CN103665305B - 高阻燃型聚异氰脲酸酯硬质泡沫及其制备方法 - Google Patents
高阻燃型聚异氰脲酸酯硬质泡沫及其制备方法 Download PDFInfo
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- CN103665305B CN103665305B CN201310655405.4A CN201310655405A CN103665305B CN 103665305 B CN103665305 B CN 103665305B CN 201310655405 A CN201310655405 A CN 201310655405A CN 103665305 B CN103665305 B CN 103665305B
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- rigid foams
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- retardant
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- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2115/00—Oligomerisation
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Abstract
本发明公开了一种易于工业化生产的高阻燃型聚异氰脲酸酯硬质泡沫及其制备方法,该高阻燃型聚异氰脲酸酯硬质泡沫是由白料组分和多异氰酸酯在10~30℃下,按照1:1.2~1:1.8的质量比例,利用聚氨酯低压发泡机混合发泡制得,其中白料组分使用至少一种聚酯多元醇,至少一种液体阻燃剂和包覆红磷的固态阻燃剂,所述的包覆红磷固态阻燃剂可方便分散入液体原料中。本发明制备的聚异氰脲酸酯硬质泡沫具备氧指数大于30的优异阻燃性能,同时在较低密度下赋予泡沫良好的尺寸稳定性和保温性能。
Description
技术领域
本发明涉及聚异氰脲酸酯硬质泡沫领域,具体涉及到高阻燃性(氧指数大于30,B1级)聚异氰脲酸酯硬质泡沫材料及其制备方法。
背景技术
广泛应用保温材料是提高能源的利用效率、降低建筑能耗的一个重要途径。有机保温材料因其优越的保温性能倍受科研领域和工业界的关注。在现有的有机保温材料中,聚氨酯保温材料导热系数小、密度轻、机械性能高、耐水性和耐老化性好,是国际上广泛应用的保温材料。近年来,聚氨酯保温材料在国内也得到了大力推广,用量逐年快速增加。
普通的聚氨酯保温材料是由碳氢氧等元素组成的有机高分子材料,燃烧危险系数高,氧指数(LOI)仅为17~18左右,并且伴随着高浓度的有毒烟雾,往往无法满足国家建材防火标准。通常在配方中额外添加大量的阻燃剂才能满足国标GB8624-2012中B2级应用的要求。为提升聚氨酯泡沫的阻燃性能,在发泡配方中采用过量的异氰酸酯官能团(-NCO)进行三聚反应形成异氰脲酸酯六元环,不仅可提高最终形成的聚异氰脲酸酯泡沫的压缩强度和尺寸稳定性,同时泡沫的热稳定性也明显提高。一般在使用芳香族聚酯多元醇的配方体系中,添加少量液体阻燃剂,泡沫产品的氧指数可提高到25~26左右,并且拥有优异的抗火焰贯穿的性能。若要达到国标GB8624-2012中的B1级阻燃要求则是报道较少。
中国专利CN102558479A公开了一种聚异氰脲酸酯(PIR)泡沫用组合聚醚及其使用方法,其中使用一种阻燃聚酯多元醇和一种高官能度聚醚多元醇为主料制备组合聚醚,以此制备聚异氰脲酸酯泡沫。该体系泡沫氧指数达到32以上,但由于使用较高用量的阻燃聚酯/聚醚多元醇,增加原料成本,并且液体的阻燃剂用量仍旧较高,烟密度较大;中国专利申请CN201110455019报道了一种成本较低的聚异氰脲酸酯泡沫组合料,其中使用可膨胀石墨、三聚氰胺、红磷、多聚磷酸铵、氢氧化铝、氢氧化镁、二氧化硅、硅酮类等固体阻燃剂。该体系能达到氧指数33以上,但是组合料存在固体阻燃剂易沉降的缺点,仅限于实验室模具中制备,无法进行工业化生产,并且使用含溴的反应型阻燃剂,环保性较差。
