CN100383224C - 复合材料组合物 - Google Patents
复合材料组合物 Download PDFInfo
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- CN100383224C CN100383224C CNB028116313A CN02811631A CN100383224C CN 100383224 C CN100383224 C CN 100383224C CN B028116313 A CNB028116313 A CN B028116313A CN 02811631 A CN02811631 A CN 02811631A CN 100383224 C CN100383224 C CN 100383224C
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- 239000000203 mixture Substances 0.000 title claims description 46
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- 239000000314 lubricant Substances 0.000 claims abstract description 40
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
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- 125000000217 alkyl group Chemical group 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
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- 239000001257 hydrogen Substances 0.000 claims description 4
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- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 3
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
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- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
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- 244000025254 Cannabis sativa Species 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XIVNZHXRIPJOIZ-UHFFFAOYSA-N octadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCC(O)=O XIVNZHXRIPJOIZ-UHFFFAOYSA-N 0.000 description 1
- WVJVHUWVQNLPCR-UHFFFAOYSA-N octadecanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCC WVJVHUWVQNLPCR-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
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- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- C10M105/34—Esters of monocarboxylic acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Lubricants (AREA)
Abstract
本发明公开了很适合于形成成型制品的复合材料组合物,所述组合物包括热塑性聚合物、纤维素、包括酸酐部分的偶联剂和包括羧酸烷基酯的润滑剂。优选所述润滑剂基本不含硬脂酸锌。
Description
相关申请的交叉参考
本申请涉及并要求2001年4月16日提交的美国临时专利申请60/284131号的优先权,该申请通过引用并入本文中。
发明领域
本发明涉及包括热塑性聚合物和纤维素纤维的复合材料组合物,涉及用于这种复合材料组合物的润滑剂/偶联剂,以及涉及由这种组合物形成的构件和构架。当将本发明的复合材料制成构件时,其非常适合用作木材替代物。
发明背景
包含有机树脂和填料的复合材料为人们所熟悉并已使用多年。例如,一直需要开发出具有天然木材外观和质感的材料。这种需求的一个原因是为了保护有限的、来自于森林的供建筑用天然木材的资源。另一原因是某些复合材料在某些方面具有优于天然木材的性能。例如,可以将复合材料配制成具有增强耐湿性的合成木材。
在建筑中全面使用木制产品除了其带来的总费用和困难外,在通常的板材二次加工中许多木材成为废料。当木材生产商将所阀树木制成各种各样用于加工成构架的长板或厚板时,产生大量的锯屑和细碎材料,诸如枝条等。因此人们一直试图利用木纤维或木屑与各种粘合材料制造原木的替代产品。这种产品已经商品化并且通常被称为“纤维板”或“碎料板”。此外,木屑或木纤维与塑料粘合剂一起使用产生了所谓的塑用木。结果,纤维素和相关材料成为常用复合材料,具体地讲,用作木材替代品的复合材料的高度所需原料。
伴随着这种复合材料生产和实现的一个问题是强力粘合纤维素纤维和热塑性粘合剂的能力。已经认识到几乎对所有已知的这种材料而言,填料和树脂混合物间的粘合稳定性是这些材料品质下降和产生断裂的一个原因。美国专利5,981,067号报导了一种解决这种问题的方法,该方法包括增强聚合物-纤维的相容性,即增强聚合物和纤维相互混和/粘合的倾向。美国专利5,120,776号(通过引用并入本文)提出用马来酸酐或邻苯二甲酸酐预处理纤维素纤维来改善纤维在聚合物基质中的粘合性和分散性。相关资料还有Maldas和Kokta在Journal Adhesion Science Technology,1991,1-14页的文章“使用马来酸酐和异氰酸酯作为涂料组分对木纤维的表面改性,以及表面改性木纤维在聚苯乙烯复合材料中的性能(Surface modification of woodfibers using maleic anhydride and isocyanate as coating components andtheir performance in polystyrene composites)”。
虽然已经有人提出将马来酸酐基的偶联剂用于制造复合材料,但是这种材料在商业中应用并未获得中决定性成功。
复合材料的商业应用通常涉及通过模塑、挤塑等对这种组合物进行成型。为了在商业竞争环境中有效实施这种操作,需要这种加工处理以较高的速率进行,同时产生最少的操作问题。为达到这个目标,在实践中需要往复合材料中使用添加剂,以助于加工处理。一种常用的操作助剂是润滑剂或脱模剂,它们可使这种复合材料的有效加工以商业可接受的速度进行。金属硬脂酸盐,特别是硬脂酸锌常在用于热塑性聚合物和纤维素纤维的复合材料的润滑复合剂(package)中使用。参见例如美国专利6,180,257 B1号(2栏,II,26-28)。
发明概述
本发明的几个方面包括新的润滑剂组合物,新的复合材料组合物,新的构件和新的制造方法。这些方面均来源于,或至少部分来源于本发明人的以下认识:某些润滑剂,特别是金属羧酸盐润滑剂如金属硬脂酸盐可负面影响某些所需偶联剂的性能。这些方面还来源于本发明人的以下发现:某些润滑剂与这种偶联剂以协同方式操作产生了令人惊异的优异性能。
本申请人发现复合材料组合物很适合于形成成型制品,这种组合物包括聚合物(优选热塑性聚合物)、纤维素、包括羧酸官能基(例如酸酐部分)的偶联剂和包括亲电子官能基(如羧酸烷基酯或其官能衍生物)的润滑剂。按照高度优选的实施方案,所述润滑剂不含具有反协同作用量的金属羧酸盐,如金属硬脂酸盐。甚至更优选基本不含金属羧酸盐,如金属硬脂酸盐。此中所用的术语“反协同作用量”是指与不含这种金属羧酸盐的相同复合材料相比,金属羧酸盐对复合材料的性质的负面影响已不可忽视的量。
