CN114340865A - 用于聚氨酯泡沫的泡沫分隔件 - Google Patents
用于聚氨酯泡沫的泡沫分隔件 Download PDFInfo
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- CN114340865A CN114340865A CN202080060819.0A CN202080060819A CN114340865A CN 114340865 A CN114340865 A CN 114340865A CN 202080060819 A CN202080060819 A CN 202080060819A CN 114340865 A CN114340865 A CN 114340865A
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- Prior art keywords
- foam
- reaction mixture
- polyurethane foam
- insulating
- housing
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- 238000000034 method Methods 0.000 claims abstract description 30
- 238000009413 insulation Methods 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims description 84
- 238000005187 foaming Methods 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
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- 238000006073 displacement reaction Methods 0.000 claims description 7
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- 239000004604 Blowing Agent Substances 0.000 description 6
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- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 4
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
- B29C44/0461—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities by having different chemical compositions in different places, e.g. having different concentrations of foaming agent, feeding one composition after the other
- B29C44/0469—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities by having different chemical compositions in different places, e.g. having different concentrations of foaming agent, feeding one composition after the other provided with physical separators between the different materials, e.g. separating layers, mould walls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
- B29C44/18—Filling preformed cavities
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
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- B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
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- B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
- B29C44/383—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length using spreading devices mounted in the mould, in front of the feed opening
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种制备绝热制品的方法,所述绝热制品包含可原位制备的绝热聚氨酯泡沫(2)、包围所述绝热聚氨酯泡沫(2)的外壳(1)和位于所述绝热聚氨酯泡沫(2)内的泡沫分隔件(5);可根据该方法制备的绝热制品;以及包含所述绝热制品的冷却系统如冰箱、蓄热系统、建筑用绝热板、绝热管道、移动运输系统、热水器、燃烧器、烟囱、仪表板、工业大厅屋顶、发动机或拖车式活动房屋。
Description
本发明涉及一种制备绝热制品的方法,所述绝热制品包含可原位制备的绝热聚氨酯泡沫、包围所述绝热聚氨酯泡沫的外壳和位于所述绝热聚氨酯泡沫内的泡沫分隔件(foam separator);可根据该方法制备的绝热制品;以及包含所述绝热制品的冷却系统(如冰箱)、蓄热系统、建筑用绝热板、绝热管道、移动运输系统、热水器、燃烧器、烟囱、仪表板、工业大厅屋顶、发动机或拖车式活动房屋(caravan)。
绝热聚氨酯(PU)泡沫可以以已知方式,通常在发泡剂、催化剂和任选的助剂和/或添加剂的存在下,通过使有机多异氰酸酯与一种或多种含有至少两个反应性氢原子的化合物(如胺或聚醚、聚酯和/或聚醚酯醇(多元醇))反应制备。
绝热PU泡沫通常是硬质闭孔泡沫,其中泡孔填充有在发泡过程中产生的气态化合物(如CO2)或作为发泡剂添加的气态化合物(如C5烃),其热导率低于空气。此类PU泡沫用于例如冰箱、管道、建筑板、拖车式活动房屋壁等。还可制备开孔PU泡沫,将其置于真空密封盖中,然后抽空。这种绝热制品的一个实例是真空绝热板。
包含绝热PU泡沫的制品可通过将PU泡沫反应混合物注入外壳中直接原位制备,其中PU泡沫在外壳内原位形成。这种外壳可例如由冰箱的内外罩、拖车式活动房屋壁的内外壁、管道的内外管等构成。对于发泡制品的机械性能和绝热性能而言,重要的是在PU泡沫反应混合物的注入过程中实现外壳的均匀填充以及均匀反应。影响填充和发泡过程的参数尤其是PU泡沫反应混合物的反应时间、注射时间和注射压力、PU泡沫反应混合物的流动特性以及待填充腔体的尺寸和几何形状。待填充腔体的几何形状可为复杂的,例如在复杂的外部形式(例如带有窗户的拖车式活动房屋壁)或在插入物的存在下(例如真空板或冰箱中冷凝器或换热器的部件)。这种复杂的几何形状成为泡沫反应混合物流动的障碍。在大腔体的情况下,可能需要注入多于一个泡沫反应混合物料流,以在泡沫反应混合物的反应时间内获得均匀的填充。在制备泡沫期间要考虑的另一个问题是腔体中存在的空气必须被泡沫替换并且必须找到离开腔体的途径。
因此,在用PU泡沫反应混合物填充腔体期间,可能存在泡沫反应混合物的两个料流在腔体内会聚并形成熔接线的情形。在会聚区域,两个料流可彼此相互作用,也可干扰彼此的流动。此外,在腔体完全填充之前,发泡反应已经开始。随着发泡反应的进行,泡沫反应混合物的化学组成及其物理性质发生变化。因此,两个单独料流的混合变得越来越困难,并且最终当泡沫反应混合物几乎达到其最终泡沫结构时,甚至变得不能混合。不幸的是,熔接线是不均匀性的一个原因,并且表现出比熔接线以外的区域更差的绝热性和机械强度。
本发明的一个目的是提供一种制备绝热制品的改进方法,所述绝热制品通过泡沫反应混合物的原位发泡制备。具体而言,应减轻在制备过程中由形成泡沫的反应混合物的料流会聚产生的问题。本发明的另一个目的是提供可通过原位发泡制备的具有改进的绝热和/或机械性能的绝热制品。
该目的通过一种制备绝热制品的方法实现,所述绝热制品包含
(i)绝热聚氨酯泡沫,和
(ii)包围绝热聚氨酯泡沫的外壳,所述外壳包括
(iia)至少一个用于注入聚氨酯泡沫反应混合物的入口,
(iib)至少一个空气出口,用于在所述聚氨酯泡沫反应混合物的发泡反应期间的空气置换,和
(iic)至少一个泡沫分隔件,
通过将所述聚氨酯泡沫反应混合物注入外壳的所述至少一个入口并使所述聚氨酯泡沫反应混合物发泡而进行制备,其中在注入和/或发泡反应期间,所述聚氨酯泡沫反应混合物的至少两个单独料流在外壳内会聚,并且其中所述泡沫分隔件沿所述至少两个料流的会聚区域设置。
该目的还通过一种可根据上述方法制备的绝热制品和通过一种包含以下部分的绝热制品来实现:
(i)原位发泡的绝热聚氨酯泡沫,和
