CN101735598A - 聚异氰脲酸酯刚性泡沫及其制造和使用方法 - Google Patents
聚异氰脲酸酯刚性泡沫及其制造和使用方法 Download PDFInfo
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Abstract
由多异氰酸酯组分以及多元醇组分制备了PIR刚性泡沫,所述多元醇组分包含至少一种聚酯型多元醇和至少一种聚醚型多元醇。所述多异氰酸酯组分以及多元醇组分以一定的量反应,使得多异氰酸酯组分与多元醇组分的体积比为100∶100至100∶110,指数为100-400。所述泡沫具有以下特征:与基材良好的粘着性,不渗透水蒸气。所述泡沫通常通过浇注法制造,可以特别有效地用作容器和罐的绝热材料。
Description
技术领域
本发明涉及聚异氰脲酸酯(PIR)刚性泡沫以及制造和使用这些PIR刚性泡沫的方法。
背景技术
EP-A 1219653揭示了一种基于芳族聚酯多元醇的PIR刚性泡沫,这种泡沫具有改进的耐火性和低热导性。另外,还提出了使用脂族、脂环族或杂环类聚酯多元醇。
US 6,495,722描述了使用基于曼尼希碱的多元醇制备纯水膨胀(purelywater-blown)体系,这是因为只有使用这种多元醇才有可能获得良好的耐火性和尺寸稳定性。基于曼尼希碱的这些多元醇的一个显著的缺陷在于,其具有高粘度,因此在用于喷雾法泡沫体系的时候,会带来加工性能方面的问题。因为具有高粘度,很容易发生混合方面的问题,因此会形成具有较差物理-机械性质的泡沫。
已知的PIR刚性泡沫具有较差的流动性质,非常的脆,而且/或者对基材的粘着性较低。
目前,人们仅仅将PIR块状泡沫体用于啤酒桶绝热。这些块状泡沫体无法完全阻止水蒸气渗透,因此经常会发生凝结问题。
发明内容
本发明的目的是提供一种PIR刚性泡沫,这种泡沫是非脆性的,具有良好的流动性质,因此可以用于灌浇工艺。另外,这些泡沫与其所施用的基材具有良好的粘着性,不渗透水蒸气,因此不会造成凝结问题。
目前发现,当使用以正确比例混合的多元醇、催化剂和发泡剂的特定组合的时候,可以制得具有以下性质的PIR刚性泡沫:低热导性,减小的脆性,极佳的尺寸稳定性,改进的表面粘着性和表面质量。这些泡沫可以原位用于灌浇工艺。
具体实施方式
本发明涉及PIR刚性泡沫形成体系,其包含有机多异氰酸酯组分以及包含对异氰酸酯基呈活性的氢原子的多元醇组分,本发明还涉及使用这些体系制备的泡沫。指数(即(异氰酸酯基与对异氰酸酯基呈活性的氢原子的摩尔比)×100)为100至400,最优选185至250。还可以包含合适的辅助性物质和添加剂,发泡剂和水以及催化剂。所述多元醇组分包含至少一种聚酯型多元醇和至少一种聚醚型多元醇。所述多元醇组分与有机多异氰酸酯组分的体积比为100∶100至100∶110。
适合用来制备本发明的PIR刚性泡沫的多异氰酸酯组分中合适的有机多异氰酸酯包括二苯基甲烷二异氰酸酯(MDI)的异构体及其低聚物的混合物。这些混合物一般称为″聚合MDI″(pMDI)。NCO含量优选为28-32重量%。NCO预聚物也可用作有机多异氰酸酯组分。合适的NCO预聚物包括通过聚合MDI与脂族或芳族聚醚型多元醇或聚酯型多元醇(例如包含1-4个羟基、数均分子量为60-4000的聚醚型多元醇或聚酯型多元醇)反应制得的那些预聚物。
在下文中,将用来制备本发明的PIR泡沫的多元醇组分、发泡剂、催化剂、阻燃剂、稳定剂和其它辅助性物质以及添加剂的混合物称为″组分A″。
本发明的PIR刚性泡沫形成体系的多元醇组分包括至少一种聚酯型多元醇和至少一种聚醚型多元醇。另外,还可将一种或多种曼尼希碱用于多元醇组分中。
适合用于本发明的PIR刚性泡沫形成体系的曼尼希碱多元醇优选可以通过以下方式制备:使用双酚A、苯酚或壬基苯酚作为起始物,还使用甲醛和二乙醇胺,随后进行丙氧基化和/或乙氧基化。它们的OH值优选为350至700毫克KOH/克,官能度为2.5至5。以组分A的总重量为基准计,它们的含量优选为0-20重量%。
