CN1735659A - 用于制造透明且不含凝胶的薄膜的苯乙烯系嵌段共聚物组合物 - Google Patents
用于制造透明且不含凝胶的薄膜的苯乙烯系嵌段共聚物组合物 Download PDFInfo
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- CN1735659A CN1735659A CNA2003801083590A CN200380108359A CN1735659A CN 1735659 A CN1735659 A CN 1735659A CN A2003801083590 A CNA2003801083590 A CN A2003801083590A CN 200380108359 A CN200380108359 A CN 200380108359A CN 1735659 A CN1735659 A CN 1735659A
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- vinylbenzene
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- 238000004458 analytical method Methods 0.000 description 2
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- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
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- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明揭示一种用于制造透明且不含凝胶的薄膜的组合物,其包含:a)至少65重量%的苯乙烯系嵌段共聚物,其具有一符合式S-(I/B)-S(1)或[S-(I/B)]nX(2)的分子结构,其中每一S均独立地为一主要由苯乙烯构成的聚合物嵌段,并且(I/B)为一主要是由异戊二烯和丁二烯构成的实质上无规聚合物嵌段,其中n为等于或大于2的整数,并且其中X为偶联剂的残基,其中所述苯乙烯系嵌段共聚物具有介于28至31重量%之间的聚(苯乙烯)含量、具有实际分子量介于10,000至15,000之间的聚(苯乙烯)嵌段S、具有介于110,000至160,000之间的整个嵌段共聚物实际分子量,并且其中二嵌段S-(I/B)含量视情况至多为20摩尔%;b)5至25重量%的第二热塑性树脂,c)1至10重量%的增塑油;所述组份a、b和c的百分比总计为100%,并且所有重量百分比均是相对于整个组合物及由其所制得的挤出、浇注或吹塑型单层或多层薄膜的重量而言。
Description
技术领域
本发明涉及用于制造透明且不含凝胶的薄膜的苯乙烯系嵌段共聚物组合物。
更特定而言,本发明涉及用于制造在个人卫生业中应用且具有改良品质的单或多层薄膜的苯乙烯系嵌段共聚物组合物,其包含一苯乙烯系嵌段共聚物,该苯乙烯系嵌段共聚物包含至少一个可由主要是异戊二烯和丁二烯的无规共聚合反应获得的中心嵌段。
背景技术
能被轻易挤压成具有低应力松弛、低滞后或永久变形及较高可恢复能量的弹性薄膜的弹性体组合物自(例如)美国专利第4,663,220号、第4,789,699号、第4,970,259号、第5,093,422号及第5,705,556号获知。
用于制造浇注挤出型薄膜及挤出型吹塑薄膜的方法必须满足组合物粘度的较高要求。
同时,在个人卫生中应用这些挤出物对机械性能有严格要求,即,即需要刚性(高模量)又需要有优良弹性(良好应力松弛及低滞后和永久变形)。
该领域中最大挑战之一仍然是在流动/粘度与上述机械特性间找到一良好平衡。
