CN100523032C - 单乙烯基芳烃/共轭二烯共聚物 - Google Patents
单乙烯基芳烃/共轭二烯共聚物 Download PDFInfo
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- CN100523032C CN100523032C CNB2004800382195A CN200480038219A CN100523032C CN 100523032 C CN100523032 C CN 100523032C CN B2004800382195 A CNB2004800382195 A CN B2004800382195A CN 200480038219 A CN200480038219 A CN 200480038219A CN 100523032 C CN100523032 C CN 100523032C
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
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- 230000002588 toxic effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
公开了一种单乙烯基芳烃/共轭二烯嵌段共聚物,其包含:(i)无规(共轭二烯x/单乙烯基芳烃y)m嵌段,其中x为约2.5wt%至约10wt%,y为约90wt%至约97.5wt%,x+y为约97.5wt%至100wt%;和(ii)(共轭二烯)n嵌段;其中n为约20wt%至约30wt%,m为约70wt%至约80wt%,m+n为约90wt%至100wt%。还公开一种制备嵌段聚合物的方法,及由所述嵌段共聚物制造制品的方法。通常所述嵌段共聚物的Tg比参考聚合物的Tg低至少约10℃,该参考聚合物与其差别仅在于x为约0wt%和y为约100wt%。
Description
技术领域
本发明一般地涉及聚合物化学领域。更具体地,本发明涉及相对于参考苯乙烯-丁二烯共聚物具有较低Tg的单乙烯基芳烃-共轭二烯共聚物。
背景技术
由单乙烯基芳烃-共轭二烯的共聚物,如苯乙烯-丁二烯共聚物,诸如K-树(Woodlands,TX的Chevron Phillips Chemical Co.),形成的制品通常具有多种优良的物理性能。但是,在需要热收缩加工步骤的制品的情况下,单乙烯基芳烃-共轭二烯共聚物通常在使用中不太有利,这是因为其玻璃化转变温度(Tg),即发生收缩的温度,通常为约95℃至约108℃。这一相对较高的Tg需要使用相对大量的热量,以达到进行收缩的温度。
因此,具有较低的Tg且更容易热收缩加工的单乙烯基芳烃-丁二烯共聚物将是令人满意的。
发明内容
在一个实施方案中,本发明涉及一种单乙烯基芳烃/共轭二烯嵌段共聚物,其包含:
无规的(共轭二烯x/单乙烯基芳烃y)m嵌段,其中x为约2.5wt%至约10wt%,y为约90wt%至约97.5wt%,x+y为约97.5wt%至100wt%;和
(共轭二烯)n嵌段;
其中n为约20wt%至约30wt%,m为约70wt%至约80wt%,m+n为约90wt%至100wt%。
在另一个实施方案中,本发明涉及一种制品,其包含以上所述的单乙烯基芳烃/共轭二烯嵌段共聚物。
在又一个的实施方案中,本发明涉及制备具有较低Tg的单乙烯基芳烃/共轭二烯嵌段共聚物的方法,其包括:
(a)进料单乙烯基芳烃单体、共轭二烯单体、引发剂和无规剂(randomizer),使聚合进行,以制备无规(共轭二烯x/单乙烯基芳烃y)m嵌段;
(b)进料单乙烯基芳烃单体、共轭二烯单体和引发剂,使聚合进行,以制备单乙烯基芳烃/共轭二烯嵌段;
