CN100412103C - 含多异氰酸酯加聚产品的复合结构 - Google Patents
含多异氰酸酯加聚产品的复合结构 Download PDFInfo
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- CN100412103C CN100412103C CNB018144179A CN01814417A CN100412103C CN 100412103 C CN100412103 C CN 100412103C CN B018144179 A CNB018144179 A CN B018144179A CN 01814417 A CN01814417 A CN 01814417A CN 100412103 C CN100412103 C CN 100412103C
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- Prior art keywords
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- isocyanic ester
- polyisocyanate polyaddition
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- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 30
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 30
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- 238000000034 method Methods 0.000 claims description 17
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- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 20
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种包含下列层结构的复合结构：(i)2至20mm金属，(ii)10至100mm多异氰酸酯加聚产品，其密度为350至1050kg/m3，通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)发泡剂存在下反应获得，(iii)2至20mm金属。
Description
本发明涉及呈现下列层结构的复合结构：
(i)2至20mm，优选5至20mm，更优选5至10mm金属，
(ii)10至100mm多异氰酸酯加聚产品，通常为聚氨酯类，其可显示脲和/或异氰酸酯结构并具有密度350至1050kg/m3，优选500至1050kg/m3和更优选800至950kg/m3，并且是通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)发泡剂存在下转化获得的，
(iii)2至20mm，优选5至20mm和更优选5至10mm金属。
本发明进一步涉及制备这些复合结构的方法和其用途。
当建造轮船，例如船体和货舱盖，或桥梁，屋顶或多层建筑物时，必须使用能够承受因外力作用而产生的相当荷载的构件。为满足这些要求，这些构件通常由通过使用合适几何体或合适支撑件增强的金属板或金属大梁构成。因此，考虑到提高的安全标准，油罐船的船体通常由内船体和外船体构成，其中各船体都由15mm厚的钢板构成，且船体间通过约2m长的钢支柱相互连接。由于这些钢板暴露于可观的力下，因此将外和内钢壳通过与其焊接的增强件支承。这些典型的构件的缺点是需要大量的钢并且涉及耗时和耗劳力的建造工艺。此外，这些构件具有相当大的重量。如此降低轮船载重吨位并且增加燃料消耗。此外，这种基于钢的典型构件需要不断维护，因为其外表面和外壳与内壳之间的钢部件的表面必须定期进行防腐蚀处理。
这些钢结构的已知替代物是SPS(夹板体系)件，它由金属和塑料的复合物构成。塑料与两层金属层附着导致比已知钢结构呈现明显优点的复合结构。这些SPS构件公开于说明书DE-A 19,825,083、DE-A 19,825,085、DE-A 19,825,084、DE-A 19,825,087和DE-A 19,8 35,727中。对制造这些复合结构的一个改进应该尤其是有效控制在塑料制造期间在金属层之间产生的反应热，特别是控制体系的相关膨胀和其在冷却期间和冷却后的后续收缩。这应不明显损害塑料与金属层的附着力或材料的性能。
因此，本发明的构思是提供新的复合结构，在塑料制造、特别是冷却后和(ii)的相关收缩期间，该结构显示(ii)与(i)和(iii)的优良附着力。所得复合结构应能够承受因外力作用造成的重荷载，并可用于例如建造轮船、桥梁和多层建筑物。所要提供的构件，又称为复合结构，应起到已知钢结构的替代物作用，并且应在重量、制造方法和所需的维护量方面呈现优点。
此目的在本发明中通过上述复合结构得以实现。
优选显示下述层结构的复合结构：
(i)2至20mm金属，
(ii)10至100mm多异氰酸酯加聚产品，其密度为350至1050kg/m3，优选500至1050kg/m3和更优选800至950kg/m3，并且是通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)发泡剂，1至50体积％(按多异氰酸酯加聚产品体积计)的至少一种气体(c)和非必要的(d)催化剂和/或(e)助剂和/或添加剂存在下转化获得的，