本发明的一目标是提供在个人卫生应用中特性平衡改进且更特定来说对于单或多层薄膜组合物特性平衡改进的组合物,即,显示出较高熔体流动速率(MFR)的组合物,其可提供更软、透明且不具有微孔/鱼眼/凝胶的薄膜,同时该些薄膜具有较低抗张强度、较低模量及较低残余变形。
发明内容
因此,本发明提供一种用于制造透明且不含凝胶的薄膜的组合物,其包含:
a)至少65重量%的苯乙烯系嵌段共聚物,其具有一根据式S-(I/B)-S(1)或[S-(I/B)]nX(2)的分子结构,其中每一S均独立地为一主要是由苯乙烯构成的聚合物嵌段,且(I/B)为一主要是由相互重量比介于30/70至70/30之间的异戊二烯与丁二烯构成的大致无规聚合物嵌段,其中所述聚合物嵌段(I/B)具有一最高为-60℃的玻璃化转变温度(Tg)(根据ASTM E-1356-98测定),其中n为一等于或大于2的整数,且其中X为偶联剂的残基,其中所述苯乙烯系嵌段共聚物具有介于28至31重量%之间的聚(苯乙烯)含量、具有实际分子量介于10,000至15,000之间的聚(苯乙烯)嵌段S、具有介于110,000至160,000之间的整个嵌段共聚物表观分子量,且其中二嵌段S-(I/B)视情况含量至多为20摩尔%。
b)5至25重量%的热塑性树脂,其与组份(a)不同,
c)1至10重量%的增塑油,组份a、b和c的百分比总计为100%,且所有重量百分比均为相对于整个组合物的重量而言。
应了解,本发明的另一方面由挤出型单或多层薄膜构成,且更特定而言由用于个人卫生应用的浇注或吹塑型单或多层薄膜构成,这些薄膜由上文所详述组合物制造。
具体实施方式
本发明的组合物包含至少65重量%的至少一种具式S-(I/B)-S或[S-(I/B)]n X的嵌段共聚物,且其主要由异戊二烯与丁二烯获得。
所述组合物较佳包含重量比为70至90重量%的所述嵌段共聚物。
在较佳组合物中,I/B嵌段中异戊二烯与丁二烯间的相互重量比介于40/60至60/40重量%之间,更佳介于45/55至55/45重量%之间,且最佳介于48/52至52/48重量%范围内。
本专利说明书全文中所用术语”主要是苯乙烯”及”主要是丁二烯”意指,对于待制备的相应嵌段,可使用大致纯的苯乙烯或包含至少95重量%苯乙烯及少量其他共聚单体的混合物,及可使用大致纯的丁二烯或包含至少95重量%丁二烯及少量其他共聚单体的混合物。
聚苯乙烯嵌段中小部分的其他共聚单体可由结构上相关的共聚单体组成,例如α-甲基苯乙烯、对-甲基苯乙烯、邻-甲基苯乙烯、对-叔丁基苯乙烯、二甲基苯乙烯及乙烯基萘或丁二烯及/或异戊二烯。
聚(异戊二烯/丁二烯)嵌段中小部分的其他共聚单体可由苯乙烯及/或结构上相关的链烷二烯组成。
然而,根据本发明应用的较佳嵌段共聚物包含由大致纯的苯乙烯及大致纯的异戊二烯与丁二烯混合物构成的嵌段。
根据本发明的嵌段共聚物可为具支链或直链,且可为三嵌段、四嵌段或多嵌段。
其结构可以下述通式表示:
S-(I/B)-S(1)或[S-(I/B)]nX (2)
其中每一S均独立地为一主要是由苯乙烯构成的聚合物嵌段,且(I/B)为一是异戊二烯与丁二烯的大致无规聚合混合物构成的共聚物嵌段,异戊二烯与丁二烯间相互重量比介于40/60至60/40重量%之间,较佳介于45/55至55/45重量%之间,且更佳介于48/52至52/48重量%之间,其中所述(I/B)嵌段具有一最高为-60℃且较佳介于-85至-75℃之间的玻璃化转变温度(Tg)(根据ASTME-1356-98测定),其中n为一等于或大于2的整数,且其中X为偶联剂的残基。
聚合物嵌段S具有介于10,000至15,000之间且较佳介于10,500至14,800之间的实际分子量。
本发明组合物中所用的较佳嵌段共聚物具有介于115,000至155,000之间的表观总分子量。
所述嵌段共聚物中聚(苯乙烯)含量(PSC)介于28至31重量%之间,且较佳介于29至30重量%之间。
