CN1813027A - 具有增强的表面性能的聚乙烯醇缩丁醛组合物和共混物以及由其制备的制品 - Google Patents
具有增强的表面性能的聚乙烯醇缩丁醛组合物和共混物以及由其制备的制品 Download PDFInfo
- Publication number
- CN1813027A CN1813027A CNA2004800183789A CN200480018378A CN1813027A CN 1813027 A CN1813027 A CN 1813027A CN A2004800183789 A CNA2004800183789 A CN A2004800183789A CN 200480018378 A CN200480018378 A CN 200480018378A CN 1813027 A CN1813027 A CN 1813027A
- Authority
- CN
- China
- Prior art keywords
- weight
- composition
- toughner
- goods
- pvb
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
- C09J155/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
- B32B2329/06—PVB, i.e. polyinylbutyral
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2355/00—Specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of index codes B32B2323/00 - B32B2333/00
- B32B2355/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2369/00—Polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2377/00—Polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2607/00—Walls, panels
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08L23/025—Copolymer of an unspecified olefin with a monomer other than an olefin
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了用聚乙烯醇缩丁醛增韧的聚合物共混的组合物,所述组合物具有增强的粘合表面性能,包括增强的表面粘合性和低表面光泽。本发明还公开了包含本文所述组合物的制品的制备。
Description
本申请要求2003年6月28日提交的美国临时专利申请60/483,336的权益。
发明领域
本发明涉及聚乙烯醇缩丁醛(PVB)与丙烯腈/丁二烯/苯乙烯(ABS)和/或聚碳酸酯(PC)和/或尼龙的共混物。更具体地讲,本发明涉及这种共混物、制备这类材料的方法以及由这类材料制备的模塑制品。
发明背景
ABS通常为有光泽的树脂,可模塑为玩具和小电器的外壳以及其他小配件,有时优选例如用作计算机外壳的垫材料和汽车内部面板。低表面光泽的ABS可通过已知的方法制备。例如具体通过本体聚合或其他附聚技术制备的含有较大(直径大于0.4微米,优选大于1微米)橡胶状基质的ABS可制备合乎要求的低光泽的ABS。
由于塑化PVB的固有粘性,可能难以作为混料挤出机的进料进行加工。类似地,PVB片材由于易于自粘附,是一种难以加工的材料。PVB片材可粘在一起或结合在一起,这种强度使得分开这些层非常困难。PVB的这种不可逆的性质在PVB生产领域称为“粘连”。一旦PVB“粘连”,会产生加工困难。这种粘连倾向会使掺入PVB的生产工艺不必要的复杂和困难。因此,以片材形式或以小碎片形式加工PVB的连续法运行费用非常高,因此是不现实的。
此外,PVB片材或小碎片与其他材料的共混物与均相的PVB组合物一样也会粘连。难于以低成本的方式得到这种PVB与其他聚合物的共混物。优选的用于制备PVB与其他聚合物的共混物的方法使用这类工业中常见的常规的失重螺旋加料器。
本领域最近的研究成果指出PVB与聚乙烯以及接枝橡胶的共混物具有足够的非粘性,可加料至混料挤出机。例如参见WO 02/12356,所述专利涉及由PVB废弃料制备粒料的方法。
本发明的一个目的为提供PVB增强的ABS和/或PC共混组合物,所述组合物具有增强的表面粘合性,使其适用于各种用途。
发明概述
本发明的一个方面为丙烯腈/丁二烯/苯乙烯(ABS)组合物,所述组合物包含:(a)约1-约30%重量的自由流动的增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的(complimentally)99-70%重量的ABS;以及(c)任选的最高达1.0%重量的偶联剂。
本发明的另一方面为一种制品,所述制品得自丙烯腈/丁二烯/苯乙烯(ABS)组合物,所述组合物包含:(a)约1-约30%重量的自由流动的增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量的ABS;以及(c)任选的最高达1.0%重量的偶联剂。
