CN109206859B - 分枝聚合物、其制备方法以及发泡体的制备方法 - Google Patents
分枝聚合物、其制备方法以及发泡体的制备方法 Download PDFInfo
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- CN109206859B CN109206859B CN201710600229.2A CN201710600229A CN109206859B CN 109206859 B CN109206859 B CN 109206859B CN 201710600229 A CN201710600229 A CN 201710600229A CN 109206859 B CN109206859 B CN 109206859B
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- branched polymer
- molecular weight
- polyethylene terephthalate
- parts
- foam
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000006260 foam Substances 0.000 title claims abstract description 31
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- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 67
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 66
- 238000009826 distribution Methods 0.000 claims abstract description 35
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- 150000001875 compounds Chemical class 0.000 claims description 4
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Classifications
-
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Abstract
本公开提供一种分枝聚合物、其制备方法以及发泡体的制备方法。该分枝聚合物包含100重量份聚对苯二甲酸乙二酯以及0.5至2重量份的多元醇所反应而成,该分枝聚合物的固有黏度由1.2dL/g至1.6dL/g、数均分子量由75,000g/mol至90,000g/mol、分子量分布由3.0至6.0、熔融指数由0.8g/10min至7.5g/10min、剪切黏度由800Pa·s至1900Pa·s、以及熔融强度由30cN至80cN。
Description
技术领域
本公开关于一种分枝聚合物、其制备方法以及其应用。
背景技术
热塑性聚酯为分子主链上具有重复酯基的聚合物,它是由多元酸和多元醇经缩合聚合而得。以二元酸和二元醇经缩合聚合可得到线型聚酯,例如聚对苯二甲酸乙二酯(Polyethylene terephthalate,PET)。聚对苯二甲酸乙二酯具有不错的机械强度、尺寸稳定性、耐化性、及较低吸湿性。举例来说,由聚对苯二甲酸乙二酯所形成的发泡材料,已被广泛应用于能源装置、光学组件、交通运输、建筑、或是包装材料中。
然而,由于传统聚对苯二甲酸乙二酯系为线型结晶性聚酯材料,在熔融态下具有较低的熔融黏度与熔融强度,且在进行发泡加工时气泡不易保持形状。因此,业界需要一种新颖的聚对苯二甲酸乙二酯,以符合发泡加工的需求。
发明内容