以共轭二烯的重量计,根据本发明使用的嵌段共聚物较佳含有比例为至多15重量%且优选为 至多10重量%的1,2-乙烯基键结及/或3,4-乙烯基键结。
在介于0至50℃之间的温度(7)下进行的粘弹性测量中,根据本发明的嵌段共聚物较佳具有介于1至10Mpa的储能模量(g1),并且在-55℃或更低温度下仅具有一个由混合异戊二烯/丁二烯聚合物嵌段导致的损耗角正切(tanδ)峰。
术语“异戊二烯与丁二烯的大致无规聚合混合物”实际上意思是所述中心(I/B)嵌段仅含有小于100单体单位、较佳小于50单体单位且更佳小于20单体单位的平均均聚物嵌段长度。
所述平均均聚物嵌段长度可以由各种方法测定。
本发明应用中所用的方法是基于碳-13NMR,并且所述方法已详细揭示于WO02/057386A的第12、13、14及15页中。
根据本发明的嵌段共聚物可通过以下制备:在一惰性有机溶剂中通过阴离子聚合反应,分别地使预定批的主要是苯乙烯单体、异戊二烯/丁二烯混合物及主要是苯乙烯进行全顺序聚合反应(对于三嵌段共聚物S-(I/B)-S而言);或使最初制备的活性二嵌段共聚物(在一惰性有机溶剂中通过阴离子聚合反应,使预定批的主要是苯乙烯及主要是异戊二烯/丁二烯进行顺序聚合反应获得)与一偶联剂偶联(以提供三嵌段或多嵌段共聚物)。
在两种制备方法中,剩余活性嵌段共聚物必须通过添加一供质子剂(例如,烷醇(例如乙醇)或水)终止。
应了解,通过用一偶联剂偶联活性二嵌段共聚物及终止剩余活性二嵌段共聚物所制备的嵌段共聚物,最终将包含少量(即,小于20摩尔%,较佳小于15摩尔%,且更佳小于10摩尔%)具有相同S嵌段的二嵌段共聚物(摩尔%是相对于总嵌段共聚物的重量而言)。
可提及的偶联剂实例为:锡偶联剂,例如二氯化锡、单甲基二氯化锡、二甲基二氯化锡、单乙基二氯化锡、二乙基二氯化锡、甲基三氯化锡、单丁基二氯化锡、二丁基二溴化锡、单己基二氯化锡及四氯化锡;卤化硅偶联剂,例如二氯硅烷、单甲基二氯硅烷、二甲基二氯硅烷、二乙基二氯硅烷、单丁基二氯硅烷、二丁基二氯硅烷、单己基二氯硅烷、二己基二氯硅烷、二溴硅烷、单甲基二溴硅烷、二甲基二溴硅烷、四氯化硅及四溴化硅;烷氧基硅烷,例如四甲氧基硅烷;二乙烯基芳香族化合物,例如二乙烯基苯及二乙烯萘;卤代烷烃,例如二氯乙烷、二溴乙烷、二氯甲烷、二溴甲烷、二氯丙烷、二溴丙烷、氯仿、三氯乙烷、三氯丙烷及三溴丙烷;卤代芳香族化合物,例如二溴苯;环氧化合物,例如双酚A二缩水甘油醚(例如,EPON 825或EPON 826,商标名)及其他偶联剂,例如安息香酯、CO2、2-氯丁二烯及1-氯-1,3-丁二烯及己二酸二乙酯或己二酸二甲酯。
在这些EPON 825中,二缩水甘油醚、二溴苯、四甲氧基硅烷及二甲基二氯硅烷较佳。
整个嵌段共聚物及每一个中间体前驱体的表观分子量已使用ASTM D 3536中所述方法通过凝胶渗透色谱法测定,并以标准聚(苯乙烯)表示。
一般而言,本发明中所用聚合物可通过使单体与一有机碱金属化合物在一合适溶剂中在介于-150℃至300℃之间(较佳0℃至100℃之间)的温度下接触制备。特别有效的聚合反应起始剂为具通式RLi的有机锂化合物,其中R为一具有1至20个碳原子的脂肪族、环脂族、经烷基取代的环脂族、芳香族或经烷基取代的芳香族烃基团,其中仲丁基较佳。
合适的溶剂包括那些可用于聚合物溶液聚合反应中者,包括脂肪族、环脂族、经烷基取代的环脂族、芳香族及经烷基取代的芳香族烃、醚及其混合物。则合适的溶剂包括脂肪族烃(例如丁烷、戊烷、己烷及庚烷)、环脂族烃(例如环戊烷、环己烷及环庚烷)、经烷基取代的环脂族烃(例如,甲基环己烷及甲基环庚烷)、芳香烃(例如,苯)及经烷基取代的烃(例如甲苯及二甲苯)及醚(例如,四氢呋喃、二乙基醚及二正丁基醚)。溶剂较佳为环戊烷或环己烷。
