CN1683146A - 冷拉伸膜 - Google Patents
冷拉伸膜 Download PDFInfo
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- CN1683146A CN1683146A CNA2004101046691A CN200410104669A CN1683146A CN 1683146 A CN1683146 A CN 1683146A CN A2004101046691 A CNA2004101046691 A CN A2004101046691A CN 200410104669 A CN200410104669 A CN 200410104669A CN 1683146 A CN1683146 A CN 1683146A
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Classifications
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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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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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
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
-
- 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
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
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Abstract
本发明涉及一种从软聚合物组分和硬聚合物组分的共混物形成的冷拉伸透气膜。软聚合物组分(SPC)是主要烯烃单体和少量烯烃单体的共聚物。主要烯烃单体是乙烯或丙烯并形成SPC的大部分。在冷拉伸之后优选的膜显示至少为100g-密耳/m2-天的水汽透过率(WVTR)。
Description
发明人:S.Srinivas;P.Brant,F.Chambon,J.P.Stokes
相关申请
本申请要求1999年9月1日提交的USSN60/151,970的优选权,并将该申请在此全文引入作为参考。
发明领域
本发明涉及从合成聚合物的共混物生产透气膜的方法。
发明背景
在其中要求透气性的应用中,已经通常使用多层膜以提供半渗透或选择性渗透性能。关于透气的,指的是膜会允许水汽和氧气透过,但不允许微生物或大块固体或液体透过。这样的性能可用于各种用途,包括新鲜产品和鲜花包装、一次性个人衣服、家用包装、和用于各种分离工艺的隔膜。透气膜特别用于衣服制品的制造,其中重要的是保护穿用者免受环境曝露的影响,或防止人体废物逸出,同时允许穿用者得到的舒适感比被不透气材料所允许的更大。这样的产品包括,但不限于,外科和卫生护理有关的产品、一次性工作装、和个人护理吸收产品。外科和卫生护理有关的产品包括外科消毒盖布和手术服等。一次性工作装包括连裤工作服和实验室外套等。个人护理吸收产品包括尿布、运动裤、失禁服、卫生巾、绷带等。
这样的透气膜的主要功能是提供液体屏障性能和/或阻止微生物的通过,但允许水分、空气、其它气体或其结合物的透过。通过降低水蒸汽浓缩和因此降低衣服制品下的皮肤水合,从透气和/或微孔膜形成的衣服穿用更舒服。然而,透气膜中的孔尺寸不能太大,特别是在保护性衣服和个人护理用途中,如工业或医疗服装、尿布等,其中液体渗透表示污染危险。此外,包含太大孔的膜可允许液体和/或病毒的通过,从而降低了保护性衣服的有效性。
用于获得商品市场用透气微孔膜的通常方式已经是伸长典型地包含无机填料的热塑性膜。当伸长或拉伸膜时,通过在填料粒子和包含填料的聚合物基体之间的界面处的分离,产生微空隙。在这些拉伸工艺之前,通常将膜加热,以使在伸长期间膜的可展性最大化。此拉伸或伸长也将膜内的分子结构取向,这样相对于在伸长方向施加的力,增加它的强度和耐用性。伸长可以在机器方向(MD)、横向(机器交叉)方向(TD)、或双轴方向(MD和TD两者)。单轴或其它不平衡伸长典型地导致不平衡的性能(如当向单轴伸长方向施加横向力时,膜倾向于更容易分裂)。不管选择的拉伸工艺,在加工填充的聚合物中存在固有的困难。
首先,填料如碳酸钙在聚合物中的均匀分散要求单独的混炼步骤和显著的机械功。第二,有时在混炼期间要求的较高熔融温度可引起聚合物的变色和有时甚至聚合物的降解。第三,要求另外的设备以保证有效的真空脱除,以除去在混炼步骤期间从填料中释放出的水。真空排气口可能堵塞和这种情况导致水处于混炼的产品中和毁坏铸塑膜。第四,当填料粒子尺寸降低,特别是小于2微米时,由于越来越难以加工填充的聚合物,可能发生模头淌料和冒烟。因此,必须筛分碳酸钙以除去小于2-3微米的粒子。更小的粒子提高混炼聚合物的粘度太高,使得通常出现设备的机械故障。最后,由于CaCO3比聚合物基体更密集,碳酸钙填充的透气膜可具有砂砾般的感觉和倾向于感觉更重。因此,非常需要一种生产透气膜的方法,该方法可避免与硬填料物质如碳酸钙有关的困难。
产生或增强透气性的其它方法包括膜的机械刺穿(参见U.S.专利No.4,747,895)或从共混聚合物形成的膜的共连续相抽出(参见U.S.专利No.4,804,472)。第三种方法使用结晶聚合物或无定形聚合物和结晶聚合物的混合物,它们产生规则的排-层结构,当在控制的条件下制备和伸长时,该结构在聚合物导致均匀的孔(参见U.S.专利Nos.3,843,761、3,801,404、4,138,459和4,620,956)。
也已经使用通过单层膜层压或共挤出生产的多层膜以产生透气材料,该材料不能透过液体而且具有持久的织物状外观和纹理。在一次性尿布上的外覆盖物仅仅是一个例子。在此方面,可以参见U.S.专利Nos.4,818,600和4,725,473。外科手术服和消毒盖布是其它的例子。参见,U.S.专利No.4,379,102。U.S.专利No.5,914,184公开了包括粘合到连续膜上的微孔填充膜的透气性多层膜层压材料。在一个或两个表面上,支撑层如纤维网可以粘合到膜层压材料上。多层膜的层压也要求另外的加工步骤和因此遇到更多的潜在加工困难。
Metcalfe的美国专利4,559,938公开了一种粘合性绷带和组分。该发明的柔性膜适用于粘合性医用绷带并包含聚合物,其特征在于该共混物包含连续的聚丁二烯相和在连续相内形成分离颗粒的不相容性聚合物。该膜含有空隙。
Joesten等的美国专利5,134,173公开了一种不透明的膜及其生产方法。这些不透明的聚合物膜包括一种热塑性聚合物基体材料,例如聚丙烯。含有形成空隙的固体颗粒,例如聚苯乙烯。形成空隙的固体颗粒是分离相,并且与基体材料不相容。
典型地,如在上述参考文献中,通过加入填料和随后伸长膜而使膜变成透气的,和通过将膜层压到具有在第一层中缺乏的性能的其它膜层上而改进耐用性。使用填料以生产透气膜和通过与其它聚合物层进行层压而改进透气膜的韧性两者都是耗时而昂贵的额外步骤。因此需要提供透气性和耐用性两者的膜,而不需要填料和多层层压之一或两者。