本发明的多元醇组分中包含的聚酯型多元醇优选是芳族聚酯型多元醇,优选是基于邻苯二甲酸或邻苯二甲酸酐与例如二乙二醇的芳族聚酯型多元醇,回收的聚对苯二甲酸乙二酯或回收的对苯二甲酸二甲酯(例如用二乙二醇进行酯交换)。所述聚酯型多元醇的OH值优选为150至350,官能度为2至2.5,以组分A的总重量为基准计,其含量优选为15-35重量%。当然,本发明的多元醇组分中可以包含一种以上的满足这些标准的聚酯型多元醇。
本发明的多元醇组分中包含的聚醚型多元醇优选是基于环氧丙烷和/或环氧乙烷与作为起始物(initiator)的山梨糖醇或蔗糖和任选的另一种二醇或多元醇(例如甘油、单丙二醇或H2O)得到的那些。所述聚醚型多元醇的OH值优选为400至600,官能度为3.5至6,以组分A的总量为基准计,其用量优选为5-30重量%。当然,本发明的多元醇组分中可以包含一种以上的满足这些标准的聚醚型多元醇。
一种特别优选的多元醇组分包含(1)基于聚对苯二甲酸乙二酯的聚酯型多元醇,其OH值为220-260毫克KOH/克,在25℃下的粘度为1500-2500mPas,官能度为2-2.5,以及(2)一种基于环氧丙烷与作为起始物的山梨糖醇和1,2-丙二醇的聚醚型多元醇,其OH值为450-500毫克KOH/克,官能度为5-6。
通常在多元醇组分中加入阻燃剂,以组分A的总重量为基准计,最优选以5-35重量%的量加入其中。合适的阻燃剂是本领域技术人员已知的,参见例如″Kunststoffhandbuch″,第7卷,″聚氨酯(Polyurethane)″,第6.1章。合适的阻燃剂的例子包括溴化的以及氯化的石蜡或磷化合物,例如正磷酸酯以及偏磷酸酯,所述磷化合物也可包含卤素。合适的阻燃剂的具体例子为:磷酸三乙酯,二乙基乙烷膦酸酯,甲苯基二苯基磷酸酯,二甲基丙烷膦酸酯,以及三(β-氯异丙基)磷酸酯。优选在室温下呈液态的阻燃剂。
发泡剂和水助发泡剂的用量是制得具有所需密度的尺寸稳定的泡沫基体所需的量。以组分A的总重量为基准计,该用量通常为0.2-1.5重量%的水助发泡剂(water co-blowing agent)以及0.5-20重量%的发泡剂。
优选将烃类用作发泡剂。合适的发泡剂的例子包括戊烷的异构体和氟代烃类,例如HFC 245fa(1,1,1,3,3-五氟戊烷),HFC 365mfc(1,1,1,3,3-五氟丁烷),HFC 134a,以及它们的混合物。还可以将不同种类的发泡剂混合起来。例如,使用正戊烷或异戊烷与HFC 245fa的75∶25(正/异戊烷∶HFC 245fa)的混合物,可以制得在10℃测得的热导率低于20mW/mK的泡沫。
可以将聚氨酯化学领域中通常使用的任意催化剂加入本发明的多元醇组分中。用来制备PIR刚性泡沫的胺催化剂(以组分A的总重量为基准计,含量优选为0.05-3重量%)和用作三聚反应催化剂的盐(以组分A的总重量为基准计,优选含量为0.1-5重量%)以一定的量使用,使得PIR泡沫适合于预期的用途(例如用于管道、墙壁、屋顶和容器(例如啤酒罐)的绝热)并且具有足够的固化时间。
合适的催化剂的例子包括:三亚乙基二胺、N,N-二甲基环己基胺、四亚甲基二胺、1-甲基-4-二甲基氨基乙基哌嗪、三乙胺、三丁基胺、二甲基苄胺、N,N′N″-三-(二甲基氨基丙基)六氢三嗪、二甲基氨基丙基甲酰胺、N,N,N′,N′-四甲基乙二胺、N,N,N′,N′-四甲基丁二胺、四甲基己二胺、五甲基二亚乙基三胺、四甲基二氨基乙醚、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂二环[3.3.0]辛烷、双(二甲基氨基丙基)脲、N-甲基吗啉、N-乙基吗啉、N-环己基吗啉、2,3-二甲基-3,4,5,6-四氢嘧啶、三乙醇胺、二乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、二甲基乙醇胺、乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)、月桂酸锡(II)、二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡、二乙酸二辛基锡、三(N,N-二甲基氨基丙基)-s-六氢三嗪、氢氧化四甲基铵、乙酸钠、辛酸钠、乙酸钾、辛酸钾、氢氧化钠,以及这些催化剂的混合物。
本发明的多元醇组分中还可加入泡沫稳定剂。优选聚醚硅氧烷。这些化合物通常是与聚二甲基硅氧烷基团相连的环氧乙烷和环氧丙烷的共聚物。以组分A的总重量为基准计,这些稳定剂的用量优选为0.5-2.5重量%。