本发明的又一方面为聚碳酸酯(PC)组合物,所述组合物包含:(a)约1-约30%重量的自由流动的增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量的PC;以及(c)任选的最高达1.0%重量的偶联剂。
本发明的再一方面为一种制品,所述制品得自聚碳酸酯(PC)组合物,所述组合物包含:(a)约1-约30%重量的自由流动的增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量的PC;以及(c)任选的最高达1.0%重量的偶联剂。
本发明的又一方面为一种三种聚合物共混物组合物,所述组合物包含:(a)约1-约30%重量的自由流动的增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)第二种聚合物(P2);(c)第三种聚合物(P3);以及(d)任选的最高达1.0%重量的偶联剂,其中所述[(b)+(c)]的合并重量百分比为约70-99%重量。
本发明的再一个方面为一种得自三种聚合物共混物组合物的制品,所述组合物包含:(a)约1-约30%重量的自由流动的增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)第二种聚合物(P2);(c)第三种聚合物(P3);以及(d)任选的最高达1.0%重量的偶联剂,其中所述[(b)+(c)]的合并重量百分比为约70-99%重量。
发明详述
本发明的一个实施方案为具有低光泽表面性质的ABS组合物。本发明的组合物包含如WO 0212356中所述的自由流动的PVB组合物作为增韧剂。WO 0212356的教导通过引用结合在本文中。本发明的组合物包含约1%重量-约30%重量,优选约5%重量-约28%重量,更优选约6%重量-约25%重量,最优选约7%重量-约25%重量的自由流动的PVB组合物。
所述增韧剂包含约20-约95%重量,优选约40%重量-约95%重量,更优选约60%重量-约95%重量,最优选约75%重量-约95%重量的PVB。本发明的组合物和共混物通常通过将所述增韧剂与ABS;PC;和/或三种聚合物共混物组合物以及任选的偶联剂和/或其他组分共混以制备具有增强的表面性能的增韧的ABS组合物、PC组合物和/或增韧的三种聚合物共混物组合物。
除了PVB外,所述增韧剂还包含至少一种组分。这种其他的组分可为单体或聚合材料或其混合物。所述其他的组分可选自具有活性官能团的聚合物和/或单体或非活性的聚合物和/或单体,例如聚乙烯、聚丙烯、聚氯乙烯、尼龙、其他的热塑性材料或其混合物。优选所述第二种组分为包含活性官能团的聚合物组合物,所述活性官能团例如酸酐官能团(例如购自E.I.DuPont de Nemours andCompany,商标为Fusabond的材料)或羧酸官能团。Fusabond聚合物为具有酸酐官能团的聚烯烃。其他的组分在增韧剂中的存在量为增韧剂中PVB量的余量,也就是构成100%重量的组合物所需的量。
本发明的双组分聚合物共混物(即增韧剂与一种其他聚合物的共混物)可包含约70-约99%重量的ABS或PC。三组分聚合物共混物(即增韧剂与两种其他聚合物的共混物)包括增韧剂与PC或ABS与第三种聚合物组分。所述第三种聚合物选自聚酰胺和聚酯。第三种组分也可为ABS或PC,即例如此处所预期的以下共混物:PC/ABS/增韧剂;PC/聚酰胺/增韧剂;PC/聚酯/增韧剂;ABS/聚酰胺/增韧剂;或ABS/聚酯/增韧剂。在三组分共混物中,两种另外的聚合物组分的存在量为增韧剂的余量。两种另外的聚合物组分可各自独立为约10%重量-约90%重量。
在本发明的组合物中可任选包含偶联剂。所述偶联剂增强了本发明的增韧的组合物的表面粘合性能。所述偶联剂可为硅烷化合物。优选的偶联剂选自:γ-氨基丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、N-2-氨基丙基三烷氧基硅烷或N-(2-氨基乙基)-3-氨基丙基甲基二烷氧基硅烷。当存在偶联化合物时,优选包含的偶联化合物至少为约0.01%重量。更优选偶联剂存在的量为约0.1-约3%重量。更优选偶联剂存在的量为约0.3%重量-约2.0%重量,最优选用量为约0.5%重量-约1.5%重量。在所述组合物中偶联剂可作为涂层或作为分散组分存在。所述偶联剂可用于增强本发明的增韧的组合物与第二种聚合物(例如热塑性弹性体(TPE))之间的粘合性。TPE由于其手感柔软而合乎需要,TPE在本文中还可称为柔软感聚合物。
本发明的另一个实施方案为一种制备本发明的增韧的组合物的方法。使用WO 0212356所描述的方法可得到本发明的增韧剂,其中将PVB与第二种聚合物组分混合得到含有相当大量的PVB的非粘连粒料。PVB为市售的产品,用于在极多的应用中赋予玻璃抗破裂性,其中用于汽车的挡风玻璃和家用和建筑窗玻璃。制备PVB是一种已知的在酸性介质中醛与醇的反应。可使用常规的增塑剂。可用的增塑剂为已知的且为市售的化合物,例如脂族二醇与脂族羧酸的双酯,例如三甘醇二2-乙基己酸酯(3GO)或四甘醇二正庚酸酯(4G7)。新鲜的增塑的PVB片材(也就是由厂商的胶辊直接得到的PVB)例如可得自DuPont,商标为BUTACITE。同样,PVB可得自其他的来源,包括得自安全或建筑用玻璃制造边角余料的PVB、从废弃的汽车或建筑用玻璃回收的PVB、认为不可用于其他工业应用的PVB以及其他类似的来源或这些来源的混合体。只要不脱离本发明的精神和范围,这些来源中的任一种均可满意地使用。