本发明还提供包括一种烷基酯和一种酰胺酯的润滑剂组合物。
本发明的方法包括将本发明的复合材料制成成型制品,优选通过挤塑成型制成成型制品。
附图概述
图1是本发明一个实施方案的构件的横截面、部分示意图。
图2是本发明另一个实施方案的构件的横截面、部分示意图。
图3是本发明再一个实施方案的构件的横截面、部分示意图。
优选实施方案的描述
本发明涉及复合材料组合物,该组合物可以高速制备成成型制品,特别是具有所需强度性能的构件。通常优选所述组合物包括约10-50重量份的热塑性聚合物、约50-90重量份纤维素纤维、有效量的偶联剂和有效量的本发明的润滑剂。此中所用的术语“有效量”是指能对组合物的相关性能产生明显,并优选显著改善的量。因此,就偶联剂来说,有效量的偶联剂使得热塑性聚合物和纤维素纤维间的相容性和/或粘合性得到明显改善,其通常(但并不只是)表现为成型制品拉伸强度的改善。就润滑剂来说,有效量使得组合物加工性能得到明显改善,其通常(但并不只是)表现为组合物可有效成型,并优选挤塑成成型制品的速度和/或效率的改善。
按照某些优选的实施方案,所述复合材料组合物优选包括约20-40重量份,更优选约25-35重量份的热塑性聚合物,约50-80重量份并更优选约50-65重量份的纤维素纤维,约1-5重量份的偶联剂和约1-5重量份的润滑剂。
本发明优选实施方案的组合物产生了比现有技术组合物的性能超乎意料改善的成型制品。更具体地说,包括马来酸酐基偶联剂和本发明的润滑剂的优选复合材料组合物生产的成型制品的拉伸强度比含大量常用的现有技术润滑剂硬脂酸锌的相同组合物的高至少约25%,并且更优选高至少约50%。优选本发明的复合材料组合物具有至少约2000psi、更优选至少约2500psi,甚至更优选3000psi的拉伸强度。
本发明,特别是本发明润滑剂组合物的另一项显著并令人惊异的优点是费用方面的优点,其源于本发明的润滑剂操作性能的改善。更具体地说,本发明的润滑剂能更有效地增强复合材料组合物的成型性能,特别是挤塑性能。这种改善可通过下面的事实说明:本发明的组合物与使用现有技术硬脂酸锌润滑剂的组合物相比,在润滑剂用量不多于约90%,甚至更优选不多于约75%的情况下可达到基本相同的加工速度。
热塑性聚合物
任何基本上具有热塑性的聚合物均可考虑用于本发明。例如,可考虑用于本发明组合物的热塑性聚合物包括聚酰胺、聚卤乙烯、聚酯、聚烯烃、对聚苯硫醚、聚甲醛、苯乙烯聚合物和聚碳酸酯。特别优选的是聚烯烃聚合物。
对基本上为热塑性的聚合物材料的主要要求是其能保持足够的热塑性,而可与纤维素纤维熔融共混,并可在挤塑和模塑的热塑性加工中有效形成成型制品。因此考虑在本发明的组合物中可包括少量的热固性树脂,而不会牺牲这些基本性能。新制备的聚合物和循环(废弃)聚合物均可使用。
此中所用的术语“聚烯烃”是指不饱和脂族烃的均聚物、共聚物和改性聚合物。在优选的聚烯烃中,最优选聚乙烯和聚丙烯。特别优选的是高密度聚乙烯(HDPE)。考虑到经济和环境方面的因素,优选使用来自瓶和膜的HDPE粉碎物料。
纤维素纤维
本发明的组合物包括含纤维素的填料。所述填料组分可包括增强性(高长径比)填料、非增强性(低长径比)填料和两者的组合。长径比定义为填料颗粒长度对有效直径的比率。高长径比提供了在相同水平填料含量下具有较高的强度和模量的优点。无机填料,如玻璃纤维、碳纤维、滑石、云母、高岭土、碳酸钙等可作为纤维素的任选辅料而包括在其中。此外,也可使用包括聚合物纤维在内的其它有机填料。
本发明的纤维素填料特别重要并且特别优选,这是因为其低的费用以及如轻的重量、在高强度热动力混和器中处理后保持高长径比的能力以及低的摩擦性能(因此可延长仪器寿命)等其它方面的原因。所述纤维素可来自任何来源,包括林木和农业副产品。所述纤维素纤维可包括硬木纤维、软木纤维、大麻纤维、黄麻纤维、谷壳、麦秸和它们中两种或多种的组合。在某些实施方案中,所述纤维素优选包括大比例的高长径比纤维,诸如硬木纤维。但是,这种高长径比纤维通常更难以处理,因此在加工速度和效率作为特别重要考虑因素的实施方案中不那么优选。
偶联剂
此中所用的术语“偶联剂”是指可促使纤维素颗粒与热塑性聚合物分散和/或相容的化合物或组合物。一般来说,发现具亲电子官能基、特别是羧酸官能基的化合物(包括有机聚合物)将可有效地满足该目的,并且所有这种化合物均可考虑用于本发明中。优选的有机化合物包括具马来酸酐官能团的聚合物。