发明概述
本发明涉及一种从软聚合物组分和硬聚合物组分的共混物形成的冷拉伸膜。软聚合物组分(SPC)是主要烯烃单体和少量烯烃单体的共聚物。主要烯烃单体是乙烯或丙烯并形成SPC的大部分。少量烯烃单体形成SPC的剩余部分和能够进行插入聚合的线性、支化、或含环C2-C30烯烃,且不同于主要烯烃单体。
在一个实施方案中,SPC的熔点大于25℃和在环境温度下的弯曲模量小于100Mpa,在环境温度下硬聚合物组分(HPC)的弯曲模量大于200MPa。
在另一个实施方案中,SPC的熔点大于25℃和在环境温度下的割线模量小于350MPa,在环境温度下硬聚合物组分(HPC)的割线模量大于400MPa。
SPC和HPC可以作为共连续相共混,但优选HPC是在SPC连续相中的分散相。
在低于最高的转变温度的温度下冷拉伸从SPC和HPC的共混物形成的初始膜,该最高转变温度是HPC的熔融温度或玻璃化转变温度。优选,拉伸温度也高于第一结晶熔化可以检测到的温度,和低于在SPC中最后结晶熔化可以检测到的最高温度。冷拉伸是单轴的或双轴的,采用足够的牵伸以生产厚度小于冷拉伸之前厚度的透气膜。
在一个实施方案中,在冷拉伸之后膜的拉伸模量优选小于或等于375MPa。在另一个实施方案中,在冷拉伸之后膜的拉伸模量优选小于或等于160MPa。在冷拉伸之后,相对于任何单独的共混物组分,优选的膜显示更大的水汽透过率(WVTR),优选大于100g-密耳/m2-天。
优选实施方案的详细描述
本发明涉及一种从SPC和HPC的共混物形成的冷拉伸透气膜,两者如上所述。
软聚合物组分
在一个实施方案中,SPC是包含主要烯烃单体和少量烯烃单体的单一共聚物。主要烯烃单体是乙烯或丙烯,和由于它是共聚物的主要组分,优选至少为SPC的80摩尔%,故称为“主要”。少量烯烃单体是能够进行插入聚合的线性、支化、或含环C2-C30烯烃,及其结合物,且不同于主要烯烃单体。SPC是半结晶的,它的熔点大于25℃,优选大于35℃,甚至更优选大于50℃。
在一个实施方案中,根据本发明的优选半结晶SPC的弯曲模量小于100MPa,更优选小于90MPa,甚至更优选小于80MPa。
在另一个实施方案中,根据本发明的优选半结晶SPC的割线模量小于350MPa。
在一个优选的实施方案中,主要烯烃单体是乙烯。在此实施实施方案中,其中SPC是聚乙烯共聚物,优选的少量烯烃单体包括能够进行插入聚合的线性、支化、或含环C3-C30烯烃,及其结合物。优选的少量烯烃单体是C3-C20线性或支化的α-烯烃,更优选C3-C8α-烯烃,甚至更优选丙烯、1-丁烯、1-己烯和1-辛烯。优选的支化α-烯烃包括4-甲基-1-戊烯、3-甲基-1-戊烯、和3,5,5-三甲基-1-己烯。优选的含环烯烃单体包含至多30个碳原子,和包括但不限于环戊烯、乙烯基环己烷、乙烯基环己烯、降冰片烯和甲基降冰片烯。
优选的含芳族基团的单体包含至多30个碳原子。合适的含芳族基团单体包括至少一个芳族结构,优选一到三个,更优选苯基、茚基、芴基或萘基部分。含芳族基团的单体进一步包括至少一个可聚合双键,这样在聚合之后,芳族结构可以悬挂于聚合物主链上。
优选的含芳族基团单体包含至少一个悬挂于可聚合烯烃部分的芳族结构。可聚合烯烃部分可以是线性、支化、含环的、或这些结构的混合。当可聚合烯烃部分包含环状结构时,环状结构和芳族结构可分享0,1或2个碳。可聚合烯烃部分和/或芳族基团的一个到所有氢原子也可被含1-4个碳原子的线性或支化烷基取代。特别优选的芳族单体包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基萘、烯丙基苯、和茚,特别是苯乙烯和烯丙基苯。
在一个实施方案中,聚乙烯共聚物是乙烯和至少一种α-烯烃、最优选C3-C8线性或支化α-烯烃的半结晶、热塑性、优选无规共聚物,它的熔点为50℃或更大,更优选60℃或更大,甚至更优选65℃或更大,最优选70℃或更大。优选,聚乙烯共聚物的熔点为125℃或更小,更优选120℃或更小。
典型地,平均乙烯含量为84摩尔%或更大,优选87摩尔%或更大,更优选89摩尔%或更大。优选,平均乙烯含量为99摩尔%或更小,更优选98摩尔%或更小。共聚物的剩余部分是能够进行插入聚合的一种或多种少量烯烃单体,更优选以上所述的一种或多种α-烯烃和非必要地少量一种或多种二烯烃单体。
聚乙烯共聚物的密度,以g/cc计,优选为0.865或更大,更优选0.870或更大。在一个实施方案中,聚乙烯的最大密度是0.930或更小。在另一个实施方案中,聚乙烯共聚物的最大密度是0.915或更小,更优选为0.865-0.900,甚至更优选为0.870-0.890。
聚乙烯共聚物的重均分子量(Mw)典型地为30,000或更大,优选50,000或更大,甚至更优选80,000或更大。聚乙烯共聚物的Mw典型地为500,000或更小,更优选300,000或更小,甚至更优选200,000或更小。
典型地使用Ziegler-Natta或金属茂催化剂体系生产聚乙烯均聚物和共聚物。特别优选的聚乙烯共聚物采用金属茂催化剂生产和显示窄的分子量分布,表示重均分子量对数均分子量的比例会等于或小于4,最典型地为1.7-4.0,优选1.8-2.8。
优选,采用金属茂催化剂生产的聚乙烯共聚物也显示窄的组成分布,表示分子到分子的分数共聚单体含量相似。这种情况可以通过由凝胶渗透色谱确定的数均或重均分子量(Mn或Mw)离散范围的傅里叶变换红外光谱分析(GPC-FTIR)而度量,和在受限制的情况下,也可以使用组成分布宽度指数或溶解度分布宽度指数以度量共聚单体分布。当采用GPC-FTIR测量时,优选的聚乙烯共聚物具有这样的共聚单体分布,使得包括10wt%或更多总洗脱共聚物的任何离散分子量范围的共聚单体含量在聚乙烯共聚物重均共聚单体含量的±30%之内,其中此平均值等于100%,更优选在±20%之内,甚至更优选在±10%之内。在通过SDBI测量是合适的情况下,聚乙烯共聚物的SDBI优选小于约35℃,一般为约10℃-约25℃,优选为约15℃-约20℃,和最优选为约15℃-约18℃。在CDBI测量是合适的情况下,聚乙烯共聚物的CDBI优选大于40%,更优选大于50%,甚至更优选大于60%。如果它满足上述GPC-FTIR,CDBI或SDBI标准,聚乙烯共聚物具有窄的组成分布。
在特别优选的实施方案中,共聚物是单点催化的“聚乙烯”,优选是使用金属茂催化生产的。在此使用的“聚乙烯”表示SPC,其中乙烯是主要烯烃单体。这样的聚乙烯可以从德克萨斯,休斯顿的ExxonMobil Chemical Company以商品名ExactTM或ExceedTM树脂购得。这些材料可以采用金属茂催化剂,在各种工艺(包括淤浆、溶液、高压和气相)中制备。采用金属茂催化剂体系制备各种聚乙烯材料的工艺是公知的。参见,例如,U.S.专利Nos.5,017,714、5,026,798、5,055,438、5,057,475、5,096,867、5,153,157、5,198,401、5,240,894、5,264,405、5,278,119、5,281,679、5,324,800、5,391,629、5,420,217、5,504,169、5,547,675、5,621,126、5,643,847和5,801,113,U.S.专利申请系列nos.08/769,191、08/877,390、08/473,693、08/798,412和60/048,965,和国际专利申请nos.EPA277,004、W092/00333和WO94/03506,每个文献在此引入作为参考,用于U.S.专利实践的目的。乙烯和环烯烃共聚物的生产描述在U.S.专利Nos.5,635,573和5,837,787,和乙烯和同碳二取代单体如异丁烯的共聚物的生产描述在U.S.专利No.5,763,556中,所有这些文献在此引入作为参考,用于U.S.专利实践的目的。