在一个优选的实施方案中,于升高的温度下(约100℃-约280℃,优选约150℃-约220℃),以间歇方法或连续方法将增塑的PVB和三种其他的组分混合得到均匀的熔融共混物,这三种组分包括:(1)活性聚合物,例如含酸酐或羧酸官能团的聚合物;(2)非活性聚合物,例如聚乙烯、聚丙烯或乙烯/丙烯酸正丁酯/CO三元共聚物;以及(3)抗氧化剂。将该共混物投至一组开炼机中进一步混合并压成片材形式。通过带式给料机将片材条连续加料至挤出机。在挤出机中,将该混合物再次熔融并通过熔体过滤器除去任何固体杂质。将干净的熔体在多孔模头中分配。使用水下切割机将这些聚合物沿模头表面切成粒料。切割时用水骤冷这些粒料并送至筛网使其与水分离。在包装之前将湿的粒料经流化干燥器干燥。
通过熔融共混将这样得到的粒料与合适的聚缩醛组合物混合。例如,适用于本文的增韧的聚缩醛共混物可通过熔融共混或熔融混合于任何合适的共混或混合装置(例如Banbury共混机、Haake混炼机、Farrell混炼机或挤出机)中得到。挤出机可为单螺杆挤出机或双螺杆挤出机,螺杆可有不同强度。混合或共混在约100℃-约250℃,优选约150℃-约230℃下进行。
由压缩剪切试验测定本发明的增韧的组合物的压缩剪切强度(CSS)值。通过向增韧的聚合物组合物中另外掺入偶联剂或交联剂得到具有进一步增强的粘合性能的本发明的增韧的组合物。例如,可将偶联剂例如Silquest A-1100(γ-氨基丙基三乙氧基硅烷,购自Crompton Corp.)这样掺入:或者加入到增韧的聚合物组合物主体中,或者涂覆于增韧的聚合物组合物的表面。在任一种方法中,所述偶联化合物可作为水溶液掺入。可使用酸(例如乙酸或柠檬酸)将该溶液的pH值降低。
本发明的另一个实施方案为一种制品,所述制品由本发明的聚合物组合物制备。本发明的制品包括层压制品、成型制品等。包含本发明的聚合物组合物的层压材料可掺入至各种其他的制品中,例如汽车、火车、车辆、设备、船舶、隔音瓦、隔音地板、墙壁、天花板、屋顶材料或希望消声、低表面光泽和/或坚韧的聚合物的其他制品。
在本发明的实践中,根据按照下述方法改进的ASTM D-523测量表面的光泽度(%)。与不含消光组合物的类似组合物比较,本发明的组合物可将光泽度降低至少约1%,优选光泽度降低至少约2%,更优选至少约2.5%,最优选至少约5%。
在一个特别优选的实施方案中,本发明的聚合物组合物可与其他的聚合材料(例如各种热塑性弹性体(TPE))层压。各种TPE为具有橡胶状性能的热塑性材料且为柔软感的聚合物。但是,通常TPE与刚性聚合物的粘合性不好。在许多情况下,TPE与本发明的聚合物层压将消除粘合问题。
在另一个优选的实施方案中,本发明的聚合物组合物可与PVB层压得到具有显著消音性能的PVB层压材料。
在再一个实施方案中,与厚度为层压的聚合物片材两倍的单片聚合物片材相比,具有至少两片片材的层压材料具有改善的强度和结构强度,所述至少两片片材包含粘附在PVB夹层的相对面上的本发明的聚合物组合物。发现这种层压材料可用于汽车车门面板、船身或其他类似的用途以赋予结构和强度。
实施例
实施例1-3和比较实施例C1
制备聚合物共混物的挤出方法和共混物的物理性质
将ECOCITETM,1与ABS(Magnum3490,购自Dow ChemicalCorp.)熔融共混。比较实施例C1不含EcociteTM。在熔融共混过程中,使用各自的可控失重加料器将各组分加入掺混机中。在40mm的Werner&Plleiderer共转双螺杆挤出机中将该混合物熔融配混,料筒的温度为约170-220℃,模头温度为约220℃。将所有的组分都加入第一料筒区。挤出在真空下通过孔进行。螺杆速率为250rpm,挤出机的总进料速率为150磅/小时。
得到的线料在水中骤冷,切成粒料,用氮气吹直到冷却。通过干燥或加入额外的水将所得粒料的水分按需要调整至0.1%-0.2%。按照ATM D294通过注塑得到拉伸样条,并按照ASTM D527测定断裂伸长率(EL-B)%,按照ASTM D527测定扯断强度,按照ISO 178测定弯曲模量(F.Mod),结果记录于表1。
1自由流动的PVB粒料按照WO 0212356的方法制备,得自E.I.DuPont de Nemours and Company(DuPont)。
光泽度测定
根据改善的ASTM D-523方法,使用Macbeth制造的Novo光泽计以60度角测定光泽度(%),记录于表1。该测定方法根据ASTMD-523,不同之处在于在两个ISO试条上18mm×29mm的末端耳柄的中心测定光泽度并取平均值。为了防止浇口处污点影响测定,在棒的非浇口端测定光泽度。
表1
比较实施例1 | 实施例1 | 实施例2 | 实施例3 | ||
Magnum3490 | 100 | 95 | 90 | 85 |
ECOCITETMH | 0 | 5 | 10 | 15 | |
密度 | 1.05 | 1.05 | 1.05 | 1.06 | |
熔体粘度280℃1/1000s-1 | Pa-s | 231.5 | 212.9 | 195.1 | 180.5 |
拉伸性质 | |||||
拉伸率% | % | 23.2 | 40.2 | 27.1 | 15.9 |
拉伸强度 | MPa | 39.0 | 34.3 | 32.1 | 29.8 |
psi | 5665 | 4971 | 4660 | 4321 | |
弯曲模量 | GPa | 2.527 | 2.493 | 2.4 | 2.33 |
psi | 366758 | 361882 | 348276 | 338188 | |