按照本发明的教导,多种具有马来酸酐官能团的化合物均可考虑用于本发明,并且所有这些化合物和它们的组合物均在本发明的范围内。在某些实施方案中,优选采用官能化聚合物,特别是马来酸酯化聚烯烃聚合物。
本领域技术人员从本申请的公开可理解用于本发明的官能化聚合物的具体性能和特征为了满足各种应用的具体需要而可作各种改变。但是,一般来说,本申请人发现通常需要选择具有与复合材料的热塑性聚合物的至少一部分大致相符的骨架的官能化聚合物。例如,在本发明的所述热塑性聚合物为聚乙烯的实施方案中,可优选利用官能化聚乙烯作为偶联剂。同样,对于所述热塑性聚合物包括聚丙烯的实施方案来说,可优选利用官能化聚丙烯作为偶联剂。但是本申请人已意外地发现了一种高度有效用于两种不同聚烯烃聚合物、优选C2-C4聚烯烃、并更优选聚乙烯和聚丙烯的偶联剂。对于本发明的需要具有偶联剂(能以高效率用于宽范围的各种复合材料组合物)的实施方案来说,本申请人已发现应优选利用马来酸酯化聚丙烯聚合物,特别是具有约10,000到15,000的分子量和平均每个聚合物链具有约1.5到2.5个马来酸酐官能团的聚丙烯。特别是对于热塑性聚合物包括聚烯烃的实施方案来说,优选偶联剂包括官能化聚烯烃,并优选具约10,000到25,000(更优选约10,000到20,000)的分子量和平均每个聚合物链约0.6到3个(更优选约0.8到2.5个)马来酸酐官能团的官能化聚乙烯、官能化聚丙烯和/或它们的组合。这种官能化聚烯烃可例如以A-C 1221、597、596和575的商品名购自HoneywellInternational。此外,官能化聚乙烯和聚丙烯公开于美国专利3,882,1945号、4,404,312号和5,001,197号中,这些专利均通过引用并入本文。
在某些实施方案中可考虑优选单独使用硅烷偶联剂,或硅烷偶联剂与其它优选的偶联剂的组合。但是,除了此中所述的优选的偶联剂外,也可使用为本领域技术人员所知的或将为本领域技术人员所知的,并未在这里具体指出的其它有效的偶联化合物,或者在某些情况下将它们作为此中所述的优选偶联剂的替代品使用。
润滑剂
本发明的组合物包括有效量的润滑剂或润滑复合剂。在一种实施方案中,所述润滑剂包括烷基酯。特别优选的是通过多元醇(即多羟基化合物)与一种或多种一元或多元羧酸或羧酸官能团反应形成的多元醇酯。
所述多元醇是由通式R(OH)n表示的多元醇,式中R为任何脂族或环脂族烃基(优选烷基),并且n至少为2。所述烃基可包含约2到20或更多的碳原子,并且所述烃基也可包含诸如氯、氮和/或氧原子取代基。所述多羟基化合物通常可包含一个或多个氧化烯基,因此所述多羟基化合物包括诸如聚醚多元醇等化合物。用于形成羧酸酯的多元醇化合物中包含的碳原子数(即碳数,其中在本申请书中所用的术语碳数是指各在酸或醇中的碳原子总数)和羟基数目(即羟基值)可有大的差别。
下面的醇是特别有用的多元醇:新戊二醇、三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、单季戊四醇、工业级季戊四醇和二季戊四醇。最优选的醇是工业级季戊四醇(如约88%单季戊四醇、10%二季戊四醇和1-2%三季戊四醇)、单季戊四醇和二季戊四醇。
优选的羧酸包括C2-C20一元酸和二元酸,优选包括己二酸和硬脂酸。
羧酸的官能化衍生物也可用于形成润滑剂。例如当形成酯时,多元酸的酸酐可代替多元酸使用。这些酸酐包括例如琥珀酸酐、戊二酸酐、己二酸酐、马来酸酐、邻苯二甲酸酐、偏苯三酸酐、桥亚甲基四氢化邻苯二甲酸酐、甲基桥亚甲基四氢化邻苯二甲酸酐、六氢邻苯二甲酸酐、硬脂酸酐和多元酸的混和酸酐。特别优选的本发明的润滑化合物是美国专利4,487,874号和6,069,195号(均通过引用并入本文)中所述的复合酯(complex esters)。
优选的本发明的烷基酯包括下面式1的烷基酯的混合物
式中:
R独立为氢或-C(O)R’,并且至少一个R为-C(O)R’;
R’为氢、具有约3到18个碳原子的不饱和或饱和烷基链,或-C(O)-X-COOH;和
X为不饱和或饱和的烷基链,可以为一价或多价,具有约3到18个碳原子。
所述烷基酯优选包括季戊四醇己二酸酯-硬脂酸酯,它是一种式1烷基酯的混合物,其中有机部分的约14%为衍生自己二酸的-C(O)-X-COOH部分,有机部分的约71%为衍生自硬脂酸和其缔合酸(主要是棕榈酸)的-C(O)R’部分。这种材料由Honeywell International Inc.以RL 710的商品名出售。