通过仅修改用于制备S-B-S型嵌段共聚物及/或S-I-S型嵌段共聚物的通用方法且代之以使用丁二烯/异戊二烯混合物即可制得通式(1)及(2)的嵌段共聚物。制备本发明嵌段共聚物时重要的是避免生成均聚物嵌段,确保适当的B/I比,并生成一其中无规嵌入段的Tg为-60℃或更低的聚合物嵌段。这通常会排除使用随机性反应器,例如Kuraray在生产氢化苯乙烯异戊二烯/丁二烯嵌段共聚物时所使用的反应器(参见美国专利第5,618,882号,该案并入本文中)。
通过在混合嵌入段形成期间添加一或两种共聚单体来修改所述方法亦很有益。
组份(b)
第二种不同的热塑性聚合物组份(b)选自由下述组成的群组:聚烯烃、聚苯乙烯树脂、香豆素-茚树脂、聚茚树脂、聚(甲基茚)树脂、α-甲基苯乙烯树脂、聚亚苯基树脂(且尤其是聚(2,6-二甲基-1,4-亚苯基醚)或所述树脂的混合物或苯乙烯与其他相容共聚单体(例如,α-甲基苯乙烯、甲基苯乙烯、乙烯基甲苯)的共聚物。
合适的聚(烯烃)树脂的实例为聚(乙烯)、聚丙烯或乙烯、丙烯单独或与其他共聚单体(例如EPDM)的共聚物。
聚(乙烯)的实例为HDPE、LDPE、LLDPE。亦可使用利用金属茂催化剂制备的乙烯或丙烯聚合物。
组份(b)较佳为聚苯乙烯,包括高分子量(即,超过30,000)的透明聚(苯乙烯)、韧性聚(苯乙烯)或其他聚(苯乙烯)均聚物或苯乙烯与其他相容共聚单体(例如,α-甲基苯乙烯、甲基苯乙烯、乙烯基甲苯)的共聚物或聚苯乙烯与聚(亚苯基)树脂的掺合物。
组份(b)更佳为BASF的PS 144c聚(苯乙烯)树脂。所述聚苯乙烯提供于本发明组合物中能形成透明的水白色薄膜。
该组合物较佳包含相对于整个组合物重量而言8至12重量%的第二种不同聚合物。
组份(c)
合适的增塑剂包括增塑油,例如低芳香含量烃油,性质为石蜡油或环烷油(芳香碳含量<5%,较佳<2%,更佳0%,根据DIN 51378测定)。那些产品在皇家荷兰/壳牌公司集团(Royal Dutch/Shell)有售,例如SHELLFLEX、CATENEX及ONDINA油。其他油包括Witco的KAYDOL油或Arco的TUFFLO油或EXXON-MOBIL的PRIMOL油。其他增塑剂包括相容性液体粘性树脂,例如REGALREZ R-1018(SHELLFLEX、CATENEX、ONDINA、KAYDOL、TUFFLO、PRIMOL及REGALREZ为商标)。
亦可添加其他的增塑剂,例如烯烃寡聚物;低分子量聚合物(<30,000g/mol),例如液态聚丁烯、液态聚异戊二烯共聚物、液态苯乙烯/异戊二烯共聚物或液态氢化苯乙烯/共轭二烯共聚物;植物油及其衍生物;或石蜡及微晶蜡。
增塑剂更佳地是指一种选自石蜡油或环烷油的增塑油,其用量相对于整个组合物的重量而言在4至6重量%之间。
额外助剂
其他橡胶组份可纳入根据本发明的粘合组合物中。在所述技术领域中也已知,可添加各种其他组份来改良本发明组合物及所得薄膜的粘性、气味、颜色。也可添加抗氧化剂和其他稳定成份来保护本发明组合物使其避免由热、光及加工而引发降解或者在储存期间发生降解。
可使用几种类型的抗氧化剂,有主要抗氧化剂(例如受阻酚)或次要抗氧化剂(例如亚磷酸盐衍生物)或其掺合物。市售抗氧化剂的实例为Ciba-Geigy的I RGANOX 565(2.4-双-(正辛硫基)-6-(4-羟基-3,5-二-叔丁基苯胺基)-1,3,5-三嗪)、Ciba-Geigy的IRGANOX 1010(四-次乙基-3,5-二叔丁基-4-羟基-氢化肉桂酸酯)甲烷)及Uniroyal的POLYGARD HR(亚磷酸三-(2,4-二叔丁基苯基)酯)。亦可使用所研制的用于保护聚丁二烯片段胶凝的其他抗氧化剂,例如Sumitomo的SUMI LIZER GS(丙烯酸2[1-(2-羟基-3,5-二叔戊基苯基)乙基])-4,6-二叔戊基苯基酯)、Sumitomo的SUMILIZER T-PD(季戊四醇四(3-十二烷基硫代丙酸酯))或其混合物。(IRGANOX、POLYGARD及SUMILIZER均为商标名)。
