燃性氨酯树脂组合物固化。以这种方式,得到包括阻燃性氨酯树脂组合物的阻燃性氨酯树脂泡沫,且形成管形的泡沫聚氨酯绝热层。
通过将阻燃性氨酯树脂组合物泡沫-固化得到的管道上的泡沫聚氨酯绝热层为聚异氰尿酸酯泡沫且具有优异的耐火性和绝热性质;因此,作为单独的层,提供了两种功能。为向管道赋予耐火性和绝热性质,单一的层(即,泡沫聚氨酯绝热层)是足够的,使得容易制备耐火性绝热涂层材料。而且,所述泡沫聚氨酯绝热层为闭孔类型,因此也具有优异的防水性质和优异的气密性。
管道、设备和施加方法
本发明还包括用用于管道或设备的耐火性绝热涂层材料涂覆的管道或设备,所述涂层材料包括含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物包含多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂和添加剂,所述添加剂包括红磷和选自磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物和针状填料的至少一种。本发明还包括用上述用于管道或设备的耐火性绝热涂层材料涂覆的管道或设备。
本发明还包括施加用于管道或设备的耐火性绝热涂层材料的方法,所述方法包括用用于管道或设备的耐火性绝热涂层材料涂覆管道或设备的外周,所述涂层材料包括含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物包含多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂和添加剂,所述添加剂包括红磷和选自磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸盐的阻燃剂、含锑的阻燃剂、金属氢氧化物和针状填料的至少一种。
耐火性测试
将所述包括阻燃性氨酯树脂组合物的阻燃性聚氨酯泡沫切割为长度10cm,宽度10cm,和厚度5cm的块。以这种方式,准备好了用于锥型量热计实验的样品。
使用用于锥型量热计实验的样品,且基于ISO-5660的测试方法,通过锥型量热计实验测量总热值,其通过在50kW/m2的辐射热强度加热所述样品20分钟。
尽管本发明已参考附图进行了描述,但本发明并不限于以上,且如下所述的多种修改是可能的。
-管2的形状不限制于通常的圆柱形,且管的横截面可为椭圆形、正方形、矩形、多边形,等。
-耐火性绝热涂层材料3施加的目标不限于管2,而可为常见建筑上的任何设备。而且,当耐火性绝热涂层材料3施加至设备时,所述施加不限于在设备的整个外周进行,而可在设备的一部分上进行以使得只有可目测观察的一部分(即,上表面或侧表面)被涂覆。
-另一层(例如,由例如玻璃布或无纺织物形成的加固材料)可设置在管2和耐火性绝热涂层材料3之间。还可在耐火性绝热涂层材料3上设置另一层(例如,由橡胶或树脂形成的防水和防潮层)。
-如图2所示,表面层4可进一步提供在耐火性绝热涂层材料3上。所述表面层4由阻燃性树脂膜(如氯乙烯)、金属板等形成,且进一步对管2赋予性质,如耐火性。表面层4可通过使用迄今已知的方法设置在耐火性绝热涂层材料3的外周周围。
参考实施例,在以下更详细描述本发明。然而,本发明不限于这些实施例。
实施例
实施例1
评估阻燃性聚氨酯泡沫的测试
按照表1所示的配方,将实施例1至19的每一种阻燃性氨酯树脂组合物的成分分成三部分,即,(1)多元醇组合物,(2)多异氰酸酯,和(3)添加剂。以下为表中各成分的详情(各成分的比例通过重量份表示,基于100重量份的聚异氰尿酸酯树脂)。按照表2所示的配方,对比例1至14的阻燃性氨酯树脂组合物的成分也以类似方式准备。
(1)多元醇组合物
-多元醇化合物
(A-1)对苯二甲酸聚酯多元醇(KawasakiKaseiChemicalsLtd.生产,产品名:MaximolRFK-505,羟基值=250mgKOH/g)
-泡沫稳定剂
基于聚亚烷基二醇的泡沫稳定剂(DowCorningTorayCo.,Ltd.生产,产品名:SH-193)
-三聚催化剂
(B-1)辛酸钾(TokyoChemicalIndustryCo.,Ltd.生产,产品号:P0048)
(B-2)三聚催化剂(TosohCorporation生产,产品名:TOYOCAT-TR20)
-氨酯化催化剂
五甲基二亚乙基三胺(TosohCorporation生产,产品名:TOYOCAT-DT)
-起泡剂
水
HFC