在另一个优选的实施方案中,主要烯烃单体是丙烯。在此实施方案中,优选的少量烯烃单体包括乙烯和线性或支化C4-C30α-烯烃或其结合物。优选的线性α-烯烃包括乙烯或C4-C8α-烯烃,更优选乙烯、1-丁烯、1-己烯和1-辛烯,甚至更优选乙烯和1-丁烯。优选的支化α-烯烃包括4-甲基-1-戊烯、3-甲基-1-戊烯和3,5,5-三甲基-1-己烯。
在聚丙烯共聚物中的低水平结晶度衍生于等规或间规聚丙烯序列,优选等规聚丙烯序列,它们是通过引入如上所述的少量烯烃单体作为共聚单体而获得的。以摩尔计,优选的聚丙烯共聚物的平均丙烯含量为49%或更大,更优选59%或更大,甚至更优选65%或更大,甚至更优选72%或更大,最优选78%或更大。以摩尔计,优选的聚丙烯共聚物的平均丙烯含量为约97%或更小。共聚物的剩余部分是如上所述的一种或多种线性或支化α-烯烃和非必要地少量一种或多种二烯烃单体。
半结晶聚丙烯共聚物的熔化热典型地为5J/g或更大,优选9J/g或更大,更优选11J/g或更大。半结晶聚丙烯共聚物的熔化热典型地为90J/g或更小,优选76J/g或更小,更优选57J/g或更小。聚丙烯共聚物的结晶度来源于可结晶的有规立构丙烯序列。
在另一个实施方案中,聚丙烯共聚物SPC的结晶度以结晶度百分比表示。最高等级聚丙烯的热能量估计为189J/g。即,100%结晶度等于189J/g。因此,根据上述的能量水平,本发明优选具有最小聚丙烯结晶度为3%或更大,更优选5%或更大,甚至更优选6%或更大,和最大聚丙烯结晶度为48%或更小,更优选30%或更小,甚至更优选25%或更小。
聚丙烯共聚物优选具有单一的宽熔融转变。典型地聚丙烯共聚物的样品会显示与主峰相邻的次级熔融峰,将这些一起考虑为单熔点。这些峰的最高点考虑为熔点。聚丙烯共聚物的熔点优选为约25℃-约110℃,优选为30℃-约105℃,更优选为约35℃-约90℃。
聚丙烯共聚物的重均分子量可以为10,000-5,000,000g/cc,优选80,000-500,000,MWD(Mw/Mn)为1.5-40.0,更优选为约1.8-5和最优选为1.8-3。在另一个实施方案中,优选聚丙烯共聚物的门尼粘度ML(1+4)@125℃小于100,更优选小于75,甚至更优选小于60,最优选小于30。
本发明的聚丙烯共聚物优选包括具有窄组成分布的无规可结晶共聚物。通过在溶剂中的热分级测量聚合物的分子间组成分布。典型的溶剂是饱和烃如己烷或庚烷。此热分级程序如下所述。典型地,大约75wt%和更优选85wt%的聚合物分离为一个或两个相邻的可溶级分,聚合物的剩余部分立即领先于或继续分级。这些级分的每一个具有组成(乙烯或其它α-烯烃的wt%含量)差值不大于聚丙烯共聚物的共聚单体(如乙烯或其它α-烯烃)的平均wt%含量的20%(相对的)和更优选10%(相对的)。如果满足上述的分级测试,聚丙烯共聚物具有窄的组成分布。
优选的聚丙烯共聚物中有规立构丙烯序列的长度和分布与基本无规统计共聚相一致。公知的是序列长度和分布和共聚反应竞聚率有关。关于基本无规,我们指的是对于这样的共聚物,反应竞聚率的乘积一般为2或更小。在立构嵌段结构中,PP系列的平均长度大于具有相似组成的基本无规共聚物的平均长度。具有立构嵌段结构的现有技术聚合物的PP系列分布与这些嵌段结构相一致,而不是无规基本统计分布。聚合物的反应竞聚率和序列分布可以通过C-13NMR测量,它定位涉及相邻丙烯残基的乙烯残基。为生产具有要求的无规度和窄组成分布的可结晶共聚物,需要使用单点催化剂。在一个实施方案中,在充分混合的、连续流动搅拌罐聚合反应器中使用单点催化剂,该反应器仅允许用于优选聚丙烯共聚物的基本所有聚合物链的单一聚合环境。
在手性金属茂催化剂与活化剂和非必要的清除剂存在的情况下,通过聚合丙烯和至少一种C2或C4-C20α-烯烃,最优选乙烯和丙烯,制备本实施方案的优选聚丙烯共聚物。优选的手性金属茂是已知有利于以主要等规聚丙烯五单元组引入丙烯和以统计无规方式引入α-烯烃或其它烯烃单体的那些。术语“金属茂”和“金属茂催化剂前体”是在本领域已知的术语,它表示具有如下的化合物:IV,V,或VI族过渡金属M,和可以被取代的环戊二烯基(Cp)配体或各种配体,至少一种非环戊二烯基衍生的配体X,和零个或一个含杂原子的配体Y,配体配合到M上和数目相应于其价数。金属茂催化剂前体一般要求采用合适的助催化剂(称为活化剂)活化,以产生一般称为有机金属配合物的活性金属茂催化剂,它具有可配合、插入和聚合烯烃的空配位点。
优选的金属茂是环戊二烯基(Cp)配合物,它含有用作配体的两个Cp环体系。Cp配体优选与金属形成弯曲的夹层配合物,和优选通过桥接基团锁定到刚性构型中。这些环戊二烯基配合物具有如下通式:
(Cp1R1 m)R3 n(Cp2R2 p)MXq其中配体(Cp1R1 m)的Cp1和配体(Cp2R2 p)的Cp2优选相同。R1和R2每个独立地是卤素或烃基、卤代二价碳基、包含至多20个碳原子的烃基取代的有机非金属或卤代二价碳基取代的有机非金属,m优选是1-5,p优选是1-5,和优选在与之相关联的环戊二烯基环的相邻碳原子上的两个R1和/或R2取代基可以结合在一起以形成4-20个碳原子的环,R3是桥接基团,n是两个配体之间直接链中的原子数和优选为1-8,最优选1-3,M是价数为3-6的过渡金属,优选来自元素周期表的IV,V,或VI族和优选处于它的最高氧化态,每个X是非环戊二烯基配体和独立地是烃基、氧烃基、卤代二价碳基、烃基取代的有机非金属、包含至多20个碳原子的氧烃基取代的有机非金属或卤代二价碳基取代的有机非金属,q等于M-2的价数。
用于本发明上述双环戊二烯基金属茂的许多例子描述在U.S.专利5,324,800、5,198,401、5,278,119、5,387,568、5,120,867、5,017,714、4,871,705、4,542,199、4,752,597、5,132,262、5,391,629、5,243,001、5,278,264、5,296,434和5,304,614,所有这些专利在此引入作为参考,为了U.S.专利实践的目的。
用于本发明上述族I中类型的优选双环戊二烯基金属茂的示例性、但非限制性例子是如下物质的外消旋异构体:
μ-(CH3)2Si(茚基)2M(Cl)2
μ-(CH3)2Si(茚基)2M(CH3)2
μ-(CH3)2Si(四氢茚基)2M(Cl)2
μ-(CH3)2Si(四氢茚基)2M(CH3)2
μ-(CH3)2Si(茚基)2M(CH2CH3)2
μ-(C6H5)2C(茚基)2M(CH3)2
其中M选自Zr、Hf或Ti。