(iii)2至20mm金属。
具体优选具有如下特征的复合结构：(ii)显示在温度范围-45至+50℃范围下弹性模量＞275MPa，与(i)和(iii)的粘结力＞4MPa，在温度范围-45至+50℃范围下膨胀＞30，抗拉强度＞20MPa和压缩强度＞20MPa。
本发明的一个基本特点是多异氰酸酯加聚产品(ii)在发泡剂(f)存在下制备并显示本发明规定的密度。
适用的发泡剂(f)是通常用于聚氨酯化学的任何发泡剂，如物理和/或化学发泡剂。这些物理发泡剂在压力1巴下其沸点高于(即温度高于)-50℃。物理发泡剂的例子为例如FCHC、HFCHC、HFHC，各自含例如4至6个碳原子的脂族烃、脂环烃，或这些材料的混合物，如三氯氟甲烷(沸点24℃)，氯二氟甲烷(沸点-40.8℃)、二氯氟乙烷(沸点32℃)，氯二氟乙烷(沸点-9.2℃)，二氯三氟乙烷(沸点27.1℃)，四氟乙烷(沸点-26.5℃)，六氟丁烷(沸点24.6℃)，异戊烷(沸点28℃)，正戊烷(沸点36℃)和环戊烷(沸点49℃)。
适用的化学发泡剂(即使其与例如异氰酸酯基反应形成气体产品的发泡剂)为例如水、含水合水的化合物、羧酸、叔醇如叔丁醇、氨基甲酸酯如说明书EP-A 1,000,955中(特别是第2页5-31行，以及第3页，21-42行上)描述的氨基甲酸酯、碳酸盐例如碳酸铵和/或碳酸氢铵、和/或氨基甲酸胍。
使用的化学发泡剂(f)优选为水和/或氨基甲酸酯。特别优选使用水和/或氨基甲酸酯作为(f)。
优选发泡剂(f)以足够获得本发明要求的(ii)的密度的量使用。此量可通过本领域熟练技术人员已知的简单常规实验确定。发泡剂(f)的用量宜为0.05-10重量％，优选0.1-5重量％，以多异氰酸酯加聚产品的总重量为基准计。
本发明的复合结构不仅显示优良的机械性能，而且具有可生产非常大尺寸的复合结构的优点。由于在合成反应期间和之后出现的塑料(ii)的收缩性，因此通过在两块金属板(i)和(iii)之间合成塑料(ii)可获得的此类复合结构迄今是非常有限的。由于塑料(ii)(如多异氰酸酯加聚产品)收缩，因此塑料(ii)与金属板(i)和/或(iii)出现局部分离。然而，塑料(ii)与金属板(i)和/或(iii)在其尽可能整个表面上的非常良好的附着对于获得该复合结构的良好机械性能是特别重要的。
用于制备(ii)的组分(c)可以为在压力1巴下沸点低于(即此时的温度低于)-50℃的公知化合物，如空气、二氧化碳、氮气、氨和/或氖。优选使用空气。组分(c)优选对组分(a)为惰性，更优选对组分(a)和(b)惰性，即该气体与(a)和(b)的反应性几乎或完全不可检测出。使用的气体(c)在原理上与用于制备发泡聚氨酯的常规发泡剂不同。常规发泡剂(f)以液体形式使用(或对于气态物理发泡剂，在多醇组分中显示低的部分可溶解性)，并在反应期间因温度升高而蒸发，或在采用水时由于与异氰酸酯基团反应生成气态二氧化碳，但组分(c)优选以气体形式用于本发明中，例如作为在多醇组分中存在的气溶胶。
用于制备(ii)的组分(e)宜是可市购的并且本领域熟练技术人员已知的常规泡沫稳定剂，例如常规聚硅氧烷-聚氧亚烷基嵌段共聚物，如由Goldschmidt出售的Tegostab 2219。这些泡沫稳定剂在制备(ii)期间的含量优选为0.001至10重量％，更优选0.01至10重量％，特别优选0.01至2重量％，按用于制备(ii)的组分(b)、(e)和非必要的(d)的重量计。使用这些泡沫稳定剂使在制备(ii)的反应混合物中的组分(c)稳定。
合成本发明复合结构可通过在(i)与(iii)之间形成可显示脲和/或异氰脲酸酯结构的多异氰酸酯加聚产品(ii)(通常为聚氨酯)进行。该加聚产品(ii)通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在发泡剂(f)和优选1至50体积％(按多异氰酸酯加聚产品体积计)的至少一种气体(c)和特别优选催化剂(d)和/或助剂和/或添加剂(e)存在下反应获得。该加聚产品与(i)和(iii)附着。
该反应优选在封闭模具中进行，即(i)和(iii)位于模具中，并加入用于制备(ii)的起始组分。当加入所述起始组分完成时将该模具密封。在用于制备(ii)的起始组分反应后，从模具中取出复合结构。
将在制备复合结构后被(ii)附着的(i)和/或(iii)的表面可用砂子或钢球喷砂。这种喷砂可通过常规方法进行。例如，这些表面可用常规砂子在高压下喷砂，并例如按此方式清洁和使其变粗糙。用于此处理的合适装置可市购。
这种对在(a)与(b)反应后与(ii)接触的(i)和/或(iii)表面的处理导致(ii)与(i)和/或(iii)的附着力的显著改进。喷砂处理优选在将用于制备(ii)的组分加入(i)与(iii)之间的空间之前即时进行。与(ii)附着的(i)和(iii)的表面宜不带有可能降低附着的无机和/或有机物质，例如油和脂或通常称为剥离剂物质。
在(i)和(iii)表面的这种优选处理之后，这些层优选以合适的关系(例如相互平行)相互固定。这种处理优选使(i)和(iii)相隔10至100mm。例如通过使用定距片，可达到(i)和(iii)的固定排列。优选可将空隙的边缘密封，以使(i)和(iii)的空间可填充(a)、(b)和(f)以及任何其它起始物质，而这些组分都不渗漏。密封可用常规塑料膜或金属箔和/或金属板(它们也可用作定距片)进行。