(c)进料共轭二烯单体,使聚合进行,以制备(共轭二烯)n嵌段;和
(d)进料含有偶联剂的反应混合物,形成单乙烯基芳烃/共轭二烯嵌段共聚物。
在又另一个实施方案中,本发明涉及一种制造制品的方法,其包括:使单乙烯基芳烃/共轭二烯嵌段共聚物成型为制品,其中所述单乙烯基芳烃/共轭二烯嵌段共聚物为如上所述。
本发明提供具有较低的Tg和更容易热收缩加工的单乙烯基芳烃-共轭二烯共聚物。
附图说明
以下附图形成为本说明书的一部分,并被包括在内以进一步说明本发明的某些方面。通过参考这些附图中的一个或多个、以及结合这里所阐述的对具体实施方案的详细描述,本发明将可以得到更好的理解。
图1示出了实施例1聚合物的差式扫描量热(DSC)试验的结果。
图2示出了实施例2聚合物的DSC试验结果。
图3示出了作为实施例1-2聚合物的参考聚合物的比较例5聚合物的DSC试验结果。
实施本发明的最佳方式
在一个实施方案中,本发明涉及一种单乙烯基芳烃/共轭二烯嵌段共聚物,其包含:
无规(共轭二烯x/单乙烯基芳烃y)m嵌段,其中x为约2.5wt%至约10wt%,y为约90wt%至约97.5wt%,x+y为约97.5wt%至100wt%;和
(共轭二烯)n嵌段;
其中n为约20wt%至约30wt%,m为约70wt%至约80wt%,m+n为约90wt%至100wt%。
用于制备共轭二烯/单乙烯基芳烃嵌段共聚物的基本原料及聚合条件公开在US4,091,053、4,584,346、4,704,434、4,704,435和5,227,419中,其公开内容通过参考引入。
这里使用的“共轭二烯”是指含有共轭的碳-碳双键并含有总计4-12个碳原子,例如4-8个碳原子,的有机化合物。示例性的共轭二烯包括但不限于1,3-丁二烯、2-甲基-1,3-丁二烯、2-乙基-1,3-丁二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、3-丁基-1,3-辛二烯,及它们的混合物。在一个实施方案中,所述共轭二烯可以是1,3-丁二烯或异戊二烯。在又一个实施方案中,所述共轭二烯可以是1,3-丁二烯。其中所述单元得自共轭二烯单体聚合的聚合物的单元是“共轭二烯单元”。
这里使用的“单乙烯基芳烃”是指含有单个的碳-碳双键、至少一个芳族部分并含有总计8-18个碳原子,例如8-12个碳原子,的有机化合物。示例性的单乙烯基芳烃包括但不限于苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、2-乙基苯乙烯、3-乙基苯乙烯、4-乙基苯乙烯、4-正丙基苯乙烯、4-叔丁基苯乙烯、2,4-二甲基苯乙烯、4-环己基苯乙烯、4-癸基苯乙烯、2-乙基-4-苄基苯乙烯、4-(4-苯基-正丁基)苯乙烯、1-乙烯基萘、2-乙烯基萘,及它们的混合物。在一个实施方案中,所述单乙烯基芳烃是苯乙烯。其中所述单元得自单乙烯基芳基单体聚合的聚合物的单元是“单乙烯基芳烃单元”。
在本发明的聚合物中,无规(共轭二烯x/单乙烯基芳烃y)m嵌段包含共轭二烯单元和单乙烯基芳烃单元。所述嵌段是“无规”的,因为任何具体单元是共轭二烯单元或单乙烯基芳烃单元的概率基本上与共轭二烯和单乙烯基芳烃在嵌段中的摩尔分数相同。这并不排出具有规则性(例如看起来不是无规)的嵌段的短伸展的可能性,但这种存在的规则伸展通常不高于偶然预期的水平。
在所述的无规(共轭二烯x/单乙烯基芳烃y)m嵌段中,共轭二烯单元可以重量分数x表示,其中x可以是约2.5wt%至约10wt%,单乙烯基芳烃单元可以重量分数y表示,其中y可以是约90wt%至约97.5wt%。
在一个实施方案中,x可以是约5wt%至约10wt%。
在一个实施方案中,y可以是约90wt%至约95wt%。