平均表面光泽度 | % | 79.7 | 65.4 | 53.7 | 47.9 |
实施例4-6和比较实施例C2
使用上述实施例1-3和C1相同的方法、步骤和试验方法进行表2中的实施例4-6和比较实施例C2,不同之处在于用Magnum9010代替Magnum3490。
表2
比较实施例2 | 实施例4 | 实施例5 | 实施例6 | ||
Magnum9010 | 100 | 95 | 90 | 85 | |
ECOCITETMH | 0 | 5 | 10 | 15 | |
密度 | 1.05 | 1.05 | 1.05 | 1.05 | |
熔体粘度@280℃1/1000s-1 | Pa-s | 216.5 | 198.9 | 180.8 | 171.2 |
拉伸性质 | |||||
拉伸率% | % | 25.6 | 24.7 | 23.4 | 13.9 |
拉伸强度 | MPa | 36.9 | 33.7 | 30.7 | 29.0 |
psi | 5355 | 4898 | 4456 | 4205 | |
弯曲模量 | GPa | 2.485 | 2.437 | 2.422 | 2.325 |
psi | 360595 | 353761 | 351490 | 337468 | |
平均表面光泽度 | % | 78.6 | 66.8 | 56.7 | 54.2 |
实施例7-9和比较实施例C3
使用上述实施例1-3和C1相同的方法、步骤和试验方法进行表3中的实施例7-9和比较实施例C3,不同之处在于用Magnum9035代替Magnum3490。
测定层压的聚合物板的粘合力的改进的压缩剪切应力(CSS)试验
根据ISO试验方法294,在注塑机中模塑2mm厚的正方形(5英寸×5英寸)板。在湿度可控(相对湿度:23%RH)的房间中将PVB薄片夹在两个板之间。于135℃热压20分钟后,将5英寸×5英寸的层压聚合物板从中心切成六块1英寸×1英寸的正方形。于60℃的真空干燥箱中将这六块正方形干燥过夜。在湿度可控(相对湿度:50%RH)的房间中在Instron试验仪中以45度角剪切每块正方形。记录剪切分开该正方形需要的力(CSS),单位为磅/英寸。计算各试样的这六块正方形的平均值以及标准偏差,并记录于表3。在一些情况中,在层压之前将硅烷或硅烷和酸(如乙酸或柠檬酸)涂覆在PVB薄片的表面。
表3
比较实施例3 | 实施例7 | 实施例8 | 实施例9 | ||
Magnum9035 | 100 | 95 | 90 | 85 | |
ECOCITETMH | 0 | 5 | 10 | 15 | |
密度 | 1.05 | 1.05 | 1.05 | 1.05 | |
熔体粘度280℃1/1000s-1 | Pa-s | 220.5 | 211.3 | 194.7 | 177 |
拉伸性质 | |||||
拉伸率% | % | 24.5 | 24.9 | 10.5 | 4.7 |
拉伸强度 | MPa | 34.3 | 31.0 | 29.3 | 29.7 |
psi | 4976 | 4501 | 4252 | 4314 | |
弯曲模量 | GPa | 2.3 | 2.2 | 2.2 | 2.1 |
psi | 331308 | 325673 | 318416 | 311365 | |
平均表面光泽度 | % | 76.8 | 71.6 | 66.6 | 63.8 |
平均CSS-psi | 0 | 88.2 | |||
CSS标准偏差-psi | -- | 55.5 | |||
表面涂有硅烷 | |||||
平均CSS-psi | 1274.7 | 1403.3 | |||
CSS标准偏差-psi | 467.7 | 169.7 |
表面涂有硅烷和乙酸 | |||||
平均CSS-psi | 545.2 | ||||
CSS标准偏差-psi | 170.1 | ||||
表面涂有硅烷和柠檬酸 | |||||
平均CSS-psi | 731.6 | ||||
CSS标准偏差-psi | 286.5 |
实施例10-11和比较实施例C4
使用上述实施例7-9和C3相同的方法、步骤和试验方法进行表4中的实施例10-11和比较实施例C4,不同之处在于用Magnum3490和尼龙-6(UltramidB-3,购自BASF Corp.)代替Magnum3490,尼龙-6使用单独的加料器加入。
表4
比较实施例4 | 实施例10 | 实施例11 | ||
UltramidB-3 | 70 | 63 | 56 | |
Magnum9035 | 30 | 27 | 24 | |
ECOCITETM H | 0 | 10 | 20 | |
密度 | 1.1 | 1.1 | 1.1 | |
熔体粘度280℃1/1000s-1 | Pa-s | 192.9 | 174.9 | 156.3 |
拉伸性质 | ||||
拉伸率% | % | 8.6 | 14.2 | 16.2 |
拉伸强度 | MPa | 63.2 | 46.6 | 36.4 |
psi | 9172 | 6763 | 5282 | |
弯曲模量 | GPa | 2.7 | 2.5 | 2.3 |
psi | 390342 | 359893 | 336244 | |
平均表面光泽度 | % | 69.3 | 59.0 | 59.7 |
表面涂有硅烷和乙酸 | ||||
平均CSS-psi | 1753.5 | 1554.9 | 1066.1 | |