如美国专利3,578,621(通过引用并入本文)中公开的那样,本发明的润滑复合剂还优选包括酰胺蜡,并且更优选硬脂酰胺蜡。特别优选的是亚乙基双硬脂酰胺(“EBS”)。
虽然在润滑复合剂中烷基酯和酰胺蜡可以考虑以宽范围的相对浓度使用,但是优选烷基酯与酰胺蜡的重量比为约30∶1到1∶1,更优选20∶1到约2∶1。
按照优选的实施方案,所述润滑复合剂包含不超过约25%重量的金属羧酸盐,更优选包含不超过10%重量的金属羧酸盐,最优选基本不含金属羧酸盐。按照更为优选的实施方案,所述润滑复合剂包含不超过约25%重量的硬脂酸锌,更优选包含不超过10%重量的硬脂酸锌,最优选基本不含硬脂酸锌。
就所述复合材料组合物来说,通常优选所述复合材料包含不超过0.5%重量的金属羧酸盐,更优选包含不超过0.25%重量的金属羧酸盐。特别优选所述复合材料包含不超过0.5%重量的硬脂酸锌,更优选包含不超过0.25%重量的硬脂酸锌。
按照某些实施方案,所述润滑剂包括氢化蓖麻油。
添加剂复合剂(additive packages)
本发明的一方面包括可用于形成具有优异加工性能和最终使用性能的复合材料组合物的添加剂组合物。更具体地说,所述添加剂复合剂包括润滑剂和/或偶联剂的独特组合,其能有效改善复合材料的加工特性而不会降低(有时甚至是增强)制成品的强度特征。
在某些优选的实施方案中,所述添加剂是一种含有少于反协同作用量的金属羧酸盐的润滑剂。特别优选的本发明的润滑剂基本不含金属羧酸盐,其大部分(重量份)为烷基酯和/或氢化蓖麻油,小部分(重量份)为酰胺蜡。在某些实施方案中,润滑复合剂还包括少量(重量份)的聚烯烃,优选聚乙烯或聚丙烯,更优选基本为线性的聚乙烯或聚丙烯。在某些优选的实施方案中,润滑组合物包括约80-97重量份的选自烷基酯、氢化蓖麻油和其两者或多者的组合的化合物,约1-10重量份的酰胺蜡和约1-10重量份的聚烯烃。
虽然本发明的润滑复合剂在某些实施方案中可考虑有益地单独使用,但是通常优选提供包括本发明的润滑剂/润滑复合剂连同本发明的偶联剂/偶联复合剂的添加剂复合剂。此外,虽然可考虑将这些复合剂按照本发明以宽范围的相对比例组合,但是通常优选提供具有约1∶1到4∶1润滑剂∶偶联剂重量比率的添加剂复合剂,在某些实施方案中更优选提供约3∶2润滑剂∶偶联剂重量比率的添加剂复合剂。
构件
正如上面所述,本发明的组合物可用于形成各种构件,所有这种构件均落入本发明的广阔范围内。但是本申请人发现可使用本发明方法和组合物形成本特别难以形成和/或因为高加工费用而从经济观点来看实际不可行的构件,特别是挤塑构件。更具体可参见图1-3,由图可见本发明包括同时具备坚固和轻质特点的构件。本领域技术人员知道这种轻质构件实际上不能通过现有的复合材料组合物挤塑生产,因为该构件具有大的横截面积。更具体地说,本发明的复合材料组合物具有高强度和高润滑性的独特结合,可以让这种高表面积构件在较高速度、经济的条件下进行挤塑。本申请人相信按照现有技术不能以商业上高效和经济合理的方式生产出所述构件。
方法
本发明包括形成成型制品的方法,该方法包括下面步骤:提供如本文所述的本发明的复合材料组合物,并将所述组合物制成所需形状的制品。所述组合物可按照任何本领域技术人员熟知的将各组分混和成均匀的复合材料组合物的技术将各组分混合来提供,所述技术公开于例如美国专利3,943,079;4,338,228;5,886,066和5,997,784中(均通过引用并入本文)。
正如在前述专利中公开的,成型步骤也可包括任何本领域技术人员熟知的将均匀的复合材料制成成型制品的技术,包括注塑和挤塑。优选通过挤塑成型。
对比实施例
本对比实施例并不一定代表现有技术,事实上可能比最接近的现有技术更接近本发明。无论如何,该对比实施例用作说明本发明优异性能的基础。
通过挤塑配混62重量份(pbw)的木纤维、33重量份的HDPE、2重量份的马来酸酯化聚乙烯偶联剂和3重量份基本上由1∶2重量比的EBS和硬脂酸锌组成的润滑剂来制备复合材料组合物。
通过已知方法,在已知条件下将所述复合材料组合物制成成型制品。得到的制品具有约2000psi的拉伸强度。
实施例1