本领域的技术人员显而易见的是,x+y可小于或等于100wt%。在一个实施方案中,x+y可以是约97.5wt%至100wt%。
在x+y小于100wt%时,无规(共轭二烯x/单乙烯基芳烃y)m嵌段重量分数的剩余部分可以包含一种或多种其它单元。可以通过乙烯基加成聚合而包含在所述聚合物中的任何其它单元可以是提供无规(共轭二烯x/单乙烯基芳烃y)m嵌段重量分数的剩余部分的其它单元。
(共轭二烯)n嵌段包含共轭二烯单元,也可以包含小量(少于约1wt%)的一种或多种其它单元。可以通过乙烯基加成聚合而包含在所述聚合物中的任何其它单元可以是包含小量的(共轭二烯)n嵌段的其它单元。
无规(共轭二烯x/单乙烯基芳烃y)m嵌段和(共轭二烯)n嵌段的比例可以通过其重量分数m和n定义。
在一个实施方案中,n可以是约5wt%至约45wt%,m可以是约55wt%至约95wt%。在又一个实施方案中,n可以是约20wt%至约30wt%,m可以是约70wt%至约80wt%。在另一个实施方案中,n可以是约25wt%,m可以是约75wt%。
本领域的技术人员显而易见的是,m+n可小于或等于100wt%。在一个实施方案中,m+n可为约90wt%至100wt%。
在m+n小于100wt%时,所述共聚物重量分数的剩余部分可以包含一种或多种其它嵌段。可以通过乙烯基加成聚合而包含在所述嵌段共聚物中的任何其它嵌段可以是提供所述共聚物重量分数的剩余部分的其它嵌段。这种嵌段的实例是聚单乙烯基芳烃嵌段,但不限于此。
本发明的聚合物包含至少一种无规(共轭二烯x/单乙烯基芳烃y)m嵌段和至少一种(共轭二烯)n嵌段。所述嵌段可以按照任何次序顺序加入聚合物中。本发明的聚合物可以含有多于一种的无规(共轭二烯x/单乙烯基芳烃y)m嵌段,多于一种的(共轭二烯)n嵌段,或两者。如果有多个的一种或两种类型嵌段存在,所述嵌段可以按照任何次序顺序加入聚合物中(例如,在无规嵌段和共轭二烯嵌段之间交替地,或在其它引入顺序中,按照一种类型的嵌段接着另一种类型的嵌段的顺序存在)。
通常,每种嵌段是通过得到所需嵌段单元的单体或单体混合物聚合形成的。聚合工艺通常相对不同嵌段之间工艺参数变化的相对缺乏而变化,但拥有本公开内容利益,技术人员可以通过常规试验对不同嵌段之间的工艺参数进行一些小的变动。通常,以下对聚合工艺的描述可以适用于形成本发明聚合物中所有类型的嵌段,但某些描述对于形成本发明聚合物中的一种或多种类型的嵌段可以具有或多或少的价值。
所述聚合工艺可以在烃稀释剂中,在约-100℃至约150℃、例如约0℃至约150℃的任何适宜温度下,在压力为足以保证反应混合物基本上处于液相中进行。在一个实施方案中,所述烃稀释剂可以是直链或环状链烷烃,或其混合物。示例性的直链或环状链烷烃包括但不限于戊烷、己烷、辛烷、环戊烷、环己烷,及其混合物。在一个实施方案中,所述链烷烃为环己烷。
所述聚合工艺可以在基本上不存在氧和水的情况下,例如在惰性气体氛围中进行。
所述聚合工艺可以在引发剂的存在下进行。在一个实施方案中,所述引发剂可以是已知用作引发剂的任何有机单碱金属化合物。在又一个实施方案中,所述引发剂可以具有式RM,其中R为含4至8个碳原子的烷基、环烷基或芳基,例如正丁基,而M是碱金属,例如锂。在一个具体的实施方案中,所述引发剂是正丁基锂。
催化剂的用量取决于所需的聚合物或嵌段的分子量,这是本领域中已知的且可容易地确定,并需考虑适当的余量,以用于原料流中的痕量毒物。在一个实施方案中,所述引发剂的存在量为约0.01phm(重量份/100重量份的总单体重量)至约1.0phm。在另一个实施方案中,所述引发剂可以存在的量为约0.01phm至约0.5phm。在又一个实施方案中,所述引发剂可以存在的量为约0.01phm至0.2phm。