根据本公开实施例,本公开提供一种分枝聚合物,其为包含100重量份聚对苯二甲酸乙二酯以及0.5至2重量份的多元醇所反应而成。该分枝聚合物的固有黏度由1.2dL/g至1.6dL/g、数均分子量由75,000g/mol至90,000g/mol、以及分子量分布(polydispersityindex、PDI)由3.0至6.0、熔融指数(melt Index、MI)由0.8g/10min至7.5g/10min、剪切黏度(shear viscosity)由800Pa·s至1900Pa·s、以及熔融强度由30cN至80cN。
根据本公开另一实施例,本公开提供一种上述分枝聚合物的制备方法,包含:将一组合物以挤出机进行酯交换反应,得到酯粒,其中该组合物包含100重量份聚对苯二甲酸乙二酯以及0.5至2重量份之多元醇,其中该聚对苯二甲酸乙二酯之数均分子量(Mn)为30,000g/mol至55,000g/mol,以及该聚对苯二甲酸乙二酯之固有黏度为0.40dL/g至0.95dL/g;对该酯粒进行干燥;以及对该酯粒进行固态聚合增黏,其中,该分枝聚合物的固有黏度由1.2dL/g至1.6dL/g、数均分子量由75,000g/mol至90,000g/mol、以及分子量分布由3.0至6.0。
根据本公开又一实施例,本公开提供一种发泡体的制备方法,包含上述分枝聚合物与聚对苯二甲酸乙二酯进行混炼合胶(compounding),该分枝聚合物与聚对苯二甲酸乙二酯的重量比系1:9至9:1;以及对该混炼物进行发泡工艺,其中,该发泡体的固有黏度由0.95dL/g至1.50dL/g、剪切黏度由600Pa·s至1400Pa·s、熔融指数由2.5g/10min至25g/10min、以及熔融强度由15cN至65cN。
具体实施方式
本公开实施例提供一种分枝聚合物以及该分枝聚合物的制备方法。通过挤出机在特定反应条件下使具有特定分子量及固有黏度的聚对苯二甲酸乙二酯与多元醇进行酯交换反应,然后对所得酯粒进行固态聚合增黏后,可得到本公开所述的分枝聚合物。由于本公开所述的分枝聚合物具有较高的熔融黏度与熔融强度,非常适合进行发泡加工,且所得的发泡体不易变形(气泡在结晶固化前不会破裂崩塌)。
根据本公开实施例,本公开所述的分枝聚合物可包含100重量份聚对苯二甲酸乙二酯以及0.5至2重量份之多元醇所反应而成,其中该分枝聚合物的固有黏度由1.2dL/g至1.6dL/g、数均分子量由75,000g/mol至90,000g/mol、分子量分布由3.0至6.0、熔融指数由0.8g/10min至7.5g/10min、剪切黏度由800Pa·s至1900Pa·s、以及熔融强度由30cN至80cN。
根据本公开实施例,当该多元醇的重量份过低时(低于0.5重量份),所得的分枝聚合物具有较少的分子链分枝程度,进一步对所得酯粒进行固态增黏后,无法有效提高熔融黏度与熔融强度,因此也无法顺利进行发泡加工。此外,当该多元醇的重量份过高时(高于2重量份),所得的分枝聚合物虽具有较高的分子链分枝程度,但因酯交换反应为一断链反应,过量的反应会使分枝聚合物黏度过低,进而造成后续的拉条造粒制程难以进行。
根据本公开实施例,本公开所使用的聚对苯二甲酸乙二酯的数均分子量(Mn)可为约30,000至55,000(例如约30,000至50,000)、以及该聚对苯二甲酸乙二酯之分子量分布(polydispersity index、PDI)可为约1.4至1.8。根据本公开实施例,该聚对苯二甲酸乙二酯可为无法发泡的聚对苯二甲酸乙二酯商品料(或回收料)。当本公开所使用的聚对苯二甲酸乙二酯的数均分子量过低时(低于约30,000),所得的分枝聚合物由于固有黏度过低而无法进一步进行加工。另一方面,该聚对苯二甲酸乙二酯的固有黏度约为0.40dL/g至0.95dL/g之间(例如0.45dL/g至0.90dL/g之间)时,较适合以挤出机对该组合物进行酯交换反应。此固有黏度范围的聚对苯二甲酸乙二酯为绝大部分商品料或回收料的黏度规格。
根据本公开实施例,本公开所述的多元醇可为具有3至8个羟基的聚醚多元醇(polyether polyol)、脂肪族多元醇(aliphatic polyol)、或上述组合。该具有3至8个羟基的聚醚多元醇的数均分子量(Mn)可为约70至2000。该脂肪族多元醇(aliphatic polyol)可例如为甘油(glycerin)、双甘油(diglycerol)、丁三醇(butanetriol)、丁四醇(erythritol)、季戊四醇(pentaerythritol)、木糖醇(xylitol)、甘露糖醇(mannitol)、山梨糖醇(sorbitol)、麦芽糖醇(maltitol)、二季戊四醇(dipentaerythritol)、或上述组合。