(ii)包围原位发泡的绝热泡沫的外壳,所述外壳包括
(iia)至少一个用于注入聚氨酯泡沫反应混合物的入口,所述聚氨酯泡沫反应混合物用于绝热泡沫原位发泡,
(iib)至少一个空气出口,用于在绝热泡沫原位发泡期间的空气置换,和
(iic)至少一个泡沫分隔件,
其中在所述绝热泡沫的原位发泡期间,所述泡沫分隔件在原位发泡的聚氨酯绝热泡沫内沿着所述聚氨酯泡沫反应混合物的至少两个料流的会聚区域定位。
该目的还通过包含上下文所述的绝热制品的冷却系统(如冰箱)、蓄热系统、建筑用绝热板、绝热管道、移动运输系统、热水器、燃烧器、烟囱、仪表板、工业大厅屋顶、发动机或拖车式活动房屋实现。
在两个或多个泡沫反应混合物料流的会聚区域设置泡沫分隔件减轻了诸如不均匀的热导率和由会聚引起的较低机械强度的缺点。泡沫分隔件的引入提供了安全的排气口,因为空气沿着所述泡沫分隔件被引导。此外,在注射入口不对称放置(这有时由于技术原因是必要的)的情况下,泡沫分隔件还使得腔体的填充更均匀。可进一步选择泡沫分隔件以向整个制品增加进一步的机械强度或增加额外的气体扩散屏障,因为它们可选自比绝热泡沫具有更高的机械强度或气体扩散屏障性能的材料。
下文更详细地描述本发明。
本发明的一个方面是一种制备绝热制品的方法,所述绝热制品包含
(i)绝热聚氨酯泡沫,和
(ii)包围所述绝热聚氨酯泡沫的外壳,所述外壳包括
(iia)至少一个用于注入聚氨酯泡沫反应混合物的入口,
(iib)至少一个空气出口,用于在聚氨酯泡沫反应混合物的发泡反应期间的空气置换,和
(iic)至少一个泡沫分隔件,
通过将所述聚氨酯泡沫反应混合物注入外壳的所述至少一个入口并使所述聚氨酯泡沫反应混合物发泡而进行制备,其中在注入和/或发泡反应期间,所述聚氨酯泡沫反应混合物的至少两个单独料流在外壳内会聚,并且其中所述泡沫分隔件沿所述至少两个料流的会聚区域设置。
在本文中,术语“会聚区域”意指在没有泡沫分隔件的情况下,泡沫反应混合物的至少两个料流会实际相遇和会聚的区域。
绝热聚氨酯泡沫及其制备是本领域技术人员已知的,参见例如PolyurethaneHandbook,1993年第2版,编辑Guenter Oertel,Carl Hanser Verlag Munich。术语“聚氨酯”是本领域技术人员已知的,不仅包括含有氨基甲酸酯基团的聚合物,还包括不含或含有极少量氨基甲酸酯基团的聚合物,只要这些聚合物衍生自二官能或多官能异氰酸酯,参见Polyurethane Handbook,1993年第2版,编辑Guenter Oertel,Carl Hanser VerlagMunich,第2.1.1章。实例为聚醚脲、聚异氰脲酸酯、聚脲和聚碳二亚胺。
根据本发明,绝热聚氨酯泡沫通过使聚氨酯泡沫反应混合物原位发泡制备。这种聚氨酯泡沫反应混合物——在下文也称为泡沫反应混合物或PU泡沫反应混合物——通常包含多元醇组分P)和异氰酸酯组分PI);所述多元醇组分P)含有一种或多种含有至少两个反应性氢原子的化合物,所述异氰酸酯组分PI)含有一种或多种具有至少两个异氰酸酯基团的有机多异氰酸酯。泡沫反应混合物的其他成分通常为发泡剂、催化剂和任选的助剂和/或添加剂。多元醇组分P)和异氰酸酯组分PI)的反应量通常使得异氰酸酯指数为80至400,优选90至280,更优选100至200,特别优选105至150。
在发泡反应期间,形成氨基甲酸酯单元,但取决于存在的组分及其比例,还可形成异氰脲酸酯和/或脲单元和/或衍生自异氰酸酯基团的其他单元。
作为有机异氰酸酯,可使用所有常规的脂族、脂环族并且优选芳族二异氰酸酯和/或多异氰酸酯。作为优选的异氰酸酯,可使用甲苯二异氰酸酯(TDI)和/或二苯基甲烷二异氰酸酯(MDI),优选MDI,并且特别优选MDI和聚合的二苯基甲烷二异氰酸酯(PMDI)的混合物。这些特别优选的异氰酸酯可使用脲二酮基团、氨基甲酸酯基团、异氰脲酸酯基团、碳二亚胺基团或脲基甲酸酯基团完全或部分改性。此外,上述异氰酸酯和预聚物的预聚物以及混合物可用作异氰酸酯组分。这些预聚物由上文所述的异氰酸酯和下文所述的聚醚、聚酯或聚醚和聚酯制备,并且其NCO含量通常为14至32重量%、优选22至30重量%。
作为具有对异氰酸酯有反应性的基团的相对高分子量的化合物,可使用具有至少两个对异氰酸酯有反应性的基团(例如OH-、SH-、NH-和CH-酸基团)的所有化合物。通常使用具有2至8个、优选2至6个对异氰酸酯有反应性的氢原子的聚醚醇和/或聚酯醇。这些化合物的OH值通常为30至850mg KOH/g、优选100至500mg KOH/g。