通过挤塑配混62.8重量份的木纤维、33重量份的HDPE、2重量份的马来酸酯化聚乙烯偶联剂和2.2重量份基本上由1∶1∶20重量比的EBS、硬脂酸锌和季戊四醇己二酸酯-硬脂酸酯组成的润滑剂制备复合材料组合物。
通过使用与对比实施例相同的方法、并在相同的条件下将复合材料组合物制成成型制品。得到的制品具有约2900psi的拉伸强度,比对比实施例提高了45%。
实施例2
通过挤塑配混62.75重量份的木纤维、33重量份的HDPE、2重量份的马来酸酯化聚乙烯偶联剂和2.25重量份基本上由2.5∶20重量比的EBS和季戊四醇己二酸酯-硬脂酸酯组成的润滑剂制备复合材料组合物。
通过使用与对比实施例相同的方法,并在相同的条件下将复合材料组合物制成成型制品。得到的制品具有约3500psi的拉伸强度,比对比实施例提高了75%。
实施例3
通过挤塑配混62.5重量份的木纤维、33重量份的HDPE、2重量份的马来酸酯化聚乙烯偶联剂和2.5重量份基本上由季戊四醇己二酸酯-硬脂酸酯组成的润滑剂制备复合材料组合物。
通过使用与对比实施例相同的方法,并在相同的条件下将复合材料组合物制成成型制品。得到的制品具有约3200psi的拉伸强度,比对比实施例提高了60%。
对比实施例2
本对比实施例并不一定代表现有技术,事实上可能比最接近的现有技术更接近本发明。无论如何,该对比实施例用于作为说明本发明优异性能的基础。
通过挤塑配混60.5重量份的木纤维、33重量份的HDPE、2重量份的马来酸酯化聚乙烯偶联剂和4.5重量份基本上由1∶2重量比的EBS和硬脂酸锌组成的润滑剂制备复合材料组合物。
通过已知挤塑方法,在已知条件下将所述复合材料组合物制成成型制品。
实施例4
通过挤塑配混62重量份的木纤维、33重量份的HDPE、2重量份的马来酸酯化聚乙烯偶联剂和3重量份基本上由2.5∶20重量比的EBS和季戊四醇己二酸酯-硬脂酸酯组成的润滑剂制备复合材料组合物。
通过使用与对比实施例2相同的方法,并在相同的条件下将复合材料组合物制成成型制品。尽管使用重量和费用均比对比实施例2低约50%的润滑剂,其成型加工的效率至少与对比实施例2相同,生产率至少大致与对比实施例2相同。
Claims (9)
1.一种用于制备成型制品的组合物,所述组合物包括:
纤维素纤维;
热塑性粘合剂;
包含马来酸酐或马来酸酐官能团的偶联剂;和
润滑复合剂,其包含羧酸烷基酯和含少于反协同作用量的金属羧酸盐。
2.权利要求1的组合物,其中所述润滑复合剂还包括羧酰胺蜡。
3.权利要求2的组合物,其中所述润滑复合剂基本不合硬脂酸锌。
4.权利要求2的组合物,其中所述润滑复合剂基本不含金属硬脂酸盐。
5.权利要求2的组合物,其中所述润滑复合剂基本不含金属羧酸盐。
6.权利要求1的组合物,其中所述润滑复合剂包括30∶1到1∶1重量比的烷基酯和酰胺蜡。
7.权利要求6的组合物,其中所述烷基酯和酰胺蜡的存在重量比为20∶1到2∶1。
8.权利要求6的组合物,其中所述烷基酯包括下面式1的烷基酯的混合物:
式(1)
式中:
R独立为氢或-C(O)R’,并且其中至少一个R为-C(O)R’;
R’为氢、具有3到18个碳原子的不饱和或饱和烷基链,或-C(O)-X-COOH;和
X为具有3到18个碳原子的不饱和或饱和的烷基链。
9.一种制备制品的方法,所述方法包括:
提供形成成型制品的组合物,该组合物包括纤维素纤维、热塑性粘合剂、含马来酸酐或马来酸酐官能团的偶联剂、和包含羧酸烷基酯的润滑剂复合剂;
确保所述润滑复合剂包含少于反协同作用量的金属羧酸盐;和
将所述组合物制成成型制品。
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2002
- 2002-04-16 US US10/123,757 patent/US20030100634A1/en not_active Abandoned
- 2002-04-16 KR KR1020037013553A patent/KR100826000B1/ko not_active IP Right Cessation
- 2002-04-16 CN CN2007101391623A patent/CN101100530B/zh not_active Expired - Fee Related
- 2002-04-16 EP EP02762106A patent/EP1409619B1/en not_active Expired - Lifetime
