CN103347942B - 制造具有经改良可膨胀性之可膨胀热塑性珠粒的方法 - Google Patents
制造具有经改良可膨胀性之可膨胀热塑性珠粒的方法 Download PDFInfo
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Abstract
本发明系关于一种制造包括空腔之可膨胀热塑性聚合物珠粒之方法,其系经由穿过模板挤出包含发泡剂之聚合物熔体及在1.5至15巴范围内之压力下于包括液体之腔室中制粒,其包括利用含有发泡剂之聚合物熔体,其中该熔体包括(各系基于含有发泡剂之聚合物熔体)0.1至5重量%之核化剂D),1至10重量%之发泡剂E),其实质上保留在聚合物珠粒内部,0.01至5重量%之形成空腔之共发泡剂F),本发明亦有关可藉由该方法获得之可膨胀热塑性聚合物珠粒材料,其包括平均直径在0.1至50μm范围内之空腔。
Description
发明所属之技术领域
本发明系关于一种制造包括空腔之可膨胀热塑性聚合物珠粒之方法,其系透过模板经由挤出包括发泡剂之聚合物熔体及在1.5至15巴压力范围下于包括液体之腔室中制粒。
先前技术
可膨胀可模制发泡体可藉由悬浮法、经由聚合物颗粒之后浸透或藉由熔体挤出法而制备。熔体挤出法在可能之起始物及添加剂方面尤其多样化。
藉由熔体浸透法制造可膨胀聚合物之方法为已知。现已证明大量材料(例如含丙烯腈之苯乙烯共聚物(WO 2009/000872)及弹性化可膨胀可模制发泡体(WO 2009/112549)可用于各种聚合物系统中。
可模制发泡体之性质明显取决于泡孔(cell)结构,例如泡孔大小或泡孔大小分布。因此例如热、机械及光学性质及触感可藉由影响泡孔大小而改变。由于应用之制程技术参数,在不改变材料组成的情况下,仅能实现有限地控制泡孔结构。
因此,经常藉由利用核化剂来实现泡孔大小之控制,实例为无机添加剂及有机核化剂诸如蜡,其中此等对系统提供界面,且因此减少在聚合物与核化剂之间之相界(phase boundary)处之异质核化能量障壁。
然而,该类型之核化剂仅具有有限适用性,因其有时具有低效率及其对发泡体之机械性或燃火性具有不利影响。例如,添加无机颗粒核化剂(诸如滑石)可减少坚韧性,其以例如弯曲能或抗龟裂为特征。尽管可能使用兼容剂或表面改性填料来改良无机核化剂之偶合,从而改良机械性,然而此等又呈现较低核化效率。
而且,无机核化剂需要核化之聚合物中应具有较低溶解度,以容许相分离。因此,例如,烯烃蜡无法使用于烯烃聚合物中。有机核化剂(诸如烯烃蜡,例如Luwax)对所有材料都不适合。而且,韧化苯乙烯发泡体无法使用烯烃核化剂,因为其在材料内部不提供相分离而代之会迁移到聚烯烃相中。进而不能有效地进行核化。同样地,可以藉由使用低溶解度发泡剂实现泡孔密度之增加。然而,该类型之发泡剂需要极高的溶解压力且在预发泡之珠粒或完全发泡之模制品中呈现长的滞留时间,亦即其具有对该方法及该应用之特定缺点。
迄今为止,未广泛叙述使用有机发泡剂及惰性气体来控制可膨胀聚合物之发泡体结构及发泡体性质。以下说明一些相关专利说明书及其不仅涵盖发泡体挤出亦包括可膨胀及已膨胀珠粒。
WO 2004/022636叙述利用水作为发泡剂制造发泡体珠粒。为改良水可相溶性,使用增溶剂诸如乙醇及丙酮。而且,使用其他发泡剂,例如戊烷、丁烷及/或CO2。加水的主要目的在于减少可膨胀颗粒中有机发泡剂之含量,及未叙述对泡孔大小之效果。
DE 198 190 58叙述具有低量之初期发泡体之可膨胀苯乙烯聚合物之制造及应用。藉由改变悬浮聚合法及熔体浸透法中之制程参数,通过使用戊烷作为发泡剂,可实现低于未发泡材料之总体密度0.1至20%之总体密度的初期发泡体。初期发泡体之强度可制造具有相对粗糙泡孔之发泡体。然而,实现该材料之均质初期发泡体高度依赖于选择之制程条件及改变范围受到限制。
WO 2005/092959叙述在多相聚合物系统中使用多种发泡剂。该目的在于经由发泡剂选择性地浸透奈米级结构及随后之发泡而制造奈米多孔发泡体。为达成微细泡孔结构之一必要前提条件为多相掺合结构。
例如,EP-A 846 141叙述使用发泡剂组合物。连续进行之用于制造可膨胀苯乙烯聚合物之方法分别或与CO2呈混合物添加作为发泡剂之C3-C7烃类。该方法包括高达某一转换率之苯乙烯聚合物之块体聚合、利用悬浮稳定剂分散所得液态预聚物于水相中及随后聚合而完成。可在任何制程步骤期间添加发泡剂。当使用CO2时,使用CO2吸收剂更为有利。未叙述CO2在制造过程之前或之后之任何具体作用。
EP-A 987 292叙述预膨胀乙烯基芳香族聚合物以产生200-600g/l之总体密度,及在利用无机气体(明确言之是利用含O2或N2之气体)浸透材料后之随后后膨胀。此处之预膨胀及后浸透步骤系发生在不同时间。后浸透步骤在所有情形下为膨胀所需。
EP-B 1 000 115叙述一种制造特定言之基于聚苯乙烯之可膨胀聚合物颗粒物之方法。在利用适宜发泡剂浸透聚合物后,进行雾化制程及后续使所得颗粒物冷却。提及之可能发泡剂尤其为烃类、氯氟碳化物、CO2、N2及空气或惰性气体。未叙述使用CO2、N2及空气之特定效果。
US 2,864,778叙述使用除脂肪族烃类之外之少量CO2来制造可膨胀苯乙烯聚合物。在藉由悬浮制程之聚合反应之前或期间添加CO2可制造具有相对微细泡孔之发泡体。其说明该目的所需之比例为极小的。在实例中,即使在0.4重量%及更小之比例下也会产生效果。其未叙述用于实现微细泡孔产物之其他系统或用于制造可膨胀苯乙烯聚合物之其他方法。
US 3,328,497叙述使用气体(具体言之N2及空气)来从可膨胀苯乙烯聚合物及互聚物制造发泡体。所述之方法包括使包括沸点低于80℃之有机发泡剂之可膨胀聚合物部份膨胀,及迅速转移至增加之气压及低温之氛围中。在最后一步中,藉由在增温下于密闭模具中进一步膨胀来获得发泡体。所述气体经颗粒物之吸收系藉由与EP 987 292相似的方法在材料之预膨胀后达成,且其未叙述对泡孔结构之特定影响。
US 5,391,581叙述使用由脂肪族烃类或脂环族烃类及CO2制成之发泡剂混合物来制造由基于乙烯之树脂制成之发泡体珠粒。经膨胀颗粒物之泡孔大小可藉由使用CO2及另外加入之无机核化剂而变得均质,但不同于可膨胀珠粒,在制造模制品之前无法进行额外膨胀。
US 2006/0022366叙述利用多种发泡剂挤出基于苯乙烯之聚合物系统之发泡体片(XPS)。与异丁烷、正戊烷、异戊烷或其混合物组合用作发泡剂之材料宜为水、CO2、醚类或沸点低于140℃之二烷基碳酸酯类。提及发泡剂及当与空气相比更迅速之渗透制程之使用在发泡制程后产生减压,且此对进一步塑形制程有利。
US 2007/0049649叙述一种制造包括微腔之发泡聚合物珠粒之方法,其中该聚合物系在高压下利用气体或在超临界态利用液体在挤出机中加工以产生均质单相混合物并挤出。
EP-A 0 761 729叙述具有少于100个直径约0.1至30μm之微腔之可膨胀苯乙烯树脂珠粒,其系经由悬浮聚合在过硫酸盐及电解质存在下获得。
发明内容
本发明之一目的系发现一种制造具有改良可膨胀性同时具有减低之发泡剂含量之可膨胀热塑性聚合物珠粒之方法,其中该熔体包括可快速预发泡且经控制调节之泡孔结构。
因此,已经发现一种制造包括空腔之可膨胀热塑性聚合物珠粒之方法,其系透过模板经由挤出包括发泡剂之聚合物熔体及在1.5至15巴压力范围下于包括液体之腔室中制粒,其包括利用含有发泡剂之聚合物熔体,其中该熔体包括(各系基于发泡剂之聚合物熔体)
0.1至5重量%,较佳系0.3至1.0重量%之核化剂D),
1至10重量%,较佳系2至6重量%之发泡剂E),其实质上保留在聚合物珠粒内部,
0.01至5重量%,较佳系0.05至1重量%之形成空腔之共发泡剂F)。
图式简单说明
图1及图2显示透过实例13之颗粒物珠粒内部具有均质分布之空腔之可膨胀颗粒物之薄切片在不同放大倍数下之透射电子显微照片。
实施方式
意外地发现使用可形成空腔之挥发性液体/气体共发泡剂F)可在可膨胀颗粒物中形成泡孔结构,从而可改良后续发泡制程及可控制泡孔大小。
适宜核化剂D)为无机或有机核化剂。适宜无机核化剂之实例为滑石、二氧化硅、云母、黏土、沸石或碳酸钙。适宜有机核化剂之实例为蜡诸如以Luwax出售之聚乙烯蜡。较好使用滑石。
基于包括发泡剂之聚合物熔体之所有组分A)至F),所用发泡剂(组份E)包括1至10重量%,较佳系3至8重量%之物理发泡剂。该发泡剂在室温(20至30℃)及大气压力下可为气态或液体。其沸点应低于聚合物混合物之软化点,一般在-40至80℃之范围内,较佳在-10至40℃范围内。适宜发泡剂之实例为卤化或不含卤素之发泡剂,例如脂肪族C3至C8-烃类、醇类、酮类或醚类。适宜脂肪族发泡剂之实例为脂肪族C3至C8-烃类,诸如正丙烷、正丁烷、异丁烷、正戊烷、异戊烷、正己烷、新戊烷、环脂族烃类诸如环丁烷及环戊烷、卤代烃诸如氯甲烷、氯乙烷、二氯甲烷、三氯氟甲烷、二氯氟甲烷、二氯二氟甲烷、氯二氟甲烷、二氯四氟乙烷及其混合物。较佳系下列不含卤素之发泡剂:异丁烷、正丁烷、异戊烷、正戊烷、新戊烷、环戊烷及其混合物。
若发泡剂较佳地包括占发泡剂之25至100重量%,尤其较佳系35至95重量%之比例之异戊烷或环戊烷,则可改良储存后之发泡剂保留性能及可实现更低的最小总体密度。尤其较佳系使用由30至98重量%,特定言之35至95重量%之异戊烷及70至2重量%,特定言之65至5重量%之正戊烷制成之混合物。
较佳使用之发泡剂E)包括脂肪族C3-C7-烃类或其混合物,尤其较佳系异丁烷、异戊烷、正戊烷及其混合物。较佳,包括发泡剂之聚合物熔体包括少于0.5重量%之水。
用于调节至该空腔形态之方法亦可称为预核化,且该等空腔实质上系由共发泡剂F)形成。
形成空腔之共发泡剂F)在聚合物中之溶解度不同于实际发泡剂E)。在制造过程中,发泡剂E)及共发泡剂F)起初在充分高压下在聚合物中完全溶解。然后较佳地在短时期内减压,因此降低共发泡剂F)之溶解度。此导致在聚合物基质内开始相分离,且产生预核化结构。因为该实际发泡剂E)具有相当高溶解度及/或具有较低扩散速率,故而其在聚合物中主要保持为不溶解。降温较好与减压同时进行,以抑制系统过量核化及降低实际发泡剂E)从材料中扩散出。此可藉由使用共发泡剂F)并联合理想制粒条件而达成。
较好至少80重量%之共发泡剂F)在24小时期间内从在25℃、大气压力及50%相对湿度储存之可膨胀热塑性珠粒中逃逸。共发泡剂F)在可膨胀热塑性珠粒中之溶解度较佳低于0.1重量%。
较佳地使用相较于实际发泡剂E)又具有更高扩散速率及/或增加可渗透性及/或增加蒸汽压之共发泡剂F);最佳系该共发泡剂F)展现多种此类特性。为提供核化制程之其他支持,可使用少量习知核化剂,例如无机颗粒诸如滑石。
在所有情形下,在预核化制程期间使用之共发泡剂F)之添加量应超过在盛行制程条件下之最大溶解度。因此,较佳地使用在聚合物中具有较低但适当之溶解度之共发泡剂F)。其中尤其是气体,诸如氮气、二氧化碳及空气或惰性气体,及最佳系氮气,其在许多聚合物中之溶解度在低温及压力下会降低。然而,也可使用其他液体添加剂。
尤其较好使用惰性气体,诸如氮气及二氧化碳。该两种气体之特征,除其适宜的物理性质以外,亦有低成本、良好获取性、易处理性及非反应性或惰性之特征。例如,在几乎所有情形下,在该两种气体存在下不会发生聚合物劣化。因为气体自身获自大气中,所以其对环境也没有影响。
文中使用之共发泡剂F)之含量应系:(i)足够少,以在熔体浸透及至制粒期间,在既定熔融温度及既定熔融压力下溶解;(ii)足够多,以在用于制粒之水压及温度下与聚合物及核化剂分离(demix)。在一个较佳实施例中,使用之至少一种发泡剂在室温及大气压力下为气态。
而且,较佳使用在预核化后,可于短时间内从可膨胀颗粒物完全逃逸及因此不会影响进一步发泡制程之共发泡剂F)。尤其较佳地使用氮气、二氧化碳、氩气、氦气或其混合物作为共发泡剂F)。
尤其较佳地使用滑石作为核化剂D),并结合氮气作为共发泡剂F)。
尤其可使用金属桶或八角形箱来运输或储存可膨胀颗粒物。若使用桶,需要考虑的是共发泡剂F)之释放有时可能会增加桶内压力。因而,使用之包装较佳系开口包装,诸如八角形箱或桶,其中此等容许经由空气从桶中渗透出而释放压力。尤其较佳系容许共发泡剂F)藉由扩散逃逸且使实际发泡剂E)藉由扩散逃逸最小化或抑制其逃逸的桶。此可以例如藉由以分别适合发泡剂及共发泡剂F)之方式选择密封材料来实现。较好该密封材料对共发泡剂F)之可渗透性比密封材料对实际发泡剂E)之可渗透性高至少20倍。
例如经由添加少量氮气及二氧化碳之预核化,可在包括发泡剂之可膨胀颗粒物内部建立泡孔形态。在珠粒中心之平均泡孔大小比周围区域更大,及在珠粒周围区域中,密度可以更高。因此,尽可能减小发泡剂损失。
预核化可达成显著较佳泡孔大小分布并在预发泡后减小泡孔大小。达成最小总体密度所需之发泡剂之含量更少,且材料之储存稳定性更佳。添加至熔体中之少量氮气或二氧化碳在恒定发泡剂含量下可导致显著减少预发泡时间或在恒定发泡时间及最小发泡体密度下显著减少发泡剂之含量。而且,预核化作用改良产物均质性及制程稳定性。
此外,以发泡剂对本发明之聚合物颗粒进行再浸透比相同构成且更密实(亦即无泡孔)结构之颗粒显著更快速。首先,扩散时间更短,且第二,由直接浸透系统类推,需要更少量用于发泡之发泡剂。
最后,预核化作用可减少需要达成某种密度之发泡剂含量,及因此可减少制造模制品或片之脱模时间。此可减少进一步加工成本及改良产品质量。
预核化制程一般可用于所有可膨胀珠粒。较佳用于对机械性质要求严格之材料及其中常用之亲核剂仅具有轻微效果之系统。例如,在弹性化发泡体之情形下,可经由添加氮气或二氧化碳达成微细泡孔结构之显著改良。
预核化原理不仅可用于悬浮技术亦可用于熔体浸透技术以制造可膨胀珠粒。较佳系用于熔体挤出过程,其中添加共发泡剂F)系经由压力辅助之水面下制粒而制粒,随后排出已吸收发泡剂之熔体。颗粒物之微结构可按上述经由选择制粒参数及共发泡剂F)而控制。
将发泡剂E)及共发泡剂F)并入聚合物熔体之混合可藉由动态混合器(诸如挤出机)或静态混合器而实现。
在相当高含量之共发泡剂F)(例如占包括发泡剂之聚合物熔体之1至10重量%之范围中)之情形下,可降低熔融温度或降低熔融黏度,从而显著增加处理量。因此,亦可在非强烈条件下将热不安定添加剂并入聚合物熔体中,例如阻燃剂。可膨胀热塑性珠粒之组成不会随之改变,因为共发泡剂实质上在熔体挤出过程期间逃逸。为利用该效果,较佳地使用CO2。N2对黏度之影响较小。因而,氮气主要用于调节所需泡孔结构。
包括液体之用于可膨胀热塑性聚合物珠粒之制粒之腔室较好在20至80℃范围之温度下、尤其较佳在30至60℃范围下操作。
可使用之热塑性聚合物之实例为苯乙烯聚合物、聚酰胺(PA)、聚烯烃(诸如聚丙烯(PP)或聚乙烯(PE))、聚丙烯酸酯(如聚甲基丙烯酸甲酯(PMMA))、聚碳酸酯(PC)、聚酯类(诸如聚对苯二甲酸乙二酯(PET)或聚对苯二甲酸丁二酯(PBT))、聚醚砜(PES)、聚醚酮类(PEK)或聚醚硫醚(PES)或其混合物。
较佳系苯乙烯共聚物,诸如苯乙烯-丁二烯嵌段共聚物、苯乙烯-α-甲基苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丙烯腈(SAN)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯(MABS)聚合物、已经藉由自由基途径聚合之冲击改性聚苯乙烯(HIPS)或玻璃状透明聚苯乙烯(GPPS)或阴离子聚合之聚苯乙烯(APS)或阴离子聚合之抗冲击聚苯乙烯(AIPS)。
可对所需模制发泡体之性质适宜地选择聚合物颗粒物之组成。作为苯乙烯共聚物组份之苯乙烯-丁二烯嵌段共聚物尤其适合改良模制发泡体之弹性及回弹。耐油性以及耐溶剂性(尤其是芳香族溶剂之耐性)及耐热性可藉由利用含丙烯腈之苯乙烯共聚物(诸如SAN及ABS)而改良。
在本发明方法中,尤其较佳使用一种聚合物熔体,其包括发泡剂及包括(各系基于含有发泡剂之聚合物熔体)
A)45至97.79重量%之苯乙烯聚合物,
B1)1至45重量%之具有105至140℃之范围之熔点之聚烯烃,
B2)0至25重量%之低于105℃之熔点之聚烯烃,
C1)0.1至25重量%之苯乙烯-丁二烯嵌段共聚物或苯乙烯-异戊二烯嵌段共聚物,
C2)0至10重量%之苯乙烯-乙烯-丁烯嵌段共聚物,
D)0.1至5重量%之核化剂,
E)1至10重量%之发泡剂,其实质上保留在聚合物珠粒内部,及
F)0.01至5重量%之形成空腔之共发泡剂。
组份A
该聚合物珠粒包括45至97.8重量%,尤其较佳系55至78.1重量%之苯乙烯聚合物A),诸如标准聚苯乙烯(GPPS)、抗冲击聚苯乙烯(HIPS)、苯乙烯-丙烯腈共聚物(SAN)或丙烯腈-丁二烯-苯乙烯共聚物(ABS)或其混合物。用于制造该发泡体珠粒P1之可膨胀热塑性聚合物较佳地包括作为苯乙烯聚合物A)之标准聚苯乙烯(GPPS)。尤其较佳系标准聚苯乙烯级,其具有经凝胶渗透层析法测定之在120,000至300,000g/mol范围、特定言之190,000至280,000g/mol之重量平均莫耳质量;及具有在1至10cm3/10min范围之熔体体积率MVR(200℃/5kg)(依据ISO113),实例为获自BASF SE之PS 158K、168N或148G。可添加自由流动级(如Empera156L(Innovene))以改良发泡体珠粒在加工期间之熔化以产生模制品。
组份B
该热塑性聚合物珠粒包括作为组份B)之具有105至140℃范围之熔点之聚烯烃B1)及具有低于105℃之熔点之聚烯烃B2)。熔点系藉由DSC(动态扫描量热仪)在加热速率10℃/分钟下测定之熔解峰值。
该热塑性聚合物珠粒包括1至45重量%,较佳系4至35重量%,尤其较佳系7至15重量%之聚烯烃B1)。使用之聚烯烃B1)较佳包括具有0.91至0.98g/l范围(依据ASTM D792测定)之密度之乙烯及/或丙烯之均聚物或共聚物,特定言之系聚乙烯。尤其可使用之聚丙烯类为射出模制级。可用之聚乙烯类为可购得之由乙烯制成之均聚物,例如LDPE(射出模制级)、LLDPE、HDPE,或下列各者之共聚物:乙烯及丙烯(例如,获自Basell之MoplenRP220及MoplenRP320,或获自Dow之Versify级)、乙烯及乙酸乙烯酯(EVA)、乙烯丙烯酸酯(EA)或乙烯-丁烯丙烯酸酯(EBA)。聚乙烯类之熔体体积指数MVI(190℃/2.16kg)通常在0.5至40g/10min之范围内,密度在0.91至0.95g/cm3之范围内。亦可使用与聚异丁烯(PIB)(例如,获自BASF Aktengesellschaft之OppanolB150)之掺合物。尤其较佳使用具有在110至125℃范围内之熔点及在0.92至0.94g/l范围内之密度之LLDPE。
其他适宜组份B1)为烯烃嵌段共聚物,其中此等系由聚烯烃嵌段PB1(硬嵌段)及聚烯烃嵌段PB2(软嵌段)组成,例如在WO 2006/099631中叙述之彼等。聚烯烃嵌段PB1较佳系由95至100重量%之乙烯组成。PB2嵌段较佳系由乙烯及α-烯烃组成,其中可使用下列作为α-烯烃类:苯乙烯、丙烯、1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯、降冰片烯、1-癸烯、1,5-已二烯或其混合物。较佳使用具有5至60重量%之α-烯烃之乙烯-α-烯烃共聚物嵌段(尤其乙烯-辛烯共聚物嵌段)作为PB2嵌段。较佳系式(PB1-PB2)n之多嵌段共聚物,其中n表示1至100之整数。该等嵌段PB1及PB2实质上形成直链并较佳地具有交替或随机分布。PB2嵌段占烯烃嵌段共聚物之比例较佳系40至60重量%。尤其较佳系具有交替硬PB1嵌段及软、弹性PB2嵌段之烯烃嵌段共聚物,此等可以商标INFUSE购得。
发泡剂保留性能会随着相对小比例之聚烯烃B1)而显著增加。此显著改良可膨胀热塑性聚合物珠粒之储存稳定性及可加工性。在4至20重量%之聚烯烃范围中,可获得具有优良储存性之可膨胀热塑性聚合物珠粒,而丝毫不损及由其制得之模制发泡体之弹性。此可藉由例如在25至35%范围内之相对低压缩形变ε形变而显见。
可膨胀热塑性聚合物珠粒包括0至25重量%,较佳系1至15重量%,尤其较佳系5至10重量%之具有熔点低于105℃之聚烯烃B2)作为聚烯烃B2)。聚烯烃B2)较佳具有0.86至0.90g/l范围(依据ASTM D792测定)之密度。基于烯烃之热塑性弹性体(TPOs)尤其适合该目的。尤其较佳系乙烯-辛烯共聚物,其例如可从Dow以商标Engage8411购得。在经加工产生发泡体模制品后,包括组份B2)之可膨胀热塑性聚合物珠粒展示在弯曲能及极限抗张强度方面之显著改良。
组份C
在多相聚合物系统领域中,已知大多数聚合物不具有或仅具有些许互混性(Flory),及产生各别相之分离因而成温度、压力及化学组成之函数。如果不兼容聚合物彼此共价相连,则在宏观程度不会发生分离而仅在微观程度(例如,在单一聚合物链之长度范围内)发生。因而,在此情况中使用术语微相分离。存在多种所得之介观(mesoscopic)构造,例如薄片状、六角形、立方形、及双连续形态,其中此等与易溶相(lyotropic phase)有强烈关联。
相溶化剂(组份C)用于控制调节至所需形态。本发明经由使用作为组份C1)之苯乙烯-丁二烯嵌段共聚物或苯乙烯-异戊二烯嵌段共聚物之混合物及作为组份C2)之苯乙烯-乙烯-丁烯嵌段共聚物(SEBS)而改良可相溶性。
相溶化剂导致富含聚烯烃及富含苯乙烯聚合物相之间之黏性改良,且与习知EPS发泡体相比,即使少量亦可显著改良发泡体之弹性。富含聚烯烃相之区域尺寸之研究已经显示相溶化剂藉由减少表面张力而稳定诸小滴。
可膨胀热塑性聚合物珠粒尤其较佳系由多相聚合物混合物组成,其包括发泡剂并具有至少一种连续相,且其具有分散在该连续相内之至少两个分散相P1及P2,其中
a)连续相实质上由组分A组成,
b)第一分散相P1实质上由组分B1及B2组成,及
c)第二分散相P2实质上由组分C1组成。
组分C2)较佳在分散相P1及连续相之间形成相界。
藉由该其他分散相,可保持分散相之区域尺寸<2μm,并具有较高软相含量。对于相同可膨胀性而言,此可在模制发泡体中产生相对较高弯曲能。
该可膨胀热塑性聚合物珠粒中之全部组份C1)及C2)较佳系在3.5至30重量%之范围,尤其较佳系在6.8至18重量%之范围。
该可膨胀热塑性聚合物珠粒中之全部组份B1)及B2)与组份C2)之重量比较佳系在5至70之范围。
该可膨胀热塑性聚合物珠粒中之组份C1)与C2)之重量比较佳系在2至5之范围。
该可膨胀热塑性聚合物珠粒包括0.1至25重量%,较佳系1至15重量%,特定言之6至9.9重量%之作为组份C1)之苯乙烯-丁二烯嵌段共聚物或苯乙烯-异戊二烯嵌段共聚物。
适用于该目的之材料为例如苯乙烯-丁二烯嵌段共聚物或苯乙烯-异戊二烯嵌段共聚物。总二烯含量较佳在20至60重量%之范围,尤其较佳在30至50重量%之范围,及总苯乙烯含量因而较佳在40至80重量%之范围,尤其较佳在50至70重量%之范围。
较佳使用具有20至60重量%,较佳系30至50重量%之丁二烯含量之苯乙烯-丁二烯-苯乙烯(SBS)三嵌段共聚物作为相溶化剂,其中此等可氢化至些许程度或不被氢化。其可例如以商标Styroflex2G66、Styrolux3G55、StyroclearGH62、KratonD 1101、KratonD 1155、TuftecH1043或EuroprenSOL T6414购得。此等包括在B嵌段及S嵌段之间具有明显转变之SBS嵌段共聚物。
该可膨胀热塑性聚合物珠粒包括0.1至10重量%,较佳系1至9.9重量%,特定言之0.8至5重量%之作为组份C2)之苯乙烯-乙烯-丁烯嵌段共聚物(SEBS)。适宜苯乙烯-乙烯-丁烯嵌段共聚物(SEBS)为例如彼等经由氢化嵌段共聚物C1)之烯烃双键而获得者。适宜苯乙烯-乙烯-丁烯嵌段共聚物为例如可购得之KratonG级,特定言之KratonG 1650。
本发明之方法可获得具有在0.1至50μm,较佳系1至30μm范围之平均直径之空腔之可膨胀热塑性聚合物珠粒。
较佳该可膨胀热塑性聚合物珠粒材料具有在0.2至2.5mm范围之平均直径及具有50至300个空腔/mm2横截面积、较佳系70至150个空腔/mm2横截面积。空腔数目可例如在光学显微镜下透过聚合物珠粒材料自一薄层计数测定。
该材料之总体密度较佳地在500至590kg/m3之范围,较佳系520至580kg/m3。
该可膨胀颗粒之预核化结构可产生较佳可发泡性及泡孔大小之可控调节,及因此显著改良加工性及发泡体性质。
为了改良可加工性,完成之可膨胀热塑性聚合物珠粒可经甘油酯、抗静电剂或抗结块剂涂布。
所得圆形或椭圆形珠粒较佳发泡成0.2至10mm范围内之直径。其总体密度较佳在10至100g/l范围内。
产生模制品之预发泡之发泡体珠粒之融合及所得机械性质尤其经由利用硬脂酸甘油酯涂布可膨胀热塑性聚合物而改良。尤其较佳地利用由50至100重量%之三硬脂酸甘油酯(GTS)、0至50重量%之单硬脂酸甘油酯(GMS)及0至20重量%之二氧化硅组成之涂料。
该可膨胀热塑性珠粒可藉由热空气或蒸汽预先发泡以产生具有在8至200kg/m3范围内、较佳在10至80kg/m3范围内、尤其在10至50kg/m3范围内之密度的发泡体珠粒,且然后在密闭模具中融合产生发泡体模制品。通常使用0.5至1.5巴,尤其0.7至1.0巴范围内之表计压力。
就达成相当密度而言,该理念之应用相较于标准EPS可显著减少发泡剂含量,且因而可使用更少会引起温室效应之发泡剂。故可以利用相同发泡剂含量实现更低的最小总体密度。而且,如在储存或运输期间发泡剂损失的情形下,实质上更容易利用发泡剂再次浸透该预核化之颗粒。因为预核化制程可使用先前从大气获得之氮气或其他惰性气体,因此用于改良热塑性可模制发泡体之膨胀性及用于泡孔结构之更加调节之该理念保护环境并节约资源。
若共发泡剂F)含量相对大,则使用之形成空腔之共发泡剂F)具有显著的增塑效果。共发泡剂F)之降黏度效果因而容许在相同温度分布下增加处理量或对于相同处理量降低熔体温度(对于其他为相同之配方)。在加压设备(诸如制粒模嘴或混合器)中之压降在此处保持相同,因为该材料具有相同熔体黏度。因而首先可减少施加在材料上的热应力,及亦可并入热感材料(诸如阻燃剂)。其次,利用相同工厂设备/设备之加压获得之处理量增加使得以更有效成本制造可膨胀珠粒。
另一方面为可减少实际发泡剂之比例而不改变熔体黏度,无需任何调节工厂处理量或方法之实行。二氧化碳由于在聚合物中之相对高溶解度,故较佳作为增塑共发泡剂F)。
由本发明之方法获得之可膨胀热塑性聚合物珠粒可经加工以产生具有较高泡孔数目亦即微细泡孔结构之发泡体。均质发泡体结构可改良发泡体之机械性质及绝热性。
另一效果为减少发泡体加工之能量成本。更快速的预发泡制程可实现更高处理量。更低发泡剂含量连同预核化制程可显著减少脱模时间,并可缩短全部发泡处理之周期时间。
实例
起始材料:
组份A:
具有2.9cm3/10min之熔体黏度指数MVI(200℃/5kg)之聚苯乙烯(获自BASF SE之PS 158K,Mw=280,000g/mol,特性黏度值IV98ml/g)
组份B:
B1:LLDPE聚乙烯(LL1201XV,Exxon Mobile,密度:0.925g/l,MVI=0.7g/10min,熔点:123℃)
B2:乙烯-辛烯共聚物聚乙烯(Engage8402获自Dow,密度:0.880g/l,MVI=18g/10min,熔点:72℃)
组份C:
C1.1:Styrolux3G55,苯乙烯-丁二烯嵌段共聚物,获自BASFSE,
C1.2:Styroflex2G66,热塑性弹性苯乙烯-丁二烯嵌段共聚物(STPE),获自BASF SE,
C2:Kraton G1651,苯乙烯-乙烯-丁烯嵌段共聚物,获自KratonPolymers LLC
组份D:
D核化剂:滑石
组份E:
E由95重量%之异戊烷及5重量%之正戊烷作成之发泡剂混合物
组份F:
F氮气共发泡剂(实例E1-E17),二氧化碳共发泡剂(实例E19-E36)
可膨胀颗粒物E1-E11之制造
可膨胀颗粒物系藉由熔体浸透法、利用静态混合机而制造。为此,聚合物首先在挤出机中增塑并藉由熔体泵传输至一系列静态混合机及热交换器中。在第一静态混合器之入口处,一起添加技术级异戊烷(95%之异戊烷/5%之正戊烷)及共发泡剂F),及浸透该熔体。相应配方见于表1。然后,藉由热交换器降低熔体温度,及熔体温度系藉由另一静态混合机均质化。经由另一熔体泵施加压力,以藉由制粒模嘴(490.60mm孔)利用加压水面下制粒(水压:12巴,水温:50℃)对该材料制粒。平均珠粒大小为约1.25mm。总处理量为70kg/h。从模嘴中排出之熔体温度为约203℃。
表1:可膨胀颗粒E1-E11之组成(重量份)
可膨胀颗粒之分析
透射电子显微照片(TEMs)显示呈球状泡孔(图1,黑色区域)之包括发泡剂之颗粒的泡孔结构,及此等进而有助于更佳膨胀性及发泡体中之更微细泡孔结构。已经吸收发泡剂之此等颗粒材料之泡孔大小等级系小于50μm,及超过1μm之泡孔大小在所记录图像中清晰可辨。
可膨胀颗粒物之加工及特征化
使用之涂料组份为70重量%之三硬脂酸甘油酯(GTS)及30重量%之单硬脂酸甘油酯(GMS)。
包括发泡剂之颗粒物在EPS预发泡器中预发泡以产生低密度(15至25g/l)之发泡体珠粒,及在0.7-1.1巴之表计压力下于自动EPS模制机中加工以产生模制品。
模制品进行各种机械测量。直接与EPS比较,本发明实例观察到显著弹性,及可见到极高回弹性。压缩强度系在10%压缩下依据DIN EN 826测定及挠曲强度系依据DIN EN 12089测定。弯曲能系由用于挠曲强度所测得之数值测定。
表2显示制程参数,诸如预发泡时间及脱模时间。显而易见添加氮气可减少预发泡时间及脱模时间。亦可实现泡孔大小之显著减小。而且,与参考例相比,发泡剂含量可更显著减少而不损及性质。
表2:由实例E1-E15获得之发泡体珠粒之加工及性质
可膨胀颗粒E12-E17之制造
可膨胀颗粒系藉由熔体浸透法制造。为此,聚苯乙烯158K(组份A)首先在挤出机中增塑。在挤出机内,熔体系利用技术级异戊烷(95%之异戊烷/5%之正戊烷)连同共发泡剂F)浸透,并均质化。相应配方见于表3。经由另一熔体泵施加压力,以藉由制粒模嘴(20.65mm孔)利用加压水面下制粒(水压:12巴,水温:47℃)对该材料制粒。平均珠粒大小为约1.25mm。总处理量为4.5kg/h。从模中排出之熔体温度为约210℃。
表3:可膨胀颗粒组成、由实例E12-E17获得之发泡体珠粒之加工及性质
图1及图2显示透过实例13之颗粒物珠粒内部具有均质分布之空腔之可膨胀颗粒物之薄切片在不同放大倍数下之透射电子显微照片。
可膨胀颗粒物之制造
可膨胀颗粒物系藉由熔体浸透法制造。为此,聚合物首先在挤出机中增塑并藉由熔体泵计量传输至一系列静态混合机及热交换器中。在第一静态混合器之入口处,一起添加技术级异戊烷(95%之异戊烷/5%之正戊烷)及共发泡剂F),及浸透该熔体。相应配方见于表。然后,藉由热交换器降低熔体温度,且熔体温度系藉由另一静态混合机均质化。经由另一熔体泵施加压力,以藉由制粒模嘴(20.65mm孔)利用加压水面下制粒(水压参见表,水温:47℃)对该材料制粒。平均珠粒大小为约1.25mm。总处理量为4.5kg/h。从模中排出之熔体温度为约207℃。
可膨胀颗粒之制造,实例19至36
可膨胀颗粒系藉由熔体浸透法利用静态混合机制造。表4给出材料组成之概览-聚合物以及滑石(组份A-D)之数量比例与实例12及1之彼等相同,及改变发泡剂E)及共发泡剂F)之比例。为此,聚合物首先在挤出机中增塑并藉由熔体泵计量传输至一系列静态混合机及热交换器中。在第一静态混合机之入口处,一起添加技术级异戊烷(95%之异戊烷/5%之正戊烷)及共发泡剂F),及浸透该熔体。程序与实例12及实例9之程序类似,但代之以CO2用作组份F)以减少热应力。相应配方见于表。然后,藉由热交换器降低熔体温度,及熔体温度系藉由另一静态混合机均质化。经由另一熔体泵施加压力,以藉由制粒模嘴(20.65mm孔)利用加压水面下制粒(水压见于表,水温:47℃)对该材料制粒。平均珠粒大小为约1.25mm。总处理量为4.5kg/h。
