CN1138060A - 具有低结晶速率的聚酯和制备该聚酯的催化剂体系 - Google Patents
具有低结晶速率的聚酯和制备该聚酯的催化剂体系 Download PDFInfo
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical class [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C08G63/82—Preparation processes characterised by the catalyst used
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Abstract
公开了制备的具有低的熔融状态结晶速率、适合于生产纺织纤维和中空体的饱和聚酯,特别是聚(对苯二甲酸乙二酯)。
Description
本发明涉及具有低的熔融态结晶速率的聚酯和由金属混合物组成的其缩聚催化剂体系。
从方法和产品考虑,半结晶态聚酯,特别是聚(对苯二甲酸乙二酯)(PET)和聚(2,6-萘二甲酸乙二酯)(PEN)常常用于结晶动力学重要的领域。
事实上对于纺织用纤维,结晶速率与其它因素一样特别重要,因为它限制了材料的纺丝速率。近年来人们已对基于适合高速纺丝法(大于3000m/min)的PET的聚酯进行不断研究(如描述于Man-Made Fiber Year Book(CTI)1993,P25以下的)。对于这些方法,有可能大辐度增加纺丝厂的生产率。然而,通常用于生产纱线和短纤维的PET不适合用在这种类型的方法中,因为增加纺丝速率会导致较高的纱线断裂数,结果使生产中断并造成生产损失。专利EP202631公开了在高速纺丝过程中纱线断裂的原因之一是由于速度高增加了取向聚酯分子的结晶速率。该专利提出了解决此问题的方法,即将共聚用单体与颗粒尺寸合适的二氧化钛惰性颗粒和羧酸的碱金属或碱土金属盐一起使用。然而,使用共聚用单体造成不符合需要地改变了其它性能如熔点、玻璃化转变温度等。同时这也是一种高成本的解决办法,因为要使用大量的共聚用单体。
对于衍生自相当厚的型坯(约6-7mm)的可再用瓶,为保持透明性,低结晶速率是基本的。
为限制聚酯、特别是PET的结晶速率,使用共聚用单体如二甘醇、间苯二酸和环己烷二甲醇在本技术领域中是已知的(见专利EP465060)。此方法有缺点如加入可降低结晶度或影响性能如机械拉伸强度的另一组分。
我们现在已通过使用由金属衍生物的特定混合物(其在最终聚合物中留下的残余物低于150ppm)制备适合于生产纺织纤维和瓶的具有低结晶速率的聚酯解决了这些问题。
据此,本发明涉及合成具有低结晶速率的聚酯的方法,该聚酯通过缩聚由酯化二羧酸或醇解其烷基酯获得的单体制备,该缩聚借助催化剂体系进行,所述催化剂体系包括:
-至少一种选自锑和锗的衍生物,其用量应使其残余金属在最终聚合物中为5至149.9ppm;
-至少一种选自I-Va、I-VIIb、VIII族和镧系金属的衍生物,其用量应使其残余金属在最终聚合物中为0.1至90ppm;
以元素表示的金属总量应使其在最终聚合物中的量低于150ppm。
在I-Va族金属中,钛是特别优选的。
在本发明的另一实施例方案中,催化剂体系任意性地包括:
-通式为RSO3H的磺酸,其用量应使硫在最终聚合物中为1至40ppm,
其中R代表含高达20个碳原子的直链或支链饱和环状或芳族有机烷基。
本发明的另一目的是用此方法获得的聚酯,这些聚酯包括聚(对苯二甲酸乙二酯)和聚(2,6-萘二甲酸乙二酯)。
使用的化合物RSO3H的量应提供含1至40ppm,优选20ppm硫(以元素硫表示)的聚酯。可用于本发明的磺酸例子为苯磺酸、对-甲苯磺酸、萘磺酸、乙烷磺酸、丙烷磺酸、环己烷磺酸。对-甲苯磺酸是优选的。除酸外,可使用相应的酸酐、酯或酰胺。
锑(III)衍生物可为各种类型,只要可溶即可。氧化锑或乙酸锑是优选的。也可使用乙二醇锑。使用的这种衍生物量应提供含5至149.9ppm锑(以元素锑表示)的聚酯。
锑衍生物可为任何类型,只要可溶即可。氧化锑或乙酸锑是优选的。也可使用乙二醇锑。
锗衍生物可为氧化物或其盐或醇盐。使用的这些衍生物量应提供含5至149.9ppm锗(以元素锗表示)的聚酯。
与锑和锗的衍生物一起使用的金属衍生物可为I-Va、I-VIIB、VIII族和镧系元素的盐、氧化物或有机金属衍生物。这些元素尤其可以其氧化物、羧酯盐(特别是乙酸盐)、醇盐(特别是乙二醇盐、甲醇盐、乙醇盐、异丙醇盐或丁醇盐)的形式使用。