用于本发明的优选聚丙烯共聚物以“第二聚合物组分(SPC)”详细描述在如下文献中:在先未决的U.S.申请USSN 60/133,966,提交日1999年5月13日,USSN 60/342,854,提交日1999年6月29日,和USSN 08/910,001,提交日1997年8月12日(现公开为WO 99/07788),和以“丙烯烯烃共聚物”进一步详细描述在USSN 90/346,460中,提交日1999年7月1日,所有这些专利在此引入作为参考,为了U.S.专利实践的目的。
除一种或多种选择的共聚单体(即,少量烯烃单体),如,但不限于,乙烯、丙烯、和含4-8个碳原子的α-烯烃和苯乙烯以外,如上所述的聚乙烯和聚丙烯共聚物可非必要地包含长支链。这些物质可以非必要地使用一种或多种α,ω二烯烃产生。或者,软聚合物组分可包含少量的至少一种二烯烃,和更优选至少一种二烯烃是非共轭的,以协助硫化和其它化学改性。二烯烃的量优选不大于约10wt%,更优选不大于约5wt%。二烯烃可选自用于乙烯丙烯橡胶硫化的那些,和优选是亚乙基降冰片烯、乙烯基降冰片烯、二环戊二烯、和1,4-己二烯(购自DuPont Chemicals)。
在另一个实施方案中,SPC可以是离散聚合物的共混物。合适的共混物可以是两种或多种聚乙烯共聚物(如上所述)的共混物、两种或多种聚丙烯共聚物(如上所述)的共混物、或至少一种每种这样的聚乙烯共聚物和聚丙烯共聚物的共混物,其中SPC共混物的每种组分可单独用作SPC。
在还有的另一个实施方案中,与醋酸乙烯酯(EVA)和/或丙烯酸甲酯(EMA)的乙烯共聚物可用作单独的SPC或在共混的SPC中的共混物组分。
硬聚合物组分
在一个实施方案中,优选的硬聚合物组分是聚苯乙烯均聚物、共聚物、或其结合物。硬聚合物组分的弯曲模量优选大于200MPa,更优选大于400MPa,甚至更优选大于800MPa。
在另一个实施方案中,优选的硬聚合物组分是聚苯乙烯均聚物、共聚物、或其结合物。硬聚合物组分的割线模量优选大于400MPa,更优选大于600MPa,甚至更优选大于800MPa。
聚苯乙烯均聚物或共聚物典型地由苯乙烯和非必要地一种或多种共聚单体的加成聚合形成。用作根据本发明硬聚合物组分的优选聚苯乙烯聚合物中的苯乙烯应当至少是50摩尔%,更优选大于70摩尔%,甚至更优选大于85摩尔%。在此可以使用苯乙烯和其它单体的任何共聚物,其它单体含有乙烯基或其它可聚合不饱和部分。优选的共聚单体包括,但不限于,对-甲基苯乙烯、丙烯腈、甲基丙烯酸甲酯、丙烯酸乙酯、乙烯基甲苯、丁二烯和C2-C20α-烯烃,特别是乙烯。
在另一个实施方案中,HPC可以是两种或多种聚苯乙烯聚合物(如上所述)的共混物,其中HPC共混物的每种组分可单独用作HPC。
在另一个实施方案中,HPC是选自聚乙烯均聚物或乙烯基共聚物的一种或多种聚合物,其中均聚物或共聚物的密度为0.93或更大。这样的均聚物和共聚物是公知的和特别用于与先前所述丙烯基SPC的共混物,和它的割线模量大于400MPa,更优选大于600MPa,甚至更优选大于800MPa。
在还有的另一个实施方案中,HPC选自,但不限于以下的一种或多种:聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、聚酰胺、聚(乙烯基环己烷)、等规聚(4-甲基1-戊烯)、聚(乙烯基吡咯烷酮)、等规聚丙烯、间规聚丙烯、和聚(2-乙烯基吡啶)。
聚合物共混物
关于生产共混物的物理工艺,应当发生充分的混合以保证在转变成膜之前,产生均匀的共混物。由于形成膜的挤出工艺包括原材料的再熔融和混合,混合方法包括粒料的简单固态共混物或原料聚合物颗料的造粒的熔融态共混物、颗料与粒料的熔融态共混物、或两种组分粒料的熔融态共混物。然而,在压缩模塑的工艺中,熔体组分的混合有限,和造粒的熔体共混物会优于组分粒料和/或颗料的简单固态共混物。本领域技术人员可以确定用于聚合物共混的合适条件,以达到组成成分的充分混合的需要和工艺经济要求之间的平衡。优选,在两种组分的较高转变温度之上,通过组分的熔融混合而制备共混物。
根据给定用途所需的形态选择共混物组分。在从共混物形成的膜中,SPC可以是和HPC共连续的,然而,优选是在连续SPC相中的分散HPC相。根据SPC和HPC的不混溶性或不相容性选择组分(参见D.R.Paul,S.Newman,聚合物共混物,Academic Press纽约1978)。这样保证在单轴或双轴伸长的情况下可以分离弱界面。本领域技术人员可以根据组分的粘度比例,选择两种组分的体积分数以生产在连续SPC基体中的分散HPC形态(参见S.Wu,聚合物工程和科学,27卷,335页,1987)。由于在伸长情况下不是每一个不混合共混物体系在界面处失败,故不混溶组分的选择对于产生界面分离是关键的。
优选,与SPC共混的HPC数量为约10-70wt%,更优选15-60wt%,甚至更优选20-50wt%,基于两种聚合物组分的总重量。在冷拉伸之前,膜的拉伸模量优选小于400MPa,更优选小于300MPa。
优选的共混物没有或基本没有相容的聚合物组成,但这样的共混物可包含典型量的通常在膜共混物中使用的其它添加剂。
膜生产
可以通过本领域公知的方法,如压缩模塑,将聚合物的SPC/HPC共混物形成膜或多层膜的层。或者,可以在两种组分的转变温度之上,在熔融状态下,将聚合物通过平模头挤出和然后冷却。或者,可以在两种组分的转变温度之上,在熔融状态下,将聚合物通过环形模头挤出和然后吹塑和冷却以形成管状膜。可以将管状膜轴向切开和伸展以形成平面膜。本发明的膜是冷拉伸的,或单轴或双轴塑性形变的(即,在横向和机器方向基本相等)。
对于本发明的目的,“冷拉伸”表示在预先选择的温度下,将膜伸长足够的量以在不相容或不混溶的HPC和SPC相之间的界面处产生分离。拉伸尺寸和拉伸温度的最优结合会根据具体的HPC和SPC及它们在共混物中的相对量而变化,但一般遵守如下所述标准。
优选的拉伸温度依赖于共混物的组分。首先,拉伸温度优选低于HPC的最高转变温度。根据HPC的组成,最高转变温度是玻璃化转变温度(Tg)或结晶熔融温度(Tm),如果材料具有Tm。对于聚苯乙烯,Tg是最低的转变和对于聚苯乙烯均聚物,在公开文献中记录为约100℃-约105℃。其次,拉伸温度大于结晶熔融可首先被DSC检测到的温度。对于聚乙烯和聚苯乙烯SPC’s,如上所述,结晶熔融的最低温度大于25℃,和可能大于30℃。
对于单一聚合物的SPC,最优选的拉伸温度在结晶熔融可首先被检测到的温度和结晶熔融基本完全或不再检测到的温度之间。在一个实施方案中,在拉伸之前,允许膜达到平衡温度,和拉伸温度为Tm-20℃到Tm+10℃,更优选为Tm-10℃到Tm+5℃,其中Tm是SPC的结晶熔融峰温度。在另一个实施方案中,在拉伸之前,允许膜达到平衡温度,和拉伸温度为Tm-50℃到Tm+10℃。
对于从两种或多种聚合物的共混物形成的SPC,由于聚合物共混物可具有多个熔融峰,此温度范围会变宽。在这样的SPC共混物情况下,转变温度上限会控制拉伸温度上限。例如,当采用单一聚合物SPC时,在拉伸之前,允许膜达到平衡温度。在此情况下,优选的拉伸温度为Tm1-20℃到Tm2+10℃,更优选为Tm1-10℃到Tm2+5℃,其中Tm1是共混SPC的最低结晶熔融峰温度和Tm2是共混SPC的最高结晶熔融峰温度。
