CN1008100B - 由缩聚聚合物制备定形制品的方法 - Google Patents
由缩聚聚合物制备定形制品的方法Info
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Abstract
模塑或纤维级别的缩合聚合物,与该缩聚物中共聚有总量为1到大约5000ppm的至少含有一个带有一个或多个次甲基单元的次甲基部份。所提到的次甲基部份吸收从约350毫微米到约450毫微米的光。不能从聚合物中萃取出来,在加工条件下稳定性。此次甲基部份虽然较低和较高的分子量也能用。但最好具有分子量从大约200到大约600,这些次甲基部份是从带有一个或多个如羟基,羧基,羧酸酯,酰基卤,氨基等的反应物(单体)中推衍出来的。
Description
本申请是1985年2月15日归档,系列号为702106的延续部份。
本发明涉及了包括聚酯,聚酰胺和共聚酰胺类的缩聚聚合物。在此某些次甲基部分曾与这些聚合物进行共聚物反应(缩聚反应),从而赋之以颜色和/或抗紫外线性能。次甲基部分在聚合物加工(包括制备)温度下,具有热稳定性,还具有不退色以及不可从其中萃取的特点。从而使这类聚合物尤其适用于制作饮料瓶,食品,药物和化妆品的容器。本发明中所用的次甲基部分的总浓度为从每百万(ppm)约1.0到约5,000份。最好是2.0到约1,500份(每百万最终聚合物重量份数所含次甲基部份的重量份数。)
本发明所述及的聚合物是线性的,热塑性模型或纤维级别的聚合物,具有特性粘度从约0.4到约1.2。最好是各种聚酯,其中酸的部份至少由50%(摩尔)的对苯二酸残基所组成,二元醇部份至少由50%(摩尔)的1,2-亚乙基二醇或1,4-环己烷二甲醇残基所组成,聚合物中含有约2到1500ppm的1个或多个次甲基部份。
根据本发明,次甲基部份至少有一个次甲基单元,在这里定义为“与共轭芳香系统相连接的基团
。此次甲基单元给于次甲基部份和聚合物以吸收紫外线或通常在约350毫微米到约650毫微米范围内的可见光。此次甲基部份最好具有分子量从约200到约600,(虽然低于或高于上述分子量也是可行的,)而且是从具有一个或几个在缩合或缩聚反应期间进行缩合而使次甲基单体部份进
入聚合物链的基团的反应物(单体)推衍出来的。这些基团包括:羟基,羧基,羧酸酯,酰基卤,氨基等,正如上面所说的,这些次甲基部份在聚合物加工过程条件下是热稳定的,其中包括所用的缩聚反应温度可直到约300℃。例如制备象聚(对苯二酸亚乙酯)这一类聚酯和聚(对苯二酸亚乙酯)与聚(对苯二酸1,4-环乙烯二亚甲基酯)共聚物时就是在这样的高温下反应的。当然,在只存在一个可缩合的基团时,此次甲基部份将以已知道的方式起链终止剂的作用。
在其广泛的具体实施方案中,本发明可定义为一个包含模塑或纤维等级的缩合聚合物,此聚合物经过与次甲基部份共聚合,从而在生成的缩聚聚合物中含有次甲基部份的总重量从1.0到大约5000ppm,即至少有一个次甲基部份,该次甲基部份带有一个或几个次甲基单元,所说的次甲基部份在大约350毫微米到大约650毫微米范围内吸收光线,该次甲基部份不能从所说的聚物中萃取出来,在聚合物加工条件下具有稳定性。
本发明所述及的次甲基部份的不可萃取性可用下述方法确定。
萃取步骤
所有的萃取过程在下面规定的时间和温度下,用蒸馏过的溶剂在玻璃容器内进行。试样形状是1/2英寸× 英寸小片,是从二升瓶子的圆柱形侧壁部份切割下来的。所有试样用冷溶剂洗涤,以除去表面杂质,然后放置在200毫升溶剂/100平方英寸表面积(2/毫升/平方英寸)里。
在相同萃取条件下,进行无聚合物的溶剂空白试验。大多数试样要重复萃取、掺料和分析。
萃取条件
1.水.室温下把试样加到溶剂中,在250°F下加热2小时。
对试样的一半进行分析,剩下部份放在120°F的烘箱中30天。
2.50%的乙醇/水。室温下把试样放入溶剂中,溶剂温度也是室温。然后放在120°F的烘箱中,分别在24小时和30天后进行分析。
3.庚烷。室温下把试样放入溶剂中,溶剂温度也是室温。在150°F下加热2小时。将部份试样冷却到室温,然后用分光光度计分析。余下部份试样分析前在120°F下老化30天。