层(i)和(iii)优选可以具有本发明规定的厚度的常规金属板，例如钢板形式使用。
(i)和(iii)之间的空间的填充可通过垂直或水平排列的(i)和(iii)进行。
用(a)、(b)和(f)以及任何其它起始物质填充(i)和(iii)之间的空间优选可使用常规输送装置，例如高压和低压设备，优选高压设备连续进行。
输送速率可根据要填充的体积变化。为确保(ii)均匀固化。选取的输送速率和输送装置应使要填充的空间可在0.5至20分钟内用用于制备(ii)的组分填充。
层(i)和(iii)(通常为板)可为任何常规的金属如铁、一般的钢，所有类型的精炼钢、铝和/或铜。
当用于制备本发明的复合结构时，(i)和(iii)都可用常规塑料涂布，例如底涂，罩面涂和/或涂布。优选未涂布的(i)和(iii)，更优选已例如通过常规喷砂清洁的层。
在大量的参考文献中已描述了通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)和非必要的(d)催化剂和/或助剂和/或添加剂(e)和/或(c)存在下反应合成多异氰酸酯加聚产品(ii)，通常为聚氨酯和可能的多异氰脲酸酯产品。
用于本发明方法的起始材料(a)、(b)、(d)和(e)以例子方式描述如下。
合适的异氰酸酯(a)为本身已知的和若必要可通过公知的方法缩二脲化和/或异氰脲酸酯化的脂族、环脂族、芳脂族和/或芳族异氰酸酯，优选二异氰酸酯。具体可提及的例如有：在亚烷基部分含4至12个碳原子的亚烷基二异氰酸酯，如1，12-十二烷二异氰酸酯、2-乙基亚丁基-1，4-二异氰酸酯、2-甲基亚戊基-1，5-二异氰酸酯、亚丁基-1，4-二异氰酸酯、赖氨酸酯二异氰酸酯(LDI)和亚己基-1，6-二异氰酸酯(HDI)，环己烷-1，3-和/或1，4-二异氰酸酯，2，4-和2，6-六氢甲苯二异氰酸酯以及相应的异构体混合物，4，4′-、2，2′-和2，4′-二环己基甲烷二异氰酸酯和相应的异构体混合物，1-异氰酸酯基-3，3，5-三甲基-5-异氰酸酯甲基环己烷(IPDI)，2，4-和/或2，6-甲苯二异氰酸酯(TDI)，4，4′-、2，4′-和/或2，2′-二苯基甲烷二异氰酸酯(MDI)，多苯基多亚甲基多异氰酸酯和/或含至少两种所述异氰酸酯的混合物。此外，在本发明的方法中亦可使用含有酯、脲、脲基甲酸酯、碳化二亚胺、二氮杂环丁二酮和/或尿烷基团的二-或多异氰酸酯。优选使用2，4′-、2，2′-和/或4，4′-MDI和/或多苯基多亚甲基多异氰酸酯，更优选含有多苯基多亚甲基多异氰酸酯和至少一种MDI异构体的混合物。
对于异氰酸酯-反应活性化合物(b)，可提及例如具有羟基、硫醇和/或伯或仲氨基作为异氰酸酯-反应活性基团并且通常具有分子量60至10,000g/mol的化合物，例如多醇，选自聚醚多醇、聚酯多醇、聚硫醚多醇、含羟基的聚甲醛和含羟基的脂族聚碳酸酯或至少两种所述多醇的混合物。这些化合物通常具有相对于异氰酸酯的2至6个官能团和分子量400至8000，并且是本领域熟练技术人员公知的。
例如，合适的聚醚多醇为通过已知技术通过将烯化氧如四氢呋喃、1，3-环氧丙烷、1，2-或2，3-环氧丁烷、苯乙烯氧化物和优选环氧乙烷和/或1，2-环氧丙烷加入常规引发剂中获得的那些。使用的引发剂可为例如含至少一个，优选2至4个羟基和/或至少一个，优选2至4个氨基的已知脂族、芳脂族、环脂族和/或芳族化合物。例如，可使用如下引发剂：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、新戊二醇、糖如蔗糖、季戊四醇、山梨糖醇、乙二胺、二氨基丙烷、新戊二胺、己二胺、异佛尔酮二胺、4，4′-二氨基二环己基甲烷、2-(乙氨基)乙胺、3-(甲氨基)丙胺、二亚乙基三胺、二亚丙基三胺和/或N，N′-双(3-氨丙基)乙二胺。
氧化烯可单独、顺序或以相互的混合物形式使用。优选使用在多醇中带来伯羟基的烯化氧。特别优选使用在末端用环氧乙烷烷氧基化并因此含伯羟基的多醇。
合适的聚酯可由含2至12个碳原子的有机二羧酸(优选含4至6个碳原子的脂族二羧酸)与多元醇(优选含2至12个碳原子、优选2至6个碳原子的二醇)生产。聚酯多醇优选具有2至4个，更优选2至3个官能团，和分子量480至3000，优选600至2000，更优选600至1500。
本发明的复合结构优选用聚醚多醇作为组分(b)与异氰酸酯反应生产。聚醚多醇宜具有相对于异氰酸酯1.5至8、优选2至6个平均官能团和分子量400至8000。
与聚酯多醇相比，使用聚醚多醇提供可观的优点，因为聚异氰酸酯加聚产品显示更好的耐水解开裂并且其粘度低。这种改进的耐水解性对于用于造船特别有利。较低粘度的聚醚多醇和含聚醚多醇的用于制备(ii)的反应混合物使得可用用于制备复合结构的反应混合物更快且更简单填充(i)与(iii)之间的空间。由于特别是造船的构件尺寸相当大，因此低粘度液体是特别有利的。
适合用作异氰酸酯-反应活性化合物的其它物质是具有10至40个碳原子的烃骨架及2至4个异氰酸酯-反应活性基团的那些化合物。术语“烃骨架”是指未插入氧原子(如醚的情况)的碳原子的不间断序列。作为这些物质(以下称为(b3))的例子，可提及蓖麻油和其衍生物。