组合物的制备
供制造薄膜用的本发明组合物的制备方法无特别限制。
因此,可使用任何方法,例如一使用辊、一班伯尼密炼机(Banbury mixer)或一Dalton捏揉机、或双螺杆挤出机的机械混合方法,由此获得目的组合物的均匀溶液。
组合物的用途
本发明的组合物可以用来制造透明、不含凝胶且较佳水白色、浇注挤出型或挤出吹塑型薄膜,已发现在处理条件下该等薄膜的机械特性与组合物粘度的组合极具吸引力。
更特定而言,所述组合物显示出在个人卫生业应用中薄膜各特性间的改良平衡,即,熔体流动速率(MFR)更高,同时可提供更软的透明水白色单或多层薄膜,所述薄膜显示出较低抗张强度、较低模量及较低残余变形并无微孔/鱼眼/凝胶。
下文中将参考下述实例及比较实例更具体地阐述本发明,然而,不应将本发明的范围限制为该些具体实施例。
顺便提一下,除非另有说明,否则所有将在下述实例中使用的“份数”及“%”标记均意指重量份数及重量%。
实例
嵌段共聚物A和B的合成。
环己烷、苯乙烯、丁二烯与异戊二烯由活性氧化铝纯化,并在一氮气气氛中在4℃下储存。
使用二溴甲烷(EDB)作为偶联剂。
合成前,制备丁二烯与异戊二烯的单体混合物(以表1中所给定的重量/重量比),并于4℃下在氮气中储存。
向装备有一螺旋形搅拌器的高压蒸汽灭菌锅装填上环己烷,将内容物加热至介于50至60℃之间的温度。
加入起始剂仲丁基锂,随后立即加入苯乙烯单体,让其聚合完全。将反应温度升至70℃,在该温度下加入一异戊二烯/丁二烯单体混合物(I/B)并使其反应。
将所得二嵌段或与过量EDB偶联,或进一步与另一批苯乙烯单体反应(对于S-(I/B)-S三嵌段共聚物,全顺序聚合反应)。
将过量偶联剂视情况用仲丁基锂清除,然后添加乙醇作为终止剂,或通过添加乙醇终止活性三嵌段共聚物。
将反应混合物冷却至40℃,转移至一掺合容器内,并添加一稳定封装(包含I RGANOX 565及磷酸三(壬基苯酚)酯,0.08/0.35phr,呈环己烷溶液形式)并于室温下搅拌。
通过蒸汽凝聚处理,然后在一恒温箱内干燥,获得干燥的嵌段共聚物。
根据美国专利第5,516,824号及第5,499,409号中所述的方法,通过GPC分析聚合物,该些专利案以引用的方式并入本文中。GPC分析结果列于表1中。
表1
聚合物 | A | B |
聚(苯乙烯)分子量*103总嵌段共聚物分子量*103偶联效率%聚(苯乙烯)含量I/B比B中乙烯基的重量%I中乙烯基的重量% | 14.81538629.550/5085 | 10.911730.050/5085 |
(I/B)嵌段中的平均均聚物嵌段长度已使用WO02/057386中所揭示的方法由13C NMR测定。
聚合物样品的13C NMR谱图由一在125MHz下操作的Bruker AMX-500FT谱仪获得。记录定量质子-去偶光谱,激发脉冲为90°13C,重复速率为10秒。使用溶于CDC13中的10%(w/w)聚合物溶液。为改良松弛时间,添加0.1mol/L的乙酰基丙酮酸铬盐。所用谱线增宽为2Hz。参考该光谱,使反式聚丁二烯的脂肪族碳为31.9ppm。
用1H NMR测定聚苯乙烯含量。玻璃化转变温度Tg已由差式扫描热量测定法测定,温度扫描为40℃/min。
转化开始时测量Tg。这些特定组合物中所用额外组份的详细情况已列于表2中。
用于制备浇注型薄膜的组合物通过在一Werner & Pfleiderer双螺杆挤出机内混合如表3中所列组份制备,同时所述组合物的相关物理特性亦在所述表3中详细列出。
表2
KRATOND1152ES | 直链苯乙烯-丁二烯-苯乙烯嵌段共聚物,PSC为29.5%,总分子量为122,000且偶联效率为83% |
KRATOND1161NS | 直链苯乙烯-异戊二烯-苯乙烯嵌段共聚物,PSC为15%,总分子量为220,000且偶联效率为81% |