根据本公开实施例,本公开所述组合物不包含有机酸(例如多元酸)、酸酐(例如多元酸酐)、或具有环氧基之化合物(例如具有多个环氧基之化合物),以避免聚对苯二甲酸乙二酯与该有机酸、酸酐、或具有环氧基的化合物进行共聚合反应。
根据本公开实施例,为避免多元醇与聚对苯二甲酸乙二酯进行共聚合反应,而不进行酯交换反应,本公开所述组合物不包含溶剂,且以挤出机对该组合物进行押出及造粒。根据本公开实施例,为避免多元醇与聚对苯二甲酸乙二酯进行共聚合反应,而不进行酯交换反应,该组合物以挤出机押出及造粒时,温度需高于220℃(例如为约220℃至270℃)。此外,该挤出机的螺杆转速可介于约100转/分钟至500转/分钟,以确保多元醇均匀分布于聚对苯二甲酸乙二酯中,与其进行酯交换反应。通过上述制程条件,本公开所述分枝聚合物其数均分子量、分子量分布、固有黏度、熔融指数、剪切黏度、以及熔融强度可落入上述特定的范围内。
根据本公开实施例,为防止本公开所述分枝聚合物的氧化降解并增强本公开所述分枝聚合物的耐热性,本公开所述的组合物可更包含约0.1至0.5重量份的抗氧化剂(以100重量份的聚对苯二甲酸乙二酯为基准)。
根据本公开实施例,本公开所述组合物可由约100重量份聚对苯二甲酸乙二酯、约0.5至2重量份(例如约0.5至1.5重量份、或1至2重量份)的多元醇、以及约0.1至0.5重量份的抗氧化剂所组成。该抗氧化剂可为受阻酚(hindered phenol)型抗氧化剂、酯类抗氧化剂、硫代酯(thioester)抗氧化剂、亚磷酸酯类抗氧化剂、或上述组合。举例来说,本公开所述抗氧化剂可例如为2,6-二叔丁基-4-甲基苯酚(2,6-di-tert-butyl-4-methylphenol)、2,5-二叔戊基对苯二酚(2,5-di-tent-amylhydroquinone)、2,5-二叔丁基对苯二酚(2,5-di-tert-butylhydroquinone)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)(4,4′-butylidene-bis(3-methyl-6-tert-butylphenol))、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)(2,2′-methylene-bis(4-methyl-6-tert-butylphenol))、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)(2,2′-methylene-bis(4-ethyl-6-tert-butylphenol))、4,4’-硫代双(2-叔丁基-5-甲基苯酚)(4,4′-thiobis(2-t-butyl-5-methylphenol))、2,2’-硫代二乙基双[3-(3,5-二叔丁基-4-羟苯基)丙酸酯](2,2′-thio diethylbis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate])、季戊四醇四[3-(3,5-二叔丁基-4-羟苯基)丙酸酯](pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate])、4,4’-硫代双(2-甲基-6-叔丁基苯酚)(4,4′-thiobis(2-methyl-6-t-butylphenol))、2,2’-硫代双(6-叔丁基-4-甲基苯酚)(2,2′-thiobis(6-t-butyl-4-methylphenol))、十八烷基[3-(3,5-二叔丁基-4-羟苯基)丙酸酯](octadecyl-[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate])、三乙二醇双[3-(3-叔丁基-4-羟基-5-甲基苯酚)丙酸酯](triethyleneglycol-bis-[3-(3-t-butyl-4-hydroxy-5-methylphenol)propionate])、硫代二亚乙基双[3-(3,5-二叔丁基-4-羟苯基)丙酸酯](thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate])、6,6’-二叔丁基-2,2’-硫代二对甲酚(6,6′-di-t-butyl-2,2′-thiodi-p-cresol)、双十八烷基3,3’-硫代二丙酸酯(dioctadecyl 3,3′-thiodipropionate)、三壬基酚亚磷酸酯(trisnonylphenol phosphite)、三苯基亚磷酸酯(triphenyl phosphite)、二苯基亚磷酸酯(diphenyl phosphite)、苯基二异癸基亚磷酸酯(phenyl diisodecylphosphite)、二苯基异癸基亚磷酸酯(diphenyl isodecylphosphite)、二苯基异辛基亚磷酸酯(diphenyl isooctyl phosphite)、四苯基二丙二醇二亚磷酸酯(tetraphenyl dipropyleneglycol diphosphite)、或上述之组合。
根据本公开实施例,本公开亦提供了上述分枝聚合物的制备方法。该制备方法包含以下步骤。首先,将一组合物以挤出机进行酯交换反应,得到一酯粒,其中该组合物的定义如上。接着,对该酯粒进行干燥及固态聚合增黏。
根据本公开实施例,在将一组合物以挤出机进行酯交换反应前,可先将组合物在压力约20Pa至100Pa及温度约90℃至130℃下进行干燥5小时以上(例如5-8小时),以去除聚对苯二甲酸乙二酯的水份。
根据本公开实施例,该固态聚合在压力10Pa至50Pa及温度180℃至240℃下进行,固态聚合时间为6小时至24小时。
举例来说,本公开所述的分枝聚合物的制备方法可包含以下步骤。首先,提供一组合物,其中该组合物由结构为(其中n例如为300)的聚对苯二甲酸乙二酯(100重量份)与丙三醇(glycerol)(1重量份)所组成。接着,将该组合物在温度220℃至270℃下以挤出机(螺杆转速系100转/分钟至500转/分钟)进行反应。此时,丙三醇会与聚对苯二甲酸乙二酯进行酯交换反应,即丙三醇去氢所形成之残基会与聚对苯二甲酸乙二酯其分子链内的乙二醇去氢所形成的残基进行交换反应,请参照化学式(II)。
聚对苯二甲酸乙二酯在与丙三醇进行酯交换反应后,由于乙二醇去氢所形成的残基被丙三醇去氢所形成的残基置换,使得聚对苯二甲酸乙二酯其由n个重复单元所构成的链段会发生断键的现象,导致所得的分枝聚合物其聚对苯二甲酸乙二酯链段(即具有重复单元的链段)的重复单元数目会小于作为反应物的聚对苯二甲酸乙二酯,并得到聚对苯二甲酸乙二酯寡聚物。由上述可知,本公开所述的分枝聚合物其化学结构较不规律且分子链纠缠度(entanglement)较高,增加该分枝聚合物熔融黏度与熔融强度。此外,当本公开所述该分枝聚合物进行后续发泡加工时,所得之发泡体不易变形(气泡在结晶固化前不会破裂崩塌)。
根据本公开实施例,本公开提供一种发泡体制备方法。该制法包含上述分枝聚合物与聚对苯二甲酸乙二酯进行混炼合胶,该分枝聚合物与聚对苯二甲酸乙二酯的重量比系1:9至9:1(例如约2:8至8:2);以及对该混炼聚合物进行发泡工艺,其中,该发泡体的固有黏度由0.95dL/g至1.50dL/g、剪切黏度由600Pa·s至1400Pa·s、熔融指数由2.5g/10min至25g/10min、以及熔融强度由15cN至65cN。
根据本公开实施例,用来与本公开所述的分枝聚合物混合的聚对苯二甲酸乙二酯可与本公开所述用来制备分枝聚合物的聚对苯二甲酸乙二酯相同或是不同。举例来说,该聚对苯二甲酸乙二酯可为无法发泡的聚对苯二甲酸乙二酯商品料(或回收料),且该聚对苯二甲酸乙二酯商品料的分子量可较本公开所述之分枝聚合物的分子量低。
根据本公开实施例,本公开所述的发泡体的密度可为约0.05~0.65g/cm3、泡孔大小可为约2~30μm、数均分子量为约45,000~70,000g/mol、分子量分布为约3.0~6.0。
根据本公开实施例,本公开所述的发泡工艺可更包含以下步骤:将该混合物及一化学发泡剂混合,并以挤出机(例如单螺杆)在约200℃至270℃下进行发泡。在此,所使用的化学发泡剂可为已知用来进行聚对苯二甲酸乙二酯的化学发泡剂,例如二亚硝基五亚甲基四胺(dinitrosopentamethylenetetramine)、偶氮二甲酰胺(azodicarbonamide)、二亚硝基-五亚甲基四胺(dinitroso-pentamethylenetetramine)、4,4’氧-双-(苯磺酰肼)(4,4’oxy-bis-(benzene-sulphonylhydrazide))、三肼基三嗪(trihydra-zinotriazine)、N,N’-二甲基-N,N’-二亚硝基-对苯二甲酰胺(N,N’-dimethyl-N,N’-dinitroso-terephthalamide)、或上述组合。
根据本公开实施例,本公开所述的发泡工艺可包含以下步骤:将该混合物形成片材,并将该片材在温度约190℃至235℃及压力为约1500psi至3000psi下含浸于一发泡剂中进行发泡。在此,所使用的发泡剂可为物理发泡剂或化学发泡剂。举例来说,该物理发泡剂可为惰性气体、饱和脂肪族烃、饱和脂环族烃、卤化烃、醚、或酮等,例如二氧化碳、氮气、丙烷、丁烷、环己烷、氯甲烷、四氟乙烷、甲基仲丁基醚、丙酮、或上述组合。
为了让本公开的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例,作详细说明如下:
分枝聚合物的制备
实施例1:
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约45,000、固有黏度(IV值)为约0.74、以及分子量分布为约1.80)、1.5重量份的季戊四醇(作为多元醇)、以及0.3重量份的2,6-二叔丁基-4-甲基苯酚(作为抗氧化剂)均匀混合,得到一组合物。接着,将该组合物在50Pa及110℃下干燥12小时。接着,将干燥后的组合物加入双螺杆挤出机(螺杆直径为50mm)中进行混料与造粒,得到酯粒(1)。其中,双螺杆挤出机温度设定为240℃、螺杆转速设定为200转/分钟。接着,测量所得酯粒(1)的固有黏度(IV)及分子量分布,结果如表1所示。
接着,在50Pa及110℃下干燥该酯粒(1)6小时后,将酯粒(1)于真空下进行固态聚合,得到分枝聚合物(1)。其中,上述固态聚合反应的温度为210℃、压力为10Pa、且反应时间为12小时。接着,测量所得的分枝聚合物(1)的固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度,结果如表1所示。关于固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度的测量方式如下:
固有黏度(IV):将样品溶于酚(phenol)/三氯乙烯(trichloroethylene,TCE)中(置于30℃恒温槽),通过搅拌马达来提供轻微搅动,并以黏度计进行测量;
数均分子量(Mn)及分子量分布(PDI):以凝胶渗透层析仪(gelpermeationchromatography、GPC)对样品进行测量;
熔融指数:依据ASTM D 1238(290℃/2.16公斤)进行测量;
剪切黏度:依据ASTM D4287(290℃@50rad/s)进行测量;
熔融强度:透过毛细管流变仪搭配熔融强度测试仪进行测量,测试温度为300℃,滚轮牵引加速度为24mm/s2。
比较例1:
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约45,000、固有黏度(IV值)为约0.74、以及分子量分布为约1.80)在50Pa及110℃下干燥8小时。接着,将聚对苯二甲酸乙二酯粒子于真空下进行固态聚合,得到聚合物(1)。其中,上述固态聚合反应的温度为210℃、压力为10Pa、且反应时间为12小时。接着,测量所得的聚合物(1)的固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度,结果如表1所示。
实施例2:
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约39,500、固有黏度(IV值)为约0.63、以及分子量分布为约1.74)、1.5重量份的季戊四醇(作为多元醇)、以及0.3重量份的2,6-二叔丁基-4-甲基苯酚(作为抗氧化剂)均匀混合,得到一组合物。接着,将该组合物在50Pa及110℃下干燥8小时。接着,将干燥后的组合物加入双螺杆挤出机(螺杆直径为50mm)中进行混料与造粒,得到酯粒(2)。其中,双螺杆挤出机温度设定为240℃、螺杆转速设定为200转/分钟。接着,测量所得酯粒(2)的固有黏度(IV)及分子量分布,结果如表1所示。
接着,在50Pa及110℃下干燥该酯粒(2)6小时后,将酯粒(2)于真空下进行固态聚合,得到分枝聚合物(2)。其中,上述固态聚合反应的温度为210℃、压力为10Pa、且反应时间为12小时。接着,测量所得的分枝聚合物(2)的固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度,结果如表1所示。
实施例3:
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约35,000、固有黏度(IV值)为约0.55、以及分子量分布为约1.52)、1.5重量份的季戊四醇(作为多元醇)、以及0.3重量份的2,6-二叔丁基-4-甲基苯酚(作为抗氧化剂)均匀混合,得到一组合物。接着,将该组合物在50Pa及110℃下干燥8小时。接着,将干燥后的组合物加入双螺杆挤出机(螺杆直径为50mm)中进行混料与造粒,得到酯粒(3)。其中,双螺杆挤出机温度设定为240℃、螺杆转速设定为200转/分钟。接着,测量所得酯粒(3)的固有黏度(IV)及分子量分布,结果如表1所示。
接着,在10Pa及110℃下干燥该酯粒(3)6小时后,将酯粒(3)于真空下进行固态聚合,得到分枝聚合物(3)。其中,上述固态聚合反应的温度为210℃、压力为10Pa、且反应时间为12小时。接着,测量所得的分枝聚合物(3)的固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度,结果如表1所示。
比较例2:
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约35,000、固有黏度(IV值)为约0.55、以及分子量分布为约1.52)在50Pa及110℃下干燥8小时。接着,将聚对苯二甲酸乙二酯粒子于真空下进行固态聚合,得到聚合物(2)。其中,上述固态聚合反应的温度为210℃、压力为10Pa、且反应时间为12小时。接着,测量所得的聚合物(2)的固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度,结果如表1所示。
表1
由表1可得知,当先将聚对苯二甲酸乙二酯与多元醇以双螺杆挤出机进行酯交换反应再将所得酯粒进行固态聚合后,所得的分枝聚合物(实施例1及2所述的分枝聚合物(1)及(2)),其具有较低的熔融指数及较高的剪切黏度及熔融强度。
比较例3:
依实施例1所述酯粒的制备方式进行,除了将多元醇由1.5重量份降低至0.3重量份,得到酯粒(4)。接着,测量所得酯粒(4)的固有黏度(IV)及分子量分布,结果如表2所示。
接着,依实施例1所述制备分枝聚合物的方式,将酯粒(4)进行固态聚合反应,得到分枝聚合物(4)。接着,测量所得的分枝聚合物(4)的固有黏度(IV)、数均分子量、分子量分布、熔融指数、剪切黏度、以及熔融强度,结果如表2所示。
比较例4:
依实施例1所述酯粒的制备方式进行,除了将多元醇由1.5重量份增加至3.0重量份,得到酯粒(5)。接着,测量所得酯粒(5)的固有黏度(IV)及分子量分布,结果如表2所示。由于酯粒(5)的固有黏过低(低于0.3dL/g),造成熔融强度不足而无法顺利进行拉条(拉条时无法保持稳定形状),因此无法进行固态聚合反应与测量固聚后的性质。
比较例5:
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约27,500、固有黏度(IV值)为约0.48、以及分子量分布为约1.58)、1.5重量份的季戊四醇(作为多元醇)、以及0.3重量份的2,6-二叔丁基-4-甲基苯酚(作为抗氧化剂)均匀混合,得到一组合物。接着,将该组合物在50Pa及110℃下干燥8小时。接着,将干燥后的组合物加入双螺杆挤出机(螺杆直径为50mm)中进行混料与造粒,得到酯粒(6)。其中,双螺杆挤出机温度设定为240℃、螺杆转速设定为200转/分钟。接着,测量所得酯粒(6)的固有黏度(IV)及分子量分布,结果如表2所示。由于酯粒(6)的固有黏过低(低于0.3dL/g),造成熔融强度不足而无法顺利进行拉条(拉条时无法保持稳定形状),因此无法进行固态聚合反应与测量固聚后的性质。
表2
由表2可得知,当组合物中多元醇的含量过低时,经酯交换反应以及固态聚合后所得的分枝聚合物(4)(比较例3),其熔融指数较高,且剪切黏度及熔融强度较低。此外,当组合物中多元醇的含量过高时,经酯交换反应所得的酯粒(5)(比较例4)其固有黏度(IV)较低,因此,该酯粒(5)的熔融强度过低,不足以进行拉条造粒,且无法进一步进行固态聚合反应。另一方面,当用来进行酯交换反应的聚对苯二甲酸乙二酯的数目分子量过低时,经酯交换反应所得的酯粒(6)(比较例5)其固有黏度(IV)较低,因此,该酯粒(6)的熔融强度过低,不足以进行拉条造粒,且无法进一步进行固态聚合反应。
发泡体的制备
比较例6
将100重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约45,000、固有黏度(IV值)为约0.74、以及分子量分布为约1.80)以射出成型机(温度为245℃)制成厚度为0.2mm的板材。接着,将此板材放置于超临界流体发泡设备中。接着,将发泡设备的超临界流体供应槽中的压力调整至2500psi,使二氧化碳气体形成超临界流体。接着,将超临界二氧化碳注入发泡设备中。调整系统压力与温度至2500psi与210℃,并维持15分钟。接着,让设备泄压并冷却至常温常压。最后,对经发泡工艺所得的产物进行性质测量,结果如表3所示。其中,发泡体比重是根据ASTM D792进行测量;而发泡体孔洞大小是以扫描式电子显微镜进行发泡体截断面测量并配合图像软件分析计算孔洞大小分布。
实施例4
将90重量份的聚对苯二甲酸乙二酯粒子(数均分子量为约45,000、固有黏度(IV值)为约0.74、以及分子量分布为约1.80)与10重量份的分枝聚合物(1)(由实施例1所制备)以双螺杆挤出机(温度为250℃)进行混炼合胶,并以射出成型机(温度为245℃)形成厚度为0.2mm的板材。接着,将此板材放置于超临界流体发泡设备中。接着,将发泡设备的超临界流体供应槽中的压力调整至2500psi,使二氧化碳气体形成超临界流体。接着,将超临界二氧化碳注入发泡设备中。调整系统压力与温度至2500psi与210℃,并维持15分钟。接着,让设备泄压并冷却至常温常压,得到发泡体(1)。对发泡体(1)进行性质测量,结果如表3所示。
实施例5
依实施例4所述的方式进行,除了将聚对苯二甲酸乙二酯粒子由90重量份降低至70重量份、并将分枝聚合物(1)由10重量份增加至30重量份,得到发泡体(2)。接着,对发泡体(2)进行性质测量,结果如表3所示。
实施例6
依实施例4所述的方式进行,除了将聚对苯二甲酸乙二酯粒子由90重量份降低至50重量份、并将分枝聚合物(1)由10重量份增加至50重量份,得到发泡体(3)。接着,对发泡体(3)进行性质测量,结果如表3所示。
实施例7
依实施例4所述的方式进行,除了将聚对苯二甲酸乙二酯粒子由90重量份降低至30重量份、并将分枝聚合物(1)由10重量份增加至70重量份,得到发泡体(4)。接着,对发泡体(4)进行性质测量,结果如表3所示。
实施例8
依实施例4所述的方式进行,除了将聚对苯二甲酸乙二酯粒子由90重量份降低至10重量份、并将分枝聚合物(1)由10重量份增加至90重量份,得到发泡体(5)。接着,对发泡体(5)进行性质测量,结果如表3所示。
表3