此外，对于异氰酸酯-反应活性化合物，本发明中不仅可使用具有常规分子量400至8000的上述化合物，而且也可使用具有分子量60至＜400的二醇和/或三醇，作为扩链剂和/或交联剂。为改进机械性能，例如硬度，加入扩链剂、交联剂或若需要其混合物将是有利的。扩链剂和/或交联剂优选具有分子量60至300。合适的化合物为例如含2至14个碳原子、优选4至10个碳原子的脂族、环脂族和/或芳脂族二醇，如乙二醇，1，3-丙二醇，1，10-癸二醇，邻-、间-或对二羟基环己烷，二甘醇，一缩二丙二醇，和优选1，4-丁二醇，1，6-己二醇和双(2-羟乙基)氢醌，三醇如1，2，4-和1，3，5-三羟基环己烷、甘油和三羟甲基丙烷，基于环氧乙烷和/或1，2-环氧丙烷的低分子量含羟基聚烯化氧和上述二醇和/或三醇作为起始物和/或二胺如二乙基甲苯二胺和/或3，5-二甲基硫-2，4-甲苯二胺。
若扩链剂、交联剂或其混合物用于制备多异氰酸酯加聚产品，则它们的用量宜为0至30重量％，优选1至30重量％，按使用的异氰酸酯-反应活性化合物(b)计。
此外，为在制备(ii)期间优化固化工艺，可将脂族、芳脂族、环脂族和/或芳族羧酸用作(b)。这些羧酸的例子有甲酸、乙酸、丁二酸、草酸、丙二酸、戊二酸、己二酸、柠檬酸、苯甲酸、水杨酸、苯乙酸、邻苯二甲酸、甲苯磺酸、所述酸的衍生物、所述酸的异构体和所述酸的任意混合物。这些酸的百分比可为0至5重量％，优选0.2至2重量％，按(b)的总重量计。
优选使用含如下组分的混合物作为(b)：
(b1)40至99重量％的具有平均官能度1.5至2.99和平均分子量400至8000的聚醚多醇，和
(b2)1至60重量％的具有平均官能度3至5和平均分子量150至8000的聚醚多醇，百分比按总混合物的重量计。
特别优选使用含如下组分的混合物作为(b)：
(b1)40至98重量％和优选50至80重量％的具有平均官能度1.9至3.2、优选2.5至3和平均分子量2500至8000的聚醚多醇，
(b2)1至30重量％和优选10至25重量％的具有平均官能度1.9至3.2、优选2.5至3和平均分子量150至399的聚醚多醇，和
(b3)1至30和优选10至25重量％的含2至14个碳原子(优选4至10个碳原子)的至少一种脂族、环脂族和/或芳脂族二醇，百分比按总混合物的重量计。
组分(b)中聚醚多醇与聚酯多醇的重量比宜大于100，更优选大于1000，特别优选不使用聚酯多醇作为制备(ii)的组分(b)。
通过将胺引发的聚醚多醇用于制备(ii)还可改进反应物的固化性能。
使用的催化剂(d)可为显著加速异氰酸酯与异氰酸酯-反应活性化合物反应的公知化合物。使用的总催化剂浓度优选为0.001至15重量％，特别是0.05至6重量％，按使用的异氰酸酯-反应活性化合物的总重量计。例如，可使用如下化合物：三乙胺、三丁胺、二甲基苄基胺、二环己基甲胺、二甲基环己基胺、N，N，N′，N′-四甲基二氨基二乙基醚、双(二甲基氨基丙基)脲、N-甲基或N-乙基吗啉、N-环己基吗啉、N，N，N′，N′-四甲基乙二胺、N，N，N′，N′-四甲基丁二胺、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、1-氮杂双环-(2，2，0)-辛烷、1，4-二氮杂双环-(2，2，2)-辛烷(Dabco)，和链烷醇胺化合物如三乙醇胺、三异丙醇胺、N-甲基和N-乙基-二乙醇胺、二甲氨基乙醇、2-(N，N-二甲氨基乙氧基)乙醇、N，N′，N″-三(二烷氨基烷基)六氢三嗪如N，N′，N″-三(二甲氨基丙基)-s-六氢三嗪、氯化亚铁(II)、氯化锌、辛酸铅，和优选锡盐如二辛酸锡、己酸二乙基锡、二月桂酸二丁基锡和/或二月桂基二丁基锡硫醇化物、2，3-二甲基-3，4，5，6-四氢嘧啶、氢氧化四烷基铵如氢氧化四甲基铵、碱金属氢氧化物如氢氧化钠、碱金属醇化物如甲醇钠和异丙醇钾，和/或含10至20个碳原子和非必要的羟基侧基的长链脂肪酸的碱金属盐。
为加速反应，已发现在(d)存在下进行合成(ii)是特别有利的。
在用于制备多异氰酸酯加聚产品(ii)的反应混合物中可选择加入助剂和/或添加剂(e)。具体的例子是填料、表面活性物质、染料、颜料、阻燃剂、抗水解剂、真菌抑制剂、有效抑制细菌的物质和泡沫稳定剂。
合适的表面活性剂的例子为有助于起始物质均化并且还可适于控制塑料结构的化合物。具体的例子是乳化剂，如硫酸蓖麻油的钠盐或脂肪酸的钠盐，以及脂肪酸与胺的盐，如二乙胺的油酸盐、二乙醇胺的硬脂酸盐、二乙醇胺的蓖麻油酸盐、磺酸盐如十二烷基苯磺酸或二萘基甲烷二磺酸和蓖麻油酸的碱金属盐或铵盐。表面活性物质的用量通常为0.01至5重量％，按使用的100重量％总异氰酸酯-反应活性化合物(b)计。
合适的阻燃剂为例如磷酸三甲苯基酯、磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(1，3-二氯丙基)酯、磷酸三(2，3-二溴丙基)酯、二磷酸四(2-氯乙基)亚乙基酯、甲基膦酸二甲酯、二乙醇氨基甲基膦酸二乙酯，以及市购的含氯阻燃多醇。除了上述卤取代磷酸酯外，还可使用无机或有机阻燃剂如红磷、水合氧化铝、三氧化锑、氧化砷、多磷酸铵和硫酸钙，片状石墨或异氰脲酸衍生物如三聚氰胺，或至少两种阻燃剂的混合物如多磷酸铵与三聚氰胺和(若需要)玉米淀粉的混合物或者多磷酸铵、三聚氰胺与片状石墨和/或非必要的芳族聚酯的混合物，以使多异氰酸酯加聚产品阻燃。本发明人发现，通常有利的是使用5至50重量％和优选5至25重量％的所述阻燃剂，按使用的异氰酸酯-反应活性化合物的总重量计。
