CN1304356A - 包含密实型多异氰酸酯加聚产物的复合体组件 - Google Patents
包含密实型多异氰酸酯加聚产物的复合体组件 Download PDFInfo
- Publication number
- CN1304356A CN1304356A CN99807067A CN99807067A CN1304356A CN 1304356 A CN1304356 A CN 1304356A CN 99807067 A CN99807067 A CN 99807067A CN 99807067 A CN99807067 A CN 99807067A CN 1304356 A CN1304356 A CN 1304356A
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- China
- Prior art keywords
- iii
- complex body
- isocyanate
- body assembly
- polyether glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 13
- 238000010276 construction Methods 0.000 claims description 12
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 230000004523 agglutinating effect Effects 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims 2
- 238000000429 assembly Methods 0.000 claims 2
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- 150000002513 isocyanates Chemical class 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- -1 aromatic isocyanate Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
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- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 4
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- 125000002947 alkylene group Chemical group 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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Abstract
层结构如下的复合体组件:(i)2—20mm厚的金属,(ii)10—100mm厚的密实型多异氰酸酯加聚产物,可通过(a)异氰酸酯与(b)异氰酸酯反应性化合物的反应而制得,如果需要的话在(c)催化剂和/或(d)助剂和/或添加剂的存在下,(iii)2—20mm厚的金属,其中(ii)在温度-45~+50℃时的弹性模量>275MPa,对(i)和(iii)的粘结强度>4MPa,温度-45~+50℃时的延伸率>30%,抗张强度>20MPa而压缩强度>20MPa。
Description
本发明涉及层结构如下的复合体组件:(ⅰ)2-20mm,优选5-20mm,特别优选5-10mm厚的金属,(ⅱ)10-100mm厚的密实型多异氰酸酯加聚产物,可通过(a)异氰酸酯与(b)异氰酸酯反应性化合物的反应而制得,如果需要的话在(c)催化剂和/或(d)助剂和/或添加剂的存在下,(ⅲ)2-20mm,优选5-20mm,特别优选5-10mm厚的金属,其中(ⅱ)在温度-45~+50℃时的弹性模量>275MPa,对(ⅰ)和(ⅲ)的粘结强度>4MPa,温度-45~+50℃时的延伸率>30%,抗张强度>20MPa而压缩强度>20MPa。