优选的双轴拉伸尺寸为约200%×200%到约850%×850%,更优选约300%×300%到约800%×800%,甚至更优选约400%×400%到约700%×700%。对于200%×200%拉伸的假想实施例表示10cm×10cm的膜样品会被伸长到公称的20cm×20cm。最小伸长或拉伸通过膜从半透明到白色的颜色可见变化而识别。不限制本发明的范围,相信膜的变白是由膜中空隙对光的散射而产生的,该空隙由在不相容HPC和SPC相之间界面处的分离引起。这些空隙也结合以形成通过膜厚度的迂回路径,因此使膜变成半渗透的,或选择性渗透的。最大伸长可以在上述极限之前在从一些非最优共混物的膜中达到,和/或在非最优拉伸温度下,在更小的牵伸比下拉伸。
在伸长力的释放之后,允许膜回缩。SPC/HPC共混物、伸长尺寸、和伸长温度的优选结合,可导致回缩到永久伸长形变的膜,相对于伸长之前的膜,形变为约150%×150%到约850%×850%,更优选约250%×250%到约800%×800%,甚至更优选约350%×350%到约700%×700%。
最终膜性能
在一个实施方案中,在冷拉伸之后,膜的拉伸模量优选小于160MPa,更优选小于100MPa,甚至更优选小于80MPa。
在另一个实施方案中,在冷拉伸之后,膜的拉伸模量优选小于375MPa,更优选小于250MPa,甚至更优选小于200MPa。
与根据每种膜共混物组分WVTR的重量平均值所期望的相比,根据本发明的膜显示更高的水汽透过率(WVTR)。根据本发明的优选膜显示的WVTR至少为100gm-密耳/m2-天,更优选至少200gm-密耳/m2-天,甚至更优选至少300gm-密耳/m2-天,甚至优选至少500gm-密耳/m2-天,最优选至少1000gm-密耳/m2-天。
在本发明的另一个实施方案中,相对于拉伸之前的模糊半透明膜,透气膜也是基本均匀的白色。
实施例
测试方法
熔点(Tm)、玻璃化转变温度(Tg)、熔化热(ΔHf)、多个熔融峰,和与结晶熔融或结晶检测有关的任何测量可由差示扫描量热法(DSC)测量或从通常可接受的出版物获得,如在聚合物体系的原理,Rodriguez,第二版,McGraw Hi1l Chemical Engineering Series,38页,表3-1中所示的典型转变温度。通过ASTM D-3417的改进版进行DSC。优选,将约6mg-约10mg在大约200℃-230℃下压挤的优选聚合物片材,采用冲压模除去和在室温下老化至少24小时。在此期间结束时,将样品放入差示扫描量热计中和冷却到约-50℃到-70℃。将样品以约10-20℃/分钟加热,以达到约200℃-约220℃的最终温度。将热输出记录为样品熔融峰下的面积,样品的最大峰温度典型地在约30℃-约150℃,和发生在约0℃-约180℃的温度之间。热输出以焦耳测量为熔化热的测量值。熔点记录为在样品熔融温度范围内的最大热吸收温度。
拉伸模量由ASTM方法D-1708测量。
弯曲模量由ASTM方法D-790测量。
割线模量由ASTM方法D-882测量。
门尼粘度由ASTM方法D-1646测量。
熔融指数(MI)由ASTM方法D-1238(E)测量。
熔体流动速率(MFR)由ASTM方法D-1238(L)测量。
通过凝胶渗透色谱在Waters 150凝胶渗透色谱检测器和Chromatic KMX-6在线性光散射光度计上,测量重均分子量和数均分子量(Mw和Mn)。在135℃下,采用1,2,4-三氯苯作为流动相使用系统。使用Showdex(购自Showa Denko America,Inc.)聚苯乙烯凝胶柱802,803,804,和805。此技术讨论在“聚合物和相关材料的液相色谱III”编辑J.Cazes,Marcel Dekker,1981,207页。不采用柱扩展的修正。从洗脱次数计算Mw/Mn。使用市售Beckman/CIS LALLS软件结合标准凝胶渗透包进行数字分析。
可以通过傅里叶变换红外光谱(FTIR),结合受GPC控制的样品,测量离散分子量范围的共聚单体含量。一种这样的方法描述在Wheeler和Willis,应用光谱,1993,47卷,1128-1130页。不同但相似的方法对于此目的起同等的功能和对本领域技术人员是公知的。
可以通过碳13核磁共振(C-13NMR)测量SPC的共聚单体含量和序列分布,这样的方法对本领域技术人员是公知的。
根据ASTM E-96-99(E)测试水汽透过率(WVTR),区别在于将温度从38℃变化到30℃和将相对湿度从90%变化到100%。WVTR测试的另一种来源是PDL塑料和弹性体的渗透性和其它膜性能,PDL手册系列,1995。
组成分布宽度指数(CDBI),定义为共聚单体含量为中值总摩尔共聚单体含量的50%之内(即在每侧为50%)的共聚物分子的重量百分数。CDBI测量可以采用升温洗脱分级(TREF)进行,如在本领域公知的那样。该技术由Wild等描述在聚合物科学杂志,聚合物物理编辑,20卷,441页(1982),和描述在1993年2月18日公开的PCT专利申请WO93/03093中。
溶解度分布宽度指数(SDBI)是测量共聚单体在含有变化分子量和MWD的组分的共聚物中的分布的措施,如在U.S.专利No.5,008,204和PCT公开的申请WO 93/03093中的那样。
在上述测试程序中参考的所有公开文献和规范在些全文引入作为参考,用于U.S.专利实践的目的。
样品制备和测试
采用如下共混物组分进行试验。
SPC1是聚丙烯共聚物,包含作为共聚单体的12wt%乙烯,剩余部分是丙烯,门尼粘度ML(1+4)@125℃为13-14。使用已知有利于统计无规引入乙烯共聚单体和丙烯加成以生产间规构型的手性金属茂催化剂,生产共聚物。共聚物是热塑性弹性体和Tm为约65℃,该值衍生自由于等规聚丙烯五单元组的结晶度。此共聚物根据以下文献的描述生产:在先未决的U.S.申请USSN 60/133,966,提交日1999年5月13日,USSN 60/342,854,提交日1999年6月29日,和以“丙烯烯烃共聚物”进一步详细描述在USSN 09/346,460中,提交日1999年7月1日。
SPC2包含14wt%乙烯的聚丙烯共聚物。该共聚物使用如上所述用于SPC1的手性金属茂催化剂生产。共聚物是热塑性弹性体和Tm为约50℃,该值衍生自由于等规聚丙烯五单元组的结晶度。
SPC3是由德克萨斯,休斯顿的ExxonMobil Chemical Company以ExactTM4033聚合物销售的聚乙烯共聚物。此共聚物的密度为0.880g/cm3,MI大约为0.8g/10min.,Tm约为60℃。
SPC4是由德克萨斯,休斯顿的ExxonMobil Chemical Company以ExactTM4011聚合物销售的聚乙烯共聚物。此共聚物的密度为0.887g/cm3,MI为2.2和熔融温度大约为68℃。
HPC1是MI为7.5g/10min.的聚苯乙烯均聚物,购自威斯康星,密尔沃基的Aldrich Chemical Company。
HPC2是由德克萨斯,休斯顿的ExxonMobil Chemical Company销售的HD7755聚乙烯聚合物。此聚合物的密度为0.95g/cm3,MI大约为0.055,Tm约为130℃。
HPC3是由德克萨斯,休斯顿的ExxonMobil Chemical Company销售的HD6705聚乙烯聚合物。此聚合物的密度为0.9525g/cm3,MI大约为19,Tm约为127℃。
HPC4是由德克萨斯,休斯顿的ExxonMobil Chemical Company销售的聚乙烯聚合物。此聚合物的密度为0.9525g/cm3,MI大约为7,Tm约为129℃。