发明内容
本发明的目的在于提供一种易于工业化生产的聚异氰脲酸酯硬质泡沫及其制备方法,制备而得的聚异氰脲酸酯硬质泡沫具备氧指数大于30的优异阻燃性能,同时在较低密度下具有良好的保温隔热性能和尺寸稳定性。
本发明的技术方案如下:
一种高阻燃型聚异氰脲酸酯硬质泡沫,是由白料组分和多异氰酸酯在10~30℃下,按照1:1.2~1:1.8的质量比例,利用聚氨酯低压发泡机混合发泡制得,其中,所述的白料组分包括以重量份数计算的以下组分:
聚酯多元醇30~60份,
液态有机阻燃剂10~40份,
固态阻燃剂4~10份,
其中所述的聚酯多元醇为芳香族聚酯多元醇,平均官能度为2~3,平均分子量为300~800。
白料组分和多异氰酸酯的质量比优选为1:1.4~1:1.6,特别优选1:1.5,上述优选及特别优选比例进一步保证白料组分和多异氰酸酯混合的均匀性,同时提供给发泡体系适当的异氰酸酯指数,避免指数过高导致泡沫脆性提高,或指数过低导致的泡沫阻燃性能不足。
本发明中使用了固态阻燃剂,尤其当固态阻燃剂用量为10重量份以下时,其分散到白料组分后可一周内无沉降现象。
优选地,所述的芳香族聚酯多元醇为邻苯二甲酸酐、对苯二甲酸、己二酸中的至少一种与二甘醇、丙三醇、三羟甲基丙烷中的至少一种进行缩聚形成的聚酯型多元醇。更优选,所述的芳香族聚酯多元醇为羟值200~350mgKOH/g的苯酐聚酯多元醇,其具有粘度较低,价格便宜,性能稳定等优点。
所述的固态阻燃剂优选为可与所述聚酯多元醇和/或液态有机阻燃剂良好共溶的包覆微胶囊化红磷,具体地可通过包覆材料的选择来实现上述效果,通常的例如,所述的微胶囊化红磷可采用密胺树脂或聚氨酯包覆。
所述液态有机阻燃剂优选包括:
液态脂肪族有机阻燃剂10~30份,
液态芳香族有机阻燃剂0~10份。
所述的液态脂肪族有机阻燃剂选自磷酸三(1-氯-乙丙基)酯(TCPP)、磷酸三(2-氯乙基)酯(TCEP)、甲基磷酸二甲酯(DMMP)、乙基磷酸二乙酯(DEEP)、磷酸三乙酯(TEP)中的一种或两种以上的混合物。特别优选磷酸三(1-氯-乙丙基)酯(TCPP)或磷酸三(2-氯乙基)酯(TCEP)等磷氯系性价比较高的阻燃剂。
所述的液态芳香族有机阻燃剂选自磷酸三苯酯(TPP)、磷酸二苯甲苯酯(DPK)、或磷酸三甲苯酯(TKP)中的一种。
优选地,所述白料组分还包括:
小分子羟基化合物0.5~2份,
水0.5~1.0份,
泡沫稳定剂1~2份,
复合催化剂2~4份,
物理发泡剂15~25份。
所述的小分子羟基化合物优选为官能度2~4,平均分子量为50~400的多元醇,例如二甘醇,丙二醇,甘油,三羟甲基丙烷,季戊四醇等多羟基醇。
所述的水优选为去离子水。
所述复合催化剂包括叔胺催化剂和羧酸金属盐类催化剂。其中叔胺催化剂可以为五甲基二乙烯三胺(PMDETA)(如空气化工PC-5)、二甲基环已胺(DMCHA)(如空气化工PC-8)、N-甲基吗琳、N-乙基吗琳、三乙胺、三乙醇胺中的一种或多种;羧酸金属盐类催化剂可以为乙酸钾(如空气化工PC-46)、异辛酸钾(如空气化工K-15)中的一种或两种组合。
所述泡沫稳定剂可选用本领域常规的硅酮类泡沫稳定剂,比如德美世创公司的AK8805、赢创公司的B8460,空气化工公司的DC-193以及迈图公司的L6900等;
所述的物理发泡剂优选自1,1-二氯-1-氟乙烷(HCFC-141b),1,1,1,3,3-五氟丙烷(HFC-245fa)或1,1,1,3,3-五氟丁烷(HFC-365mfc),更优选1,1-二氯-1-氟乙烷(HCFC-141b),其与多元醇相容性更好。
本发明所使用的多异氰酸酯优选为NCO百分含量为30~32%的聚合MDI,例如拜尔公司的44V20L,巴斯夫的M20S,日本聚氨酯的MR200以及烟台万华的PM200等。