KRATOND1102CS | 直链苯乙烯-丁二烯-苯乙烯嵌段共聚物,PSC为29.5%,总分子量为127,000且偶联效率为84% |
BASF PS 144c | 聚(苯乙烯)均聚物 |
PRIMOL 352 | 石蜡油 |
IRGANOX 565 | 抗氧化剂,购自CIBA-GEIGY |
EPOLENE C-10 | 低密度聚(乙烯),购自EASTMAN |
DOWLEX SC 2107 | 直链低密度聚(乙烯),购自DOW CHEMI CAL |
表3
实例 | I | II | III | IV | V | VI | VII | VIII | IX | X | I |
嵌段共聚物A | 70 | 70 | 85 | 90 | 85 | 90 | 85 | 90 | |||
嵌段其聚物B | 85 | 90 | |||||||||
KRATON D-1152ES | 70 | ||||||||||
KRATOND-1102CS | |||||||||||
KRATON D-1161NS | 15 | 20 | 15 | ||||||||
BASF PS 144c | 10 | 10 | 10 | 10 | 10 | 10 | 10 | ||||
Epolene C-10 | 10 | 10 | |||||||||
Dowlex SC2107 | 10 | 10 | |||||||||
Primol352 | 5 | 5 | 5 | 5 | 5 | 5 | |||||
Irganox565 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
MFR(200℃/5kg) | 21.7 | 12 | 14.5 | 6 | 23 | 12.5 | 11.5 | 6.5 | 22 | 12.5 | 13.5 |
浇注薄膜结果 | 透明,平均量/大小凝胶 | 透明,不含凝胶;最佳 | 透明,不含凝胶,最佳 | 透明,不含凝胶,最佳 | 不透明,橙色表皮 | 稍微不透明,橙色表皮 | 透明,少量凝胶;第三佳 | ||||
100%模量(MPa) | 1.22 | 1.62 | 1.83 | 2.79 | 1.99 | 2.25 | 2.22 | 2.57 | 1.75 | 2.22 | 1.39 |
200%模量(MPa) | 1.52 | 1.87 | 2.28 | 3.48 | 2.10 | 2.4 | 2.46 | 2.87 | 2.28 | 2.91 | 1.74 |
300%模量(MPa) | 1.85 | 2.22 | 2.64 | 4.13 | 2.25 | 2.58 | 2.68 | 3.24 | 3.05 | 3.66 | 2.14 |
500%模量(MPa) | 2.72 | 3.01 | 3.43 | 5.14 | 2.51 | 2.83 | 3.06 | 3.86 | 5.48 | 6.13 | 3.2 |
TS(MPa) | 5.1 | 5.4 | 6.2 | 9.2 | 5.1 | >8 | >8 | >14 | 11.7 | 21.4 | 6.8 |
EB(%) | 1170 | 1520 | 1710 | 1725 | 1655 | >2000 | >2000 | >2000 | 1435 | 1800 | 1420 |
第一滞后(%) | 52.5 | 63.9 | 55.6 | 572 | 61.7 | 65.3 | 61.0 | 62.5 | 284 | 39.0 | 51.9 |
第二滞后(%) | 36.5 | 44.0 | 33.8 | 33.4 | 34.2 | 36.7 | 345 | 36.3 | 16.0 | 19.3 | 35.8 |
残余变形(%) | 5.8 | 10.7 | 4.5 | 4.8 | 5.7 | 6.3 | 5.5 | 5.7 | 4.3 | 5.6 | 7.1 |