CSS标准偏差-psi | 361.5 | 281.4 | 52.5 | |
表面涂有硅烷和柠檬酸 | ||||
平均CSS-psi | 1747.3 | 1700.1 | 1134.2 | |
CSS标准偏差-psi | 495.4 | 388.7 | 190.6 |
实施例12和比较实施例C5
将ECOCITETM和聚碳酸酯(Makrolon3102,购自Bayer Corp.)共混,然后加入注塑机中制备拉伸试条和用于CSS的2mm厚的正方形(5英寸×5英寸)板,而不是在挤出机中熔融共混。按照与实施例1-3中相同的试验方法测定表5中所有的物理性质。
表5
比较实施例5 | 实施例12 | ||
PC Makrolon3102 | 100 | 95 | |
ECOCITETM H | 0 | 5 | |
拉伸性质 | |||
拉伸率% | % | 34.4 | 59.7 |
拉伸强度 | MPa | 47.9 | 49.5 |
psi | 6948 | 7189 | |
弯曲模量 | GPa | 2.3 | 2.3 |
平均表面光泽度 | % | 158.7 | 134.9 |
实施例13-16和比较实施例C6
使用上述实施例12和C5相同的方法、步骤和试验方法进行表6中的实施例13-16和比较实施例C6,不同之处在于用PC和ABS合金(BayblendT45,购自Bayer Corp.)代替聚碳酸酯Makrolon。
表6
比较实施例6 | 实施例13 | 实施例14 | 实施例15 | 实施例16 | ||
BayblendT45 | 100 | 95 | 90 | 85 | 70 | |
ECOCITETM H | 0 | 5 | 10 | 15 | 30 | |
拉伸性质 | ||||||
拉伸率% | % | 37.539 | 5.157 | 4.559 | 6.121 | 3.87 |
拉伸强度 | MPa | 36.3 | 37.5 | 37.4 | 37.2 | 36.6 |
psi | 5267.3 | 5435.7 | 5423.0 | 5393.5 | 5315.8 | |
弯曲模量 | GPa | 1.99 | 1.93 | 1.97 | 1.96 | 1.96 |
平均表面光泽度 | % | 86.36 | 82.7 | 83.7 | 84.3 | 81.1 |
平均CSS-psi | 2148 | 1431 | 1269 | 1672 | ||
CSS标准偏差-psi | 569 | 523 | 537 | 616 |
实施例17和比较实施例C7
使用上述实施例12和C5相同的方法、步骤和试验方法进行表7中的实施例17和比较实施例C7,不同之处在于用PC和PET合金(MakroblendUT400,购自Bayer Corp.)代替聚碳酸酯Makrolon。
表7
比较实施例7 | 实施例17 | ||
MakroblendUT400 | 100 | 95 | |
ECOCITETM H | 0 | 5 | |
拉伸性质 | |||
拉伸率% | % | 3.6 | 4.1 |
拉伸强度 | MPa | 57.9 | 54.5 |
psi | 8408.9 | 7915.6 | |
弯曲模量 | GPa | 2.3 | 2.3 |
平均表面光泽度 | % | 60.9 | 45.0 |
平均CSS-psi | 2402 | 2258 | |
CSS标准偏差-psi | 338 | 191 |
Claims (26)
1.一种丙烯腈/丁二烯/苯乙烯(ABS)组合物,所述组合物包含:(a)约1-约30%重量的自由流动的消光增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量ABS;以及(c)任选的最高达1.0%重量的偶联剂。
2.一种得自丙烯腈/丁二烯/苯乙烯(ABS)组合物的制品,所述组合物包含:(a)约1-约30%重量的自由流动的消光增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量ABS;以及(c)任选的最高达1.0%重量的偶联剂。
3.一种聚碳酸酯(PC)组合物,所述组合物包含:(a)约1-约30%重量的自由流动的消光增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量的PC;以及(c)任选的最高达1.0%重量的偶联剂。
4.一种得自聚碳酸酯(PC)组合物的制品,所述组合物包含:(a)约1-约30%重量的自由流动的消光增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)余量的99-70%重量的PC;以及(c)任选的最高达1.0%重量的偶联剂。
5.一种三种聚合物共混物组合物,所述组合物包含:(a)约1-约30%重量的自由流动的消光增韧剂,所述增韧剂包含约20%重量-约95%重量的聚乙烯醇缩丁醛(PVB);(b)第二种聚合物(P2);(c)第三种聚合物(P3);以及(d)任选的最高达1.0%重量的偶联剂,其中所述[(b)+(c)]的合并重量百分比为约70-99%重量。
6.权利要求5的组合物,其中P2为ABS。
7.权利要求6的组合物,其中P3为聚酯。
8.权利要求7的组合物,其中所述聚酯选自聚对苯二甲酸丁二醇酯(PBT)和/或聚对苯二甲酸乙二醇酯(PET)。
9.权利要求6的组合物,其中P3为聚酰胺。
10.权利要求6的组合物,其中P3为PC。
11.权利要求5的组合物,其中P2为PC。