所述聚合工艺可以进一步涉及包括小量的无规剂。在一个实施方案中,所述无规剂可以是极性的有机化合物,例如醚、硫醚、或叔胺。在另一个实施方案中,所述无规剂可以是醇的钾盐或钠盐。所述无规剂可以包含在所述烃稀释剂中,以改进引发剂的有效性、使混合单体进料中的至少部分单乙烯基芳烃单体无规化、或两者。当形成本发明聚合物的无规(共轭二烯x/单乙烯基芳烃y)m嵌段时,无规剂的引入具有价值。示例性的无规剂包括但不限于二甲醚、二乙醚、乙基·甲基醚、乙基·丙基醚、二正丙基丁醚、二正辛基醚、苯甲醚、二噁烷、1,2-二甲氧基乙烷、二苄基醚、二苯基醚、1,2-二甲氧基苯、四亚甲基氧化物(四氢呋喃或THF)、叔戊醇钾(KTA,potassiumtert-amylate)、二甲硫、二乙硫、二正丙硫、二正丁硫、甲基·乙基硫醚、二甲基乙基胺、三正乙胺、三正丙胺、三正丁胺、三甲基苯胺、三乙胺、四甲基乙二胺、四乙基乙二胺、N,N-二甲基苯胺、N-甲基-N-乙基苯胺、N-甲基吗啉,及其混合物。
在一个实施方案中,所述无规剂是四氢呋喃。当使用四氢呋喃时,通常所述四氢呋喃的存在量为约0.01phm至约1.0phm,例如约0.02phm至约1.0phm。
在另一个实施方案中,所述无规剂是叔戊醇钾(KTA)。当使用KTA时,所述KTA的存在量为约0.01phm至约1.0phm,例如约0.1phm至约1.0phm。
当形成具体的嵌段时,每种单体进料或单体混合物进料在溶液聚合条件下聚合,以使每种单体进料或单体混合物进料形成具体嵌段的聚合在加入随后的进料之前基本上完成。这里使用的“进料”是指向反应区如反应器容器的内部引入化合物。
聚合完成后可以加入偶联剂。适宜的偶联剂包括但不限于二-或多乙烯基芳烃化合物;二-或多环氧化物;二-或多异氰酸酯、二-或多亚胺;二-或多醛;二-或多酮;烷氧基锡化合物;二-或多卤化物,例如卤化硅和卤代硅烷;单-、二-或多酸酐;二-或多酯,例如单醇与多羧酸的酯;一元醇与二羧酸的二酯;一元酸与多元醇如甘油的二酯;以及其中两种或更多种这类化合物的混合物。
可用的多官能偶联剂包括但不限于环氧化植物油,例如环氧化大豆油、环氧亚麻籽油,及它们的混合物。在一个实施方案中,所述偶联剂是环氧大豆油。环氧化植物油可以商标商购自AtofinaChemicals(PA的Philadelphia)。
可以使用任何有效量的偶联剂。在一个实施方案中,相对于活性聚合物碱金属为化学计量的偶联剂量常会促进最大程度的偶联。但是,可以使用比化学计量多或少的量,以改变对具体产品所需要的偶联效率。通常,聚合中所使用的偶联剂总量为约0.1phm至约20phm,例如约0.1phm至约5phm,或约0.1phm至约2phm。
偶联反应完成后,可以用终止剂如水、醇、酚或直链饱和的脂族单-二羧酸处理聚合反应混合物,以除掉嵌段共聚物中的碱金属,以及用于颜色控制。在一个实施方案中,所述终止剂为水与二氧化碳的混合物。
终止后,聚合物胶泥(在聚合溶剂中的聚合物)通常含有约10至40wt%、更经常约20-35wt%的固体。所述聚合物胶泥可以被闪蒸,以蒸发掉一部分溶剂来增加固含量至浓度为约50至99wt%固体,接着通过真空烘箱或除灰分挤出机干燥,以除掉剩余的溶剂。
所述嵌段共聚物可以被回收,并加工为要求的形状,例如通过混炼、挤出或注射。所述嵌段共聚物也可以含有添加剂,例如抗氧化剂、防粘连剂、脱模剂、填料、增量剂及染料等。
在特定的聚合工艺中,典型的引发剂、单体及单体混合物进料顺序包括下述,但不限于此:
进料实施方案1:
(a)无规剂、引发剂、共轭二烯/单乙烯基芳烃单体混合物
(b)引发剂、共轭二烯/单乙烯基芳烃单体混合物
(c)共轭二烯单体
(d)偶联剂
进料实施方案2:
(a)引发剂、单乙烯基芳烃单体
(b)无规剂、引发剂、共轭二烯/单乙烯基芳烃单体混合物
(c)共轭二烯单体