本发明进一步涉及一种制造这类复合体组件的工艺及其用途。
轮船如船体和舱壁、桥梁或高层建筑物的建造需要采用能承受较大外力的结构组件。基于此类需求,这些结构组件一般都包含通过适当的几何形状或适宜的加固支柱而强化的金属板或金属支撑件。因此随着安全标准的提高,油槽船的壳体一般由内壳和外壳构成,每个壳体都由通过长约2m的钢支柱彼此相连的15mm厚钢板构成。因为这些钢板要承受较大的力,所以钢的内壳和外壳都借助焊接上的增强组件来达到强化的目的。这类标准结构组件的缺点是需要钢的量很大而且制造起来既费时又费力。除此之外,这类结构组件的重量较大,因而会降低轮船的吨位并增加燃料的消耗。而且因为外表面以及外壳和内壳之间的钢件表面需要定期的防腐处理,所以这类钢质的标准结构组件在维护和保养上要花很多的功夫。
本发明的一个目的是研制能承受较大的外力并且可用于比如轮船制造、桥梁修建或高层建筑物建造的结构组件。所研制的结构组件,也称为复合体组件,可作为现有钢质构件的替代品并且尤其在机械性能上有其优越之处。
已经发现,可通过前述的复合体组件来实现此目的。
本发明的复合体组件的制造方法是,在(ⅰ)和(ⅲ)之间通过(a)异氰酸酯与(b)聚醚多元醇的反应制备出与(ⅰ)和(ⅲ)粘结的密实型多异氰酸酯加聚产物,如果需要的话在(c)催化剂和/或(d)助剂和/或添加剂的存在下。
对在复合体组件的制造结束之后才与(ⅱ)粘结的(ⅰ)和/或(ⅲ)表面优选经喷砂处理。喷砂处理可按常法进行。比如,表面可经普通砂在高压下进行喷砂处理并因此而得以清洁和粗糙化。于此处理方法适宜的设备市面有售。
对在(a)和(b)间,如果需要的话在(c)催化剂和/或(d)的存在下的反应结束之后才与(ⅱ)接触的(ⅰ)和(ⅲ)表面进行处理,可大大提高(ⅱ)与(ⅰ)和(ⅲ)之间的粘结强度。在向(ⅰ)和(ⅲ)间的空隙中引入各个组份以形成(ⅱ)之前优选即刻进行喷砂处理。
在(ⅰ)和(ⅲ)的表面经过优选处理之后,各层优选按适当的排列方式固定下来,比如彼此平行。选择间隔的标准一般是(ⅰ)和(ⅲ)间的空隙宽度为10~100mm。(ⅰ)和(ⅲ)比如可借助垫板固定到位。优选对中间空隙的四周进行密封,以便(ⅰ)和(ⅲ)间的空隙能充满(a)和(b)以及,如果需要的话,(c)和/或(d),并避免这些组份的渗漏。可采用普通的塑料膜或金属箔和/或也可用作垫板的金属板进行密封。
(ⅰ)和(ⅲ)层优选本发明所规定厚度的普通金属板,比如钢板。
在(ⅰ)和(ⅲ)间的空隙中装入按垂直排列的(ⅰ)和(ⅲ)或水平排列的(ⅰ)和(ⅲ)。
可采用普通的进料设备将(a)、(b)和,如果需要的话,(c)和/或(d)充填入(ⅰ)和(ⅲ)间的空隙中,此操作优选连续进行,比如借助高和低压设备,优选高压设备。
进料速率的大小取决于所要填充的体积。为确保(ⅱ)固化均匀,所选的进料速率和进料设备要能保证所要填充的空隙能在5-20min内充满制备(ⅱ)所需的各个组份。
就(ⅰ)和(ⅲ)层而言,多数是板,可采用普通的金属,比如铁、普通钢、各类合金钢、铝和/或铜。
(ⅰ)和(ⅱ)在用于制造本发明的复合体组件时都可覆以涂层,比如底涂、油漆和/或以普通塑性体进行刷涂处理。优选采用未经涂覆的(ⅰ)和(ⅲ),并特别优选在使用前比如以普通的喷砂处理进行清洁。
通过(a)异氰酸酯与(b)异氰酸酯反应性化合物,如果需要的话在(c)催化剂,(d)助剂和/或添加剂的存在下的反应来制备密实型多异氰酸酯加聚产物(ⅱ),一般是聚氨酯和,如果需要的话,聚异氰脲酸酯产物,特别是聚氨酯弹性体,对此已做过大量的报道。就本发明的目的而言,密实型多异氰酸酯加聚产物没有比如聚氨酯泡沫所常见的那种多孔结构。为得到这种密实型结构,禁止向制备(ⅱ)所需的起始组份中添加发泡剂。为彻底杜绝发泡现象,起始组份(b)和,如果采用的话,(c)和(d)以及同各个反应组份接触的(ⅰ)和(ⅲ)表面优选经干燥处理。
包含(a)、(b)和,如果采用的话,(c)和/或(d)的反应混合物其水含量优选0~0.03wt.%,基于反应混合物的质量。水含量,特别是组份(b)的水含量可通过比如蒸馏而相应调整。也可向反应混合物添加能与水结合并因此而避免发泡作用的化合物。这类化合物一般是已知的,比如分子筛。比如可采用适当的,优选粉状的硅酸盐或噁唑烷。这些化合物优选添加到反应混合物,优选组份(b)中,用量为0.05~5wt.%,基于反应混合物的质量。