聚醚醇通过已知方法获得,例如在催化剂的存在下,通过环氧烷与至少一种包含2至8个、优选2至6个键合形式的反应性氢原子的起始分子的加成的阴离子聚合。作为催化剂,可使用碱金属氢氧化物(例如氢氧化钠或氢氧化钾)或碱金属醇盐(例如甲醇钠、乙醇钠或乙醇钾、或异丙醇钾),或在阳离子聚合的情况下,可使用路易斯酸(例如五氯化锑、三氟化硼醚化物或漂白土)。此外,称为DMC催化剂的双金属氰化物化合物也可用作催化剂。此外,可使用胺作为催化剂制备聚醚醇,例如在WO2011/134866或WO2011/134856A1中所公开的。优选使用一种或多种在亚烷基中具有2至4个碳原子的环氧烷,例如环氧乙烷、1,2-环氧丙烷、1,3-环氧丙烷、1,2-或2,3-环氧丁烷或四氢呋喃,在每种情况下单独或以混合物形式使用,特别优选环氧乙烷和/或1,2-环氧丙烷作为环氧烷。可能的起始分子为例如乙二醇、二乙二醇、丙三醇、三羟甲基丙烷、季戊四醇、糖衍生物(如蔗糖)、己糖醇衍生物(如山梨糖醇)、以及甲胺、乙胺、异丙胺、丁胺、苄胺、苯胺、甲苯胺、甲苯二胺,特别是邻位甲苯二胺、萘胺、乙二胺、二亚乙基三胺、4,4'-亚甲基二苯胺、1,3,-丙二胺、1,6-己二胺、乙醇胺、二乙醇胺、三乙醇胺和其他二元或多元醇,或单官能或多官能胺。优选乙二醇、二乙二醇、丙三醇、三羟甲基丙烷、季戊四醇、糖衍生物(如蔗糖)和己糖醇衍生物(如山梨糖醇)以及TDA,优选邻位TDA。
所用的聚酯醇通常由具有2至12个碳原子的多官能醇与具有2至12个碳原子的多官能羧酸的缩合制备;所述多官能醇为例如乙二醇、二乙二醇、丁二醇、三羟甲基丙烷、丙三醇或季戊四醇,所述多官能羧酸为例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸的异构体,或所述酸的酸酐。作为聚酯制备中的其他起始材料,还可同时使用疏水材料。疏水材料是水不溶性材料,其包含非极性有机基团并具有至少一个选自羟基、羧酸、羧酸酯或其混合物的反应性基团。疏水材料的当量重量优选为130至1000g/mol。例如,可使用脂肪酸(如硬脂酸、油酸、棕榈酸、月桂酸或亚油酸),以及油脂和油(如蓖麻油、玉米油、葵花油、大豆油、椰子油、橄榄油或妥尔油(tall oil))。
所用的聚酯醇的官能度优选为1.5至5,特别优选1.8至3.5。如果异氰酸酯预聚物用作异氰酸酯,则在具有对异氰酸酯有反应性的基团的化合物含量的计算中包括用于制备异氰酸酯预聚物的具有对异氰酸酯有反应性的基团的化合物。
本发明绝热元件的聚氨酯泡沫通常通过至少一种物理或化学发泡剂制备,例如选自非卤代烃、部分卤代的烃和水。
部分卤代的烃的实例为C2至C6氟代烯烃,特别优选C3至C6氟代烯烃(例如,具有3至6个氟取代基的丙烯、丁烯、戊烯和己烯),其中可存在其他取代基(例如氯),实例为四氟丙烯、氟氯丙烯(如三氟一氯丙烯)、五氟丙烯、氟氯丁烯、六氟丁烯或其混合物。
特别优选作为用于制备闭孔硬质聚氨酯泡沫的发泡剂的氟化烯烃选自顺式或反式1,3,3,3-四氟丙-1-烯、1,1,1-三氟-2-氯丙-1-烯、1-氯-3,3,3-三氟丙-1-烯、顺式或反式1,1,1,2,3-五氟丙-1-烯、1,1,1,4,4,4-六氟丁-2烯、1-溴五氟丙-1-烯、2-溴五氟丙-1-烯、3-溴五氟丙-1-烯、1,1,2,3,3,4,4-七氟-1-丁烯、3,3,4,4,5,5,5-七氟-1-戊烯、1-溴-2,3,3,3-四氟丙-1-烯、2-溴-1,3,3,3-四氟丙-1-烯、3-溴-1,1,3,3-四氟丙-1-烯、2-溴-3,3,3-三氟丙-1-烯、(E)-1-溴-3,3,3-三氟丙-1-烯、3,3,3-三氟-2-(三氟甲基)丙-1-烯、1-氯-3,3,3-三氟丙-1-烯、2-氯-3,3,3-三氟丙-1-烯、1,1,1-三氟-2-丁烯及其混合物。
非卤代烃发泡剂的实例是无环戊烷异构体和/或环戊烷,尤其是环戊烷。优选使用3重量%至12重量%的无环戊烷异构体和/或环戊烷,基于聚氨酯泡沫反应混合物的总量计。优选环戊烷、以及环戊烷含量为至少70重量%的异戊烷和环戊烷的混合物,并且特别优选使用纯度为至少90重量%、尤其是至少95重量%的环戊烷。
水是化学发泡剂,其尤其优选以1重量%至8重量%、优选1.2重量%至6重量%、更优选1.4重量%至5重量%、最优选1.5重量%至3.5重量%的浓度使用,基于不含物理发泡剂的聚氨酯泡沫反应混合物的总量计。
作为催化剂,可使用加速异氰酸酯-水反应或异氰酸酯-多元醇反应的所有化合物。所述化合物是已知的并且记载在例如“Kunststoffhandbuch,第7卷,Polyurethane”,Carl Hanser Verlag,1993年第3版,第3.4.1章。其包括基于胺的催化剂和基于有机金属化合物的催化剂。作为基于有机金属化合物的催化剂,可使用例如有机锡化合物(如有机羧酸的锡(II)盐,例如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II),以及有机羧酸的二烷基锡(IV)盐,例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡),以及羧酸铋(例如新癸酸铋(III)、2-乙基己酸铋和辛酸铋)、或羧酸的碱金属盐(例如乙酸钾或甲酸钾)。还可使用促进异氰脲酸酯基或脲基形成的催化剂。