12.权利要求12的组合物,其中P3为聚酯。
13.权利要求12的组合物,其中P3为尼龙。
14.权利要求13的组合物,其中所述消光增韧剂包含一种或多种具有酸酐官能团的聚合物和一种或多种具有羧酸官能团的聚合物。
15.权利要求14的组合物,其中所述消光增韧剂还包含非活性聚合物,所述非活性聚合物选自聚乙烯、聚丙烯、聚氯乙稀、尼龙、烯烃共聚物及其混合物。
16.权利要求15的组合物,其中所述偶联剂为氨基硅烷化合物,存在量为约0.1-约1%重量。
17.权利要求16的制品,其中所述制品为由至少一个聚乙烯醇缩丁醛片材和至少一个与所述聚乙烯醇缩丁醛相邻的聚合物片材形成的层压材料,其中所述至少一个片材得自权利要求16的组合物,其中所述层压材料的压缩剪切强度至少为450磅/英寸2(psi)。
18.权利要求17的层压材料,其中所述层压材料具有消声性能。
19.一种制品,所述制品包含权利要求17的层压材料。
20.权利要求17的制品,其中所述制品为船舶、汽车、火车、飞机、屋顶、墙壁、建筑物、工具、设备。
21.权利要求17的制品,其中所述制品为钮扣或开关、电子设备或电子器件、立体声系统、光碟播放器、电话机、电视机、遥控器、计算机、键盘或触摸屏。
22.权利要求17的制品,其中所述制品通过注塑或压塑方法形成。
23.权利要求17的制品,所述制品不含填料,并且与不含所述消光增韧剂的组合物相比,表面光泽度降低了至少约1%。
24.一种增加权利要求1的聚合物组合物的粘合力的方法,所述方法包括加入硅烷偶联剂的步骤。
25.权利要求24的方法,其中所述偶联剂涂覆于所述聚合物组合物或所述PVB薄片的表面。
26.权利要求24的方法,其中所述偶联剂以pH小于7的水溶液形式涂覆。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US48333603P | 2003-06-28 | 2003-06-28 | |
US60/483,336 | 2003-06-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1813027A true CN1813027A (zh) | 2006-08-02 |
Family
ID=33563918
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2004800183789A Pending CN1813027A (zh) | 2003-06-28 | 2004-06-25 | 具有增强的表面性能的聚乙烯醇缩丁醛组合物和共混物以及由其制备的制品 |
Country Status (10)
Country | Link |
---|---|
US (1) | US20050059781A1 (zh) |
EP (1) | EP1639041A1 (zh) |
JP (1) | JP2007521373A (zh) |
KR (1) | KR20060028430A (zh) |
CN (1) | CN1813027A (zh) |
AU (1) | AU2004253946A1 (zh) |
CA (1) | CA2526203A1 (zh) |
MX (1) | MXPA05013264A (zh) |
TW (1) | TW200512249A (zh) |
WO (1) | WO2005003231A1 (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101942173A (zh) * | 2010-09-29 | 2011-01-12 | 广州市奥吉斯新材料有限公司 | 一种增强型丙烯腈-苯乙烯-丁二烯共聚物及其制备方法与应用 |
CN105237877A (zh) * | 2015-10-26 | 2016-01-13 | 陈鹤忠 | 高分子纳米户外用防滑板及其制备方法 |
CN105385141A (zh) * | 2015-12-29 | 2016-03-09 | 常熟市华锡塑料制品有限公司 | 一种耐磨塑料板 |
CN108997704A (zh) * | 2018-06-25 | 2018-12-14 | 滁州宇美塑业有限公司 | 一种abs复合pvb材料的合金颗粒及其制备方法 |
CN110396270A (zh) * | 2019-06-24 | 2019-11-01 | 安徽天分仪表有限公司 | 一种氧化锆氧量分析仪用高韧性外壳材料及其制备方法 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1751234A4 (en) * | 2004-06-04 | 2009-04-15 | Designer Molecules Inc | RADICALLY HARDENABLE POLYESTERS AND METHOD OF USE THEREOF |
US7875688B2 (en) | 2004-06-04 | 2011-01-25 | Designer Molecules, Inc. | Free-radical curable polyesters and methods for use thereof |
US20060079621A1 (en) * | 2004-06-24 | 2006-04-13 | Win-Chung Lee | Toughened polyacetal compositions and blends having low surface gloss |