A1是购自北卡罗来纳,Greensboro,Ciba-Geigy Corp.的抗氧剂IrganoxTMIR 1076。
将选自如上所列的软聚合物和硬聚合物以如表1-6中所示的重量比共混,和成形为压挤膜用于进一步的测试和评价。对于相似尺寸的混合机,每种共混物部分是大约40克。在Brabender混合机中,在190℃-200℃下,将每种共混物混合5分钟,混合头速度为约60rpm。然后使用Carver压力机,将每种共混物压挤成约10cm×10cm×254微米厚的膜。在接触压力下,首先将共混的聚合物部分放置在压力机上一段时间,然后在负荷下保持固定的时间,和最后在不同的负荷下冷却一段时间。混合和压挤工艺的具体时间、压力和温度见表1-6。
在T M Long伸长机器上进行伸长之前,在环境条件(23℃和大气压)下,将在表1-6中制备的所有膜老化至少2周。在伸长或拉伸之前,从原始膜切割尺寸大约为5cm×5cm的样品。膜变白的观察用作指示空隙形成,和进而指示透气性。拉伸尺寸、条件和时间和拉伸膜的操作性能也见表1-6。
表1-膜制备和测试
实施例 | 1 | 2 | 3 | 4 | 5 |
SPC1(wt.%) | - | - | - | - | - |
SPC2(wt.%) | - | - | - | - | - |
SPC3(wt.%) | 80 | 75 | 70 | 70 | 70 |
HPC1(wt.%) | 20 | 25 | 30 | 30 | 30 |
HPC2(wt.%) | - | - | - | - | - |
HPC3(wt.%) | - | - | - | - | - |
A1(wt.%) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
混合温度(℃) | 190 | 190 | 190 | 190 | 190 |
混合时间(min.) | 5 | 5 | 5 | 5 | 5 |
压挤温度(℃) | 180 | 180 | 180 | 180 | 180 |
压力机中时间@接触压力(min.) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
压力机中时间@负荷(min.@lbs.) | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 |
冷硬板上时间@负荷(min.@lbs.) | 2@5000 | 2@5000 | 2@5000 | 2@5000 | 2@5000 |
预热温度,°F(℃) | 130(54) | 130(54) | 130(54) | 120(49) | 140(60) |
握紧压力(psi) | 450 | 450 | 450 | 450 | 450 |
伸长速率(in./sec) | 1 | 1 | 1 | 1 | 1 |
预热时间(sec) | 15 | 15 | 15 | 15 | 15 |
预伸长时间(sec) | 5 | 5 | 5 | 5 | 5 |
在MD和TM两者上的伸长(%) | 600 | 650 | 650 | 650 | 650 |
变白 | 是 | 是 | 是 | 是 | 是 |
弹性 | 是 | 是 | 是 | 是 | 是 |
WVTR(gm-密耳/m2-天) | 57 | 258 | 472 | 370 | 2063 |
备注:所有的wt.%基于是100%的SPC+HPC
SPC3具有预测的约47gm-密耳/m2-天的WVTR。HPC1的渗透性显然比SPC3差。因此,预期SPC3和HPC1的任何共混物具有比单独SPC3更低的WVTR。相反,表1中实施例1-5显示所有五种共混物都具有比单独SPC3更大的WVTR。
实施例1-3显示WVTR随共混物中HPC的重量分数而增加。然而,根据组分的粘度比例,应当限制最大的HPC含量,以保持HPC在分散相中。
实施例3-5显示WVTR随着伸长操作进行的温度而增加。然而,由于连续SPC组分的软化和/或熔融,应当限制最大的拉伸温度以防止膜的撕裂。此温度会根据SPC和HPC共混物组分的特定选择和它们在共混物中的相对含量而变化。
表2-膜制备和测试
实施例 | 6 | 7 | 8 | 9 | 10 | 11 |
SPC1(wt.%) | 80 | 75 | 70 | 60 | 50 | 40 |
SPC2(wt.%) | - | - | - | - | - | - |
SPC3(wt.%) | - | - | - | - | - | - |
HPC1(wt.%) | 20 | 25 | - | - | - | - |
HPC2(wt.%) | - | - | 30 | 40 | 50 | 60 |
HPC3(wt.%) | - | - | - | - | - | - |
A1(wt.%) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
混合温度(℃) | 190 | 190 | 190 | 190 | 190 | 190 |
混合时间(min.) | 5 | 5 | 5 | 5 | 5 | 5 |
压挤温度(℃) | 180 | 180 | 180 | 180 | 180 | 180 |
压力机中时间@接触压力(min.) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
压力机中时间@负荷(min.@lbs.) | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 |
冷硬板上时间@负荷(min.@lbs.) | 2@5000 | 2@5000 | 2@5000 | 2@5000 | 2@5000 | 2@5000 |
预热温度,°F(℃) | 140(60) | 150(66) | 150(66) | 150(66) | 150(66) | 165(74) |
握紧压力(psi) | 300 | 300 | 300 | 300 | 300 | 300 |
伸长速率(in./sec) | 1 | 1 | 1 | 1 | 1 | 1 |
预热时间(sec) | 15 | 15 | 15 | 15 | 15 | 15 |
预伸长时间(sec) | 5 | 5 | 5 | 5 | 5 | 5 |
在MD和TM两者上的伸长(%) | 500 | 600 | 500 | 500 | 550 | 550 |
变白 | 是 | 是 | 是 | 是 | 是 | 是 |
弹性 | 是 | 是 | 是 | 是 | 是 | 是 |
WVTR(gm-密耳/m2-天) | 436 | 3756 | 98 | 55 | 27 | 1275 |
备注:所有的wt.%基于是100%的SPC+HPC
SPC1具有预测的约65gm-密耳/m2-天的WVTR。HPC1和HPC2每种比SPC1渗透性基本更小。因此,预期SPC3与HPC1或HPC2的任何共混物具有比单独SPC1更低的WVTR。
实施例6-7显示WVTR随共混物中HPC的重量分数而增加。然而,再次,根据组分的粘度比例,应当限制最大的HPC含量,以保持HPC在分散相中。