预聚物按一般方法由二酸或其甲酯通过酯化或醇解反应制备。用于醇解步骤的最通用催化剂是乙酸镁、钴、锰、锌、钙等和乙醇钛。
在制备PET中,对苯二甲酸优选用作代替酯的原料。在此情况下,通常不使用催化剂。
将对苯二甲酸双(2-羟乙基)酯在260-290℃温度和低于100Pa(1毫巴)压力下、在稳定剂和本发明的缩聚催化剂存在下转化为聚(对苯二甲酸乙二酯)。
因此拟用的催化剂体系具有如下特点:
-在以熔融态聚合和以固态聚合过程中都保持高活性;
-无过多副反应,如形成二甘醇和乙醛、在最终物料中产生不需要的颜色、形成链末端羧酸基团;
-它们有助于使重金属的存在量低于150ppm。
-低成本。
聚合物特征在于如下参数。
在最终聚合物中的金属含量以元素的ppm表示(基于称量和加入反应混合物中的催化剂量)。结晶温度(Tcc)由示差扫描量热法通过熔化聚合物5min并以10℃/min速率冷却来测量。它表示结晶速率的量度,并且速率越低,结晶温度越低。
用本发明方法获得的聚合物都具有低的金属含量、很低的结晶温度,因此其结晶速率慢。由于这些性质,它们特别适合生产可再用的容器和瓶(在此结晶速率低是所需的基本要求)。此外,它们特别适合生产纺织纤维,因为低金属含量可降低对模的污染。
下列实施例提供了对本发明的更好理解但不是对本发明范围的限制,表1给出了相应于根据实施例6-13所得聚合物的数据。
实施例1(比较例)
将下列化合物加入处在惰性气体气氛中的40升不锈钢反应器中:7.8kg PET预聚物、11.62kg对苯二甲酸和6.51kg乙二醇。最后加入2.92g乙酸锑和2.19g四水合乙酸钴在乙二醇中的溶液。
将1.89g磷酸和6.88g乙酸锑在乙二醇中的溶液加入反应混合物中,并使其加热到230℃并保持此温度直至完全蒸馏出水。
然后将压力降至201Pa(1.5托)并将温度升至285℃,将这些条件保持2小时10分钟并除去过量的乙二醇。
用氮气使反应器回到大气压后,将聚合物挤出并造粒。
将所得产品用Perkin Elmer的DSC7进行DSC(示差扫描量热法)分析。
得到在熔融状态下191℃的结晶温度值(Tcc)。
实施例2
将7kgPET预聚物、11.62kg对苯二甲酸和6.51kg乙二醇加入在惰性气氛中的40l不锈钢反应器中。并加入1.96g乙酸锑、1.31g四水合乙酸钴和0.63g***在乙二醇中的溶液。
将2.62g磷酸三甲酯和1.17g对-甲苯磺酸钠在乙二醇中的溶液加入反应混合物中,将温度升至230℃并保持此温度约3小时直至完全蒸馏出水。
然后将压力降至201Pa(1.5托)并将温度升至285℃,将这些条件保持2小时50分钟并除去过量的乙二醇。
用氮气使反应器回到大气压后,将聚合物挤出并造粒。
得到的Tcc为176℃。
实施例3
将7kg PET预聚物、11.62kg对苯二甲酸和6.51kg乙二醇加入在惰性气氛中的40l不锈钢反应器中,并加入2.50g乙酸锑、2.19g四水合乙酸钴和0.93g氧化钕在乙酸和乙二醇中的溶液。
将2.62g磷酸三甲酯在乙二醇中的溶液加入反应混合物中,将温度升至230℃并保持此温度约2小时10分钟直至完全蒸馏出水。
然后将压力降至110Pa(0.9托)并将温度升至285℃,将这些条件保持3小时10分钟并除去过量乙二醇。
用氮气使反应器回到大气压后,将聚合物挤出并造粒。
获得的Tcc值为187℃。
实施例4
将7kg PET预聚物、11.62kg对苯二甲酸和6.51kg乙二醇加入在惰性气氛中的40l不锈钢反应器中。再加入2.50g乙酸锑、2.19g四水合乙酸钴和1.05g***在乙二醇中的溶液。
将2.62g磷酸三甲酯在乙二醇中的溶液加入反应混合物中,将温度升至230℃并保持此温度约2小时20分钟直至完全蒸馏出水。
然后将压力降至110Pa(0.9托)并将温度升至285℃,将这些条件保持2小时40分钟并除去过量的乙二醇。
用氮气使反应器回到大气压后,将聚合物挤出并造粒。
得到的Tcc值为177℃。
实施例5
将7kgPET预聚物、11.62kg对苯二甲酸和6.51kg乙二醇加入在惰性气氛中的40l不锈钢反应器中。
再加入3.93g乙酸锑、2.19g四水合乙酸钴和0.21g***在乙二醇中的溶液。
将1.89g磷酸在乙二醇中的溶液加入反应混合物中,将温度升至230℃并保持此温度约3小时30分钟直至完全蒸馏出水。
然后将压力降至110Pa(0.9托)并将温度升至285℃,将这些条件保持3小时40分钟并除去过量乙二醇。
用氮气使反应器回到大气压后,将聚合物挤出并造粒。
所得Tcc值为180℃。
实施例6
将下列产品加入在惰性气氛中的40l不锈钢反应器中:
19.40kg(100mol)对苯二甲酸二甲酯;