上述的高阻燃型聚异氰脲酸酯硬质泡沫的制备方法为,将上述各组分(包括多异氰酸酯)单独计量,其中固体原料成分提前混合入液体原料得混合组合料,然后进行低压发泡,低压发泡可以采用低压发泡机进行,可以使用连续线或间歇箱式发泡;或,将白料组分中各原料全部混合均匀得到白料组分后与多异氰酸酯做双组分进行低压发泡,例如可以进行箱式发泡。
上述制备方法还优选,将混合组合料或白料组分置于带有低速搅拌功能的储罐中进行搅拌,以控制固体阻燃剂(包覆微胶囊化红磷)长期不沉降,方便工厂生产。
本发明制得的聚异氰脲酸酯硬质泡沫可按照所需形状切割成管道或厚度可变的板材等,应用于高阻燃的建筑外墙,储罐,冷库,管道等保温领域。
在本发明的范畴中,需对以下术语做出如下的说明:
A.聚异氰脲酸酯(PIR)是指通过上述所用白料与多异氰酸酯反应制得的泡沫产品,在反应的过程中羟基与异氰酸酯会生成大量的氨基甲酸酯键(PUR),而配方中存在过多的异氰酸酯在催化剂作用下发生三聚反应生成大量的异氰脲酸酯键;
B.异氰脲酸酯指数(Index)的计算方法是:泡沫配方体系中异氰酸酯(-NCO)摩尔数除以羟基(-OH)等活泼氢的摩尔数,再乘以100,该指数代表PIR配方中的异氰酸酯过量的程度。通常该指数提高越多,泡沫体系交联度和热稳定性提高越多,阻燃性能较好;
C.低压发泡机是指将上述白料组分与多异氰酸酯混合的机器,主要是通过混合头的高速搅拌进行混合,与普通的高压发泡机使用压缩空气使原料雾化进行混合不同。
与现有技术相比,本发明的有益效果如下:
1.本发明的原料之一聚酯多元醇主要使用低羟值聚酯多元醇,尤其是苯酐聚酯多元醇,提高了最终产品聚异氰脲酸酯硬质泡沫的苯环含量,由此制备的聚异氰脲酸酯硬质泡沫的异氰脲酸酯指数为250~400,得到的聚异氰脲酸酯硬质泡沫交联度适当,具有优异的阻燃性能、尺寸稳定性及压缩强度;
2.本发明用阻燃效率高效的包覆微胶囊化红磷复配液态有机阻燃剂替换常规的液态有机阻燃剂,同时通过微胶囊化红磷包覆材料的选择和微胶囊化红磷与其他液体组分配比的选择保证微胶囊化红磷能方便地分散入液体原料中,流动性良好,大大降低了计量过程流量泵的计量误差,并且混合后的白料组分可长期不发生沉降,同时还能减少常规液态有机阻燃剂的用量,所得聚异氰脲酸酯硬质泡沫的阻燃性能提高至B1级;此外,还可将所有组分混合后得到的混合组合料或白料组分置于带有低速搅拌功能的储罐中,以控制包覆红磷长期不沉降,方便工厂生产;
3.本发明制备的聚异氰脲酸酯硬质泡沫具备氧指数大于30的优异阻燃性能,同时在较低密度下赋予泡沫良好的保温性能和尺寸稳定性。
当然,实施本发明的任一产品并不一定需要同时达到以上所述的所有优点。
具体实施方式
本发明提供的高阻燃型聚异氰脲酸酯硬质泡沫,是由白料组分和多异氰酸酯在10~30℃下,按照1:1.2~1:1.8的质量比例,利用聚氨酯低压发泡机混合发泡制得,
其中,所述的白料组分至少包括以重量份数计算的以下组分:
聚酯多元醇30~60份,
液态有机阻燃剂10~40份,
固态阻燃剂4~10份,
其中所述的聚酯多元醇为芳香族聚酯多元醇,平均官能度为2~3,平均分子量为300~800。进一步优选所述的芳香族聚酯多元醇为羟值200~350mgKOH/g的苯酐聚酯多元醇。
在本发明的优选实施方式中,白料组分包括以重量份数计算的以下组分:
聚酯多元醇30~60份,
小分子羟基化合物0.5~2份,
水0.5~1.0份,
液态脂肪族有机阻燃剂10~30份,
液态芳香族有机阻燃剂0~10份,
固态阻燃剂4~10份,
泡沫稳定剂1~2份,
复合催化剂2~4份,
物理发泡剂15~25份,
上述固态阻燃剂优选为可与所述聚酯多元醇和/或液体阻燃剂良好共溶的包覆微胶囊化红磷。