- 2002-04-16 ES ES02762106T patent/ES2393185T3/es not_active Expired - Lifetime
- 2002-04-16 CA CA002444252A patent/CA2444252A1/en not_active Abandoned
- 2002-04-16 CN CNB028116313A patent/CN100383224C/zh not_active Expired - Fee Related
- 2002-04-16 WO PCT/US2002/011787 patent/WO2002083824A1/en active Application Filing
- 2002-04-16 JP JP2002582163A patent/JP2004532315A/ja active Pending
-
2004
- 2004-09-14 US US10/941,766 patent/US7816431B2/en not_active Expired - Fee Related
-
2008
- 2008-11-14 JP JP2008292521A patent/JP5078849B2/ja not_active Expired - Fee Related
-
2012
- 2012-03-01 JP JP2012045367A patent/JP2012144731A/ja active Pending
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US5866641A (en) * | 1996-06-22 | 1999-02-02 | Wood Composite Technologies Inc | Process for the production of lightweight cellular composites of wood waste and thermoplastic polymers |
US5936018A (en) * | 1996-11-28 | 1999-08-10 | Bayer Aktiengesellschaft | Melt-processable polyurethanes containing special wax mixtures |
US5973035A (en) * | 1997-10-31 | 1999-10-26 | Xyleco, Inc. | Cellulosic fiber composites |
Also Published As
Publication number | Publication date |
---|---|
CN101100530A (zh) | 2008-01-09 |
CN101100530B (zh) | 2013-04-17 |
JP2012144731A (ja) | 2012-08-02 |
US20030100634A1 (en) | 2003-05-29 |
KR100826000B1 (ko) | 2008-04-29 |
US20050154095A1 (en) | 2005-07-14 |
EP1409619A4 (en) | 2010-03-03 |
KR20040038910A (ko) | 2004-05-08 |
CA2444252A1 (en) | 2002-10-24 |
JP2004532315A (ja) | 2004-10-21 |
WO2002083824A1 (en) | 2002-10-24 |
EP1409619A1 (en) | 2004-04-21 |
JP2009074096A (ja) | 2009-04-09 |
CN1514872A (zh) | 2004-07-21 |
JP5078849B2 (ja) | 2012-11-21 |
ES2393185T3 (es) | 2012-12-19 |
EP1409619B1 (en) | 2012-09-05 |
US7816431B2 (en) | 2010-10-19 |
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