4.使用任何合适的分析技术和仪器测定从聚合物内萃取出来的次甲基部份。分析发现,次甲基部份从聚合物内的可萃取性基本上不存在。
为本发明所用的次甲基反应物或单体具有下列通用分子式:
其中A从下列基团中选择。这些基团由其在表中的范例号指定。
其中R和R′选自氢、氟、氯、溴、烷基、烷氧基、苯基、苯氧基、硫代烷基和芳硫基;n为0,1,2;
R1和R2从下列基团中选择:氢;环烷基;用一个或两个烷基,羟基,烷氧基,卤素或取代有羟基的烷基取代的环烷基、苯基;以烷基,烷氧基,卤素,烷基酰氨基,羧基,氰基或烷氧基羰基所取代的苯基;直链或支链的低分子量链烯基;有1-8个碳的直链或支链的烷基和以下述各基团所取代的这种烷基:羟基;卤素;氰基;琥珀酰亚胺基;羟基琥珀酰亚胺基;酰氧基琥珀酰亚氨基,戊二酰亚胺基;苯氨基甲酰氧基(phenylcarbamoyloxy);苯二(甲)酰亚氨基,4-羧基苯二(甲)酰亚氨基,苯并(C)吡咯酮基,2-吡咯烷酮基;环己基;苯基;以烷基,烷氧基,卤素,羟基,链烷酰氨基,羧基,氰基,或烷氧基羰基取代的苯基;烷基氨磺酰;乙烯磺酰基;丙烯酰氨基;氨磺酰基;糖精基(benzoylsulfonicimido);烷基磺酰胺;苯基磺酰氨基;烷氧基羰氨基;烷基氨基甲酰基氧基;烷氧基羰基;烷氧基羰氧基;烯基羰基氨基;具有以下分子式的基团,
其中y是-NH-,
烷基,-O-,-S-,或-CH2O-;-S-R14;SO2CH2CH2SR14;其中R14是烷基,苯基,以卤素,烷基,烷氧基,烷酰基氨基,氰基或烷氧基羰基取代的苯基;吡啶基;嘧啶基;苯并噁唑基;苯并咪唑基;苯并噻唑基,具有以下分子式的基团;
-OXR16;-NHXR16;-X-R16;-CONR15R15和-SO2NR15R15;其中R15从下列基团中选择;氢,芳(香)基,烷基和以卤素,羟基,苯氧基,芳(香)基,氰基,环烷基,烷基磺酰基,烷硫基,链烷酰氧基或烷氧基取代的烷基;X是-CO-,-COO-,或-SO2-,R16从下列各基团中选择,烷基和以卤素,羟基,苯氧基,芳(香)基,氰基,环烷基,烷基氨磺酰基,烷基硫代、链烷酰氧基和烷氧基所取代的烷基;当X是-CO-时,R16也可能是氢,氨基,链烯基,烷基氨基,二烷基氨基,芳基氨基,芳(香)基或呋喃基,烷氧基;以羟基,氰基, 烷酰氧基或烷氧基所取代的烷氧基,苯氧基;以一个或多个烷基,烷氧基,羧基,烷酯基或卤素所取代的苯氧基;R1和R2可能是单一复合基团,例如,1,5-亚戊基,1,4-亚丁基,乙烯氧基乙烯,乙烯磺酰基乙烯,亚乙基
亚乙基与相连的氮形成一个环R17是烷基,芳基,或环烷基;R3是亚烷基、亚芳基、芳亚烷基,亚烷氧基或亚烷氧基亚烷基,Z为直单链,OCO,O,S,SO2,R17SO2N=,
R4,R5和R6分别选自氢和烷基中;
R7为羧基,烷酯基或(R)n;
R10为氢,烷基和芳基;
R8和R9选自氢和经取代或未经取代的烷基;芳基或环烷基;
R11和R12为氢,烷基,羟基或酰氧基,
B表示为形成5个或6个元素组成的环所必需的原子数。B可从以下基团中选择
P和Q从下列基团中选择,氰基,烷酯基,苄巴基芳氧基(carbar-yloxy),卡巴烷基芳氧基(carbaralkyloxy),氨基甲酰,羧基N-烷基氨基甲酰,N-烷基-N-芳基氨基甲酰,N,N-二烷基氨基甲酰,N-芳基氨基甲酰,N-环己基氨甲酰,芳基,2-苯并噁唑基,2-苯并噻唑基,2-苯并咪唑基,1,3,4-噻二唑-2-基,1,3,4-噁二唑-2-基,烷基砜基,芳基砜基和酰基
其中R17已在上文定义。R18是指氰基,羧基,羰基烷基(CO2Alkyl),氨基甲酰或N-烷基氨基甲酯,其中对每一个染料分子,A,P和Q中至少有一个必须是或含有可缩合的基团。这一基团从下述中选择:羧基,烷酯基,卡巴基氧基,N-烷基氨基甲酰氧基(N-alkylcarbamyloxy),酸基,氯代羰基,氨基甲酰氧基,N(烷基)2氨基甲酰氧基(N-(alkyl)2carbamyloxy),氨基烷氨基,羟基,N-苯基氨基甲酰氧基(N-phenylcarbamyloxy),环己酰氧基和羰环己基氧基;其中,在上面的各定义中,基团的每一个烷基,芳基或环烷基部份在适当的位置可以用下述基团取代:羟基,酸基,烷基,氰基,烷氧基羰基,卤素,烷氧基或烷基,芳氧基或环烷基。在上面的各定义中,对每一个染料分子,A,P和Q中也至少有一个必须是或含有一个在聚合反应条件下能够反应的基团,把次甲基染料加入聚合物上。此基团包括:羧基,烷酯基,卡巴基氧基,N-烷基氨基甲酰氧基,酸基,氯代羰基,氨基甲酰氧基,N-烷基氨基甲酰氧基,氨,烷基氨基,羟基,N-苯基氨基甲酰氧基,碳环己基氧基;其中烷基和/或芳基基团可能含有普通的取代基,例如羟基,氰基,酸基,烷酯基,苯基和卤素。这些取代基不影响缩聚反应。