(d)无规剂、引发剂、共轭二烯/单乙烯基芳烃单体混合物
(e)共轭二烯单体
(f)偶联剂。
在其它实施方案中,本发明的单乙烯基芳烃/共轭二烯嵌段共聚物可以包含以下的结构,其中(B/S)是无规单乙烯基芳烃/共轭二烯嵌段;<B/S>是递变单乙烯基芳烃/共轭二烯嵌段;B是共轭二烯嵌段;S是单乙烯基芳烃嵌段;CA是偶联剂残基;-是嵌段之间的共价键。
●(B/S)-(B/S)-B-CA
●(B/S)-B-CA
●(B/S)-(B/S)-B-(B/S)-B-CA
●(B/S)-B-(B/S)-B-CA
●S-(B/S)-B-(B/S)-B-CA
●<B/S>1-<B/S>2-<B/S>3-<B/S>4-<B/S>5-CA
●<B/S>2-<B/S>3-<B/S>4-<B/S>5-CA
●(B/S)1-(B/S)2-<B/S>3-<B/S>4-<B/S>5-CA
●(B/S)1-(B/S)2-(B/S)3-(B/S)4-(B/S)5-CA;
其中<B/S>1、<B/S>2、(B/S)1和(B/S)2各自具有含量为约2.5wt%至约10wt%的共轭二烯,<B/S>3、<B/S>4、<B/S>5、(B/S)3、(B/S)4和(B/S)5各自具有含量为约30wt%至约70wt%的共轭二烯。
本发明的单乙烯基芳烃/共轭二烯嵌段共聚物可以具有的Tg为比参考聚合物低至少约10℃,参考聚合物与其差别仅仅在于x为约0wt%,y为约100wt%。
Tg是聚合物的玻璃化转变温度,即低于该温度时,聚合物处于相对较硬和脆性的玻璃态,高于该温度时,聚合物处于相对软和挠性的塑性状态。Tg可以通过已知的技术和设备测量,例如差式扫描量热法(DSC)。各种聚合物内在地具有玻璃化转变温度。
就嵌段特性及m和n数值而言,这里使用的参考聚合物是与本发明的单乙烯基芳烃/共轭二烯嵌段共聚物相同的聚合物。所述参考聚合物的差别仅仅在于x为约0wt%,y为约100wt%(即替代无规(共轭二烯x/单乙烯基芳烃y)m嵌段的是,参考聚合物的嵌段基本由单乙烯基芳烃组成)。
如上所述,在一个实施方案中,本发明的单乙烯基芳烃/共轭二烯嵌段共聚物可以具有的Tg比参考聚合物的Tg低至少约10℃。在另一个实施方案中,本发明的单乙烯基芳烃/共轭二烯嵌段共聚物可以具有的Tg比参考聚合物的Tg低至少约20℃。在又一个实施方案中,本发明的单乙烯基芳烃/共轭二烯嵌段共聚物可以具有的Tg比参考聚合物的Tg低至少约30℃。
这种较低的Tg使得单乙烯基芳烃/共轭二烯嵌段共聚物在其它制品中更容易加工形成为收缩薄膜。
在一个实施方案中,本发明涉及一种制品,该制品包含以上所述的单乙烯基芳烃/共轭二烯嵌段共聚物。
所述制品可以是全部或部分地由本领域中已知的单乙烯基芳烃/共轭二烯嵌段共聚物,例如可以商品名K-树购得的苯乙烯/丁二烯共聚物(Woodlands,TX的Chevron Phillips Chemical Co.),制造的任何制品。
示例性的制品包括但不限于容器、医用包装、医疗器械、玩具、衣服架,以及柔性及刚性包装材料。
在一个实施方案中,所述制品是收缩薄膜,其定义为当暴露在约60℃至约80℃温度时收缩的薄膜。
在另一个实施方案中,本发明涉及制备具有低Tg的单乙烯基芳烃/共轭二烯嵌段共聚物的方法,其包括:
(a)进料单乙烯基芳烃单体、共轭二烯单体、引发剂和无规剂,使聚合进行,以制备包含无规(共轭二烯x/单乙烯基芳烃y)m嵌段的反应混合物;
(b)进料引发剂和共轭二烯单体,使聚合进行,以制备包含(共轭二烯)n嵌段的反应混合物;和
(c)进料含有偶联剂的反应混合物,形成单乙烯基芳烃/共轭二烯嵌段共聚物。
进料步骤(a)-(c)可以根据以上所阐述的说明进行。对于拥有本公开内容利益的本领域技术人员来说,各进料步骤中所添加各种组分的比例属于常规试验的问题。