US8043534B2 (en) | 2005-10-21 | 2011-10-25 | Designer Molecules, Inc. | Maleimide compositions and methods for use thereof |
US7868113B2 (en) | 2007-04-11 | 2011-01-11 | Designer Molecules, Inc. | Low shrinkage polyester thermosetting resins |
WO2008130894A1 (en) | 2007-04-16 | 2008-10-30 | Designer Molecules, Inc. | Low temperature curing acrylate and maleimide based formulations and methods for use thereof |
US8487225B2 (en) | 2007-10-15 | 2013-07-16 | E I Du Pont De Nemours And Company | Microwave field director structure having metal vanes |
US20090306249A1 (en) * | 2008-05-30 | 2009-12-10 | Optechnology, Inc. | Cementitious composites |
CN102532783B (zh) * | 2010-12-16 | 2015-06-24 | 合肥杰事杰新材料股份有限公司 | 一种流动性良好的abs/pbt合金材料及其制备方法 |
JP5610392B2 (ja) * | 2010-12-16 | 2014-10-22 | 東レ・デュポン株式会社 | 熱可塑性エラストマー樹脂組成物および複合成形体 |
EP3133120A4 (en) * | 2014-03-31 | 2017-11-29 | Glass Techno Synergy Co., Ltd. | Polyvinyl butyral resin composition, molded article and method for producing polyvinyl butyral resin composition |
CN108822482A (zh) * | 2018-06-25 | 2018-11-16 | 滁州宇美塑业有限公司 | 一种abs合金颗粒及其制备方法 |
CN112649298B (zh) * | 2020-12-31 | 2023-04-21 | 河北可为金属制品集团有限公司 | 一种清洁型智能退火黑铁丝强度检测装置 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3804802A (en) * | 1971-03-01 | 1974-04-16 | Du Pont | Thermoplastic composites with low alkali glass fillers |
JPS60156750A (ja) * | 1984-01-26 | 1985-08-16 | Idemitsu Petrochem Co Ltd | ポリカ−ボネ−ト樹脂組成物 |
KR100358667B1 (ko) * | 1995-04-27 | 2003-04-16 | 폴리플라스틱스 가부시키가이샤 | 열가소성수지조성물및그제조방법 |
WO1997012965A1 (en) * | 1995-10-04 | 1997-04-10 | Monsanto Company | Porous polymeric biosupports and their use in the biotreatment of aqueous waste streams |
EP1311562B1 (en) * | 2000-08-10 | 2004-05-19 | E.I. Dupont De Nemours And Company | Process for conversion of polyvinyl butyral (pvb) scrap into processable pellets |
US6821701B2 (en) * | 2001-04-03 | 2004-11-23 | Seiko Epson Corporation | Toner and image forming apparatus |
-
2004
- 2004-06-25 CA CA002526203A patent/CA2526203A1/en not_active Abandoned
- 2004-06-25 MX MXPA05013264A patent/MXPA05013264A/es unknown
- 2004-06-25 AU AU2004253946A patent/AU2004253946A1/en not_active Abandoned
- 2004-06-25 US US10/877,547 patent/US20050059781A1/en not_active Abandoned
- 2004-06-25 JP JP2006518708A patent/JP2007521373A/ja active Pending