HFC-365mfc(1,1,1,3,3-五氟丁烷,SolvayJapan,Ltd.生产)和HFC-245fa(1,1,1,3,3-五氟丙烷,CentralGlassCo.,Ltd.生产),混合比:
HFC-365mfc:HFC-245fa=7:3,下文称为“HFC”
HFO
SOLSTICELBA(反-1-氯-3,3,3-三氟丙烯,HoneywellJapanInc.生产,下文称为“HFO”)
(2)多异氰酸酯
MDI(TosohCorporation生产,产品名:MillionateMR-200),粘度:167mPa·s
(3)添加剂
(C-1)红磷(RinKagakuKogyoCo.,Ltd.生产,产品名:NovaExcel140)
(C-2)磷酸二氢铵(TaiheiChemicalIndustrialCo.,Ltd.生产)
(C-3)三(β-氯丙基)磷酸酯(DaihachiChemicalIndustryCo.,Ltd.生产,产品名:TMCPP,下文称为“TMCPP”)
(C-4)三甲苯基磷酸酯(DaihachiChemicalIndustryCo.,Ltd.生产,产品名:TCP,下文称为“TCP”)
(C-5)甲苯基二苯基磷酸酯(DaihachiChemicalIndustryCo.,Ltd.生产,产品名:CDP,下文称为“CDP”)
(C-6)六溴苯(ManacIncorporated生产,产品名:HBB-b,下文称为“HBB”)
(C-7)硼酸锌(Hayakawa&Co.,Ltd.生产,产品名:FirebrakeZB)
(C-8)三氧化锑(NihonSeikoCo.,Ltd.生产,产品名:PatoxC)
(C-9)氢氧化铝(AlmorixLtd.生产,产品名:B-325)
(C-10)针状填料(KinseiMatecCo.Ltd.生产,硅灰石,产品名:SH1250)
按照表1和2所示的配方,(1)多元醇组合物的组分和(3)添加剂的组分在1000-mL聚丙烯烧杯中称重,且混合物在25℃以500rpm搅拌1分钟,使用通用搅拌器(HEIDON生产,产品名:BL1200)。(2)将多异氰酸酯的组分添加至在将(1)多元醇组合物的组分和(3)添加剂的组分搅拌后得到的捏和材料,且使用上述通用搅拌器将混合物在1000rpm搅拌约10秒。以这种方式,生成泡沫。所得阻燃性氨酯树脂组合物随时间的进展失去流动性,从而获得阻燃性氨酯树脂泡沫。所述泡沫根据以下标准评估。表1和2显示结果。
热值的测量
将所述固化产物切割为10cmx10cmx5cm的尺寸以得到用于锥型量热计实验的样品,且基于ISO-5660,最大释热率和总热值通过以50kW/m2的辐射热强度加热10分钟或20分钟而测量。表1和2显示结果。
所述测量方法通过日本建筑综合试验所(GeneralBuildingResearchCorporation)规定,其为在建筑标准法施行令(EnforcementOrdinanceofBuildingStandardsAct)第108(2)规定的公共制度,为对应于锥形量热计方法的标准的测试方法。所述测量方法基于ISO-5660的测试方法。
当使用锥形量热计加热20分钟测量的总热值为8MJ/m2或更少时,其评估为“通过”。在所述测试中,当加热20分钟测量的总热值为8MJ或更少时给出“A”,当加热10分钟测量的总热值为8MJ或更少时给出“B”,且当加热10分钟测量的总热值超过8MJ/m2时给出“C”。
膨胀测量
在ISO-5660的测试中,当加热后模制制品与点火器接触时,给出“差”,当其不接触时,给出“好”,如表1和2所示。
变形测量(破裂)
在ISO-5660的测试中,当变形达到测试样品的背部时,给出“差”,而当在测试样品的背部没有观察到变形时,给出“好”,如表1和2所示。
收缩测量
在ISO-5660的测试中,当在测试样品的宽度方向观察到1cm或更多的变形且在厚度方向观察到5mm或更多的变形时,给出“差”,而当没有观察到变形时,给出“好”,如表1和2所示。
当热值、膨胀、变形和收缩的测量结果都为“好”时,所述样品确定为可接受的(“是”);否则,所述样品确定为不可接受的(“否”)。
导热性的测量
将所述固化产物切成为20cmx20cmx5cm的尺寸以得到用于导热性测量的样品,且导热性基于JISA1412-2测量,其中上板在37.5℃且下板在12.5℃,温度差异为25℃,平均温度为25℃。表1和2显示测量结果。导热性测试仪HC-074(EKOInstrumentsCo.,Ltd.生产)用作测量设备。
表1
表1(续)
表2
表2(续)
Claims (4)