在一个实施方案中,进料步骤(a)中所述组分的比例可以选择为使得在产物嵌段中,x为约2.5wt%至约10wt%,y为约90wt%至约97.5wt%,x+y为约97.5wt%至100wt%。
在一个实施方案中,进料步骤(a)和(b)中所述组分的比例可以选择为使得在产品聚合物中,n为约20wt%至约30wt%,m为约70wt%至约80wt%,m+n为约90wt%至100wt%。
步骤(a)和(b)的顺序可以变化,步骤(a)和(b)的一个或两个可以进行一次或多次。
在另一个实施方案中,本发明涉及一种制造制品的方法,其包括:使单乙烯基芳烃/共轭二烯嵌段共聚物成型为制品,其中所述单乙烯基芳烃/共轭二烯嵌段共聚物为如上所述。
所述制品可以是以上提及的任何制品。
在成型步骤中,可通过任何适宜的技术使聚合物成型为制品或其组件。适宜技术的实例包括但不限于片材挤出、热成型、注塑、吹塑、薄膜吹制及薄膜流延。对于拥有本公开内容利益的本领域技术人员来说,对成型技术的选择属于常规试验的问题。
以下实施例被引入以例举说明本发明的具体实施方案。本领域的技术人员应当理解,在接下来的所述实施例中公开的技术表示了由本发明人发现的技术,其在本发明的实践中作用良好。但是,通过参考本公开内容,本领域的技术人员应当理解,在不背离本发明精神及范围下,可以对公开的具体实施方案作很多变化,并且仍然得到相同或相似的结果。
实施例1-2:无规(共轭二烯
x
/单乙烯基芳烃
y
)
m
/(共轭二烯)
n
嵌
段共聚物的合成
两个嵌段共聚物合成如下:
实施例1:
除上述外,在初始环己烷进料后的每次进料后都加入0.21b环己烷(试验结束时环己烷总计为9.01b)。
实施例2:
除上述外,在初始环己烷进料后的每次进料后都加入0.21b环己烷(试验结束时环己烷总计为9.01b)。
在两个实施例中,最终进料后5分钟时,反应容器的内容物被转移到含有3g Be Square Wax的放空容器中(在放空容器被预热前加入)。反应器和所有管线用0.51b环己烷漂洗,和将漂洗液转移至放空容器。然后将所述放空反应器加热至178℃,闪蒸聚合物得到聚合物绳状物(rope)。在真空烘箱中(约180℉至180℉)干燥所述聚合物绳状物2.5小时,剁碎并保存,以供进一步研究。
比较例3:参考聚合物的合成
除上述外,在初始环己烷进料后的每次进料后都加入0.21b环己烷(试验结束时环己烷总计为9.01b)。
反应后,重新得到聚合物,并采用以上实施例1-2所描述的相同步骤进行处理。
实施例4-5和比较例6:无规(共轭二烯
x
/单乙烯基芳烃
y
)
m
/(共轭二
烯)
n
嵌段共聚物和参考聚合物的Tg
对实施例1-2中产生的聚合物及具有与实施例1-2的聚合物的无规丁二烯/苯乙烯嵌段基本相同的数量及重量的苯乙烯嵌段的对比参考聚合物进行差式扫描量热测量(DSC)。各种聚合物的Tg通过对DSC产生的热流/温度图分析的标准技术确定。
实施例4
对实施例1的聚合物进行DSC测量。结果见图1中所示。Tg为73.32℃。
实施例5
对实施例2的聚合物进行DSC。结果见图1中所示。Tg为63.96℃。
比较例6
对比较例3的参考聚合物进行DSC测量。结果见图3中所示。Tg为95.50℃。
实施例4-5和对比例6的结果显示,用约5-10wt%的丁二烯替代丁二烯/苯乙烯嵌段共聚物的苯乙烯嵌段导致Tg的下降相对于参考聚合物为至少约10℃,例如约20或30℃。
就本公开内容而言,可以在不进行过度试验的情况下制造和执行这里所公开的所有组合物和方法。尽管已根据具体实施方案描述了本发明的组合物和方法,但对于本领域的技术人员来说,明显的是可以在不背离由所述权利要求所定义的本发明精神和范围下,将各种变动施加到所述组合物和方法及步骤中,或施加到在这里所描述方法步骤的顺序中。