13.64kg(220mol)乙二醇;
乙二醇溶液,含有:0.70g四水合乙酸锰、3.06g四水合乙酸镁、1.25g二水合乙酸锌、2.84g四水合乙酸钴、1.64g苯甲酸钠。
将此反应混合物升温至180℃并保持此温度约4小时直至完全蒸馏出甲醇,然后将温度升至225℃并加入0.23g四异环氧化钛、1.84g一水合对-甲苯磺酸、1.92g三氧化锑、6.30g磷酸在乙二醇中的溶液。
然后将压力逐渐降至79.9Pa(0.6托)并将温度升至285℃。经3小时10分钟反应后,用氮气使反应器回到大气压并将聚合物挤出和造粒。
实施例7
将下列产品加入在惰性气氛中的40l不锈钢反应器中:
11.62kg(70mol)对苯二甲酸;
6.51kg(105mol)乙二醇;
7.0kg PET预聚物;
乙二醇溶液;含有:2.19g四水合乙酸钴、3.93g乙酸锑、0.115g四异丙醇钛。
将此反应混合物升温至230℃并保持此温度约4小时直至完全蒸馏出水,然后将温度升至255℃并加入1.90g磷酸、0.92g对-甲苯磺酸在乙二醇中的溶液。
随后将压力逐渐降至79.9Pa(0.6托),并将温度升至285℃。经2小时50分钟反应后,用N2使反应器回到大气压,将聚合物挤出并造粒。
实施例8
将下列产品加入在惰性气氛中的40l不锈钢反应器中:
20.0kg PET预聚物;
2.0kg乙二醇;
乙二醇溶液,含:2.19g四水合乙酸钴、3.93g乙酸锑;
乙二醇溶液,含:0.115g四异丙醇钛、1.90g磷酸、0.92g对-甲苯磺酸。
将此混合物逐渐升温至285℃,并将压力降至79.9Pa(0.6托)。经2小时50分钟除去过量乙二醇后,用N2使反应器回到大气压,将聚合物挤出并造粒。
实施例9
将下列产品加入在惰性气氛中的40l不锈钢反应器中:
11.62kg(70mol)对苯二甲酸;
6.51kg(105mol)乙二醇;
7.0kg PET预聚物
乙二醇溶液,含有:2.19g四水合乙酸钴,
1.97g乙酸锑,
0.115g四异丙醇钛。
将此反应混合物升温至230℃并在此温度下保持约4小时直至完全蒸馏出水,然后将温度升至255℃。再加入1.90g磷酸和0.92g对-甲苯磺酸在乙二醇中的溶液。随后将压力逐渐降至79.9Pa(0.6托)并将温度升至285℃,经3小时15分钟反应后,用N2使反应器回到大气压,将聚合物挤出并造粒。
实施例10
将下列产品加入在惰性气氛中的40l不锈钢反应器中:
11.62kg(70mol)对苯二甲酸;
6.51kg(105mol)乙二醇;
7.0kg PET预聚物;
乙二醇溶液,含有:
5.0g乙酸,
2.19g四水合乙酸钴,
1.23g乙酸锑;
0.115g四异丙醇钛。
将此反应混合物升温至230℃并在此温度下保持约4小时直至完全蒸馏出水,然后将温度升至260℃。再加入1.90g磷酸和0.92g对-甲苯磺酸在乙二醇中的溶液。然后将压力逐渐降至79.9Pa(0.6托)并将温度升至285℃。经3小时20分钟反应后,用N2使反应器加到大气压,将聚合物挤出并造粒。
实施例11(比较例)
将19.4kg(100mol)对苯二甲酸二甲酯、13.64kg(220mol)乙二醇加入在惰性气氛中的40l不锈钢反应器中。再加入含0.70g四水合乙酸锰、3.06g四水合乙酸镁、1.25g二水合乙酸锌、2.84g四水合乙酸钴、1.64g苯甲酸钠的乙二醇溶液。
将此反应混合物升温至180℃并在此温度下保持约4小时直至完全蒸馏出水,然后将温度升至225℃。再加入3.68g三氧化锑和10g磷酸三甲酯在乙二醇中的溶液。随后将压力逐渐降至79.9Pa(0.6托)并将温度升至285℃。经2小时50分钟反应后,用N2使反应器回到大气压,将聚合物挤出并造粒。
最终物料呈灰色并证明具有高含量乙醛。
实施例12(比较例)
按实施例11制备聚合物,但作如下变化:
三氧化锑加入量为2.76g,反应时间为3小时10分钟。
最终物料呈灰色并证明有高含量乙醛。
实施例13(比较例)
按实施例11制备聚合物,但作如下变化:
三氧化锑加入量为1.84g,反应时间为5小时。
得到难以挤出的极易流动的聚合物。证明若单独使用80ppm锑,得不到聚合产品。
表1实施例 IV DEG Tm Tcc 颜色
%6 0.60 0.74 253 189 无色7 0.67 0.70 252 183 无色8 0.65 0.98 251 186 无色9 0.58 0.68 252 179 无色10 0.50 1.15 251 178 无色11 0.66 0.74 252 195 灰色12 0.50 0.51 255 206 灰色13 0.30 n.d 256 209 无色n.d:未测定