为了影响PIR刚性泡沫的λ老化性质,改进其阻燃性质和其它机械性质,可以向所述多元醇组分中加入固体添加剂,例如纳米颗粒、石灰、矿物质、颜料或石墨。可以任选的加入本发明的多元醇组分中的其它固体添加剂的例子可参见文献得到。以组分A的总重量为基准计,这些固体添加剂的用量为0-30重量%。
还可以在组分A中加入硬化剂,例如OH值为800-2000、官能度为2-3的多元醇。合适的硬化剂的例子是单乙二醇,单丙二醇,以及甘油。以组分A的总重量为基准计,所述硬化剂的用量优选为0-5重量%。
本发明的PIR刚性泡沫优选通过一步法制备,更优选通过灌浇工艺制得。这些一步法是本领域技术人员已知的。在一步法中,所述反应组分在一起连续地或者分批地反应,然后在合适的模具/基材之内或之上固化。这些方法在以下文献中描述,美国专利第2764565号,G.Oertel著的″Kunststoff-Handbuch″,第VII卷,Carl Hanser Verlag,第三版,慕尼黑,1993,第267页,K.Uhlig著的″Polyurethan Taschenbuch″,Carl Hanser Verlag,第二版,维也纳,2001,第83-102页。
本发明的PIR刚性泡沫体在作为绝缘材料方面具有许多的应用。在建筑工业中这些应用的例子为墙壁绝热,用于管道截面或管道半截面,屋顶绝热,壁板和地板。具体来说,它们可以用于容器和罐子的绝热,特别是用于啤酒罐的绝热。
本发明还提供了用本发明的PIR刚性泡沫绝热的容器/容器壁,特别是啤酒罐。这些容器具有壁,所述壁由本发明的PIR刚性泡沫芯和与之永久性相连的背衬层组成。所述背衬层可以是挠性的或刚性的。背衬层的例子是纸制背衬层,无纺织物背衬层,金属背衬层(例如钢,铝),木材和复合背衬层。这种类型的容器壁的制造是本领域技术人员已知的。
用于制备PIR刚性泡沫的异氰酸酯组分、多元醇组分、其它添加剂和辅助物质、催化剂和发泡剂的反应混合物可以原位浇铸在所述罐或容器(特别是啤酒罐)的壁之上或之间。
用本发明的刚性泡沫制造的容器壁的一个特别的优点是提高了背衬层的粘着性,良好的流动性和极佳的燃烧性质。
下面借助以下实施例更具体地解释本发明。
实施例
以下的多元醇按照表1所示的用量使用,制得PIR刚性泡沫:
多元醇1:一种聚醚型多元醇,其羟值为530毫克KOH/克,官能度为3,在25℃的粘度为11000mPas,基于环氧丙烷,以双酚胺和双酚A作为起始物(可以从树脂化学BV公司(Resina Chemie BV)购得,商品名为M530)。
多元醇2:一种聚酯型多元醇,羟值约为240毫克KOH/克,在25℃的粘度约为2000mPas,官能度为2,基于回收的聚对苯二甲酸乙二酯(购自合成艾思迫诺拉公司(Synthesia Espanola),商品名为F-1396)。
多元醇3:一种聚醚型多元醇,其羟值为475毫克KOH/克,官能度为5.5,在25℃的粘度为19000mPas,基于环氧丙烷,以山梨糖醇和1,2-丙二醇作为起始物(可以从树脂化学BV公司(Resina Chemie BV)购得,商品名为475s)。
使用包含表1所示量的多元醇1、多元醇2和多元醇3的多元醇组分,在实验室中制备PIR刚性泡沫。依照表1所示的用量,将阻燃剂、泡沫稳定剂、催化剂、水和发泡剂加入所述多元醇组分中,依照表1所示的用量将由此制得的混合物与多异氰酸酯(MDI异构体及其高级同系物的混合物,NCO含量为31重量%,购自拜尔材料科学AG公司(Bayer MaterialScienceAG),商品名为44V40L)混合起来。在中等压力范围、组分温度为35℃的条件下,使用混合装置进行混合。然后将混合物倒入模具中。泡沫配方及其物理性质如表1所示。
报道的密度是通过测量10×10×10立方厘米的立方体的重量而计算得到的。λ值是根据DIN 52616的热流法,在10℃的中心温度测定的(Fox装置)。燃烧性质根据DIN 4102测定。粘着性根据DIN 53292测定。
表1:
实施例1 | 实施例2 | 实施例3 | 实施例4 | |
多元醇1[pbw] | 10 | 20 | 30 | 0 |