在所有上述定义中,不同基团的烷基或亚烷基部份含有1到8个碳,可以是直链的,或支链的。
这些次甲基部份比其它可共聚合能形成聚酯的部份的优越之处包括(1)较高的热稳定性-例如偶氮染料在聚合反应温度下通常不稳定,(2)紫外线吸收特性-所选择的次甲基染料吸收适当波长的光以保护包装内的东西,(3)紫外线下具有稳定性-例如某种蒽醌染料吸收420毫微米的光线,这种染料对紫外线一般是不稳定的,
(4)高消光系数-只需要较少的染料就可提供相同的颜色和(5)低费用一次甲基染料比蒽醌的费用通常低得多。
本发明所用的各类聚酯是用1个或多个二元醇以及一个或多个二元羧酸与次甲基部分由通常的合成工艺聚合而成的线性,热塑性,结晶或非结晶材料。这些材料与次甲基部份进行共聚合。这些有代表性的聚酯是已公布的那些。例如美国专利4,359,570,在这里作为参考文献。
聚酯的二元醇组分可选自如下:1,2-亚乙基二醇,1,4-环己二甲醇,1,2-丙二醇,1,3-丙二醇,1,4-丁二醇,2,2-二甲基-1,3丙二醇,1,6-己二醇,1,2-环己二醇,1,4-环己二醇,1,2-环己二甲醇,1,3-环己二甲醇,×,8-双(羟甲基)三环-〔5·2·1·0〕-癸烷,其中×可以是3,4或5;在分子链中二元醇包含一个或多个氧原子。例如二甘醇,三甘醇,二聚丙烯甘醇,三聚丙烯甘醇等等。一般地说,这些二元醇含有2到18个碳原子,最好是含有2到12个碳原子。可以使用顺式或反式的环脂族二醇,也可用两者混合物。
聚酯的酸部份(脂族,脂环族或芳香族二羧酸类)可以如下述的各类酸中选择:对苯二酸,异酞酸,1,4-环己二羧酸,1,3-环己二羧酸,戊二酸,琥珀酸,己二酸,癸二酸,1,12-十二烷基二酸等。在聚合物制备中,最好用官能团酸的衍生物,例如二元羧酸的二甲酯,二乙酯或二丙酯。也可使用这些酸的酐。
更受人欢迎的共聚酯尤其适用于制造装饮料用的吹塑成型瓶子或容器和装食物用的成型包装袋等。在这些应用场合中,上述这些共聚聚酯在适当热凝固后,具有色泽稳定,特性粘度稳定以及在直达约100℃的温度下具有热变形稳定或“热装”稳定的特性。用
这些共聚聚酯成型的制品显示良好的薄壁硬度,优良的透明度以及对水,大气尤其是二氧化碳和氧显示良好的防护层特性。
对于具有“热填充物料”稳定性的制品,最优的聚酯包括聚对苯二酸亚乙酯和用直到大约5%(摩尔)的1,4-环己二甲醇改性的聚对苯二酸亚乙酯,此聚物用已知的工艺方法进行充分热凝固及定向处理后,给以所希望的结晶度。根据定义,由此聚合物制造的容器在预定的温度下充以液体时,体积变化小于2%,则此聚合物在该温度是“热装”稳定的。在聚酯用于制作吹塑成型饮料瓶时,最佳的聚酯具有特性粘度从0.65到0.85,玻璃化温度Tg>70℃,从瓶上切割下来的膜片具有水蒸汽透过率1.5到2.5克。密耳/100英吋2-24小时,二氧化碳的透过率是20~30毫升·密耳/100英吋2。24小时大气压,氧气的透过率是4~8毫升·密耳/100英吋224小时大气压。Tg用不同的扫描量热计在20℃/分的扫描速率下进行测量,氧气透过率用按Elk River,Minnesota的现代控制公司所生产的MOCON OXTRAN 100型仪器所说明的标准操作步骤测定。CO2的透气性用同一公司生产的MOCONPERMATRANC Ⅱ型仪器的标准操作步骤测定。
一般地说,按照本发明,可用任何聚酰胺或共聚酰胺酯。其中有代表性的是在美国专利上公布的那些聚合物:3,562,206;4,252,920;4,237,251-4,438,240;4,420,603;4,420,602;4,436,898;4,436,872;4,251,652;3,560,448;以及每一专利所引用的大批参考文献。所有这些都作为本发明的参考文献。下面的例子表示含有本发明所提及的次甲基部份的聚酰胺材料的制备。
聚(环己二甲酸)和次甲基染料共聚合物的制备。
把73克(0.5摩尔)己二酸,内含58.01克(0.5001摩尔)六亚甲基二胺的82.77克水溶液和0.0226克(200ppm)(0.0001摩尔)的
加入到500毫升单颈,园底烧瓶中,其中装有氮气进气管,搅拌器,真空出气管和冷凝烧瓶。把它放在100℃的Belmont金属浴中,反应混合物以上充以氮气。用45分钟,把Belmont金属浴的温度提高到215℃,维持215℃20分钟,再升温至285℃,维持285℃30分钟。将烧瓶抽以真空,真空度是0.3到0.5毫米汞柱,维持285℃38分钟。将烧瓶从金属浴中移去并使其冷却,在聚酰胺结晶时,在其上维持氮气压力。所生成的聚合物呈黄色,在苯酚/四氯乙烷重量比为60/40的溶剂中,聚合物浓度为0.5克/100毫升溶剂时具有比浓对数粘度0.63,聚合物熔点为264℃,聚合物膜上的紫外可见光谱表明在420毫微米上有很强的吸收。
一般来说,次甲基反应物(单体)可这样制备,例如将上述的芳烃部份A上经氢化的母体与Vilsmeier络合物反应生成醛,此母体是富电子的。〔Bull.Societe Chim.de France,第10期1898-1899,1962年10月;Angewandte Chemie 72第22期836-845,1960年11月21日〕。考虑到试剂的价格和操作方便,磷酰氯(pocl3)和N-N-二甲基甲酰胺(DMF)是较理想的试剂。据上所述,芳香胺,例如苯胺,间-甲苯胺,2,5-二甲基苯胺,2,5-二甲氧基苯胺等经Vils
meier反应可以高收率转换成相应的醛,在碱,例如派啶的存在下,所生成的醛与亚甲基
反应生成次甲基单体,如下述反应顺序所示。
四氢化喹啉(Tetrahydroquinolines)吲哚己环,氮茚噻唑和Fischer碱也能通过Vilsmeier反应生成醛。经过上述途径制备次甲基单体和中间产品醛在许多已发表的专利中有详细介绍。这些专利包括:U.S.2,649,471;U.S.2,850,520;U.S.3,247,211;U.S.3,260,737;U.S.3,326,960;U.S.3,349,098;U.S.3,386,491;U.S.3,390,168;U.S.3,453,270;U.S.3,453,280;U.S.3,468,619;U.S.3,504,010;U.S.3,555,016;U.S.3,597,434;U.S.3,652,636;U.S.3,661,899;U.S.3,728,374;U.S.3,787,476;U.S.3,829,410;U.S.3,829,461;U.S.3,846,069;U.S.3,869,495;U.S.3,869,498;U.S.3,879,434;U.S.3,920,719;和U.S.4,077,962。已经知道,由于Vils-meier反应混合物能直接发生反应生成所需产品,因此没有必要在制备次甲基单体以前把中间产物醛分离出来。(U.S.3,917,604和4,088,673)所有上述专利所指导的内容均作为本发明的参考文
献。
由于Vilsmeier络合物也能使羟基转化成卤素,因而必须用其它方法制备含有羟基的次甲基单体。如,次甲基单体可用下面的方案制备,即
N,N-二β-羟乙基苯胺和甲醛与间-氮苯磺酸在浓盐酸和铁粉的存在下发生反应,生成中间产物4′-(二-β-羟乙基胺)-亚苄基苯胺-间-磺酸,它能和活性亚甲基反应生成单体(U.S.2,583,551)。
生产含有二氰乙烯基团的次甲基单体的另一种方法在美国专利U.S.4,006,178中有介绍,其中芳香胺与1-卤代-2,2-二氰甲烷反应生成的相应的次甲基化合物。
当然,含有如酸基,或烷氧羰基基团的中间产物醛化合物能水解制备分别含有羟基或羧基的次甲基单体,此次甲基单体能与缩聚聚合物发生聚合反应。
下述各例子表明芳香醛和活性亚甲基之间的普通反应生成典型次甲基单体。
例1
将4-(N,N-二甲基胺)肉桂醛(1.75克,0.01M),氰基醋酸甲酯(0.99克,0.01M),甲醇(20毫升)和派啶(3滴)混合在一起,加热,回流30分钟。在反应混合物冷却后,将其过滤。桔红色染料(2.5克)用甲醇洗并用空气干燥,此产品染料有如下结构式:
这是黄色染料,吸收λ最大为464毫微米的光线,克分子消光系数为38,000。
例2
在甲基中碱催化剂的存在下,由4-(二甲基胺)苯甲醛和丙二酸二乙酯反应可制备由下所示的乙基〔〔4-(二甲基胺)苯)亚甲基)-丙烯酯。此淡黄色染料吸收λ最大为373毫微米的紫外光线,摩尔
消光系数为33000。
以下诸表举例有用的次甲基反应物以进一步说明本发明。
见表1-18
表4
表6
表12
根据本发明制备的典型染色聚酯的实施例如下:
本发明所涉及的每个染色共聚酯的比浓对数粘度(I.V.)用Vineland,N.J.Lab Glass公司制造的Wagner粘度计,按照ASTMD2587-70所规定的步骤进行测定。该粘度计具有1/2毫升容积的毛细胞,把聚合物放在重量比为60/40的苯酚/四氯乙烷的溶剂中,聚合物浓度为0.5%(重量百分数)操作步骤如下,在120℃下加热聚合物/溶剂系统15分钟以增强聚合物的溶解度,然后冷却到25℃。测量25℃时的流动时间,I.V.用下式计算:
其中:(η)=聚合物浓度为0.5克/100毫升溶剂,温度为25℃时的比浓对数粘度;
ln:自然对数;
ts:试样流动时间;
to:溶剂流动时间(无聚合物);和
C:聚合物浓度〔克/100毫升溶剂〕=0.50
例757
聚(对苯二酸亚乙酯)和次甲基染料进行共聚合的典型合成反应如下:97克(0.5摩尔)对苯二酸二甲酯,62克(1.0摩尔)1,2-亚乙基二醇,0.0192克(200ppm)染料
和0.29毫升乙酰基三异丙基的正丁醇溶液,每毫升该溶液中含0.03克钛。所有上述各组分称好后放入500毫升单颈园底烧瓶内,瓶上装有氮气进气口,搅拌浆,真空出口管和冷凝烧瓶。在Belmont金属浴内,将烧瓶和反应物在200℃下加热60分钟,在210℃下加热75分钟,230℃下加热50分钟,同时,发生酯交换时在反应物上方通有氮气。使金属浴温度提高到270℃。缓慢地施加真空,抽吸进入反应系统的氮气10分钟,直到压强减到100毫米汞柱。在这一真空压强下,将烧瓶和反应物在270℃下加热30分钟,再将金属浴温度提高到285℃,再缓慢地提高真空度,在10分钟内使压强降低到4到5毫升汞柱。在此真空压强下,将烧瓶和反应物在285℃下反应25分钟,再提高真空度,使压强降低到0.3到0.5毫升汞柱,在285℃下继续缩聚反应16分钟。从金属浴内移走烧瓶。在聚酯结晶的同时,使反应物在氮气压力下冷却。生成的聚合物呈光亮的黄色,用上述方法测定的比浓对数粘度为0.58在430毫微米处,非结晶的聚合物膜上紫外线可见光谱显示强烈的吸收峰。
例758
聚对苯二酸亚乙酯与31%(摩尔)的1,4-环己二甲醇和次甲基染料共聚的典型合成反应如下:97克(0.5摩尔)对苯二酸二甲酯,23克(0.16摩尔)1,4-环己二甲醇(70%反式异构异体,30%顺式异构体),52.1克(0.84摩尔)1,2
-亚乙基二醇,0.0217克(200ppm)染料,
和0.33毫升乙酰基三异丙基钛酸酯的正丁醇溶液。每毫升该溶液中含有0.03克钛。所有上述各组分称重后加入500毫升,单颈园底烧瓶中,瓶上有氮气进气管,搅拌浆,真空出口管和冷却烧瓶。烧瓶和反应液在200℃下加热35分钟,在225℃下加热70分钟,同时,发生酯交换时在反应物上方通有氮气。提高金属浴温度达270℃,缓慢地施加真空,抽吸进入反应系统的氮气,在10分钟内,使真空度降到100毫升汞柱。在此压强下,使烧瓶和反应物在270℃下反应30分钟,再提高金属浴温度达285℃,缓慢抽以真空,在10分钟内,使真空度慢慢降至4到5毫升汞柱。在4至5毫米汞柱真空下使烧瓶和反应物在285℃下反应25分钟。真空度然后降至0.3至0.5毫米汞柱。缩聚反应在285℃下继续反应22分钟。将烧瓶从金属浴内移出。在氮气压强下,使反应物冷却。生成的非结晶聚合物在压缩成型成15密耳(1密耳=0.001英吋)厚的薄片时呈光亮的黄色。非结晶聚合物膜上的紫外线可见光谱在385毫微米处显示强烈的吸收率。生成的聚合物用上述方法测量时具有比浓对数粘度0.80。经水解的聚酯样品通过气相色谱分析表明聚酯含有30%(摩尔)的1,4-环己二甲醇。