为证明增塑作用及处理量增加及可实现之分别减少之熔体温度,在各例中使用静态混合机中之压力损失作为熔体黏度之量值。静态混合机之直径为25mm及其L/D比为15。此处之压力损失及层流区之黏度之间之关系如下:
其中,Re、Ne、L及D分别为雷诺数(Reynolds number)、Ne数、平均剪切黏度、平均流速、静态混合机之长度及静态混合机之直径。对于CSE-X/8静态混合机而言,Ne及Re值系恒定且为1200。平均流速为:
其中,ρ及A分别为容积处理量、基于质量之处理量、熔体密度及混合机之横截面积。在平均剪切速率下之聚合物熔体之平均剪切黏度计算如下:
基于此等原理,熔体之剪切黏度在各种温度及处理量下测定(表4)。实例19至36各例中给出CO2对黏度及压力损失(在静态混合机/外加混合机中)的效果。此处之压力损失为涉及技术限制之变量,因为在混合机中存在最大可容许压力损失及可容许总系统压力。藉由利用CO2,相较于仅包括戊烷之系统,可减少热应力(24/25,33/34)或相同压力损失下增加处理量(26/27,35/36)。此处使用CO2对发泡性无不利影响。
Claims (5)
1.一种制造包括空腔的可膨胀热塑性聚合物珠粒的方法,其通过穿过模板挤出包含发泡剂的聚合物熔体以及在1.5至15巴范围内的压力下于包括液体的腔室中制粒,其包括使用含有发泡剂的聚合物熔体,其中该熔体包括:
0.1至5重量%的核化剂D),
1至10重量%的发泡剂E),其实质上保留在聚合物珠粒内部,
0.01至5重量%的形成空腔的共发泡剂F),
各自基于含有发泡剂的聚合物熔体计;
其中该包含发泡剂的聚合物熔体包括脂肪族C3-C7烃或其混合物作为发泡剂E),且
其中该包含发泡剂的聚合物熔体包括氮气、二氧化碳、氩气、氦气或其混合物作为形成空腔的共发泡剂F)。
2.权利要求1的方法,其中该包含发泡剂的聚合物熔体包括滑石、二氧化硅、云母、黏土、沸石、碳酸钙或聚乙烯蜡作为核化剂D)。
3.权利要求1或2的方法,其中该包含发泡剂的聚合物熔体包括小于0.5重量%的水。
4.权利要求1或2的方法,其中该包括液体的腔室是在20至80℃范围内的温度下操作。
5.权利要求1或2的方法,其中该包含发泡剂的聚合物熔体包括:
A)45至97.79重量%的苯乙烯聚合物,
B1)1至45重量%的具有105至140℃范围内熔点的聚烯烃,
B2)0至25重量%的熔点低于105℃的聚烯烃,
C1)0.1至25重量%的苯乙烯-丁二烯嵌段共聚物或苯乙烯-异戊二烯嵌段共聚物,
C2)0至10重量%的苯乙烯-乙烯-丁烯嵌段共聚物,
D)0.1至5重量%的核化剂,
E)1至10重量%的发泡剂,其实质上保留在聚合物珠粒内部,以及
F)0.01至5重量%的形成空腔的共发泡剂,各自基于含有发泡剂的聚合物熔体计。
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EP2733165A1 (de) | 2012-11-20 | 2014-05-21 | Basf Se | Verfahren zur herstellung von halogenfrei flammgeschützten styrolpolymerschaumstoffen |
BR112015031074B8 (pt) * | 2013-06-13 | 2021-02-23 | Basf Se | processo para produzir péletes expandidos |
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JP2017115114A (ja) * | 2015-12-21 | 2017-06-29 | 株式会社カネカ | 発泡性スチレン系樹脂粒子の製造方法 |
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WO2018078726A1 (ja) * | 2016-10-25 | 2018-05-03 | 積水化成品工業株式会社 | オレフィン系エラストマー樹脂粒子、発泡性粒子、発泡粒子及び発泡成形体 |
CN107383854B (zh) | 2017-08-04 | 2018-04-13 | 南通德亿新材料有限公司 | 一种热塑性聚氨酯微气囊弹性体材料的制备方法 |
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