分子参数 | 嵌入段 | 步骤I | MW | PSC | CE | 偶联 |
嵌段共聚物A | 50/50B/I | 14.8 | 153 | 29.5 | 86 | 全 |
嵌段共聚物B | 50/50B/I | 10.9 | 117 | 30 | 100 | 顺序 |
测试法
·熔体流动速率(MFR):ASTM D 1238-95(230℃,2.16kg)
·符合ASTM D 882-81的抗张特性(在薄膜上测试)
·滞后:将薄膜以100mm/sec伸长至80%延伸率(负载步骤)并保持30秒,然后松弛至力为零(无负载步骤)。在第一循环之后立即进行一第二循环。所测量滞后为负载与无负载步骤间的能量差。所测量永久变形为第一循环的原始样品长度(力等于零)与第二循环前的样品长度(力等于零)间的差。
由表4结果可了解到,与包含SBS与SIS嵌段共聚物的掺合物的组合物相比,在组合物I至X中使用嵌段共聚物A及B(S-(I/B)-S)能提供改良的处理稳定性、改良的薄膜品质及至少相等的机械特性。
Claims (10)
1、一种用于制造透明且不含凝胶的薄膜的组合物,其包含:
a)至少65重量%的苯乙烯系嵌段共聚物,其具有一符合式S-(I/B)-S(1)或[S-(I/B)]nX(2)的分子结构,其中每一S均独立地为一主要是由苯乙烯构成的聚合物嵌段,并且(I/B)为一主要是由相互重量比介于30/70至70/30之间的异戊二烯与丁二烯构成的实质上无规聚合物嵌段,其中所述聚合物嵌段(I/B)具有最高为-60℃的玻璃化转变温度(Tg)(根据ASTM E-1356-98测定),其中n为等于或大于2的整数,并且其中X为偶联剂的残基,其中所述苯乙烯系嵌段共聚物具有介于28至31重量%之间的聚(苯乙烯)含量、具有实际分子量介于10,000至15,000之间的聚(苯乙烯)嵌段S、具有介于110,000至160,000之间的整个嵌段共聚物表观分子量,并且其中所述二嵌段S-(I/B)含量视情况至多为20摩尔%,
b)5至25重量%的第二热塑性树脂,
c)1至10重量%的增塑油,所述组份a、b与c的百分比总计为100%,并且所有重量百分比均是相对于所述整个组合物的重量而言。
2、根据权利要求1所述的组合物,其中所述组份(a)的重量比介于70至90重量%之间。
3、根据权利要求1所述的组合物,其中所述聚合物嵌段(I/B)的平均均聚物嵌段长度PB、PI分别小于100个单体单位,较佳小于50个单体单位且更佳小于20个单体单位。
4、根据权利要求3所述的组合物,其中异戊二烯与丁二烯间的所述相互重量比介于48/52至52/48之间。
5、根据权利要求1所述的组合物,其中组份(b)的重量比介于8至12重量%之间。
6、根据权利要求1所述的组合物,其中组份(b)选自:聚(苯乙烯)、聚乙烯、聚丙烯或乙烯与丙烯的共聚物。
7、根据权利要求1所述的组合物,其中所述组份(c)的重量比介于4至6重量%之间。
8、根据权利要求1所述的组合物,其中所述组份(a)包含具有一介于10,500至15,000之间的实际分子量的聚(苯乙烯)嵌段S,并且所述嵌段共聚物具有115,000至155,000的表观分子量,具有29至30%的聚(苯乙烯)含量并具有0至15摩尔%的二嵌段S-(I/B)含量。
9、一种由根据权利要求1至8所述的组合物制得的挤出型单层或多层薄膜。
10、一种由根据权利要求1至8所述的组合物制得的用于个人卫生应用中的浇注型或吹塑型单层或多层薄膜。
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- 2003-12-03 AU AU2003298341A patent/AU2003298341A1/en not_active Abandoned
- 2003-12-03 CN CN200380108359A patent/CN100588667C/zh not_active Expired - Fee Related