Claims (17)
1.一种单乙烯基芳烃/共轭二烯嵌段共聚物,其包含:
无规(共轭二烯x/单乙烯基芳烃y)m嵌段,其中x为2.5wt%至10wt%,y为90wt%至97.5wt%,x+y为97.5wt%至100wt%;和
(共轭二烯)n嵌段;
其中n为20wt%至30wt%,m为70wt%至80wt%,m+n为90wt%至100wt%。
2.权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物,其中x为5wt%至10wt%。
3.权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物,其中y为90wt%至95wt%。
4.权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物,其中n为25wt%,m为75wt%。
5.权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物,其中Tg比参考聚合物的Tg低至少10℃,其中所述参考聚合物与其差别仅在于x为0wt%和y为100wt%。
6.权利要求5的单乙烯基芳烃/共轭二烯嵌段共聚物,其中所述Tg为比参考聚合物的Tg低至少20℃。
7.权利要求6的单乙烯基芳烃/共轭二烯嵌段共聚物,其中所述Tg为比参考聚合物的Tg低至少30℃。
8.权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物,其进一步包含单乙烯基芳烃/共轭二烯嵌段。
9.权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物,其进一步包含单乙烯基芳烃嵌段。
10.一种制品,其包含权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物。
11.权利要求10的制品,其中所述制品为收缩膜。
12.一种制备具有低Tg的权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物的方法,其包括:
(a)进料单乙烯基芳烃单体、共轭二烯单体、引发剂和无规剂,使聚合进行,以制备无规(共轭二烯x/单乙烯基芳烃y)m嵌段,其中x为2.5wt%至10wt%,y为90wt%至97.5wt%,x+y为97.5wt%至100wt%,和m为70wt%至80wt%;
(b)进料单乙烯基芳烃单体、共轭二烯单体和引发剂,使聚合进行,以制备单乙烯基芳烃/共轭二烯嵌段;
(c)进料共轭二烯单体,使聚合进行,以制备(共轭二烯)n嵌段,其中n为20wt%至30wt%,和m+n为90wt%至100wt%;和
(d)进料含有偶联剂的反应混合物,形成单乙烯基芳烃/共轭二烯嵌段共聚物。
13.一种单乙烯基芳烃/共轭二烯嵌段共聚物,其是通过权利要求12的方法制备的。
14.一种制备具有低Tg的权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物的方法,其包括:
(a)进料引发剂和单乙烯基芳烃单体,使聚合进行,以制备单乙烯基芳烃嵌段;
(b)进料无规剂、引发剂、共轭二烯/单乙烯基芳烃单体混合物,使聚合进行,以制备无规(共轭二烯x/单乙烯基芳烃y)m嵌段,其中x为2.5wt%至10wt%,y为90wt%至97.5wt%,x+y为97.5wt%至100wt%,和m为70wt%至80wt%;
(c)进料共轭二烯单体,使聚合进行,以制备共轭二烯嵌段;
(d)进料无规剂、引发剂、共轭二烯/单乙烯基芳烃单体混合物,使聚合进行,以制备无规(共轭二烯x1/单乙烯基芳烃y1)m1嵌段,其中x1为2.5wt%至10wt%,y1为90wt%至97.5wt%,x1+y1为97.5wt%至100wt%,和m1为70wt%至80wt%;