多元醇2[pbw] | 30 | 20 | 10 | 40 |
多元醇3[pbw] | 60 | 60 | 60 | 60 |
实施例1 | 实施例2 | 实施例3 | 实施例4 | |
TCPP[pbw],阻燃剂 | 50 | 50 | 50 | 50 |
Dabco BL 11[pbw],催化剂 | 0.15 | 0.15 | 0.15 | 0.15 |
Kosmos 33[pbw],PIR催化剂 | 1 | 1 | 1 | 1 |
Cardura E10P[pbw],稳定剂 | 1 | 1 | 1 | 1 |
Dabco DC193[pbw],泡沫稳定剂 | 1 | 1 | 1 | 1 |
Struksilon 8015[pbw],泡沫稳定剂 | 1.7 | 1.7 | 1.7 | 1.7 |
水[pbw] | 0.65 | 0.65 | 0.65 | 0.65 |
发泡剂365/245[pbw] | 22.2 | 22.2 | 22.2 | 22.2 |
总计[pbw] | 177.7 | 177.7 | 177.7 | 177.7 |
25℃下的粘度[mPa.s] | 280 | 260 | 240 | 300 |
25℃下的密度[kg/m3] | 1210 | 1211 | 1212 | 1185 |
异氰酸酯[pbw] | 180.5 | 180.4 | 180.3 | 184.5 |
指数 | 193 | 193 | 193 | 95 |
乳化时间[秒] | 10 | 9 | 9 | 11 |
胶凝时间[秒] | 50 | 47 | 40 | 52 |
泡沫密度[kg/m3],EN 1602 | 50.4 | 50 | 50 | 50 |
压缩强度[千帕],10%压缩,EN 826 | 302 | 310 | 315 | 290 |
弹性模量[N/mm2],根据EN 826测定 | 17.1 | 17.1 | 17.1 | 17.1 |
实施例1 | 实施例2 | 实施例3 | 实施例4 | |
尺寸稳定性[%],24小时,-25℃,EN1604: | ||||
长 | -0.1 | -0.1 | -0.1 | -0.1 |
宽 | -0.1 | -0.1 | -0.1 | -0.1 |
厚 | 0.0 | 0.0 | 0.0 | 0.0 |
粘着强度[千帕],DIN 53292 | 160 | 150 | 140 | 170 |
10℃时的λ[W/mK],根据DIN 52612测定 | 0.0218 | 0.0220 | 0.0221 | 0.0217 |
燃烧性质[mm],DIN 4102第一部分 | 90 | 87 | 85 | 102 |
Pbw=重量份数
TCPP:三(β-氯异丙基)磷酸酯
Dabco BL11:双(2-二甲基氨基乙基)醚,70%的二丙二醇溶液
Cardura E10P:C13H24O3,饱和单羧酸的高度支化的C10异构体混合物的缩水甘油酯
Dabco DC 193,购自航空产品公司(Air Products)的硅油
Struksilon 801:聚醚改性的二甲基聚硅氧烷
发泡剂365/245:HFC 365mfc和HFC 245fa的60∶40的混合物
Kosmos 33:购自格登施密兹公司(Goldschmidt GmbH)的乙酸钾的30%的二乙二醇溶液
虽然在前文中为了说明起见,对本发明进行了详细的描述,但应理解,这些详细描写仅仅是为了说明,在不偏离本发明的精神和范围的情况下,本领域技术人员可对其进行修改,本发明仅由权利要求书限定。
Claims (9)
1.PIR刚性泡沫,包含以下组分a)、b)和c)的反应产物:
a)有机多异氰酸酯组分
和
b)多元醇组分,其包含
(i)至少一种聚酯型多元醇;和
(ii)至少一种聚醚型多元醇;
和任选的
(c)一种或多种辅助性物质和添加剂、发泡剂、水和催化剂,
上述组分a)、b)和c)的用量使得多元醇组分与有机多异氰酸酯组分的体积比为100∶100至100∶110,指数为100-400。
2.如权利要求1所述的PIR刚性泡沫,其特征在于,指数为185-250。
3.如权利要求1所述的PIR刚性泡沫,其特征在于,所述有机多异氰酸酯组分包含MDI异构体与其高级同系物的混合物,所述混合物的NCO含量为28-32重量%。