实施例8-11显示WVTR最后随共混物中HPC的重量分数而增加。然而,当HPC含量增加时,这些实施例显示WVTR的初始降低。不希望限制本发明的范围或受任何理论的约束,相信这是由于不希望的共混物形态,该形态是由于HPC相对于SPC的高粘度。因此,包含具有相对于SPC更高粘度的HPC(在熔融相中,在通常温度下)的共混物应当具有在HPC/SPC共混物中的优选HPC含量范围,该含量比具有较低相对粘度的HPC的优选HPC含量更高。
表3-膜制备和测试
实施例 | 12 | 13 | 14 | 15 | 16 |
SPC1(wt.%) | - | - | - | - | - |
SPC2(wt.%) | 70 | 70 | - | - | - |
SPC3(wt.%) | - | - | 70 | 80 | 60 |
HPC1(wt.%) | - | - | 30 | 20 | 40 |
HPC2(wt.%) | - | 30 | - | - | - |
HPC3(wt.%) | 30 | - | - | - | - |
Al(wt.%) | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
混合温度(℃) | 190 | 190 | 190 | 190 | 190 |
混合时间(min.) | 5 | 5 | 5 | 5 | 5 |
压挤温度(℃) | 180 | 180 | 180 | 180 | 180 |
压力机中时间@接触压力(min.) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
压力机中时间@负荷(min.@lbs.) | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 | 1.5@1500然后3@15000 |
冷硬板上时间@负荷(min.@lbs.) | 2@5000 | 2@5000 | 2@5000 | 2@5000 | 2@5000 |
预热温度,°F(℃) | 100(38) | 100(38) | 120(49) | 120(49) | 200(93) |
握紧压力(psi) | 400 | 300 | 400 | 400 | 400 |
伸长速率(in./sec) | 1 | 1 | 1 | 1 | 1 |
预热时间(sec) | 15 | 15 | 20 | 20 | 20 |
预伸长时间(sec) | 5 | 5 | 5 | 5 | 5 |
在MD和TM两者上的伸长(%) | 650 | 550 | 600 | 600 | 400 |
变白 | 是 | 是 | 是 | 是 | 是 |
弹性 | 是 | 是 | 是 | 是 | 是 |
WVTR(gm-密耳/m2-天) | 160 | 73 | >200 | >200 | >200 |
备注:所有的wt.%基于是100%的SPC+HPC
SPC2和SPC3分别具有预测的65gm-密耳/m2-天和47gm-密耳/m2-天的WVTR。HPC1,HPC2和HPC3每种的渗透性比SPC2或SPC3基本较小。因此,预期SPC2或SPC3与HPC1,HPC2或HPC3的任何共混物具有比单独SPC更低的WVTR。相反,表3中实施例12-16显示所有五种共混物都具有比单独SPC更大的WVTR。
实施例12-13进一步显示当HPC的相对(对于SPC)粘度增加时,WVTR降低,如在实施例8-11中讨论的那样。
实施例14-16显示WVTR随共混物中HPC的重量分数而增加。然而,根据组分的粘度比例,应当限制最大的HPC含量,以保持HPC在分散相中,如在实施例1-3中讨论的那样。
表4-膜制备和测试
实施例 | 17 | 18 | 19 | 20 | 21 | 22 |
SPC | SPC1 | SPC1 | SPC2 | SPC2 | SPC1 | SPC2 |
HPC | HPC2 | HPC2 | HPC3 | HPC3 | HPC2 | HPC2 |
重量分数 | 60∶40 | 60∶40 | 70∶30 | 70∶30 | 70∶30 | 70∶30 |
伸长温度°F(℃) | 95(35) | 145(63) | 100(38) | 150(66) | 100(38) | 100(38) |
最大拉伸(%) | - | 400 | 600 | 150 | 300 | 550 |
可伸长性 | 差 | 好 | 好 | 差 | 差 | 好 |
外观 | - | 白色 | 白色 | 白色 | 白色 | 白色 |
基本如在表1描述的那样,制备实施例17-22和在T M Long机器上伸长。在这些实施例中伸长温度的变化显示,在低温下,SPC1的可伸长性较差,几乎立即发生膜撕裂,但对于SPC2是良好的。SPC1具有大约65℃的Tm。SPC2具有大约50℃的Tm。
实施例17和21,相对于实施例18,显示显著低于SPC熔融温度的伸长温度产生差的可伸长性。实施例20,相对于实施例19和22,显示显著高于SPC熔融温度的伸长温度产生差的可伸长性。
表5-膜制备和测试
实施例 | 23 | 24 | 25 |
SPC | SPC4 | SPC4 | SPC4 |
HPC | HPC2 | HPC2 | HPC2 |
重量分数 | 70∶30 | 60∶40 | 50∶50 |
伸长温度°F(℃) | 145(63) | 145(63) | 145(63) |
最大拉伸 | 550 | 550 | 550 |
可伸长性 | 好 | 好 | 好 |
外观 | 模糊 | 模糊 | 模糊 |
基本如在表1描述的那样,制备实施例23-25和在T M Long机器上伸长。实施例23-25是不混溶的共混物体系,相对于实施例1-22,它具有更低的χSPC/HPC相互作用参数。在导致良好可伸长膜的拉伸条件下,对于任何共混物没有观察到变白现象。这说明没有空隙形成或较差的空隙形成,和因此较差的透气性。
表6-膜制备和测试
实施例 | 26 | 27 |
SPC | SPC1 | SPC1 |
HPC | HPC4 | HPC2 |
体积分数 | 70∶30 | 70∶30 |
伸长温度°F(℃) | 150(66) | 150(66) |
最大拉伸 | 500 | 500 |
可伸长性 | 好 | 好 |
外观 | 模糊 | 白色 |
包括实施例26和27用于完整说明,但相信实施例26在实验程序或这样实验的记录中有误差。
因此,本发明的膜具有高的水汽透过率,它赋予许多种功能,包括水汽渗透性、化学品气和/或液体不渗透性。此外,这样的膜可以连接到支撑层上以形成层压材料。
不限制本发明的范围,相信本发明的功能性涉及一种聚合物与另一种聚合物的平衡界面混合深度,它可以从两种聚合物A和B的Flory-Huggins χAB参数计算。(E.Helfand,Accounts of ChemicalResearch 8,295(1975))。已经列出几种聚合物结合物的渗透深度。(E.Helfand和A.M.Sapse,J.Chem.Phys.62(4),1327(1975))。一般情况下,界面厚度是相容性的量度,或在本发明情况下,是不相容性的量度。在此不相容性原理下生产透气膜的其它优选SPC/HPC共混物包括:上述聚丙烯共聚物SPC和作为HPC的聚(乙烯基吡咯烷酮);上述聚丙烯共聚物SPC和作为HPC的聚(2-乙烯基吡啶);上述聚乙烯共聚物SPC和作为HPC的聚(乙烯基吡咯烷酮);上述聚乙烯共聚物SPC和作为HPC的聚(2-乙烯基吡啶);上述聚乙烯共聚物SPC和作为HPC的等规聚丙烯;EVA SPC和聚(4-甲基戊烯-1)HPC;EVA SPC和聚苯乙烯HPC;EVA SPC和聚(甲基丙烯酸甲酯)(PMMA)HPC、EMA SPC和聚(4-甲基戊烯-1)HPC;EMA SPC和聚苯乙烯HPC;EMA SPC和PMMA HPC。