对于填料，特别是更有效的填料，是指通常的有机和无机填料、增强剂、填充剂、用于改进漆、涂料组合物的耐磨特性的试剂，等等。其具体的例子是无机填料如含硅矿物，如层状硅酸盐如叶蛇纹石、蛇纹石、角闪石(hornblende)、角闪石(amphibole)、镁铁尖晶石(chrisotile)和滑石粉，金属氧化物如高岭土、氧化铝、二氧化钛和氧化铁，金属盐如白垩、重晶石，和无机颜料如硫化镉和硫化锌，以及玻璃等。优选使用高岭土(瓷土)、硅酸铝、和硫酸钡与硅酸铝的共沉淀物，以及天然和合成纤维状矿物如硅灰石及金属和玻璃短纤维。合适的有机填料为例如煤、三聚氰胺、松香、环戊二烯基树脂和接枝聚合物，以及纤维素纤维和聚酰胺、聚丙烯腈、聚氨酯或基于芳族和/或脂族二羧酸的聚酯纤维，和特别优选碳纤维。无机和有机填料可单独或以混合物形式使用。
在制备(ii)期间，优选使用10至70重量％的填料作为助剂和/或添加剂(按(ii)的重量计)。使用的填料优选为滑石粉、高岭土、碳酸钙、重晶石、玻璃纤维和/或玻璃微球。填料的颗粒尺寸优选应使它们不形成阻碍将用于制备(ii)的组分填充入(i)与(iii)之间的空隙的过程。特别优选具有颗粒尺寸低于0.5mm的填料。
填料优选以与用于形成多异氰酸酯加聚产品的反应中的多醇组分的掺混物形式使用。
填料可起到降低多异氰酸酯加聚产品的热膨胀系数(该系数大于钢)，以使其等于钢的作用。这对于在层(i)、(ii)和(iii)之间形成耐久的强粘结力是特别有利的，因为它降低在热荷载下层之间出现的应力。
(ii)的重量，按其定义的，等于用于制备(ii)的组分(a)、(b)和(c)和非必要的(d)和/或(e)的重量。
为制备本发明的多异氰酸酯加聚产品，将多异氰酸酯与异氰酸酯-反应活性化合物按这样的比例反应：异氰酸酯(a)中的NCO基团与异氰酸酯-反应活性化合物(b)和非必要的(f)中的活性氢原子总和之当量比为0.85至1.25∶1，优选0.95至1.15∶1，和更优选1至1.05∶1。若(ii)含至少一些连接的异氰脲酸酯基团，则使用的NCO基团与活性氢原子总和之比为1.5至60∶1，优选1.5至8∶1。
多异氰酸酯加聚产品通常通过一步法或通过预聚法，使用例如高压或低压技术制备。
我们已发现，通过双组分法操作并将异氰酸酯-反应活性化合物(b)、发泡剂(f)和非必要的催化剂(d)和/或助剂和/或添加剂(e)结合或优选充分混合形成组分(A)并用异氰酸酯(a)作为组分(B)，是特别有利的。
可将组分(c)加入含(a)、(b)、(f)和非必要的(d)和/或(e)的反应混合物中，或加入上述各组分(a)、(b)、(A)和/或(B)中。与(c)混合的组分通常以液体形式存在。优选将这些组分混合形成(b)。
合适的组分与(c)的混合可通过本领域公知的技术进行。例如可将(c)用本领域公知的加料装置如液压加料装置，优选在加压下，例如自压力容器经所谓喷嘴加入合适的组分中或通过压缩机压入。优选将相应的组分与(c)充分混合，以使(c)在常规液体组分中的气泡尺寸优选为0.0001至10，更优选0.0001至1mm。
(c)在用于制备(ii)的反应混合物中的含量可通过用公知的测量装置测量高压设备的回流管中的反应混合物的密度确定。(c)在反应混合物中的含量可基于此密度，通过控制单元优选自动调节。该组分的密度可在设备中的物料以常规或极低循环速率通常再循环期间在线测定和调节。
夹层件可通过密封待填充用于制备(ii)的起始组分的(i)与(iii)之间的空隙(除起始物质的入口和出口外)，并优选通过常规高压装置将优选充分混合的起始组分(a)、(b)、(f)和非必要的(c)、(d)和/或(e)经入口灌入(i)与(iii)之间的空隙而制备。
起始组分通常在温度0至100℃，优选20至60℃下混合并按如上所述注入(i)与(iii)之间的空隙。掺混可借助搅拌器或螺旋搅拌器机械进行，但优选用通常在高压装置中使用的对流原理进行，其中组分A流体和组分B流体在高压下相互撞击并在混合头混合。若需要将各组分的流体分开。反应温度，即进行转化时的温度通常大于20℃，优选50至150℃。
通过本发明方法制备的复合物结构的多异氰酸酯加聚产品(ii)在温度范围-45至+50℃范围下弹性模量宜＞275MPa(根据DIN 53，457)，与(i)和(iii)的粘结力＞4MPa(根据DIN 53，530)，在温度范围-45至+50℃范围下伸长＞30％(根据DIN 53，504)，拉伸强度＞20MPa(根据DIN 53，504)和压缩强度＞20MPa(根据DIN 53，421)。
通过本发明生产的复合物结构与已知结构相比具有如下优点：
·与较高密度的聚氨酯相比，当体系在反应后冷却时因使用发泡剂(f)而导致较少收缩。如此实现(ii)与(i)和(iii)更好地附着，因为避免了在冷却期间分离。
·优选使用的(c)还可避免(ii)收缩，如此改进(ii)与(i)和(iii)附着。
因此，通过本发明方法生产的复合结构主要用于其中要求承受很大力的构件，如造船中的构件，如船体，如具有外和内壁的船的双层船体，和货舱盖，或建筑结构如桥梁中的构件，或作为房屋，特别是多层建筑物的构件。
不要将本发明的复合结构与含聚氨酯和/或聚异氰脲酸酯作为芯并且通常用于热绝缘的传统夹层构件混淆。这些已知的夹层件因其相当低的机械稳定性不适合所述应用领域。
Claims (9)
1. 一种呈现下列层结构的构件：
(i)2至20mm厚的金属，
(ii)10至100mm厚的多异氰酸酯加聚产品，其密度为350至1050kg/m3，通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)水和/或氨基甲酸酯存在下反应获得，
(iii)2至20mm厚的金属；
其中(ii)在(i)和(iii)之间，并且
其中(ii)在-45至+50℃温度范围内弹性模量＞275MPa，与(i)和(iii)的粘结力＞4MPa，在-45至+50℃温度范围内伸长＞30％，拉伸强度＞20MPa和压缩强度＞20MPa。
2. 一种呈现下列层结构的构件：
(i)2至20mm厚的金属，
(ii)10至100mm厚的多异氰酸酯加聚产品，其密度为350至1050kg/m3，通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)水和/或氨基甲酸酯，按多异氰酸酯加聚产品体积计1至50体积％的至少一种气体(c)，和可选择加入的(d)催化剂和/或(e)助剂和/或添加剂存在下反应获得，
(iii)2至20mm厚的金属，
其中(ii)在(i)和(iii)之间，并且
其中(ii)在-45至+50℃温度范围内弹性模量＞275MPa，与(i)和(iii)的粘结力＞4MPa，在-45至+50℃温度范围内伸长＞30％，拉伸强度＞20MPa和压缩强度＞20MPa。
3. 如权利要求2的构件，其中含泡沫稳定剂作为(e)。
4. 如权利要求1或2的构件，其中将至少一种聚醚多醇用作(b)。
5. 如权利要求2的构件，其中(ii)包含按(ii)的重量计10至70重量％填料作为(e)助剂和/或添加剂。
6. 一种制备如权利要求1的构件的方法，其中在(i)与(iii)之间通过(a)异氰酸酯与(b)异氰酸酯-反应活性化合物在(f)水和/或氨基甲酸酯存在下反应制备多异氰酸酯加聚产品(ii)，该产品(ii)与(i)和(iii)相粘附。
7. 如权利要求6的方法，其中该反应在封闭模具中进行。
8. 权利要求1至5任何一项的构件或由权利要求7的方法获得的构件的用途，用于作为造船中的构件或建筑结构中的构件。
9. 如权利要求8的用途，其中所述造船中的构件包括船体和货舱盖，所述建筑结构包括桥梁。
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| NO (1) | NO336168B1 (zh) |
| PL (1) | PL360838A1 (zh) |
| WO (1) | WO2002016460A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10056378A1 (de) * | 2000-11-14 | 2002-05-23 | Basf Ag | Verbundelemente enthaltend Polyisocyanat-Polyadditionsprodukte |
| DE10340541A1 (de) * | 2003-09-01 | 2005-03-24 | Basf Ag | Verbundelemente, insbesondere Karosserieteile |
| DE10350238A1 (de) * | 2003-10-27 | 2005-05-19 | Basf Ag | Verbundelemente |
| EP2115026B1 (en) * | 2007-01-30 | 2018-05-02 | Dow Global Technologies LLC | Amine-initiated polyols and rigid polyurethane foam made therefrom |
| BRPI0922910A2 (pt) * | 2008-12-17 | 2016-01-26 | Basf Se | "elemento de construção de forma plana feito de material compósito, processo para produzir um elemento de construção de forma plana,e, uso de um elemento de construção de forma plana". |
| EP3849798B1 (de) * | 2018-09-14 | 2022-08-03 | Basf Se | Laminate aus metall und einer polymerzwischenschicht aus thermoplastischem polyurethan |
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| CN1073691A (zh) * | 1991-12-17 | 1993-06-30 | 帝国化学工业公司 | 聚氨酯泡沫塑料 |
| CN1126134A (zh) * | 1994-06-15 | 1996-07-10 | 通用电气公司 | 低导热率的聚氨酯泡沫塑料的制备方法 |
| WO1999064233A1 (de) * | 1998-06-05 | 1999-12-16 | Basf Aktiengesellschaft | Verbundelemente enthaltend kompakte polyisocyanat-polyadditionsprodukte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2524834C3 (de) * | 1975-06-04 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Polyurethanschaumstoffen mit geschlossener Außenhaut |