优选使用包含至少一种叔胺的混合物作为催化剂。这些叔胺也可带有对异氰酸酯有反应性的基团,例如OH、NH或NH2基。一些最常用的催化剂为双(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-三乙基氨基乙氧基乙醇、二甲基环己胺、二甲基苄胺、三乙胺、三亚乙基二胺、五甲基二亚丙基三胺、二甲基乙醇胺、N-甲基咪唑、N-乙基咪唑、四甲基六亚甲基二胺、三(二甲基氨基丙基)六氢三嗪、二甲基氨基丙胺、N-乙基吗啉、二氮杂双环十一碳烯和二氮杂双环壬烯。优选使用包含至少两种不同叔胺的混合物作为催化剂。
泡沫稳定剂是在发泡期间促进形成规则泡孔结构的材料。实例为:含硅氧烷的泡沫稳定剂,例如硅氧烷氧化烯共聚物和其他有机聚硅氧烷。还有以下物质的烷氧基化产物:脂肪醇、氧代醇、脂肪胺、烷基酚、二烷基酚、烷基甲酚、烷基间苯二酚、萘酚、烷基萘酚、萘胺、苯胺、烷基苯胺、甲苯胺、双酚A、烷基化双酚A、聚乙烯醇;以及以下物质的缩合产物的烷氧基化产物:甲醛和烷基酚、甲醛和二烷基酚、甲醛和烷基甲酚、甲醛和烷基间苯二酚、甲醛和苯胺、甲醛和甲苯胺、甲醛和萘酚、甲醛和烷基萘酚,以及甲醛和双酚A,或这些泡沫稳定剂中的两种或更多种的混合物。泡沫稳定剂的用量优选为0.5至5重量%,特别优选1至3重量%,基于组分的总重量计。
任选地,阻燃剂可用作泡沫的添加剂。作为阻燃剂,通常可使用现有技术中已知的阻燃剂。合适的阻燃剂为例如不可并入的(nonincorporable)溴化物质、溴化酯、溴化醚(Ixol)或溴化醇(如二溴新戊醇、三溴新戊醇和PHT-4-二醇),以及氯化磷酸酯(如磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯(TCPP)、磷酸三(1,3-二氯丙基)酯、磷酸三甲苯酯、磷酸三(2,3-二溴丙基)酯、四(2-氯乙基)亚乙基二磷酸酯)、甲基膦酸二甲酯、二乙醇氨基甲基膦酸二乙酯,以及市售含卤素的阻燃多元醇。可使用磷酸酯或膦酸酯(如乙基膦酸二乙酯(DEEP)、磷酸三乙酯(TEP)、丙基膦酸二甲酯(DMPP)、磷酸二苯甲苯酯(DPK))等作为其他液体阻燃剂。除上述阻燃剂之外,还可使用无机或有机阻燃剂以使硬质聚氨酯泡沫具有阻燃性,例如红磷、包含红磷的制剂、氧化铝水合物、三氧化二锑、氧化砷、多磷酸铵和硫酸钙、可膨胀石墨、或氰尿酸衍生物(例如三聚氰胺),或至少两种阻燃剂的混合物(例如多磷酸铵和三聚氰胺以及任选的玉米淀粉;或多磷酸铵、三聚氰胺、可膨胀石墨和任选的芳族聚酯)。优选的阻燃剂为所列举的含磷阻燃剂,特别优选丙基膦酸二甲酯(DMPP)、乙基膦酸二乙酯(DEEP)、磷酸三乙酯(TEP)、磷酸二苯甲苯酯(DPK)、磷酸三苯酯(TPP)和三-(2-氯丙基)磷酸酯(TCPP),尤其优选TCPP。
其他助剂和/或添加剂可任选地添加到泡沫反应混合物中以制备聚氨酯泡沫,例如表面活性物质、泡孔调节剂、填料、染料、颜料、阻燃剂、水解抑制剂、抑制真菌和抑制细菌的物质。
绝热聚氨酯泡沫优选为硬质聚氨酯泡沫。这种特别适用于绝热应用的硬质聚氨酯泡沫详细记载在Polyurethane Handbook,1993年第2版,编辑Guenter Oertel,CarlHanser Verlag Munich,第6章。
绝热聚氨酯泡沫可为开孔或闭孔泡沫,优选其为闭孔泡沫。如本文所用,术语“闭孔”意指泡沫的开孔含量为最高达20%,优选最高达10%,且最优选最高达5%,参见Polyurethane Handbook,第2版,1993,编辑Guenter Oertel,Carl Hanser VerlagMunich,第6.3.1.4章。开孔的含量可根据2016年生效的DIN EN ISO 4590确定。此类泡沫是本领域技术人员已知的,并且因其绝热性能而特别受重视。
特别优选地,绝热聚氨酯泡沫为硬质闭孔聚氨酯泡沫。
绝热聚氨酯泡沫的密度优选为15至300kg/m3,更优选16至200kg/m3,甚至更优选18至150kg/m3,最优选20至100kg/m3,且特别优选22至70kg/m3。
通常,泡沫反应混合物通过直接混合各组分而制备,然后将所述泡沫反应混合物注入外壳。起始组分通常在10至30℃、优选15至30℃且特别是15至25℃的温度下混合,并引入外壳中。混合通常在高压混合头中进行。外壳的温度有利地为10至70℃,优选30至50℃。混合后的聚氨酯泡沫反应混合物通常直接注入外壳中。