如下举例描述本发明工艺中的起始物质(a)、(b)、(c)和(d):
适宜的异氰酸酯(a)是其本身已知并可借由公知的方法可选通过引入缩二脲和/或异氰脲酸酯基团而改性的脂肪族、脂环族、芳代脂肪族和/或芳香族异氰酸酯,优选二异氰酸酯。特定例子为:4~12碳亚烷基的亚烷基二异氰酸酯,比如十二烷基1,12-二异氰酸酯、二乙基四亚甲基1,4-二异氰酸酯、2-甲基五亚甲基1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯、赖氨酸酯二异氰酸酯(LDI)、亚己基1,6-二异氰酸酯(HDI)、环己烷1,3-和/或1,4-二异氰酸酯,六氢化亚甲苯基2,4-和2,6-二异氰酸酯及其对应的异构体混合物,二环己基甲烷4,4’、2,2’-和/或2,4’-二异氰酸酯及其对应的异构体混合物,1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(IPDI)、甲苯2,4-和/或2,6-二异氰酸酯(TDI)、二苯基甲烷4,4’-、2,4’-和/或2,2’-二异氰酸酯(MDI)、多苯基多亚甲基多异氰酸酯和/或至少包含两种所述异氰酸酯的混合物。并且本发明工艺中可采用含有酯、脲、脲基甲酸酯、碳化二亚胺、脲二酮和/或氨基甲酸酯基团的二异氰酸酯和/或多异氰酸酯。优选采用2,4’-、2,2’-和/或4,4’-MDI和/或多苯基多亚甲基多异氰酸酯,特别优选包含多苯基多亚甲基多异氰酸酯以及至少一种MDI异构体的混合物。
就(b)异氰酸酯反应性化合物而言,最好采用平均官能度为1~8,优选1.5~6,而分子量为60~10,000并以所含的羟基、巯基和/或伯和/或仲氨基作为异氰酸酯反应性基团的化合物。有用的化合物比如,选自聚醚多元醇的多元醇如聚四氢呋喃、聚酯多元醇、聚硫醚多元醇、含羟基多聚乙缩醛和含羟基脂肪族聚碳酸酯或者至少两种所述多元醇的混合物。优选采用聚酯多元醇和/或聚醚多元醇。多羟基化合物的羟基数目一般为28~850mg KOH/g并优选35~600mgKOH/g。
聚醚多元醇的适宜例可借由已知的方法通过烯化氧比如四氢呋喃、1,3-氧化丙烯、1,2-或2,3-氧化丁烯、氧化苯乙烯或优选氧化乙烯和/或1,2-氧化丙烯在常用的引发物质上的加成反应而制得。可采用的引发物质比如是含有至少一个羟基和/或至少一个氨基的脂肪族、芳代脂肪族、脂环族和/或芳香族化合物。适宜的引发物质的例子是乙二醇、二甘醇、1,2-或1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、甘油、三羟甲基丙烷、新戊基二醇、糖比如蔗糖、季戊四醇、山梨醇、乙二胺、丙二胺、新戊二胺、亚己基二胺、异佛尔酮二胺、4,4’-二氨基二环己基甲烷、2-(乙基氨基)乙基胺、3-(甲基氨基)丙胺、二亚乙基三胺、二亚丙基三胺和/或N,N’-双(3-氨基丙基)亚乙基二胺。
烯化氧可单独、顺次或以混合物的形式采用。优选采用能在多元醇上形成伯羟基的烯化氧。所用的多元醇特别优选在烷氧基化反应结束之后经氧化乙烯烷氧基化并因而带有伯羟基。
适宜的聚酯多元醇比如可制备自2~12个碳原子的有机二元羧酸,优选4~6个碳原子的脂肪族二元羧酸与2~12个碳原子、优选2~6个碳原子的多元醇,优选二醇。聚酯多元醇的官能度优选2~4,特别是2~3,而分子量为480~3000,特别是600~2000。
进一步适宜的异氰酸酯反应性化合物是烃骨架包含10~40个碳原子及2~4个异氰酸酯反应性基团的物质。就本发明的目的而言,烃骨架指的是碳原子的完整序列,其间不能插入类似醚一样的氧原子。这类物质,以下也称为(b3),可采用比如蓖麻油及其衍生物。
本发明工艺中所用的异氰酸酯反应性化合物,如果需要的话,也可包括起链增长剂和/或交联剂作用的分子量为60~<400的二醇和/或三醇。添加链增长剂、交联剂,如果需要的话,或其混合物,的确有利于机械性能,比如硬度的提高。链增长剂和/或交联剂的分子量优选60~300。适宜的链增长剂/交联剂比如是,2~14个碳原子、优选4~10个碳原子的脂肪族、脂环族和/或芳代脂肪族二醇,比如乙二醇、1,3-丙二醇、1,10-癸二醇、对-、间-、邻-二羟基环己烷,一缩二乙二醇、一缩二丙二醇并优选1,4-丁二醇、1,6-己二醇和双(2-羟基乙基)氢醌,三醇比如1,2,4-或1,3,5-三羟基环己烷、甘油和三羟甲基丙烷、基于氧化乙烯和/或1,2-氧化丙烯的低分子含羟基聚烯化氧以及作为引发分子的上述二醇和/或三醇和/或二胺比如二乙基甲苯二胺和/或3,5-二甲基硫代-2,4-甲苯二胺。
如果在多异氰酸酯加聚产物的制备过程中采用了链增长剂、交联剂或其混合物,其用量最好是0~30wt.%,优选2~20wt.%,基于所用的(b)异氰酸酯反应性混合物的质量。
除了上述的异氰酸酯反应性化合物以外,在(ⅱ)的制备过程中还可采用脂肪族、芳代脂肪族、脂环族和/或芳香族羧酸,以改进固化行为。这类羧酸的例子是甲酸、乙酸、琥珀酸、草酸、丙二酸、戊二酸、己二酸、柠檬酸、苯甲酸、水杨酸、苯乙酸、蓖麻油酸、邻苯二甲酸、甲苯磺酸、所述酸的衍生物,优选蓖麻油酸,所述酸的异构体以及所述酸的任意混合物。这些酸的百分数可以是0~5wt.%,优选0.2~2wt.%,基于(b)的总质量。
所用的组份(b)优选混合物,包含:(b1)占40~99wt.%的平均官能度为1.5~2.99而平均分子量为400~8000的聚醚多元醇,以及(b2)占1~60wt.%的平均官能度为3~5而平均分子量为150~8000的聚醚多元醇
所用的组份(b)特别优选混合物,包含:(b1)占40~98wt.%的平均官能度为1.5~2.99而平均分子量为400~8000的聚醚多元醇,(b2)占1~60wt.%的平均官能度为3~5而平均分子量为150~8000的聚醚多元醇,以及(b3)占1~50wt.%的至少一种属异氰酸酯反应性且烃骨架包含10~40个碳原子及2~4个异氰酸酯反应性基团的化合物。
优选的所述混合物特别是可进一步包含上述羧酸。
使用聚醚多元醇的优点是,这类物质比聚酯多元醇更耐水解并除此之外,其粘度较低。低粘度会大大简化并加快向(ⅰ)和(ⅲ)之间的空隙中加料的过程。这是一个很大的优势,特别是在制造大型复合体组件时,比如所述的舱壁或船体。除此之外,通过使用胺引发的聚醚多元醇可改进(ⅱ)制备用反应混合物的固化行为。所用的化合物(b)以及组分(c)和(d),其水含量优选尽可能低,以避免通过水与异氰酸酯基团的反应生成二氧化碳。
对于催化剂(c),可采用对异氰酸酯与异氰酸酯反应性化合物间的反应有强催化作用的已知化合物;催化剂的优选用量为0.001~15wt.%,特别是0.05~6wt.%,基于所用的异氰酸酯反应性化合物的总量。比如可采用如下的化合物:三乙基胺、三丁基胺、二甲基苄基胺、二环己基甲基胺、二甲基环己基胺、双(N,N-二甲基氨基乙基)醚、双(二甲基氨基丙基)脲、N-甲基吗啉或N-乙基吗啉、N-环己基吗啉、N,N,N’,N’-四甲基亚乙基二胺、N,N,N’,N’-四甲基丁烷二胺、N,N,N’,N’-四甲基己烷-1,6-二胺、五甲基二亚乙基三胺、二甲基哌嗪、N-二甲基氨基乙基哌啶、1,2-二甲基咪唑、氮杂双环[2.2.0]辛烷、1,4-二氮杂双环[2.2.2]辛烷(Dabco)以及烷醇胺化合物比如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺和N-乙基-二乙醇胺、二甲基氨基乙醇、2-(N,N-二甲基氨基乙氧基)乙醇,N,N’,N”-三(二烷基氨基烷基)六氢化三嗪比如N,N’,N”-三(二甲基氨基丙基)六氢化三嗪,氯化铁(Ⅱ)、氯化锌、辛酸铅并优选锡盐比如二辛酸锡、二乙基己酸锡、二月桂酸二丁基锡和/或二丁基二月桂基硫醇锡,2,3-二甲基-3,4,5,6-四氢化嘧啶、四烷基氢氧化铵比如四甲基氢氧化铵,碱金属氢氧化物比如氢氧化钠,碱金属醇盐比如甲醇钠和异丙醇钾,和/或10~20个碳原子并可选带有OH侧基的长链脂肪酸的碱金属盐。
已发现最好在(c)的存在下制备(ⅱ),以加快反应速度。
可向制备多异氰酸酯加聚产物(ⅱ)的反应混合物中引入助剂和/或添加剂(d)。可提及的例子是填料、表面活性物质、染料、颜料、阻燃剂、水解抑制剂、防霉和杀菌剂。
可能的表面活性物质比如是有助于起始物质均匀化并且还能适当调节塑料空隙结构的化合物。可提及的例子是乳化剂比如蓖麻油硫酸酯或脂肪酸的钠盐,还有脂肪酸的铵盐比如油酸二乙胺、硬脂酸二乙醇胺、蓖麻油酸二乙醇胺,磺酸盐比如十二烷基苯-或二萘基甲烷二磺酸的碱金属或铵盐,以及蓖麻油酸。表面活性物质的用量一般为0.01~5wt.%,基于所有所用的异氰酸酯反应性化合物(b)的100wt.%。
适宜的阻燃剂比如是三甲酚磷酸酯、三(2-氯乙基)磷酸酯、三(2-氯丙基)磷酸酯、三(1,3-二氯丙基)磷酸酯、三(2,3-二溴丙基)磷酸酯、四(2-氯乙基)亚乙基二磷酸酯、二甲基甲烷膦酸酯、二乙醇氨基甲基膦酸二乙基酯以及市售的阻燃性含卤素多元醇。除了上述的卤素取代的磷酸酯以外,也可采用无机或有机阻燃剂比如红磷、水合氧化铝、三氧化锑、氧化砷、多聚磷酸铵和硫酸钙、膨胀型石墨或者氰脲酸衍生物比如密胺,或者是至少两种阻燃剂的混合物比如多聚磷酸铵与密胺以及如果需要的话,玉米淀粉或多聚磷酸铵、密胺与膨胀型石墨和/或芳香族或脂肪族聚酯,从而赋予多异氰酸酯加聚产物以阻燃性能。总体而言,已发现最好采用5~50wt.%,优选5~25wt.%的所述阻燃剂,基于所用异氰酸酯反应性化合物的总量。
就本发明的目的而言,填料,特别是增强型填料,是本身已知的普通有机和无机填料、增强物质、填充剂、能改善油漆、涂料等磨损性能的物质。特定例子是:无机填料比如,含硅矿物如片状硅酸盐如叶蛇纹石、蛇纹石、角闪石、闪石、纤蛇纹石和滑石,金属氧化物如高岭土、氧化铝、氧化钛和氧化铁,金属盐如白垩、重晶石以及无机颜料如硫化镉和硫化锌,还有玻璃等等。优选采用高岭土(陶土)、硅酸铝和硫酸钡与硅酸铝的共沉淀物以及天然和合成的矿物纤维如硅灰石及金属和玻璃短纤维。适宜的有机填料比如是:碳、密胺、松香、环戊二烯树脂和接枝聚合物,还有纤维素纤维、聚酰胺-、聚丙烯腈-、聚氨酯-或基于芳香族和/或脂肪族二羧酸酯的聚酯纤维以及,特别是碳纤维。无机和有机填料可单独或混用。
在(ⅱ)的制备过程中,基于(ⅱ)的质量,优选采用10~70wt.%的填料作为(d)助剂和/或添加剂。优选的填料是滑石、高岭土、碳酸钙、重晶石、玻璃纤维和/或玻璃微球。优选对填料粒子的尺寸进行选择,目的是为了不妨碍向(ⅰ)和(ⅲ)间的空隙中引入制备(ⅱ)的各个组份。特别优选填料粒径<0.5mm。
填料在多异氰酸酯加聚产物的制备反应中优选与多元醇组份混用。
填料可起到降低多异氰酸酯加聚产物比钢等大得多的热膨胀系数的作用,并因此而与钢匹配。因为减少了各层间因温度变化而产生的应力,因此特别有利于实现(ⅰ)、(ⅱ)和(ⅲ)层之间永久性的牢固结合。
(ⅱ)的质量定义为制备(ⅱ)时所用的组份(a)、(b)和如果采用的话,(c)和/或(d)的总质量。
为制备本发明的多异氰酸酯加聚产物,异氰酸酯与异氰酸酯反应性化合物按如下量发生反应,异氰酸酯的NCO基团对异氰酸酯反应性化合物的反应性氢原子总数的当量比为0.85-1.25∶1,优选0.95-1.15∶1,且特别是1-1.05∶1。如果(ⅱ)至少含有一些异氰脲酸酯基团,一般采用NCO基团对反应性氢原子总数为1.5-60∶1、优选1.5-8∶1的比例。
多异氰酸酯加聚产物一般是通过单釜法或预聚物法制备的,比如借助高压或低压技术。
已发现采用双组份工艺是特别有利的,异氰酸酯反应性化合物(b)与选用的催化剂(c)和/或助剂和/或添加剂以及填料(d)混合作为组份(A)并优选彼此均匀混合,并以异氰酸酯作为组份(B)。起始组份一般在0~100℃,优选20~60℃混合,并且按上述方法引入到(ⅰ)和(ⅲ)之间的空隙中。可通过搅拌器或搅拌螺杆进行机械混合,或者对于高压操作的情况则采用逆流式混合。反应温度,即发生反应的温度,一般>20℃,优选50~150℃。
本发明所制复合体组件的多异氰酸酯加聚产物(ⅱ),其在温度-45~+50℃时的弹性模量>275MPa(按照DIN 53457)、对(ⅰ)和(ⅲ)的粘结强度>4MPa(按照DIN 53530)、温度-45~+50℃时的延伸率>30%(按照DIN 53504)、抗张强度>20MPa(按照DIN 53504)而压缩强度>20MPa(按照DIN 53421)。
同已知的构件相比,本发明工艺制造的复合体组件其优点如下:●实际上无需支柱和类似的增强组件。由于节省了材料因而大大降低了制造成本并且也明显简化了防腐过程。●当用于造船时,重量减轻的结果是提高了吨位或降低了燃料消耗。●保养过程大大简化,比如从防腐处理的角度而言。这样就可以有较长的保养间隔期。●包含多异氰酸酯加聚产物如聚氨酯弹性体的夹心结构,能提高能量吸收性能并因此而降低裂缝的扩散。已知的钢构件经过钻孔后在进一步的应力作用之下极易形成裂缝,即裂缝在船体上大面积扩散。裂缝扩散能力的减弱因此降低了在事故或极高应力下遭受损坏的几率。这种提高的安全标准特别适合于油槽船。●多异氰酸酯加聚产物中填料的优选含量降低了(ⅱ)的热膨胀系数并因而实现了与(ⅰ)和(ⅲ)系数之间的匹配。通过本发明可降低(ⅰ)、(ⅱ)和(ⅲ)之间因温度,特别是环境温度的变化,比如就船体而言不同的水温而产生的应力。最终提高了(ⅱ)对(ⅰ)和(ⅲ)的粘结耐久性。●对(ⅰ)和(ⅲ)表面的优选喷砂处理明显提高了(ⅱ)对(ⅰ)和(ⅲ)的粘结性。粘结强度的提高能得到更稳定且更耐久的结构组件。
因此,本发明所制得的复合体组件主要用于结构组件需要承受较大应力的领域,比如在造船上用作结构组件,比如船体如包含一个外壳和一个内壳的双层船壳以及舱壁,或者是建筑物比如桥梁,或者在房屋建造中作为结构构件,特别是在高层建筑中。
本发明的复合体组件不应与包含聚氨酯和/或聚异氰脲酸酯泡沫硬质内核并一般用作隔热材料的普通夹心组件混为一谈。因为其机械强度相对较低,这类已知的夹心式组件可能不适合于所述的用途。
Claims (8)
1.层结构如下的一种复合体组件:
(ⅰ)2-20mm厚的金属,
(ⅱ)10-100mm厚的密实型多异氰酸酯加聚产物,可通过(a)异氰酸酯与(b)异氰酸酯反应性化合物的反应而制得,如果需要的话在(c)催化剂和/或(d)助剂和/或添加剂的存在下,
(ⅲ)2-20mm厚的金属,其中(ⅱ)在温度-45~+50℃时的弹性模量>275MPa,对(ⅰ)和(ⅲ)的粘结强度>4MPa,温度-45~+50℃时的延伸率>30%,抗张强度>20MPa而压缩强度>20MPa。
2.权利要求1的复合体组件,其中(b)是混合物,包含:
(b1)占40~99wt.%的平均官能度为1.5~2.99而平均分子量为400~8000的聚醚多元醇,以及
(b2)占1~60wt.%的平均官能度为3~5而平均分子量为150~8000的聚醚多元醇。
3.权利要求2的复合体组件,其中(b)是混合物,包含:
(b1)占40~98wt.%的平均官能度为1.5~2.99而平均分子量为400~8000的聚醚多元醇,
(b2)占1~60wt.%的平均官能度为3~5而平均分子量为150~8000的聚醚多元醇,以及
(b3)占1~50wt.%的至少一种属异氰酸酯反应性且烃骨架包含10~40个碳原子及2~4个异氰酸酯反应性基团的化合物。
4.权利要求1的复合体组件,其中(ⅱ)包含10~70wt.%的填料作为(d)助剂和/或添加剂,基于(ⅱ)的质量。
5.一种制造权利要求1~4任意一项复合体组件的工艺,其中与(ⅰ)和(ⅲ)粘结的密实型多异氰酸酯加聚产物是在(ⅰ)和(ⅲ)之间通过(a)异氰酸酯与(b)聚醚多元醇的反应而制备的,如果需要的话在(c)催化剂和/或(d)助剂和/或添加剂的存在下。
6.一种可通过权利要求5的工艺制得的复合体组件。
7.权利要求1~4或6任意一项复合体组件的用途,作为轮船如船体和舱壁制造或建筑物如桥梁建设上的结构组件。
8.包含权利要求1~4或6任意一项复合体组件的轮船或桥梁。
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DE19825085A DE19825085A1 (de) | 1998-06-05 | 1998-06-05 | Verbundelemente enthaltend kompakte Polyisocyanat-Polyadditionsprodukte |
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CN100361810C (zh) * | 2002-05-29 | 2008-01-16 | 智能工程(巴哈马)有限公司 | 改进的结构夹层板构件 |
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DE19825083A1 (de) | 1998-06-05 | 1999-12-09 | Basf Ag | Verbundelemente enthaltend kompakte Polyisocyanat-Polyadditionsprodukte |
DE19914420A1 (de) | 1999-03-30 | 2000-10-05 | Basf Ag | Verbundelemente enthaltend Polyisocyanat-Polyadditionsprodukte |
DE19953240A1 (de) | 1999-11-04 | 2001-05-10 | Basf Ag | Verbundelemente |
DE10041162A1 (de) * | 2000-08-21 | 2002-03-07 | Basf Ag | Verbundelemente enthaltend Polyisocyanat-Polyadditionsprodukte |
GB2368041B (en) * | 2000-10-17 | 2004-04-21 | Intelligent Engineering | Sandwich plate stepped risers |
DE10056378A1 (de) * | 2000-11-14 | 2002-05-23 | Basf Ag | Verbundelemente enthaltend Polyisocyanat-Polyadditionsprodukte |
DE10058982A1 (de) * | 2000-11-28 | 2002-05-29 | Basf Ag | Verfahren zur Herstellung von Verbundelementen |
DE10062129A1 (de) * | 2000-12-13 | 2002-06-20 | Basf Ag | Verbundelemente enthaltend Polyisocanat-Polyadditionsprodukte |
DE10130651A1 (de) * | 2001-06-27 | 2003-01-16 | Basf Ag | Verfahren zur Herstellung von Verbundelementen |
DE10130650A1 (de) * | 2001-06-27 | 2003-01-16 | Basf Ag | Verfahren zur Einbringung von Flüssigkeiten mittels einer Fördereinrichtung in eine Form |
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DE10158491A1 (de) * | 2001-11-28 | 2003-06-12 | Bayer Ag | Metall-Polyurethan-Laminate |
DE10205608A1 (de) * | 2002-02-11 | 2003-08-21 | Degussa | Bei niedriger Temperatur härtbare feste uretdiongruppenhaltige Polyurethan-Pulverlackzusammensetzungen |
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DE10350240B4 (de) * | 2003-10-27 | 2013-07-25 | Basf Se | Verfahren zur Einbringung von Flüssigkeiten mittels einer Fördereinrichtung in eine Form |
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US5391686A (en) * | 1992-12-17 | 1995-02-21 | W. R. Grace & Co.-Conn. | Polyurethane compositions having enhanced corrosion inhibiting properties |
US5442028A (en) * | 1993-08-20 | 1995-08-15 | Morton International, Inc. | Curatives for aqueous adhesives |
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