- 2004-06-25 WO PCT/US2004/020825 patent/WO2005003231A1/en active Application Filing
- 2004-06-25 EP EP04756329A patent/EP1639041A1/en not_active Withdrawn
- 2004-06-25 KR KR1020057025035A patent/KR20060028430A/ko not_active Application Discontinuation
- 2004-06-25 CN CNA2004800183789A patent/CN1813027A/zh active Pending
- 2004-06-28 TW TW093118895A patent/TW200512249A/zh unknown
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101942173A (zh) * | 2010-09-29 | 2011-01-12 | 广州市奥吉斯新材料有限公司 | 一种增强型丙烯腈-苯乙烯-丁二烯共聚物及其制备方法与应用 |
CN105237877A (zh) * | 2015-10-26 | 2016-01-13 | 陈鹤忠 | 高分子纳米户外用防滑板及其制备方法 |
CN105237877B (zh) * | 2015-10-26 | 2018-07-31 | 陈鹤忠 | 高分子纳米户外用防滑板及其制备方法 |
CN105385141A (zh) * | 2015-12-29 | 2016-03-09 | 常熟市华锡塑料制品有限公司 | 一种耐磨塑料板 |
CN108997704A (zh) * | 2018-06-25 | 2018-12-14 | 滁州宇美塑业有限公司 | 一种abs复合pvb材料的合金颗粒及其制备方法 |
CN110396270A (zh) * | 2019-06-24 | 2019-11-01 | 安徽天分仪表有限公司 | 一种氧化锆氧量分析仪用高韧性外壳材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2005003231A1 (en) | 2005-01-13 |
KR20060028430A (ko) | 2006-03-29 |
TW200512249A (en) | 2005-04-01 |
EP1639041A1 (en) | 2006-03-29 |
AU2004253946A1 (en) | 2005-01-13 |
US20050059781A1 (en) | 2005-03-17 |
CA2526203A1 (en) | 2005-01-13 |
MXPA05013264A (es) | 2006-03-09 |
JP2007521373A (ja) | 2007-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1813027A (zh) | 具有增强的表面性能的聚乙烯醇缩丁醛组合物和共混物以及由其制备的制品 | |
EP0628596A1 (en) | Heat-resistant, propylene resin-based molding materials and molded products obtained therefrom | |
US20040121172A1 (en) | Co-extrudable multi-layer polymer | |
CN1255475C (zh) | 刚度改进的增韧的玻璃充填的聚酰胺组合物及共混物 | |
US8092919B2 (en) | Toughened polyacetal compositions and blends having low surface gloss | |
US20050032950A1 (en) | Polyacetal and polyvinylbutyral compositions and blends having enhanced surface properties and articles made therefrom | |
US20060079621A1 (en) | Toughened polyacetal compositions and blends having low surface gloss | |
CN1761718A (zh) | 聚酰胺和聚乙烯醇缩丁醛组合物和具有提高的表面性能的共混物以及由其制造的制品 | |
US20040266931A1 (en) | Polyamide and polyvinylbutyral compositions and blends comprising mineral filler and articles made therefrom | |
WO2020242232A1 (ko) | 열가소성 수지 조성물 및 이를 이용한 성형품 | |
CN1813028A (zh) | 具有增强的表面性能的聚缩醛和聚乙烯醇缩丁醛组合物和共混物及由其制备的制品 | |
JPH01204947A (ja) | 自動車外装部品用熱可塑性樹脂組成物 | |
JP2000265035A (ja) | 熱可塑性エラストマー組成物およびその成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |