CN1033392C - 水溶性和/或水分散性聚酯制造方法 - Google Patents
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Abstract
本发明涉及水溶性和/或水分散性共聚多酯制造方法,其中具有对苯二酸酯,间苯二酸酯,磺芳基二羧酸酯,乙二醇和聚氧亚乙基二醇单元,其特征在于其中依序包括以下步骤:
一方面的对苯二酸二甲酯和磺芳基二羧酸二甲酯以及另一方面的乙二醇间的酯基转移反应(互换);
间苯二酸和另外量的乙二醇间的直接酯化反应;
缩聚反应。
本发明还涉及这些共聚多酯在纺纱线上浆过程中的应用。
Description
本发明涉及水溶性和/或水分散性聚酯制造方法以及这些聚酯在纱线上浆,特别是聚酯纱上浆过程中的应用。
本文中“纱”指长单丝束或不连续纤维制成的纱线束。
FR-A-1602002公开了同时具有对苯二酸酯,间苯二酸酯,5-氧磺酰钠间苯二酸酯,乙二醇和聚乙二醇单元的水溶性或水分散性共聚多酯,将对苯二酸二甲酯,间苯二酸二甲酯,5-氧磺酰钠间苯二酸酯以及聚乙二醇占至少20%的乙二醇和聚乙二醇的混合物共缩聚而得,这些共聚多酯可在纺织工业上用作浆料,因此该法包括用相当昂贵的二醇如二亚乙基二醇。
按JP-A-88-256619,上述方法不容易得到适当的缩聚度。为克服这一缺陷,JP-A-88-256619建议先将对苯二酸,间苯二酸和乙二醇直接酯化后再进行5-氧磺酰钠间苯二酸二甲酯和另外量的乙二醇间的酯基转移反应,最后进行缩聚,该法可达到最小比例,如2%以下的二亚乙基二醇单元。
本发明方法提出制造水溶性和/或水分散性共聚多酯,其中除亚乙基二醇-OCH2-CH2-O-单元外还包括各种聚氧乙基二醇单元-O-(CH2-CH2-O)-n,其中n为2-4。
还提出制造玻璃化点低于JP-A-88-256619所述并可按要求应用调节的共聚多酯。
本发明涉及水溶性和/或水分散性共聚多酯制造方法,其中具有对苯二酸酯,间苯二酸酯,磺芳基二羧酸酯,乙二醇和聚氧亚乙基二醇单元,其特征在于其中依序包括以下步骤:
一方面的对苯二酸二甲酯和磺芳基二羧酸二甲酯以及另一方面的乙二醇间的酯基转移反应(互换);
间苯二酸和另外量的乙二醇间的直接酯化反应;
缩聚反应。
更具体地讲,本发明涉及水溶性和/或水分散性共聚多酯制造方法,其中加入对苯二酸酯,间苯二酸酯,磺芳基二羧酸酯,乙二醇和聚氧亚乙基二醇单元,其特征在于其中依序包括以下步骤:
一方面的对苯二酸二甲酯和磺芳基二羧酸二甲酯以及另一方面的乙二醇间的酯基转移反应(互换),乙二醇/二酯mol比1.8-3.5,优选2.0-3.0;
间苯二酸和另外量的乙二醇间的直接酯化反应,乙二醇/间苯二酸mol比1.8-3.0,优选2.0-2.8;
缩聚反应。
M为氢或优选为钠,钾或锂原子,
Q为苯基或几个邻位稠合或周环并合体或几个苯基由惰性基如单键,亚烷基,醚基,酮基或砜基相互连接。
式(I)化合物具体例子为以下酸,即羧二酸二甲酯,其砜官能团游离或由钠,钾或锂原子成盐:磺基对苯二酸,磺基间苯二酸,磺基邻苯二酸,4-磺基萘-2,7-二羧酸,4,4′-磺基-双(羟羰基)-二苯基砜,磺二苯基二羧酸,4,4 ′-磺基-双(羟羰基)-二苯基甲烷和5-磺基苯氧间苯二酸。
用于本发明方法的式(I)化合物中可特别提到5-氧磺酰钠间苯二酸二甲酯。
互换在能从反应介质中去除反应中形成的甲醇的温度下进行,一般蒸馏去除甲醇。
优选互换反应温度等于或高于130℃,特别是140-250℃。
该反应通常在大气压下,也可在低压下进行。
该反应优选还在酯基转移催化剂存在下进行,所说催化剂一般为金属衍生物。
最广泛应用的是羧酸金属盐如乙酸锰,乙酸锌,乙酸钴或乙酸钙;有机钛酸酯或盐如钛酸丁酯或2,2′,2″一次氮基三乙基钛酸酯(或氨基三乙醇钛)和无机钛酸盐如钛酸钙,优选用有机钛酸酯或盐,特别是如上述。
催化剂量一般至少0.005wt%,优选0.01-2wt%/反应剂总量。
互换反应一般持续到蒸出基本上所有甲醇,即至少90%生成甲醇为止。优选是反应开始时以化学计量过量引入的乙二醇中至少一部分也在去除甲醇后蒸出。