根据本发明,术语“外壳”意指形成腔体的外部壳体,发泡反应混合物注入到所述腔体中,并且由聚氨酯泡沫通过发泡反应进行填充。在发泡反应结束时,外壳包围在反应期间形成的聚氨酯泡沫。外壳可由一个或多个部件组成,例如:冰箱门包括槽形外金属板和由真空拉制热塑性塑料制成的内衬。在这种情况下,本发明的外壳由外金属板和内衬组成。在绝热管道的情况下,所述管道包括外管和直径小于外管的内管。两根管之间的腔体由绝热泡沫填充。在这种情况下,外壳由内管和外管组成。
外壳可在泡沫反应混合物的注入开始时完全组装以及在注入和发泡过程期间完全组装,即形成外壳的所有部件在注入和发泡过程期间就位。外壳还可尚未完全组装,即外壳的至少一部分尚未结合,并且泡沫反应混合物通过由至少一个缺失部件留下的开口引入外壳中。在发泡反应完成之前,通过插入一个或多个缺失部件封闭未完全组装的外壳。这确保所形成的泡沫尽可能完全地呈所述外壳的形式。在这种情况下,注射入口由一个或多个缺失部件留下的开口形成。优选地,外壳在泡沫反应混合物的注入开始时完全组装以及在注入和发泡过程期间完全组装。
所述外壳包括至少一个用于注入聚氨酯泡沫反应混合物的入口、至少一个用于在聚氨酯泡沫反应混合物的发泡反应期间的空气置换的空气出口和至少一个泡沫分隔件。
泡沫分隔件可由不同的材料制成,例如铝和钢等金属;木头;泡沫;塑料如聚酰胺、聚酯(如聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯)、聚苯乙烯、苯乙烯-丙烯腈共聚物;和增强塑料。泡沫分隔件可涂覆有粘附促进剂,这增强了所产生的绝热泡沫和泡沫分隔件之间的附着力,例如树脂粘合剂,如环氧树脂。优选地,泡沫分隔件为层状的,即大体上是二维的。泡沫分隔件可为平的或弯曲的。层状泡沫分隔件的厚度取决于其尺寸、材料和应用,并且可为例如0.1至5mm,优选1至2mm。泡沫分隔件可为部分的或完整的。“部分泡沫分隔件”在本文中意指泡沫分隔件不延伸到整个会聚区域,例如,由于在外壳中设置空气出口,其与外壳在一侧不直接连接。图1a)和1b)中示出了这种部分空气出口的实例。根据本发明,泡沫分隔件覆盖至少50%的会聚区域,优选至少约70%,且最优选至少90%的会聚区域。术语“完全泡沫分隔件”意指泡沫分隔件覆盖整个会聚区域并与外壳接触。这种泡沫分隔件的一个实例可见于图1c)。
外壳包括至少一个空气出口。该空气出口通常是外壳中可透气的开口,例如圆形、角形或狭缝状孔。至少一个空气出口的尺寸取决于出口的形式和应用,并且例如对于圆形出口的直径和矩形出口的边长可为1至5mm。狭缝状出口的宽度可为0.5至5mm,优选1至3mm,并且长度为其宽度的至少两倍。
根据本发明的一个实施方案,至少一个空气出口设置在泡沫分隔件上端处的外壳中。通常待替换的空气的密度低于泡沫反应混合物的密度,并且更容易上升。在泡沫分隔件上方设置空气出口提高了泡沫对腔体的完全填充,而离开腔体的空气产生的干扰较少。根据本发明的另一个实施方案,从至少两个会聚料流的流动方向看,至少一个空气出口设置在泡沫分隔件后端处的外壳中。术语“从至少两个会聚料流的流动方向看,泡沫分隔件后端处”意指靠近泡沫分隔件的后端,并且在完全泡沫分隔件的情况下可定义为泡沫分隔件和外壳在会聚料流的流动方向上的实际连接位置。在部分泡沫分隔件的情况下,所述术语意指假想的交叉点,是泡沫分隔件的延长线与外壳在会聚料流的流动方向上相交的位置。出于技术原因,可能需要将空气出口稍远离数学上精确的点,这种空气出口的偏离位置应包括在术语“从至少两个会聚料流的流动方向看,泡沫分隔件后端处”中,只要它们足够接近数学上精确的点以允许空气在泡沫分隔件的后端排出。这种偏离的一个实例为图1c)中的空气出口(4,4’)的位置。空气出口的位置也可同时位于泡沫分隔件的上端和后端,参见例如图1b)中的空气出口(4)。
根据本发明,聚氨酯反应混合物的至少两个单独料流在注入和/或发泡过程期间会聚。“在注入和/或发泡过程期间”意指在注入期间,泡沫反应混合物流入外壳并填充由外壳和任选地存在的障碍物形成的腔体。在发泡反应开始的同时或不久之后,泡沫反应混合物膨胀,这也有助于填充腔体,并且随着时间推移,这两个过程叠加。两个料流的会聚可发生在腔体填充的各个阶段。
聚氨酯泡沫反应混合物的至少两个会聚料流可由聚氨酯泡沫反应混合物料流通过位于外壳内的障碍物在聚氨酯泡沫反应混合物料流的流动方向内产生,其中所述障碍物将料流分成至少两个单独料流。根据本发明,术语“障碍物”是指存在于外壳内并改变泡沫反应混合物的注入料流的流动的任何物品。所述物品可旨在置于绝热泡沫中,例如冰箱壁中的管道、换热器、冷凝器、真空绝热板等。障碍物还可为穿过外壳的连续开口,例如在拖车式活动房屋的侧部包括窗户的情况下,拖车式活动房屋侧部的内壁和外壁形成外壳,并且由窗户形成的孔是连续开口形式的障碍物。外壳可包含一个、两个或更多个障碍物。