| JPS5852492B2 (ja) | 1978-08-18 | 1983-11-22 | 株式会社ブリヂストン | 耐火性積層体 |
| DE2845631A1 (de) * | 1978-10-19 | 1980-04-30 | Metzeler Schaum Gmbh | Verfahren zur herstellung einer verbundplatte |
| JPS5812433U (ja) * | 1981-07-16 | 1983-01-26 | 大日本インキ化学工業株式会社 | 拘束型制振材 |
| JP2606352B2 (ja) * | 1989-02-16 | 1997-04-30 | 三菱化学ダウ株式会社 | 金属サイディング材 |
| JPH08336922A (ja) * | 1995-06-09 | 1996-12-24 | Isuzu Motors Ltd | 断熱パネル及び断熱箱 |
| US5789451A (en) * | 1996-07-29 | 1998-08-04 | The Dow Chemcial Company | Alkanolamine/carbon dioxide adduct and polyurethane foam therewith |
| US6050208A (en) * | 1996-11-13 | 2000-04-18 | Fern Investments Limited | Composite structural laminate |
| US6706406B1 (en) * | 1996-11-13 | 2004-03-16 | Fern Investments Limited | Composite steel structural plastic sandwich plate systems |
| US5778813A (en) * | 1996-11-13 | 1998-07-14 | Fern Investments Limited | Composite steel structural plastic sandwich plate systems |
| JPH1134222A (ja) * | 1997-07-14 | 1999-02-09 | Kansai Paint Co Ltd | サンドイッチ構造パネル及びその製造方法 |
| DE19851880A1 (de) * | 1998-11-10 | 2000-05-11 | Basf Ag | Verfahren zur Herstellung von abriebarmen Polyisocyanat-Polyadditionsprodukten |
| US6329440B2 (en) * | 1998-05-09 | 2001-12-11 | Basf Aktiengesellschaft | Preparation of polyisocyanate polyaddition products |
| DE19820917A1 (de) * | 1998-05-09 | 1999-11-11 | Basf Ag | Verfahren zur Herstellung von Polyisocyanat-Polyadditionsprodukten |
| DE19825087B4 (de) | 1998-06-05 | 2018-12-27 | Basf Se | Verfahren zur Herstellung von Schiffsrümpfen, Laderaumabdeckungen oder Brücken enthaltend Verbundelemente |
| DE19825083A1 (de) * | 1998-06-05 | 1999-12-09 | Basf Ag | Verbundelemente enthaltend kompakte Polyisocyanat-Polyadditionsprodukte |
| DE19825084A1 (de) | 1998-06-05 | 1999-12-09 | Basf Ag | Verbundelemente enthaltend kompakte Polyisocyanat-Polyadditionsprodukte |
| DE19835727A1 (de) | 1998-08-07 | 2000-02-10 | Basf Ag | Verbundelemente |
| DE19852681A1 (de) * | 1998-11-16 | 2000-05-18 | Basf Ag | Carbamatlösungen |
| JP3976429B2 (ja) * | 1998-12-08 | 2007-09-19 | 日本特殊塗料株式会社 | 中空部を形成する厚物鋼板の共鳴振動防止方法 |
| DE19914420A1 (de) | 1999-03-30 | 2000-10-05 | Basf Ag | Verbundelemente enthaltend Polyisocyanat-Polyadditionsprodukte |
-
2000
- 2000-08-21 DE DE2000141162 patent/DE10041162A1/de not_active Withdrawn