4.如权利要求3所述的PIR刚性泡沫,其特征在于,所述多元醇组分包含以下组分的混合物:(i)基于聚对苯二甲酸乙二酯的聚酯型多元醇,其OH值为220-260毫克KOH/克,在25℃下的粘度为1500-2500mPas,官能度为2-2.5,以及(ii)一种基于环氧丙烷、使用山梨糖醇和1,2-丙二醇作为起始物的聚醚型多元醇,其OH值为450-500毫克KOH/克,官能度为5-6,水,发泡剂和催化剂。
5.如权利要求1所述的PIR刚性泡沫,其特征在于,所述多元醇组分包含以下组分的混合物:(i)基于聚对苯二甲酸乙二酯的聚酯型多元醇,其OH值为220-260毫克KOH/克,在25℃下的粘度为1500-2500mPas,官能度为2-2.5,以及(ii)一种基于环氧丙烷、使用山梨糖醇和1,2-丙二醇作为起始物的聚醚型多元醇,其OH值为450-500毫克KOH/克,官能度为5-6,水,发泡剂和催化剂。
6.一种用来制备PIR刚性泡沫的方法,该方法包括使得以下组分a)、b)和c)反应
a)有机多异氰酸酯组分
和
b)多元醇组分,其包含
(i)至少一种聚酯型多元醇;和
(ii)至少一种聚醚型多元醇;
和
(c)一种或多种辅助性物质和添加剂、发泡剂、水和催化剂,上述组分a)、b)和c)的用量使得多元醇组分与有机多异氰酸酯组分的体积比为100∶100至100∶110,指数为100-400。
7.一种绝热容器,包含权利要求1所述的PIR刚性泡沫。
8.一种绝热罐,包括至少一个用权利要求1所述的PIR刚性泡沫绝热的壁的罐。
9.一种啤酒罐,用权利要求1所述的PIR刚性泡沫绝热。
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EP08019496A EP2184305A1 (de) | 2008-11-07 | 2008-11-07 | PIR-Hartschaumstoffe, ein Verfahren zu deren Herstellung und deren Verwendung |
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EP (2) | EP2184305A1 (zh) |
CN (1) | CN101735598A (zh) |
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CN106167541A (zh) * | 2016-08-01 | 2016-11-30 | 山东诺威新材料有限公司 | 连续式生产pir 大块泡用组合聚醚及其制备方法和应用 |
CN106167541B (zh) * | 2016-08-01 | 2019-03-15 | 山东一诺威新材料有限公司 | 连续式生产pir大块泡用组合聚醚及其制备方法和应用 |
CN112218903A (zh) * | 2018-04-24 | 2021-01-12 | 科思创有限公司 | 适合用作板绝热材料的硬质聚氨酯泡沫 |
CN112218903B (zh) * | 2018-04-24 | 2022-05-03 | 科思创有限公司 | 适合用作板绝热材料的硬质聚氨酯泡沫 |
CN110862505A (zh) * | 2019-10-10 | 2020-03-06 | 佳化化学(上海)有限公司 | 一种聚异氰脲酸酯泡沫及其制备方法 |
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US20100116829A1 (en) | 2010-05-13 |
EP2184305A1 (de) | 2010-05-12 |
RU2009140879A (ru) | 2011-05-20 |
BRPI0904276A2 (pt) | 2010-07-20 |
EP2184306A1 (de) | 2010-05-12 |
MX2009011894A (es) | 2010-05-27 |
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