外壳还可包括至少一个用于聚氨酯泡沫反应混合物的第二入口,并且所述聚氨酯泡沫反应混合物的至少两个会聚料流中的至少一个源自注入到第一入口的聚氨酯泡沫反应混合物,并且所述聚氨酯泡沫反应混合物的所述至少两个会聚料流中的至少一个源自注入到第二入口的聚氨酯泡沫反应混合物。
上述至少两个单独料流的两个可能来源的组合也是可能的。
图1a)、b)和c)示意性地示出了已经填充有绝热聚氨酯泡沫的外壳的示例。在图1a)至c)中,外壳(1)示出了填充有绝热聚氨酯泡沫(2)并具有一个或两个用于注入聚氨酯泡沫反应混合物的入口(3,3’)、一个或两个空气出口(4,4’)、一个泡沫分隔件(5),并且在图1a)和c)的情况下,障碍物(6)可为置于外壳内的插入物或垂直于纸面延伸穿过外壳的连续开口。
图1a)和c)示出了一个注入料流的示例,所述一个注入料流被存在于外壳中的障碍物(6)分成两个单独料流。两个料流在通过障碍物(6)后会聚。根据本发明,泡沫分隔件(5)沿两个料流的会聚区域放置,并且从至少两个会聚料流的流动方向看,一个或两个空气出口(4,4’)设置在泡沫分隔件(5)后端处的外壳(1)中。
在图1b)中示出了外壳具有两个用于注入泡沫反应混合物的入口(3,3'),其位于外壳(1)的相对两侧,两个空气出口(4,4’),其位于外壳(2)的相对两侧,和泡沫分隔件(5),其沿着通过两个入口(3,3’)注入的两个料流的会聚区域设置。从至少两个会聚料流的流动方向看,两个空气出口(4,4')设置在泡沫分隔件(5)后端处,因为在这种情况下,每个注入的料流都由泡沫分隔件(5)引导向两个方向。
根据一个实施方案,空气出口设置在泡沫分隔件的后端处并且具有狭缝状形式,该狭缝状形式平行于外壳中的泡沫分隔件延伸。所述狭缝状空气出口的宽度通常为0.5至5mm,优选1至3mm,长度通常根据泡沫分隔件的尺寸选择,例如泡沫分隔件面向外壳的长度或+/-10%。还可沿着外壳中泡沫分隔件设置两个或更多个空气出口,以允许将空气均匀地排出外壳,例如可在外壳中沿着泡沫分隔件放置一连串的两个或更多个圆形或方形孔,或在外壳中泡沫分隔件的每一侧上设置狭缝状空气出口,该空气出口平行于泡沫分隔件延伸,其中所述泡沫分隔件直接连接到外壳上,参见例如图1c)中空气出口(4)和(4')。
在注入泡沫反应混合物和产生泡沫的过程中,空气出口可完全打开。空气出口也可通过盖或封闭件封闭,其可透气但不透过泡沫反应混合物。这种盖或封闭件可为例如允许空气移动到外部、但不允许泡沫反应混合物移动到外部的开孔泡沫,或粘性的泡沫反应混合物不能通过的致密织造网络。至少一个空气出口可在泡沫形成过程之后通过致密的盖或密封件封闭,以避免外部化合物从外部进入外壳,或避免外壳内部和外部之间的化合物交换。
如上所述的方法特别适于制备绝热制品,其中绝热制品为冷却应用的壳体;蓄热系统的壳体;管道;建筑板;拖车式活动房屋侧壁,工业大厅屋顶用面板;热水器、燃烧器或烟囱的壳体;仪表板的盖板;或发动机外壳。
本发明还涉及可通过本发明的方法制备的绝热制品。
本发明还涉及一种绝热制品,其包含:
(i)原位发泡的绝热聚氨酯泡沫,和
(ii)包围原位发泡的绝热泡沫的外壳,所述外壳包括
(iia)至少一个用于注入聚氨酯泡沫反应混合物的入口,所述聚氨酯泡沫反应混合物用于绝热泡沫原位发泡,
(iib)至少一个空气出口,用于在绝热泡沫原位发泡期间的空气置换,和
(iic)至少一个泡沫分隔件;
其中在绝热泡沫的原位发泡期间,所述泡沫分隔件在原位发泡的聚氨酯绝热泡沫内沿着所述聚氨酯泡沫反应混合物的至少两个料流的会聚区域设置。
本发明还涉及包括如上所述的绝热制品的冷却系统(如冰箱)、蓄热系统、建筑用绝热板、绝热管道或移动运输系统、热水器、燃烧器、烟囱、仪表板、工业大厅屋顶、发动机或拖车式活动房屋。
上文列出的所有实施方案和优选的实施方案优选地可彼此自由组合,除非上下文明确反对。
表述“包括”和“包含”优选还涵盖表述“由……组成(“consisting”,“consistingof”or“consists of”)”。
本发明通过以下实施例更详细地说明而不限制本发明。
实施例
通过3D CFD模拟(计算流体动力学)对两种不同的外壳进行填充过程随时间的模拟。OpenFoam(www.openfoam.com)Volume of Fluid(VOF)求解器已扩展到发泡体系。需要随时间变化的密度和粘度的单独函数。开始时,反应流体体系以特定的质量流量注入。在发泡反应期间,外壳中存在的空气被置换,并且发泡体系在出口方向上延伸。
借助模拟数据示出了在填充有泡沫反应混合物的外壳中存在泡沫分隔件的效果。根据待填充的腔体的几何形状确定待发泡的体积。预定义模拟结束时的目标密度。该预定义值确定待注入流体的所需量,并结合3至8秒的典型注入时间来计算入口处的质量流速。
