CN1058221A - 可降解发泡材料 - Google Patents

可降解发泡材料 Download PDF

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CN1058221A
CN1058221A CN91104913.4A CN91104913A CN1058221A CN 1058221 A CN1058221 A CN 1058221A CN 91104913 A CN91104913 A CN 91104913A CN 1058221 A CN1058221 A CN 1058221A
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H·S·哈梅尔
R·O·约克
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143Halogen containing compounds
    • C08J9/144Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/916Cellular product having enhanced degradability

Abstract

采用含氟烃发泡的聚羟基酸树脂产品,该材料为 可降解的,当废弃后引起极小的环境影响。

Description

本发明是关于发泡材料,特别是用于饮食和食品包装业的发泡材料。本发明的材料是可降解的,既可生物降解亦可水解。并且,它们不含破坏臭氧层的化学物质,也不含具有明显光化活性的化学物质。同时,与含氯氟烃相比,这种材料几乎没有使地球变暖的潜在效应。因此,本发明提供了对环境影响最小而易于降解的发泡包装材料。
目前,在饮食业和食品包装业使用最为广泛的材料是泡沫聚苯乙烯,通常采用含氯氟烃(CFC)或烃类(HC)发泡剂发泡。这些材料构成了严重的环境问题。
首先,聚苯乙烯不可降解,无论是埋藏或是路边废弃状态均如是。因此,除非将聚苯乙烯发泡材料收集起来并回收利用,否则这种材料将永远留在埋藏或者废弃状态。
其次,CFC发泡剂封闭于发泡材料中,它终将散逸、进入同温层并参与消耗臭氧层的循环。
再者,HC发泡剂一旦从泡沫中释放出来,因具有光化学活性从而促使烟雾生成。
因而,需要一种采用不参与破坏环境的化学反应的发泡剂发泡生产的可降解树脂发泡材料。
本发明的发泡包装材料为发泡的、可降解热塑性聚合物树脂,含有至少一种选自下列的羟基酸单元:
(1)(O(CR2R2)nCO)p
(2)(OCR1R2COOCR1R2CO)q
(3)(OCR1R2CR1R2OCR1R2CO)r
(4)(OCR1R2CF1R2OCR1R2CR1R2CO)Hs
(5)(NH(CR1R2)nCO)t
其中,n为整数2、4、5,p、q、r、s、t之和为350到约5,000,R1与R2可以相同或不同,它们可以是氢、含1到12个碳原子的烃基或含有1到12个碳原子的取代烃基。这种聚羟基酸树脂,最好是含有至少50%的单元(1)。p、q、r、s、t的比值必须调整适当,以便获得在这方面已知的、生产定向膜要求的适当结晶度和结晶速率;该聚羟基酸树脂含有如下式表示的发泡剂:
Figure 911049134_IMG2
其中,每一个A独立地为氢或氟,而n=1-4。
可见,本发明的产品系采用一种环境良性的含氟烃(HFC)发泡剂发泡的、可降解树脂。扼要地说,本发明系采用式(6)这一类HFC作为发泡剂由式(1)-(5)单元构成的树脂生产极为有用的、环境性能优异的发泡材料。
较好的聚合物是式(1)中R为氢或甲基的那些聚合物,这时该聚合物分别为聚乙交酯和聚丙交酯。
这种聚合物可以直接由酸母体合成,或依酸的类型不同由相应的环状单体或二聚体内酯聚合而成。由环状内酯聚合的方法有利于获得高分子量聚合物,因为当直接用酸合成时,产物与中间产物、环状二聚体以及低分子量组分间的平衡反应对于生成的聚合物分子量具有实际上的限制。
本发明的聚合物具有分子量从大约50,000到大约600;000;最好是从大约100,000到大约450,000。为了获得足够的粘度和强度以便使聚合物能形成可支承的泡沫体,需要高分子量。如果分子量过高,在对该组成进行熔融加工所需的温度下会出现过度降解。
该聚合物组成通常含有一些未反应单体和低分子量齐聚物。为了避免挤出和发泡过程的问题,希望把分子量保持低些,低于450,聚合物单元数小于约7 1/2 。
而且,聚合物的组成较好是具有50-97%主要组分,最好是具有与上述单元(2)相对应的乳酸L对映体约85到96分子百分数,其中R1是甲基,R2是氢原子。该较好组成中的次要组分可以是上述单元(1)至单元(5)中任选的另外一种,这里一个限制条件是,若仍旧采用乳酸单元,则必须是其D构型。
这里对聚乳酸酯聚合物所使用的“可降解”一词意指该可降解材料的聚乳酸酯部分为可生物降解,且更重要的是可水解。其降解速率与其预定的用途是一致的,也就是说在正常贮存和使用过程中该产品不发生明显的降解,但在被废弃一段合理的时间后会发生明显的降解。正如在本技术中已了解的那样,水解降解与聚合物结晶度有关;结晶度越高,聚合物降解越慢。对于水解降解来说,采用微酸性或微碱性条件有利于过程的进行。通过水解降解获得的单体单元,如果打算转化为有用的聚乳酸酯聚合物则可加以回收,否则可做为一种环境良性废物而抛弃。
合格的发泡剂必须具备下列性质:
-环境可接受性
-低毒性
-适当的挥发性
-充分的溶解性
-低反应活性
-合适的扩散速率
-比较低的分子量
所谓环境可接受性,意指该发泡剂当由材料里释放出来后不具有消耗同温层臭氧的潜在危害。从这种意义上来说,含氯原子的发泡剂是不可接受的。而且,发泡剂在释放后必须对红外线具有最小的吸收性,同时又有一个适当的大气寿命,这样才不具很大的有使地球变暖的潜在危害又几乎不具光化学活性,因而不会促使烟雾生成。
在发泡材料加工时为了保护工人的健康,要求发泡剂的毒性低。而发泡材料的使用中也必须不具毒性,这一点在饮食业和食品包装业中尤其重要。
配合本发明的热塑性树脂使用的发泡剂还必须有适当的挥发性。这样的发泡剂必须提供将粘稠聚合物树脂膨胀并形成泡沫体所需要的溶解压力。
发泡剂必须具有充分的溶解性,意思是说当发泡剂按规定的发泡度要求的浓度加入时,很容易分散在聚合物熔融体中。如果在发泡剂膨胀之前就从聚合物树脂中分离出来,就会导致气袋或不均匀发泡浓度的生成。
发泡剂必须具有低反应活性,意即在通常典型热塑性树脂泡沫材料加工温度和压力下,它既不会与树脂反应也不会分解。类似地,发泡剂必须在正常使用条件下不具反应性以防止材料的降解。
合适的扩散速率对于做为本发明泡沫材料的发泡剂是必须的。最好是具有一个很低的扩散速率,这样在将发泡片材热加工为诸如汉堡包盒、碟子等物品的热成形过程易于实现。
希望发泡剂具有比较低的分子量。分子量决定了产生给定体积气体所需发泡剂的磅数,因此使用低分子量发泡剂可降低单位产品的发泡剂成本。
已经发现,当用于采用式(1)到式(5)所示单元的聚合物树脂制做发泡产品时,考虑到上述的性质,选自式(6)所代表的HFC发泡剂是完全适宜的。对于特定的、由式(1)到式(5)单元所组成的聚合物树脂,何种式(6)代表的HFC发泡剂适用,可用常规的技术很容易地确定。
下列HFC均为生产本发明的发泡材料适用的发泡剂:
HFC-32 CH2F2
HFC-125 CF3CF2H
HFC-134 HCF2CF2F
HFC-134a CF3CFH2
HFC-143a CF3CH3
HFC-152 CH2F-CH2F
HFC-152a CH3-CHF2
HFC-227 EA CF3-CHF-CF3
HFC-356 MFF CF3-CH2-CH2-CF3
HCC-365 MFC CF3-CH2-CF2-CH3
较好的HFC含有1到2个碳原子。
本发明的发泡材料具有独特的性能组合,使这种材料具有环境可接受性,这既指对大气环境方面也指用后处理方面。关于处理方法,可以采用埋藏,在这过程中材料将发生生物降解和/或水解降解转变为无害降解产物,也可以用水解方法进行回收,最好是在微酸或微碱条件下生成可用于生产聚合物的单体。
本发明的发泡材料可以用传统的技术制造。此时,聚合物树脂连同其中的发泡剂在低于树脂和发泡剂降解或反应的适当温度下,被加压挤出。发泡产品可以是片材也可以制成诸如汉堡包盒、托盘、碟子、箱子以及类似的物品。这些产品,因其具有低毒性与环境可接受性的结合,在食品包装和饮食业容器方面具有极为广泛的用途。
除聚合物和发泡剂之外,还可加入传统的辅料,比如硅酸钙滑石粉这样的典型成核剂、加工助剂,如矿物油、挤出助剂,如隣苯二甲酸二辛酯(DOP)以及着色剂。这些添加剂的浓度通常与发泡剂的加入量无关。
HFC的制造方法是已知的。请参阅A.M.Lovelace等人的“脂族氟化合物”、1958年版第55页。
使用一套4 1/2 英寸和6英寸、备有圆环状模板和心轴的串联螺杆挤出机系统,混合喂料为:2 1/2 磅/时硅酸钙滑石粉成核剂、472.5磅/时聚乳酸熔体(85%为L对映体,其余15%为D和/或L对映体以及少量低分子量丙交酯和齐聚物,聚合物分子量约为300,000),以500磅/时的速率连续制成发泡片材。向挤出机内聚合物熔体加入25磅/时CF3-CFH2(HFC-134a)。4 1/2 英寸挤出机内物料温度维持在400°F,压力2,500磅/平方英寸(表)。物料在到达6英寸挤出机出口前应使温度降得足够低,以防止排出后气泡破裂。HFC从聚合物中的溶解状态逸出,而形成了一种定向、可降解、热塑性发泡产品。这种产品为44英寸宽、0.1英寸厚、密度为6磅/立方英尺的发泡硬片材。
将这些发泡片材喂入热成形机,并被冲压成12英寸圆盘子。
按照同样的步骤,制成厚度0.05到0.1英寸的片材并热压成带翻盖的食品盒。
实例2至6
按照实例1的步骤和下表所列配方制成PHA/HFC盘子及食品盒:
实例  聚乳酸  硅酸钙滑石
号 发泡剂 分子量 磅/时 组成磅/时 粉成核剂
2 CH2F252 2.55 85%L 494.95 2.5
(HFC-32)
3 CH3CHF266 3.24 70%L 494.26 2.5
(HFC-152a)
4 CF3-CH2F 102 5 60%L 492.5 2.5
(HFC-134a)
5 CF3CHFCF3170 8.33 75%L 489.17 2.5
(HFC-227  EA)
6 CF3CH2CF2CH3166 8.14 50%L 489.36 2.5
(HFC-365  MFC)
聚乳酸的其余组分为D聚乳酸异构体加上小于7%的低分子量丙交酯和齐聚物。

Claims (9)

1、一种包含发泡的可降解树脂和含氟烃发泡剂的产品。
2、按照权利要求1的产品,其中酸树脂含有至少一种选自下式的酸单元:
(1)(O(CR2R2)nCO)p
(2)(OCR1R2COOCR1R2CO)q
(3)(OCR1R2CR1R2OCR1R2CO)r
(4)(OCR1R2CF1R2OCR1R2CR1R2CO)Hs
(5)(NH(CR1R2)nCO)t
其中,n为整数2、4和5,p、q、r、s、t之和为350至大约5,000,R1和R2可以相同也可以不同,可为氢或含1到12个碳原子的烃基或含有1到12个碳原子的取代烃基。
3、按照权利要求1的产品,其中聚羟基酸单元选自聚丙交酯或聚乙交酯。
4、按照权利要求1的产品,其中聚羟基酸单元包含至少50%式(1)单元。
5、按照权利要求1的产品,其中50%以上的聚乳酸酯树脂为L异构体聚合物单元。
6、按照权利要求4的产品,其中聚合物树脂含有不足7%的丙交酯及乳酰乳酸酯齐聚物单元,其分子量不足450。
7、按照权利要求1的产品,其中发泡剂选自下式,
Figure 911049134_IMG1
其中每一个A均独立地是氢或氟,n=1-4。
8、按照权利要求7的产品,其中n=1。
9、按照权利要求7的产品,其中n=2。
CN91104913.4A 1990-07-16 1991-07-16 可降解发泡材料 Pending CN1058221A (zh)

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AU (1) AU8007591A (zh)
IE (1) IE912473A1 (zh)
MX (1) MX9100210A (zh)
PT (1) PT98330A (zh)
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