上述高阻燃型聚异氰脲酸酯硬质泡沫的制备方法为,将上述各组分(包括多异氰酸酯)按照上述配比单独计量,其中固体原料成分提前混合入液体原料形成混合组合料,然后利用聚氨酯低压发泡机发泡,可以使用连续线或间歇箱式发泡;或,将白料组分中各原料全部混合均匀得到白料组分后与多异氰酸酯做双组分利用聚氨酯低压发泡机混合发泡,例如可以进行箱式发泡。其中,优选将混合组合料或白料组分置于带有低速搅拌功能的储罐中进行搅拌,可以控制包覆微胶囊化红磷长期不沉降,方便工厂生产。
下面结合具体实施例,进一步阐述本发明。应该理解,这些实施例仅用于说明本发明,而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整,仍属于本发明的保护范围。
实施例
以下实施例中涉及的原材料有:
聚酯多元醇1:改性的邻苯二甲酸酐型聚酯多元醇,羟值为230~250mgKOH/g,官能度为2,在25℃的粘度为3000mPa.s左右,平均分子量为400~500,产品牌号HF-8725,购自浙江华峰新材料股份有限公司。
聚酯多元醇2:改性的邻苯二甲酸酐型聚酯多元醇,羟值为230~250mgKOH/g,官能度为2,在25℃的粘度为3000mPa.s左右,平均分子量为400~500,产品牌号HF-8724,购自浙江华峰新材料股份有限公司。
聚酯多元醇3:邻苯二甲酸酐型聚酯多元醇,羟值为190~200mgKOH/g,官能度为2,在25℃的粘度为15000mPa.s左右,平均分子量为500~600,产品牌号HF-8020,购自浙江华峰新材料股份有限公司。
聚酯多元醇4:邻苯二甲酸酐型聚酯多元醇,羟值为300~330mgKOH/g,官能度为2,在25℃的粘度为2500mPa.s左右,平均分子量为320~380,产品牌号HF-8031,购自浙江华峰新材料股份有限公司。
水:选用去离子水。
复合催化剂:使用美国空气化工公司的几种催化剂复配制得,其中包含10%PC-5,25%PC-8,25%PC-46和40%K-15。
包覆微胶囊化红磷:为密胺包覆的红磷,粒径为2000目,购自科威阻燃新材料有限公司。
液态脂肪族有机阻燃剂:TCPP,或TCEP,购自扬州晨化有限公司。
液态芳香族有机阻燃剂:TKP,或DPK,购自南京科邦阻燃技术有限公司。
泡沫稳定剂:AK8805购自南京德美世创公司,DC-193购自美国空气化工公司,L6900购自美国迈图公司。
物理发泡剂:1,1-二氯-1-氟乙烷(HCFC-141b),购自浙江巨化股份有限公司。
小分子羟基化合物:二甘醇,或三羟甲基丙烷,购自上海中国石化有限公司。
所使用的多异氰酸酯:NCO含量为30.5~32%,购自德国Bayer公司,商品名为Desmodur44V20L。
以下还同时制备了对照例,其中实施例1-5与对照例配方及按照下述配方和上述方法制备得到的聚异氰脲酸酯硬质泡沫的性能对比如下表1。其中,以下实施例1、实施例2、实施例4和对比例的制备方法采用将上述各组分按照上述配比单独计量,固体原料成分提前混合入液体原料得混合组合料,然后在低压发泡机中进行低压发泡制得成品,其中低压发泡机的机头转速3000转/分钟;实施例3和实施例5为按照白料组分的比例混合得到白料组分,利用白料组分和多异氰酸酯在低压发泡机中进行双组份低压发泡,其中低压发泡机的机头转速3000转/分钟,出料1000g,进入矩形模具进行自由发泡。实施例1-5和对比例所得样品室温熟化3天后进行测试,测试标准均参照现行国标。
表1
将上述实施例1-5与对照例对比可发现,对照例中由于添加了大量的液态有机阻燃剂导致其所得聚异氰脲酸酯硬质泡沫制品压缩强度下降明显,尺寸稳定性不足,同时阻燃性能不足B1级。而本发明的实施例1-5中用阻燃效率高效的包覆微胶囊化红磷替换大多数的液态有机阻燃剂,同时通过包覆微胶囊化红磷包覆材料的选择以及包覆微胶囊化红磷与其他液体组分配比的选择保证固体红磷(包覆微胶囊化红磷)能方便地分散入液体原料中,大大降低了计量过程流量泵的计量误差,而且达到了很好的阻燃效果;此外以上实施例1-5还可将混合组合料置于带有低速搅拌功能的储罐中,以控制包覆红磷长期不沉降,方便工厂生产。通过表1的性能测试数据可看出,本发明实施例1-5制备的聚异氰脲酸酯硬质泡沫产品均能通过国标GB8624-2012中B1级的要求,同时兼具良好的尺寸稳定性和较低的导热系数,可以方便用于建筑外墙、管道、冷库等保温领域。