可将间苯二酸和乙二醇加入反应介质而进行酯化反应,加料温度相当于互换步骤结束时的温度,而直接酯化反应温度一般210-280℃,优选220-260℃。
该直接酯化反应通常在催化剂存在下进行,催化剂由上述互换反应催化剂构成,而且互换反应和直接酯化反应用相同催化剂,这时可在互换阶段引入催化剂总量或分多次引入。
直接酯化反应催化剂量以其应用的间苯二酸和乙二醇重量计为一般至少0.005wt%,优选0.01-2wt%。
在直接酯化反应期间,蒸馏去除反应中形成的水和过量乙二醇。直接酯化反应结束时,即从反应混合物中去除水和过量乙二醇时,就进行缩聚反应。
缩聚反应一般催化进行,三氧化锑和二氧化锗可作为该催化剂,可在直接酯化反应结束时或提前引入反应介质中,缩聚反应温度一般230-280℃,优选240-260℃,并优选在低于大气压的压力下进行。
优选的是,反应器内的压力从初始压逐渐降到可达10Pa的压力,该降压操作可持续几分钟至几小时,但常见为30分钟至2小时。
本发明方法可得水溶性和/或水分散性共聚多酯,其结构和性能使其很适于纱线上浆。制成的共聚多酯重均分子量一般40000-60000,但必要时可超出该范围,该重均分子量由凝胶色谱在溶剂介质中(60℃)测得,其中二甲基乙酰胺或N-甲基吡咯烷酮含5×10-3N的LiBr,这些结果以聚苯乙烯当量表示。
这些聚酯中实质上插入了对苯二酸酯,5-氧磺酰钠间苯二酸酯,间苯二酸酯,乙二醇和聚氧亚乙基二醇单元链。
本文中应注意到,在水溶性和/或水分散性共聚多酯聚合物链中不同单元表示如下:
磺芳基二羧酯单元=磺芳基二羧酸残基
聚氧亚乙基二醇单元为由氧分开的亚乙基链,一般如下式:
-O-CH2CH2-O-CH2CH2-O-,常称为二乙二醇(或1,4,7-三氧七亚甲基),
-O-CH2CH2-O-CH2CH2-O-CH2CH2-O-,常称为四乙二醇(或1,4,7,10,13-五氧十三亚甲基)。
在本发明方法制成的共聚多酯中,乙二醇和聚氧亚乙基二醇单元mol百分比以所说单元总量计为:
乙二醇(EG)单元35-60%
二乙二醇(DEG)单元20-50%
三乙二醇(TEG)单元5-25%
四乙二醇(QEG)单元0-5%
本发明方法所用每种二酸的单元按以下分式分布,其中mol百分比以二酸所得所有单元计:
对苯二酸酯(TER)单元10-75%
间苯二酸酯(ISO)单元15-70%
磺芳基二羧酸酯单元,特别是5-氧磺酰钠间苯二酸酯(NaS-ISO)单元8-20%。
本发明方法可制成85%相对湿度下玻璃化点等于或高于15℃并等于或低于40℃的水溶性和/或水分散性共聚多酯。
这些共聚多酯因此特别宜于纱线上浆,因为可在两种阻碍性缺陷之间达到可能最好的折衷方案,这两种缺陷为主辊并纱时“堵塞”(辊粘)或织机上的辊筒上散开和灰尘污染织机(极具代表性的磨损现象)。
本发明方法得到的水溶性和/或水分散性共聚多酯在例如10-25%水溶液中随着时间的推移而具有很好的稳定性。这些共聚酯水溶液浊度值低,随着时间的推移,不会混浊或仅稍为变浊,并因而在贮存数天或数星期后溶液中不会出现沉淀。
本发明还涉及经纱纱线上浆方法,其中包括借助含水介质施涂本发明方法制成的水溶性和/或水分散性共聚多酯。该工艺原理是将纱线浸入处于要求温度下的含要求浓度共聚多酯的水浴中,然后将纱线通过辊而将其挤干并最后在干燥室中将上浆纱线干燥,该经纱即可作为织造备用品。
在长丝纱线上浆的常见方法中,例如可参见欧洲系统,典型或英式系统和单端上浆或日本系统。
本发明共聚多酯特别宜于合成乙二醇聚对苯二酸酯长丝纱线或纺纱线,也是属于最难上浆的纺纱线或长丝纱线之列的整理,而且也可用于乙二醇聚对苯二酸酯必要时混有天然纤维的短纤纱或纤维,还用于天然纤维如棉纤维,适用于玻璃纤维或其它纤维如合成纱线如丙烯酰类,聚酰亚胺,聚氯乙烯纤维,聚乙烯,聚丙烯或人造纱线如乙酸酯,三乙酸酯和粘胶丝。
而且可将任何无规纱线上浆,其中不管是否膨松,是否弯曲,并且可用任何无规上浆法,即欧洲式,英国式或日本式系统。
这些产品的极重要优点是,能够解决新织机的输出限制,可使上浆和织造高速进行,而且还可容易用水去除。
下述实施例详述本发明。
例1
向装有锚式搅拌器,传热液体循环用双层壳和电磁阀调节的蒸馏柱的7.5l不锈钢反应器中冷条件下引入:
2262g(11.648mol)对苯二甲酸二甲酯(DMT),
577g(1.947mol)5一氧磺酰钠间苯二酸二甲酯(SIPD),
2453g(39.56mol)乙二醇(EG),
0.91g氨基三乙醇钛作互换催化剂,
0.237g三氧化锑作缩聚催化剂。
二醇/二酯mol比MR1=2.91。
开始搅拌后反应器中物料迅速加热到182℃,此时甲醇开始蒸馏。反应混合物温度然后升到220-230℃,耗时大致120分钟,以蒸出所有甲醇和部分过量的乙二醇。在反应物质处于230℃时。1小时内引入以下间苯二酸/乙二醇悬浮液:
495g(2.98mol)间苯二酸(AI),
472g(7.615mol)乙二醇(EG)。
二醇/二酸mol比MR2=2.555。
在加料期间,温度不下降到227℃以下并且不超过233℃。在引入上述悬浮液后,反应物质1小时加热到230-250℃,其间蒸出水/乙二醇混合物。
250℃下将反应物质转入预热到250℃的蒸压釜中。压力然后50分钟从100KPa(大气压)降到130Pa并让缩聚持续大约45分钟。之后将聚合物倒出并冷却。
然后再进行以下分析:
1)在N-甲基吡咯烷酮中60℃经凝胶色谱(GC)评估重均分子量,其值以聚苯乙烯当量计。
2)经聚合物的预先甲醇解析和经气相色谱(VPC)估量乙二醇和聚氧亚乙基二醇单元含量,结果以每单元中按所说单元总量计为mol百分比。
3)聚合物成膜状在85%相对湿度下调制8天而检测玻璃化点(Tg℃)。
4)贮存10天后刚溶解即测定浊度,用25%聚合物的软化水溶液在Hach浊度计上测定,结果以通用浊度单位(NTU)表示,而设备已预先用福尔吗啉校准。
所得共聚多酯性能如表1所列。
例2
按以下操作程序重复例1,其中改变mol比,引入的是以下量的物质:
催化剂:0.91g氨基三乙醇钛和0.237g三氧化锑。
这样得到的共聚多酯A1性能如下表1。
例3
催化剂:0.91g氨基三乙醇钛和0.237g三氧化锑。
这样得到的共聚多酯A2性能如下表1所列。
例4
按以下操作程序重复例1,只是改变mol比,其中引入以下量物质:
催化剂:0.91g氨基三乙醇钛和0.237g三氧化锑。
这样得到的共聚多酯A3性能如表1所列。
例5
催化剂:0.91g氨基三乙醇钛和0.237g三氧化钛。
这样得到的共聚多酯A4性能如表1所列。
例6
为将上述本发明方法所得共聚多酯与不同结构的共聚多酯比较,按以下操作制备共聚多酯B和B1。
如上述向相同钢反应器中冷条件下引入以下试剂:
-DMT :2006g(10,329mol)
-DMI* :512g(2,641mol)
-SIPD :512g(1,727mol)
-EG :518g(8,37mol)
-DEG**:2071g(19,54mol) RM3=EG/DEG=30/70
*DMI=间苯二酸二甲酯
**DEG=二乙二醇
催化剂:0.83g氨基三乙醇钛,0.215g三氧化钛和2.25g乙酸钠。
共聚多酯B性能列于表2。
开始搅拌后反应器中物料迅速加热到182℃,此时甲醇开始蒸馏。反应混合物温度升到182-250℃,耗时大约2小时40分钟,以蒸出所有甲醇。在250℃下将反应物质转入预热到250℃的蒸压釜中。压力50分钟内从100KPa降到130Pa,缩聚持续60分钟。
例7
按以下操作程序重复例6,但改变乙二醇(EG)和二乙二醇(DEG)各自的量。
-DMT:2006g(10,329mol)
-DMI:512g(2,641mol)
-SIPD:512g(1,727mol)
-EG:865g(13,96mol)
-DEG:1480g(13,96mol) RM3=EG/DEG=50/50
催化剂:0.83g氨基三乙醇钛,0.215g三氧化锑和2.25g乙酸钠。
共聚多酯B1性能列于表2。
从表中可以看出,本发明方法所得共聚多酯A到A4水溶液贮存浊度稳定,而现有技术方法所得共聚多酯浊度会迅速增大。贮存1月后,共聚多酯A到A4溶液仍均匀,而共聚多酯B和B1溶液会出现沉淀并且不再能用于纺织纱线上浆。
表1
共聚多酯 | 二醇量 | 分子量 | Tg℃85%HR | 浊度NTU0天 10天 | ||||
%mol /ε二醇 | Mw* | Mn** | ||||||
EG | DEG | TEG | QEG | |||||
A | 41 | 39 | 17,5 | 2,5 | 45 700 | 21 900 | 15 | 49 49 |
A1 | 48,5 | 32,7 | 17,1 | 1,6 | 50 210 | 23 600 | 25 | 49 49 |
A2 | 56 | 33,1 | 7,5 | <0,5 | 41 970 | 18 520 | 38 | 48 50 |
A3 | 51 | 35,7 | 10,9 | 2,4 | 46 780 | 21 000 | 29 | 53 54 |
A4 | 47,2 | 36,4 | 14,1 | 2,3 | 48 640 | 21 420 | 23 | 49 49 |
*Mw=重均分子量
**Mn=数均分子量
表2
共聚多酯 | 二醇量 | 分子量 | Tg℃85%HR | 浊度NTU0天 10天 | ||||
%mol /ε二醇 | Mw | Mn | ||||||
EG | DEG | TEG | QEG | |||||
B | 21 | 78,25 | 0 | 0,75 | 43 000 | 20 770 | 13 | 58 119 |
B1 | 35,9 | 60,15 | 2,8 | 1,05 | 48 000 | 23 000 | 21 | 59 75 |
Claims (16)
1.水溶性和/或水分散性共聚多酯制造方法,其中具有对苯二酸酯,间苯二酸酯,磺芳基二羧酸酯,乙二醇和聚氧亚乙基二醇单元,其特征在于其中依序包括以下步骤:
一方面的对苯二酸二甲酯和磺芳基二羧酸二甲酯以及另一方面的乙二醇间的酯基转移反应(互换);
间苯二酸和另外量的乙二醇间的直接酯化反应;
缩聚反应。
2.按照权利要求1的方法,其中加入对苯二酸酯,间苯二酸酯,磺芳基二羧酸酯,乙二醇和聚氧亚乙基二醇单,其特征在于其中依序包括以下步骤:
一方面的对苯二酸二甲酯和磺芳基二羧酸二甲酯以及另一方面的乙二醇间的酯基转移反应(每换),乙二醇/二酯mol比1.8-3.5;
间苯二酸和另外量的乙二醇间的直接酯化反应,乙二醇/间苯二酸mol比1.8-3.0;
缩聚反应。
3.按照权利要求1或2的方法,其特征在于磺芳基二羧酸二甲酯为5-氧磺酰钠间苯二酸二甲酯。
4.按照权利要求1或2的方法,其特征在于互换反应温度等于或高于130℃。
5.按照权利要求1或2的方法,其特征在于互换反应在一般选自金属衍生物的酯基转移催化剂存在下进行。
6.按照权利要求5的方法,其特征在于催化剂量至少为0.005wt%反应剂总量。
7.按照权利要求1和2之一的方法,其特征在于直接酯化反应于210-280℃下进行。
8.按照权利要求7的方法,其特征在于直接酯化反应在一般选自金属衍生物的催化剂存在下进行。
9.按照权利要求8的方法,其特征在于直接酯化反应催化剂量以其中应用的间苯二酸和乙二醇重量计为至少0.005wt%。
10.按照权利要求1和2之一的方法,其特征在于缩聚反应在230-280℃进行。
11.按照权利要求10的方法,其特征在于缩聚反应在选自三氧化锑和二氧化钛的催化剂存在下进行。
12.按照权利要求11的方法,其特征在于缩聚反应在低于大气压的压力下进行。
13.按照权利要求5的方法,其特征在于金属衍生物选自羧酸金属盐,有机钛酸酯或盐和无机钛酸盐。
14.按照权利要求13的方法,其特征在于所述羧酸金属盐选自乙酸锰、乙酸锌、乙酸钴或乙酸钙;有机钛酸酯或盐选自钛酸丁酯或2,2’,2”-次氮基三乙基钛酸酯(或氨基三乙醇钛);无机钛酸盐选自钛酸钙。
15.按照权利要求8的方法,其特征在于金属衍生物选自羧酸金属盐,有机钛酸酯或盐和无机钛酸盐。
16.按照权利要求15的方法,其特征在于所述羧酸金属盐选自乙酸锰、乙酸锌、乙酸钴或乙酸钙;有机钛酸酯或盐选自钛酸丁酯或2,2’,2”-次氮基三乙基钛酸酯(或氨基三乙醇钛);无机钛酸盐选自钛酸钙。
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FR9113595A FR2682956B1 (fr) | 1991-10-29 | 1991-10-29 | Procede de preparation de polyesters hydrosolubles et/ou hydrodispersables et utilisation de ces polyesters pour l'encollage de fils textiles. |
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JPS48103883A (zh) * | 1972-04-13 | 1973-12-26 | ||
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JPS5763325A (en) * | 1980-10-02 | 1982-04-16 | Toyobo Co Ltd | Copolyester |
JPS592285A (ja) * | 1982-06-28 | 1984-01-07 | Fujitsu Ltd | 磁気バブルメモリの駆動方式 |
JPS59144611A (ja) * | 1983-02-01 | 1984-08-18 | Teijin Ltd | ポリエステル繊維 |
JPS6157618A (ja) * | 1984-08-29 | 1986-03-24 | Teijin Ltd | 改質ポリエステルの製造方法 |
JPS6289725A (ja) * | 1985-10-15 | 1987-04-24 | Teijin Ltd | 改質ポリエステルの製造方法 |
FR2602777B1 (fr) * | 1986-08-12 | 1988-11-10 | Rhone Poulenc Films | Procede de revetement de films en polyester et nouveaux films comportant un revetement de surface |
FR2608506B1 (fr) * | 1986-12-23 | 1989-03-31 | Rhone Poulenc Films | Procede d'obtention de films polyester composites epais a adherence amelioree et nouveaux films composites |
FR2609665B1 (fr) * | 1987-01-21 | 1989-04-14 | Rhone Poulenc Films | Procede d'obtention de films polyester a revetement de polychlorure de vinylidene et nouveaux films composites ainsi obtenus |
JP2530649B2 (ja) * | 1987-04-15 | 1996-09-04 | 東レ株式会社 | 改質ポリエステルの製造法 |
FR2640983B1 (zh) * | 1988-12-28 | 1992-09-25 | Rhone Poulenc Films |
-
1991
- 1991-10-29 FR FR9113595A patent/FR2682956B1/fr not_active Expired - Lifetime
-
1992