例759
聚(对苯二酸亚乙酯)与3.5%(摩尔)的1,4-环己二甲醇和次甲基染料共聚合反应物的制备。把下面各组分放入500毫升,单颈园底烧瓶内
97克(0.5摩尔)对苯二酸二甲酯;
2.52克(0.0175摩尔)1,4-环己二甲酸(70%反式异构体,30%顺式异构体);
60.9克(0.9825摩尔)1,2-亚乙基二醇;
0.0195克(200ppm)
0.29毫升乙酰基三异丙基钛酸酯的正丁醇溶液,每升该溶液含0.03克钛。该聚合物的酯交换和缩聚反应按例757的步骤进行。生成的聚合物呈现黄色,比浓特性粘度为0.70。经水解的该聚酯试样通过气相色谱分析表明此聚酯含有3.5%(摩尔)的1,4-环己二甲醇,此非结晶聚合物薄膜上的紫外线可见光谱表明在435毫微米处有强烈的吸收峰。
例760
吹塑瓶子用的绿色聚酯的制备-聚(对苯二酸二甲酯)的合成在15磅间歇反应器内进行,得到吹塑2升瓶子用的绿色聚合物。把下列各组分加入15磅间歇反应器内:
15磅对苯二酸二甲酯;
14.5磅1,2-亚乙基二醇;
0.4克(59ppm)
0.445克(66ppm)酞菁兰色颜料,和21毫升乙酰基三异丙基钛酸酯的正丁醇溶液(内含90ppm钛)。
使用下列逐渐加热程序以发生酯交换和缩聚反应。
在190℃和氮气压强及搅拌下反应3小时;
在210℃和氮气压强及搅拌下反应2.5小时;
在280℃和氮气压强及搅拌下反应0.5小时;和在真空压强0.5到0.8毫米汞柱,280℃和搅拌下反应1.25小时。
迫使聚合物从反应器底部流出并进入水中,从水中分离出聚合物,然后用Wiley机磨碎聚合物,使其通过3毫米筛子。聚合物呈绿色,比浓对数粘度为0.594。聚合物颗粒进一步增加了流化床内固态的比浓对数粘度。使用氮气作为强化流态气体,用热油作为热源加热强化流态化。加热此强化流态剂到达215℃聚合物温度,在215℃下反应5分钟,然后使其冷却。生成的聚合物具有比浓对数粘度0.723。用新Britain成型机,使非结晶聚合物在277℃下模塑成型为2升型坯。连续吹塑型坯成2升带有绿色的瓶子。
例761
吹塑瓶子用的琥珀色聚酯的制备-聚(对苯二酸二甲酯)的合成在15磅间歇反应器内进行以制得琥珀色聚合物为吹塑2升瓶子用。将下述各组分加入15磅反应器。
15磅对苯二酸二甲酯;
14.5磅1,2亚乙基二醇;
3.26克(484ppm)
1.52g(225ppm)
0.32克(47ppm)酞菁兰染料和21毫升乙酰基三异丙基钛酸酯的正丁醇溶液(内含90ppm酞。)
如例760所述的方法进行酯交换,熔融相缩聚和固态缩聚反应。生成的聚合物的比浓对数粘度为0.728,非结晶聚合物用新Bri-tain成型机在277℃下模塑成型为2升的型坯,连续吹塑型坯制成成琥珀色2升瓶子。
本发明用详细的说明描述了可取的具体化实施例,但应理解的是在本发明的精神实质和范围内可实现各种改变和改进。
Claims (2)
1、制造用于包装的定形制品的方法,其特征包括:
(1)制备含有模塑或纤维等级的缩合聚合物的组合物,聚合物中共聚有总量为1到大约5000ppm的至少一种选自下式的反应化合物:
其中每一个A从下列基团中选择:
其中:
R和R′可为氢,氟,氯,溴,烷基,烷氧基,苯基,苯氧基,烷硫基,芳硫基,n为0,1或2;
R1和R2从下列各基团中选择:氢;环烷基;被一个或两个烷基,羟基,烷氧基,囟素或取代有羟基的烷基取代的环烷基;苯基;由烷基,烷氧基,囟素,烷酰基氨基,羧基,氰基或烷氧基羰基取代的苯基;直链或支链的低级链烯基;基链或支链含有1-8个碳的烷基以及由下列基团取代的这种烷基:羟基;囟素;氰基;琥珀酰亚胺基;羟基琥珀酰琥珀酰亚胺基,酰氧基琥珀酰亚胺基;戊二酰亚胺基;苯基氨基甲酰基氧基;苯二(甲)酰亚氨基;4-羧基苯二甲酰亚氨基;苯并[C]吡咯酮基(phthalimidino);2-吡咯烷基酮基;环己基;苯基;被烷基,烷氧基,卤素,羟基,链烷酰氨基,羧基,氰基,或烷氧基羰基取代的苯基;烷基氨磺酰基;乙烯磺酰基,丙烯酰氨基;氨磺酰基;苄基磺酰亚胺基;烷基磺酰氨基;苯基磺酰氨基;烷氧羰氨基;烷基氨基甲酰氧基;烷氧基羰基;烷氧基羰基氧基;链烯基羰基氨基,具有下式结构的基团