在本发明及上述实施例的教导下,本领域技术人员很容易预见到,本发明所列举的各原料和方法都能实现本发明,以及各原料和工艺的上下限取值、区间值都能实现本发明,在此不一一列举实施例。
Claims (11)
1.一种高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,是由白料组分和多异氰酸酯在10~30℃下,按照1:1.2~1:1.8的质量比例,利用聚氨酯低压发泡机混合发泡制得,其中,所述的白料组分包括以重量份数计算的以下组分:
聚酯多元醇30~60份,
液态有机阻燃剂10~40份,
固态阻燃剂4~10份,
小分子羟基化合物0.5~2份,
水0.5~1.0份,
泡沫稳定剂1~2份,
复合催化剂2~4份,
物理发泡剂15~25份;
其中所述的聚酯多元醇为邻苯二甲酸酐、对苯二甲酸、己二酸中的至少一种与二甘醇、丙三醇、三羟甲基丙烷中的至少一种进行缩聚形成的芳香族聚酯多元醇,平均官能度为2~3,平均分子量为300~800;
所述的固态阻燃剂为可与所述聚酯多元醇和/或液态有机阻燃剂良好共溶的密胺树脂或聚氨酯包覆微胶囊化红磷。
2.如权利要求1所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述的芳香族聚酯多元醇为羟值200~350mgKOH/g的苯酐聚酯多元醇。
3.如权利要求1所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述的多异氰酸酯为NCO百分含量为30~32%的聚合MDI。
4.如权利要求1所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述液态有机阻燃剂包括:
液态脂肪族有机阻燃剂10~30份,
液态芳香族有机阻燃剂0~10份。
5.如权利要求4所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述的液态脂肪族有机阻燃剂选自磷酸三(1-氯-异丙基)酯、磷酸三(2-氯乙基)酯、甲基磷酸二甲酯、乙基磷酸二乙酯、磷酸三乙酯中的一种或几种的混合物。
6.如权利要求4所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述的液态芳香族有机阻燃剂选自磷酸三苯酯、磷酸二苯甲苯酯、或磷酸三甲苯酯中的其中一种。
7.如权利要求1所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述的小分子羟基化合物为官能度2~4,平均分子量为50~400的多元醇。
8.如权利要求1所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述复合催化剂包括叔胺催化剂和羧酸金属盐类催化剂。
9.如权利要求1所述的高阻燃型聚异氰脲酸酯硬质泡沫,其特征在于,所述的物理发泡剂选自1,1-二氯-1-氟乙烷,1,1,1,3,3-五氟丙烷或1,1,1,3,3-五氟丁烷。
10.权利要求1-9中任一项所述的高阻燃型聚异氰脲酸酯硬质泡沫的制备方法,其特征在于,将上述各组分单独计量,其中固体原料成分提前混合入液体原料中得到混合组合料,然后利用聚氨酯低压发泡机发泡;或,将白料组分中各原料全部混合均匀得到白料组分后与多异氰酸酯做双组分,利用聚氨酯低压发泡机发泡。
11.如权利要求10所述的高阻燃型聚异氰脲酸酯硬质泡沫的制备方法,其特征在于,将混合组合料或白料置于带有低速搅拌功能的储罐中进行搅拌。
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