- 1992-08-17 ES ES92402292T patent/ES2118671T3/es not_active Expired - Lifetime
- 1992-08-17 DE DE0540374T patent/DE540374T1/de active Pending
- 1992-08-17 EP EP92402292A patent/EP0540374B1/fr not_active Expired - Lifetime
- 1992-08-17 DE DE69230460T patent/DE69230460T2/de not_active Expired - Lifetime
- 1992-08-17 AT AT92402292T patent/ATE187975T1/de not_active IP Right Cessation
- 1992-09-30 AU AU26131/92A patent/AU655078B2/en not_active Ceased
- 1992-10-15 CN CN92111622A patent/CN1033392C/zh not_active Expired - Fee Related
- 1992-10-19 TW TW081108293A patent/TW227025B/zh active
- 1992-10-19 CA CA002080883A patent/CA2080883C/fr not_active Expired - Lifetime
- 1992-10-22 JP JP4308066A patent/JP2573543B2/ja not_active Expired - Lifetime
- 1992-10-28 RU RU92004361A patent/RU2102405C1/ru active
- 1992-10-28 KR KR1019920019958A patent/KR970002080B1/ko not_active IP Right Cessation
- 1992-10-29 US US07/968,306 patent/US5290631A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0540374A1 (fr) | 1993-05-05 |
KR970002080B1 (ko) | 1997-02-22 |
JP2573543B2 (ja) | 1997-01-22 |
ES2118671T3 (es) | 2000-04-01 |
FR2682956B1 (fr) | 1994-01-07 |
TW227025B (zh) | 1994-07-21 |
KR930008015A (ko) | 1993-05-20 |
CA2080883C (fr) | 1999-01-05 |
JPH05295097A (ja) | 1993-11-09 |
AU2613192A (en) | 1993-05-06 |
EP0540374B1 (fr) | 1999-12-22 |
ATE187975T1 (de) | 2000-01-15 |
AU655078B2 (en) | 1994-12-01 |
CA2080883A1 (fr) | 1993-04-30 |
DE69230460T2 (de) | 2000-08-03 |
RU2102405C1 (ru) | 1998-01-20 |
CN1072691A (zh) | 1993-06-02 |
ES2118671T1 (es) | 1998-10-01 |
US5290631A (en) | 1994-03-01 |
DE69230460D1 (de) | 2000-01-27 |
FR2682956A1 (fr) | 1993-04-30 |
DE540374T1 (de) | 1998-11-19 |
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