其中Y是-NH-,
烷基,-O-,-S-,或-CH2O-;-S-R14;SO2CH2CH2SR14;其中R14为烷基,苯基,被囟素,烷基,烷氧基,烷酰氨基,氰基或烷氧基羰基取代的苯基,吡啶基,嘧啶基,苯并噁唑基,苯并咪唑基,苯并噻唑基,具有下式结构的基团
-OXR16;-NHXR16,-X-R16,-CONR15R15和-SO2NR15R15,其中R15从下列基团中选择:氢,芳基,烷基以及被囟素,羟基,苯氧基,芳基,氰基,环烷基,烷基磺酰基,烷硫基,链烷酰氧基或烷氧基取代的烷基,X为羰基,羧基或磺酰基;R16从下列基团中选择:烷基,以及被囟素,羟基,苯氧基,芳基,氰基,环烷基,烷硫基,烷基磺酰基,烷酰氧基和烷氧基取代的烷基;当X是羰基时,R16也可以是氢,氨基,链烯基,烷氨基,二烷氨基,芳氨基,芳基或呋喃基,烷氧基,被羟基,氰基,烷酰氧基或烷氧基取代的烷氧基,苯氧基,被一个或多个烷基,羧基,烷氧基,烷酯基或卤素取代的苯氧基,R1和R2可为一个复合基团,例如1,5-亚戊基,四亚甲基,亚乙基氧基亚乙基,乙烯磺酰乙烯或亚乙基
R3为亚烷基,亚芳基,芳亚烷基,亚烷氧基或亚烷氧基亚烷基,
Z是直接单键,OCO,O,S,SO2,R17,SO2N=,
R4,R5,及R6各自可为氢或烷基;
R7为羧基,烷酯基或(R)n;
R10为氢,烷基或芳基;
R8和R9各自可为氢或取代的或未取代的烷基、芳基或环烷基;
R11和R12各自可为氢,烷基,羟基或酰氧基;
B代表组成五元环或六元环所需的原子数,B从下列基团中选择:
每个P和Q从下列基团中选择:氰基,烷酯基,卡巴基芳氧基,卡巴基芳烷氧基,氨基甲酰基,羧基,N-烷基氨基甲酰,N-烷基-N-芳基氨基甲酰基,N,N-二烷基氨基甲酰,N-芳基氨基甲酰,N-环己基氨基甲酰,芳基,2-苯并噁唑基,2-苯并噻唑基,2-苯并咪唑基,1,3,4-噻二唑-2-基,1,3,4-噁二唑-2-基,烷基砜基,芳基砜基和酰基或P或Q可结合成
其中R17由上文所定义,R18为氰基,羧基,CO2烷基,氨基甲酰或N-烷基氨基甲酰;其中,对每一个染料分子,A,P和Q中至少有一个必须是或含有从下列基团中选择出来的可缩合基团:羧基,烷酯基,卡巴基,芳氧基,N-烷基氨基甲酰氧基,酰氧基,氯代羰基,氨基甲酰氧基,N-(烷基)2氨基甲酰基氧基,氨基,烷氨基,羟基,N-苯基氨基甲酰氧基,环己酰氧基和碳环己基氧基,在上面各定义中,每个基团的烷基、芳基或环烷基部分在合适的地方可能被羟基,酰氧基,烷基,氰基,烷氧基羰基,囟素,烷氧基,芳基,芳氧基,或环烷基所取代;所说的化合物有一个或多个次甲基单元,能吸收从约350毫微米到约650毫微米范围内的光线,不可以从所提及的聚合物中萃取出来,而且在聚合物加工条件下,具有稳定性;
(2)由上述聚合物的组合物制造定形制品。
2、根据权利要求1的方法制备的定形制品。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70210685A | 1985-02-15 | 1985-02-15 | |
US702,106 | 1985-02-15 | ||
US823,424 | 1986-01-28 | ||
US06/823,424 US4617373A (en) | 1985-02-15 | 1986-01-28 | Condensation polymers and products therefrom |
Publications (2)
Publication Number | Publication Date |
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CN86101649A CN86101649A (zh) | 1987-01-21 |
CN1008100B true CN1008100B (zh) | 1990-05-23 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN86101649A Expired CN1008100B (zh) | 1985-02-15 | 1986-02-15 | 由缩聚聚合物制备定形制品的方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US4617373A (zh) |