- 2003-12-03 JP JP2004558106A patent/JP4430546B2/ja not_active Expired - Fee Related
- 2003-12-03 WO PCT/EP2003/050931 patent/WO2004052989A1/en active IP Right Grant
- 2003-12-03 DE DE60308061T patent/DE60308061T2/de not_active Expired - Lifetime
- 2003-12-03 KR KR1020057010176A patent/KR100702724B1/ko not_active IP Right Cessation
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Cited By (5)
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CN103298879A (zh) * | 2010-12-30 | 2013-09-11 | 科腾聚合物美国有限责任公司 | 弹性膜/纤维配方 |
CN103298879B (zh) * | 2010-12-30 | 2016-01-27 | 科腾聚合物美国有限责任公司 | 弹性膜/纤维配方 |
CN110408220A (zh) * | 2018-04-30 | 2019-11-05 | 科腾聚合物有限责任公司 | 具有改进功效的凝胶组合物用嵌段共聚物 |
US11759758B2 (en) | 2018-04-30 | 2023-09-19 | Kraton Corporation | Block copolymers for gel compositions with improved efficiency |
CN113825648A (zh) * | 2019-05-31 | 2021-12-21 | 株式会社普利司通 | 树脂成型体、轮胎、汽车用部件和树脂组合物 |
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TWI304824B (en) | 2009-01-01 |
EP1569999B1 (en) | 2006-08-30 |
KR100702724B1 (ko) | 2007-04-03 |
EP1426411A1 (en) | 2004-06-09 |
US7838598B2 (en) | 2010-11-23 |
DE60308061T2 (de) | 2006-12-14 |
KR20050085371A (ko) | 2005-08-29 |
DE60308061D1 (de) | 2006-10-12 |
CN100588667C (zh) | 2010-02-10 |
WO2004052989A9 (en) | 2005-08-11 |
AU2003298341A8 (en) | 2004-06-30 |
WO2004052989A1 (en) | 2004-06-24 |
JP2006509089A (ja) | 2006-03-16 |
JP4430546B2 (ja) | 2010-03-10 |
TW200426185A (en) | 2004-12-01 |
US20060155044A1 (en) | 2006-07-13 |
EP1569999A1 (en) | 2005-09-07 |
AU2003298341A1 (en) | 2004-06-30 |
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