事实上,应当理解对于上述实施方案,可以进行宽范围的变化和改进。因此希望上述描述用于说明本发明而不是限制本发明,和如下的权利要求,包括所有的同等物,确定本发明。例如,本领域技术人员熟悉典型地用于这样膜的添加剂,添加剂是例如、但不限于染料、颜料、填料、蜡、增塑剂、抗氧剂、热稳定剂、光稳定剂、防粘连剂、加工助剂、及其结合物,和进一步包括填料。尽管已知在透气膜的生产中使用填料,然而,本发明的膜是透气的,而不需要这样的填料。然而,通过将填料加入到本发明的SPC/HPC共混物中,可以优化用于具体用途的膜的加工性能和透气性。
对于某些用途,可以将本发明的膜曝露在电晕放电或等离子体(氧、氟、氮等)下。对于其它用途,可以采用接技剂或偶合剂对膜表面进行化学改性或化学氧化以促进键合和/或粘合性能,或改变、增加或减少液体或气体的通量。
Claims (8)
1.一种冷拉伸膜,包括如下物质的共混物:
a)主要烯烃单体和少量烯烃单体的半结晶共聚物组分,该共聚物组分的熔点大于25℃和由ASTM D-790测得弯曲模量小于100MPa,其中该主要烯烃单体是丙烯,该少量烯烃单体是选自乙烯和能够进行插入聚合的C4-C20α-烯烃的一种或多种,及其结合物,和
b)聚乙烯均聚物或共聚物组分,该组分的密度为0.93g/cc或更大和由ASTM D-790测得弯曲模量大于200MPa,
其中该半结晶共聚物在该膜中以连续相存在和由ASTM D-1708测得该膜的拉伸模量小于160MPa。
2.权利要求1的膜,其中该半结晶共聚物的MWD为1.5-4.0,和具有窄的组成分布。
3.权利要求1的膜,其中该主要烯烃单体在该半结晶共聚物中的存在量大于或等于49摩尔%和小于或等于90摩尔%。
4.权利要求1的膜,其中该半结晶共聚物包含5-40wt%的结晶度。
5.权利要求1的膜,其中该少量烯烃单体是乙烯。
6.权利要求1的膜,包括30-90wt%的该共聚物组分和70-10wt%的该聚乙烯组分,基于共混物组分的总重量。
7.权利要求1的膜,进一步包括一种或多种选自如下的添加剂:染料、颜料、填料、蜡、增塑剂、抗氧剂、热稳定剂、光稳定剂、防粘连剂、加工助剂、及其结合物。
8.权利要求1的膜,其中该膜没有填料,和水汽透过率大于任意一种组分单独形成的膜。
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2000
- 2000-09-01 KR KR1020027002849A patent/KR100674761B1/ko not_active IP Right Cessation
- 2000-09-01 US US09/653,439 patent/US6444302B1/en not_active Expired - Lifetime
- 2000-09-01 AT AT00959751T patent/ATE350418T1/de not_active IP Right Cessation
- 2000-09-01 CN CNB008136122A patent/CN1209404C/zh not_active Expired - Fee Related
- 2000-09-01 EP EP00959751A patent/EP1228140B1/en not_active Expired - Lifetime
- 2000-09-01 CN CNB2004101046691A patent/CN100551675C/zh not_active Expired - Fee Related
- 2000-09-01 DE DE60032790T patent/DE60032790T2/de not_active Expired - Lifetime
- 2000-09-01 CA CA002383051A patent/CA2383051A1/en not_active Abandoned
- 2000-09-01 JP JP2001520779A patent/JP2003508570A/ja not_active Withdrawn
- 2000-09-01 MX MXPA02002276A patent/MXPA02002276A/es active IP Right Grant
- 2000-09-01 WO PCT/US2000/024061 patent/WO2001016228A1/en active IP Right Grant
- 2000-09-01 BR BR0014148-8A patent/BR0014148A/pt not_active IP Right Cessation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102438809A (zh) * | 2009-03-09 | 2012-05-02 | 伊欧维新有限责任公司 | 空穴化的取向聚乙烯聚合物组合物 |
WO2014088065A1 (ja) * | 2012-12-06 | 2014-06-12 | 三菱樹脂株式会社 | 透湿性フィルムおよびその製造方法 |
CN112048128A (zh) * | 2020-08-10 | 2020-12-08 | 金旸(厦门)新材料科技有限公司 | 一种软触感、耐划擦聚丙烯复合材料及其制备方法 |
CN112048128B (zh) * | 2020-08-10 | 2022-05-17 | 金旸(厦门)新材料科技有限公司 | 一种软触感、耐划擦聚丙烯复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60032790T2 (de) | 2007-11-08 |
CN100551675C (zh) | 2009-10-21 |
CN1209404C (zh) | 2005-07-06 |
EP1228140B1 (en) | 2007-01-03 |
ATE350418T1 (de) | 2007-01-15 |
EP1228140A1 (en) | 2002-08-07 |
MXPA02002276A (es) | 2002-07-30 |
BR0014148A (pt) | 2002-05-07 |
US6444302B1 (en) | 2002-09-03 |
CN1377385A (zh) | 2002-10-30 |
WO2001016228A1 (en) | 2001-03-08 |
KR20020029398A (ko) | 2002-04-18 |
KR100674761B1 (ko) | 2007-01-25 |
JP2003508570A (ja) | 2003-03-04 |
CA2383051A1 (en) | 2001-03-08 |
DE60032790D1 (de) | 2007-02-15 |
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