EP (1) | EP0215054B1 (zh) |
JP (1) | JPH07116281B2 (zh) |
KR (1) | KR910004880B1 (zh) |
CN (1) | CN1008100B (zh) |
AU (1) | AU579923B2 (zh) |
CA (1) | CA1282528C (zh) |
DE (1) | DE3667990D1 (zh) |
TR (1) | TR22552A (zh) |
WO (1) | WO1986004904A1 (zh) |
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-
1986
- 1986-01-28 US US06/823,424 patent/US4617373A/en not_active Expired - Lifetime
- 1986-02-13 EP EP86901615A patent/EP0215054B1/en not_active Expired - Lifetime
- 1986-02-13 KR KR1019860700663A patent/KR910004880B1/ko not_active IP Right Cessation
- 1986-02-13 WO PCT/US1986/000298 patent/WO1986004904A1/en active IP Right Grant
- 1986-02-13 DE DE8686901615T patent/DE3667990D1/de not_active Expired - Fee Related
- 1986-02-13 AU AU55136/86A patent/AU579923B2/en not_active Ceased
- 1986-02-13 CA CA000501770A patent/CA1282528C/en not_active Expired - Fee Related
- 1986-02-13 JP JP61501257A patent/JPH07116281B2/ja not_active Expired - Fee Related
- 1986-02-15 CN CN86101649A patent/CN1008100B/zh not_active Expired
- 1986-02-17 TR TR7735/86A patent/TR22552A/xx unknown
Also Published As
Publication number | Publication date |
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KR910004880B1 (ko) | 1991-07-15 |
AU5513686A (en) | 1986-09-10 |
CA1282528C (en) | 1991-04-02 |
JPS62501856A (ja) | 1987-07-23 |
JPH07116281B2 (ja) | 1995-12-13 |
DE3667990D1 (de) | 1990-02-08 |
EP0215054B1 (en) | 1990-01-03 |
EP0215054A1 (en) | 1987-03-25 |
AU579923B2 (en) | 1988-12-15 |
TR22552A (tr) | 1987-10-22 |
KR870700078A (ko) | 1987-02-28 |
US4617373A (en) | 1986-10-14 |
CN86101649A (zh) | 1987-01-21 |
WO1986004904A1 (en) | 1986-08-28 |
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