由表3可得知,将原本无法发泡的聚对苯二甲酸乙二酯进一步与本公开所述的分枝聚合物进行混合后,可形成具有高熔融黏度与熔融强度的发泡体。
虽然本公开已以数个实施例公开如上,然其并非用以限定本公开,任何本技术领域普通技术人员,在不脱离本公开之精神和范围内,当可作任意的更动与润饰,因此本公开的保护范围当视所附的权利要求所界定的为准。
Claims (16)
1.一种分枝聚合物,为包含100重量份聚对苯二甲酸乙二酯以及0.5至2重量份的多元醇的组合物所反应而成,其中所述分枝聚合物的固有黏度由1.2dL/g至1.6dL/g、数均分子量由75,000g/mol至90,000g/mol、分子量分布由3.0至6.0、熔融指数由0.8g/10min至7.5g/10min、剪切黏度由800Pa·s至1900Pa·s、以及熔融强度由30cN至80cN。
2.根据权利要求1所述的分枝聚合物,其中所述聚对苯二甲酸乙二酯的数均分子量为30,000g/mol至55,000g/mol,分子量分布为1.4至1.8,固有黏度为0.40dL/g至0.95dL/g。
3.根据权利要求1所述的分枝聚合物,其中所述多元醇为3至8个羟基的聚醚多元醇、脂肪族多元醇、或上述组合。
4.根据权利要求1所述的分枝聚合物,其中所述组合物不包含有机酸、酸酐、具有环氧基的化合物或溶剂。
5.根据权利要求1所述的分枝聚合物,其中所述组合物还包含0.1至0.5重量份的抗氧化剂。
6.根据权利要求5所述的分枝聚合物,其中抗氧化剂为选自受阻酚型抗氧化剂、酯类抗氧化剂、硫代酯型抗氧化剂和亚磷酸酯类抗氧化剂所构成的群组。
7.一种如权利要求1所述的分枝聚合物的制备方法,包含:
将一组合物以挤出机进行酯交换反应,得到一酯粒,其中所述组合物包含100重量份聚对苯二甲酸乙二酯以及0.5至2重量份的多元醇,其中所述聚对苯二甲酸乙二酯的数均分子量为30,000g/mol至55,000g/mol,以及所述聚对苯二甲酸乙二酯的固有黏度为0.40dL/g至0.95dL/g;
对所述酯粒进行干燥;以及
对所述酯粒进行固态聚合增黏,
其中,所述分枝聚合物的固有黏度由1.2dL/g至1.6dL/g、数均分子量由75,000g/mol至90,000g/mol、以及分子量分布由3.0至6.0。
8.根据权利要求7所述的分枝聚合物的制备方法,其中所述挤出机为双螺杆挤出机。
9.根据权利要求7所述的分枝聚合物的制备方法,其中所述聚对苯二甲酸乙二酯的分子量分布为1.4至1.8。
10.根据权利要求7所述的分枝聚合物的制备方法,其中所述酯交换反应的温度为220℃至270℃,以及所述挤出机的螺杆转速为100转/分钟至500转/分钟。
11.根据权利要求7所述的分枝聚合物的制备方法,其中对所述酯粒进行干燥是在压力20Pa至100Pa及温度90℃至130℃下,进行5小时以上。
12.根据权利要求7所述的分枝聚合物的制备方法,其中所述固态聚合是在压力10Pa至50Pa及温度180℃至240℃下进行,固态聚合时间为6小时至24小时。
13.一种发泡体的制备方法,包含:
将权利要求1所述的分枝聚合物与聚对苯二甲酸乙二酯进行混炼合胶,所述分枝聚合物与聚对苯二甲酸乙二酯的重量比为1:9至9:1;以及对所述混炼物进行发泡工艺,
其中,所述发泡体的固有黏度由0.95dL/g至1.50dL/g、剪切黏度由600Pa·s至1400Pa·s、熔融指数由2.5g/10min至25g/10min、以及熔融强度由15cN至65cN。
14.根据权利要求13所述的发泡体的制备方法,其中所述发泡工艺还包含:
将所述混炼物及化学发泡剂混合,并通过挤出机在200℃至270℃下进行发泡。
15.根据权利要求14所述的发泡体的制备方法,其中所述发泡工艺还包含:
将所述混炼物形成片材,并将所述片材在温度190℃至235℃及压力为1500psi至3000psi下含浸于发泡剂中进行发泡。
16.根据权利要求13所述的发泡体的制备方法,其中所述发泡体的密度为0.05~0.65g/cm3、泡孔大小为2~30μm、数均分子量为45,000~70,000g/mol、分子量分布为3.0~6.0。
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