外壳填充的模拟结果如图2和图3的3D方案所示。在图2a)和3a)中,示出了外壳具有一个用于注入的侧向入口(3)和障碍物(6),该障碍物(6)将通过侧向入口(3)注入的泡沫反应混合物料流分成两个料流。两个外壳都显示具有泡沫分隔件(5)。图2a)和3a)的外壳的空气出口的布置不同。在图2a)中,在泡沫分隔件(5)的后端设置有狭缝状的空气出口(4),其沿垂直于泡沫分隔件的整个壁在外壳上端延伸。在图3a)中,外壳和泡沫分隔件(5)的上端设置两个小的空气出口(4,4'),一个在靠近障碍物的右端,一个在分隔件和上壁的交叉点处的左端。在图2b)和c)中示出了图2a)的外壳不使用和使用泡沫分隔件的填充结果,并且在图3b)和c)中示出了图3a)的外壳不使用和使用泡沫分隔件的填充结果。泡沫内的深灰色区域表示密度分布不均匀的区域,表明由障碍物产生的两个料流的不均匀流动和较差混合。在图2b)中可见倾斜的熔接线,而在图2c)中,泡沫分隔件使得在会聚区域形成直线并且均匀填充外壳。在图3b)和c)中示出了外壳右上角的放大图,表明泡沫分隔件使得更好地填充外壳后端的边缘,并抑制倾斜的熔接线。
Claims (18)
1.一种制备绝热制品的方法,所述绝热制品包含
(i)可通过使泡沫反应混合物发泡原位制备的绝热聚氨酯泡沫,和
(ii)包围所述绝热聚氨酯泡沫的外壳,所述外壳包括
(iia)至少一个用于注入聚氨酯泡沫反应混合物的入口,
(iib)至少一个空气出口,用于在所述聚氨酯泡沫反应混合物的发泡反应期间的空气置换,和
(iic)至少一个泡沫分隔件,
通过将所述聚氨酯泡沫反应混合物注入外壳的至少一个入口并使所述聚氨酯泡沫反应混合物发泡而进行制备,其中在注入和/或发泡反应期间,所述聚氨酯泡沫反应混合物的至少两个单独料流在外壳内会聚,并且其中所述泡沫分隔件沿所述至少两个料流的会聚区域设置。
2.根据权利要求1所述的方法,其中所述聚氨酯泡沫反应混合物的所述至少两个会聚料流由所述聚氨酯泡沫反应混合物料流通过位于外壳内在所述聚氨酯泡沫反应混合物料流的流动方向内的障碍物产生,所述障碍物将料流分成至少两个单独料流。
3.根据权利要求1所述的方法,其中所述外壳包括至少一个用于所述聚氨酯泡沫反应混合物的第二入口,并且其中所述聚氨酯泡沫反应混合物的至少两个会聚料流中的至少一个源自注入到第一入口的聚氨酯泡沫反应混合物,并且所述聚氨酯泡沫反应混合物的所述至少两个会聚料流中的至少一个源自注入到第二入口的聚氨酯泡沫反应混合物。
4.根据权利要求1至3中任一项所述的方法,其中所述外壳包括连续开口。
5.根据权利要求1至4中任一项所述的方法,其中所述泡沫分隔件为层状的。
6.根据权利要求1至5中任一项所述的方法,其中至少一个空气出口设置在所述泡沫分隔件上端处的外壳中。
7.根据权利要求1至6中任一项所述的方法,其中从所述聚氨酯泡沫反应混合物的至少两个会聚料流的流动方向看,至少一个空气出口位于所述泡沫分隔件后端处。
8.根据权利要求7所述的方法,其中所述至少一个空气出口为沿所述泡沫分隔件后端处布置的狭缝状开口。
9.根据权利要求1至8中任一项所述的方法,其中所述至少一个空气出口用透气材料封闭。
10.根据权利要求1至9中任一项所述的方法,其中所述泡沫分隔件由金属如铝和钢,木头,泡沫,塑料如聚酰胺、聚酯、聚苯乙烯、苯乙烯-丙烯腈共聚物和增强塑料制成。
11.根据权利要求1至10中任一项所述的方法,其中所述泡沫分隔件涂覆有粘附促进剂。
12.根据权利要求1至11中任一项所述的方法,其中所述绝热聚氨酯泡沫为硬质聚氨酯泡沫。
13.根据权利要求1至12中任一项所述的方法,其中所述绝热聚氨酯泡沫为闭孔泡沫。
14.根据权利要求1至13中任一项所述的方法,其中所述绝热聚氨酯泡沫的密度为20至300kg/m3。
15.根据权利要求1至14中任一项所述的方法,其中所述绝热制品为冷却应用的壳体;蓄热系统的壳体;管道;建筑板;拖车式活动房屋侧壁,工业大厅屋顶用面板;热水器、燃烧器或烟囱的壳体;仪表板的盖板;或发动机外壳。
16.可根据权利要求1至15中任一项制备的绝热制品。
17.一种绝热制品,其包含:
(i)原位发泡的绝热聚氨酯泡沫,和
(ii)包围原位发泡的绝热泡沫的外壳,所述外壳包括
(iia)至少一个用于注入聚氨酯泡沫反应混合物的入口,所述聚氨酯泡沫反应混合物用于绝热泡沫原位发泡,
(iib)至少一个空气出口,用于在绝热泡沫原位发泡期间的空气置换,和
(iic)至少一个泡沫分隔件;
其中在所述绝热泡沫的原位发泡期间,所述泡沫分隔件在原位发泡的聚氨酯绝热泡沫内沿着所述聚氨酯泡沫反应混合物的至少两个料流的会聚区域设置。
18.包含根据权利要求16或17所述的绝热制品的冷却系统如冰箱、蓄热系统、建筑用绝热板、绝热管道、移动运输系统、热水器、燃烧器、烟囱、仪表板、工业大厅屋顶、发动机或拖车式活动房屋。
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