1.一种用于管道或设备的耐火性绝热涂层材料,所述涂层材料包括含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物含有多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂、及添加剂,所述添加剂含有红磷和选自以下中的至少一种:磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸的阻燃剂、含锑的阻燃剂、金属氢氧化物及针状填料。
2.根据权利要求1的用于管道或设备的耐火性绝热涂层材料,其中基于100重量份包含多异氰酸酯及多元醇的聚氨酯树脂组合物,所述阻燃性氨酯组合物包含:
三聚催化剂,其量在0.1重量份至10重量份的范围内,
起泡剂,其量在0.1重量份至30重量份的范围内,
泡沫稳定剂,其量在0.1重量份至10重量份的范围内,且
添加剂,其量在4.5重量份至70重量份的范围内,且
其中所述添加剂包含其量在3重量份至18重量份范围内的红磷,和其量在1.5重量份至52重量份范围内的除红磷以外的至少一种添加剂。
3.一种管道或设备,其由权利要求1或2的用于管道或设备的耐火性绝热涂层材料所涂覆。
4.一种为管道或设备施加耐火性绝热涂层材料的方法,所述方法包括:
利用用于管道或设备的耐火性绝热涂层材料涂覆管道或设备的外周,所述涂层材料包括包含阻燃性氨酯组合物的泡沫聚氨酯绝热层,所述阻燃性氨酯组合物含有多异氰酸酯、多元醇、三聚催化剂、起泡剂、泡沫稳定剂及添加剂,所述添加剂含有红磷与选自以下中的至少一种:磷酸酯、含磷酸盐的阻燃剂、含溴的阻燃剂、含硼酸的阻燃剂、含锑的阻燃剂、金属氢氧化物及针状填料。
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CN106715589A (zh) * | 2014-09-26 | 2017-05-24 | 积水化学工业株式会社 | 阻燃性聚氨酯树脂组合物 |
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CN106715589B (zh) * | 2014-09-26 | 2021-05-11 | 积水化学工业株式会社 | 阻燃性聚氨酯树脂组合物 |
CN108997921A (zh) * | 2018-08-06 | 2018-12-14 | 无锡市明江保温材料有限公司 | 管道用耐火保温包覆材料 |
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CN116925682A (zh) * | 2023-07-13 | 2023-10-24 | 南通科顺建筑新材料有限公司 | 胶料组合物、阻燃型非沥青基防水卷材胶料及其制备方法和应用 |
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Also Published As
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JP6370340B2 (ja) | 2018-08-08 |
EP3112739A4 (en) | 2017-10-25 |
EP3112739A1 (en) | 2017-01-04 |
JP5973068B2 (ja) | 2016-08-23 |
JPWO2015129844A1 (ja) | 2017-03-30 |
JP2018173174A (ja) | 2018-11-08 |
US20160245451A1 (en) | 2016-08-25 |
KR20160124738A (ko) | 2016-10-28 |
JP6867444B2 (ja) | 2021-04-28 |
CN105793633B (zh) | 2018-10-09 |
JP6568624B2 (ja) | 2019-08-28 |
JP2019184068A (ja) | 2019-10-24 |
KR102156009B1 (ko) | 2020-09-15 |
JP2016205624A (ja) | 2016-12-08 |
WO2015129844A1 (ja) | 2015-09-03 |
TW201546174A (zh) | 2015-12-16 |
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