(e)进料共轭二烯单体,使聚合进行,以制备共轭二烯嵌段;和
(f)进料含有偶联剂的反应混合物,形成单乙烯基芳烃/共轭二烯嵌段共聚物。
15.一种单乙烯基芳烃/共轭二烯嵌段共聚物,其是通过权利要求14的方法制备的。
16.一种制造制品的方法,该方法包括:
使权利要求1的单乙烯基芳烃/共轭二烯嵌段共聚物成型为制品。
17.权利要求16的方法,其中成型包括片材挤出、热成型、注塑、吹塑、薄膜吹制或薄膜流延。
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- 2004-11-05 CN CN2010105161340A patent/CN102030874A/zh active Pending
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- 2004-11-05 WO PCT/US2004/037279 patent/WO2005047355A2/en active Application Filing
- 2004-11-05 CN CNA2008100962665A patent/CN101429268A/zh active Pending
- 2004-11-05 CN CNB2004800382195A patent/CN100523032C/zh not_active Expired - Fee Related
- 2004-11-05 JP JP2006539728A patent/JP4928269B2/ja not_active Expired - Fee Related
- 2004-11-05 KR KR1020067008934A patent/KR101168442B1/ko active IP Right Grant
- 2004-11-05 BR BRPI0416549-7A patent/BRPI0416549A/pt not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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US20050101743A1 (en) | 2005-05-12 |
BRPI0416549A (pt) | 2007-01-09 |
WO2005047355A3 (en) | 2005-09-09 |
KR101168442B1 (ko) | 2012-07-27 |
SG126933A1 (en) | 2006-11-29 |
WO2005047355A2 (en) | 2005-05-26 |
EP1687352A2 (en) | 2006-08-09 |
CN102030874A (zh) | 2011-04-27 |
KR20060120082A (ko) | 2006-11-24 |
CA2545747A1 (en) | 2005-05-26 |
JP4928269B2 (ja) | 2012-05-09 |
CN1902248A (zh) | 2007-01-24 |
TW200535155A (en) | 2005-11-01 |
JP2007510803A (ja) | 2007-04-26 |
US7037980B2 (en) | 2006-05-02 |
CN101429268A (zh) | 2009-05-13 |
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