-
2001
- 2001-08-16 US US10/362,323 patent/US7914880B2/en not_active Expired - Fee Related
- 2001-08-16 KR KR1020037002468A patent/KR100700465B1/ko active IP Right Grant
- 2001-08-16 ES ES01976084.2T patent/ES2611965T3/es not_active Expired - Lifetime
- 2001-08-16 AU AU2001295466A patent/AU2001295466B2/en not_active Ceased
- 2001-08-16 WO PCT/EP2001/009436 patent/WO2002016460A1/de active Application Filing
- 2001-08-16 JP JP2002521554A patent/JP4711597B2/ja not_active Expired - Lifetime
- 2001-08-16 DK DK01976084.2T patent/DK1315768T3/en active
- 2001-08-16 EP EP01976084.2A patent/EP1315768B1/de not_active Expired - Lifetime
- 2001-08-16 BR BR0113380A patent/BR0113380A/pt not_active Application Discontinuation
- 2001-08-16 CA CA 2420115 patent/CA2420115C/en not_active Expired - Lifetime
- 2001-08-16 PL PL36083801A patent/PL360838A1/xx not_active Application Discontinuation
- 2001-08-16 AU AU9546601A patent/AU9546601A/xx active Pending
- 2001-08-16 CN CNB018144179A patent/CN100412103C/zh not_active Expired - Fee Related
-
2003
- 2003-02-19 NO NO20030783A patent/NO336168B1/no not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073691A (zh) * | 1991-12-17 | 1993-06-30 | 帝国化学工业公司 | 聚氨酯泡沫塑料 |
| CN1126134A (zh) * | 1994-06-15 | 1996-07-10 | 通用电气公司 | 低导热率的聚氨酯泡沫塑料的制备方法 |
| WO1999064233A1 (de) * | 1998-06-05 | 1999-12-16 | Basf Aktiengesellschaft | Verbundelemente enthaltend kompakte polyisocyanat-polyadditionsprodukte |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10041162A1 (de) | 2002-03-07 |
| ES2611965T3 (es) | 2017-05-11 |
| CA2420115A1 (en) | 2002-02-28 |
| JP4711597B2 (ja) | 2011-06-29 |
| BR0113380A (pt) | 2003-07-15 |
| KR100700465B1 (ko) | 2007-03-28 |
| US20030148080A1 (en) | 2003-08-07 |
| AU9546601A (en) | 2002-03-04 |
| US7914880B2 (en) | 2011-03-29 |
| EP1315768B1 (de) | 2016-10-12 |
| NO20030783L (no) | 2003-02-19 |
| EP1315768A1 (de) | 2003-06-04 |
| KR20030029830A (ko) | 2003-04-16 |
| WO2002016460A1 (de) | 2002-02-28 |
| DK1315768T3 (en) | 2017-01-30 |
| JP2004506556A (ja) | 2004-03-04 |
| PL360838A1 (en) | 2004-09-20 |
| AU2001295466B2 (en) | 2006-06-01 |
| CA2420115C (en) | 2008-10-21 |
| NO20030783D0 (no) | 2003-02-19 |
| CN1447826A (zh) | 2003-10-08 |
| NO336168B1 (no) | 2015-06-01 |
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