Claims (16)
1.可用于生产制品的低结晶速率的无色聚酯,通过缩聚由二酸酯化或其烷基酯醇解得到的单体制备。
2.用于制备权利要求1的聚酯的催化剂体系,包括:
-至少一种选自锑和锗的衍生物,其用量应使该残余金属在最终聚合物中为5至149.9ppm;
-至少一种选自I-Va、I-VIIb、VIII和镧系金属的衍生物,其用量应使该残余金属在最终聚合物中为0.1至90ppm;
以元素表示的金属总量在最终聚合物中低于150ppm。
3.根据权利要求2的催化剂体系,其特征在于选自IV-B族金属的衍生物为钛,其用量应使残余钛在最终聚合物中为0.1至4ppm。
4.根据权利要求2的催化剂体系,其特征在于该组合物中还包括:
-具有如下通式的磺酸:
RSO3H
其用量应使硫在最终聚合物中为1至40ppm,其中R代表含高达20个碳原子的直链或支链饱和环状或芳族有机烷基。
5.根据权利要求4的催化剂体系,其特征在于硫在最终聚合物中为1至20ppm。
6.根据权利要求4的催化剂体系,其特征在于磺酸为芳族磺酸。
7.根据权利要求4的催化剂体系,其特征在于芳族磺酸为对-甲苯磺酸。
8.根据权利要求2的催化剂体系,其特征在于锑或锗的衍生物为氧化物。
9.根据权要求2的催化剂体系,其特征在于锑衍生物为乙酸酯。
10.根据权利要求2的催化剂体系,其特征在于锑或锗的衍生物为醇盐。
11.根据权利要求10的催化剂体系,其特征在于醇盐为乙二醇盐。
12.根据权利要求2的催化剂体系,其特征在于钛衍生物为醇盐。
13.根据权利要求3的催化剂体系,其特征在于将钛衍生物以含羧酸的乙二醇溶液加入组合物中。
14.根据权利要求1-13的聚合物,其特征在于聚酯为聚(2,6-萘二甲酸乙二酯)。
15.将权利要求1-15的聚酯用于制备适合于以特别高的速率纺丝的聚酯纤维的用途。
16.将权利要求1-15的聚酯用于制备适合于可再用中空体和瓶的用途。
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ITMI951142A IT1275415B (it) | 1995-06-01 | 1995-06-01 | Poli (etilene) tereftalato a lenta velocita' di cristallizzazione e catalizzatori di policondensazione per la sua preparazione |
IT001142A/95 | 1995-06-01 | ||
ITMI952702 IT1277678B1 (it) | 1995-12-21 | 1995-12-21 | Poliesteri a bassa velocita' di cristallizzazione e sistema catalitico per la loro preparazione |
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WO2002059178A1 (fr) | 2001-01-25 | 2002-08-01 | Mitsubishi Chemical Corporation | Resine polyester, article moule a base de cette resine polyester et procede permettant de produire cette resine polyester |
JP4393004B2 (ja) | 2001-02-06 | 2010-01-06 | 三菱化学株式会社 | ポリエステル樹脂 |
KR100450886B1 (ko) * | 2001-07-04 | 2004-10-01 | 주식회사 새 한 | 기계적 물성이 우수한 포화 폴리에스테르의 제조방법 |
US6699545B2 (en) | 2001-12-21 | 2004-03-02 | E. I. Du Pont De Nemours And Company | Method for increasing solid state polymerization rate of polyester polymers |
US6953768B2 (en) | 2002-11-26 | 2005-10-11 | Teck Cominco Metals Ltd. | Multi-component catalyst system for the polycondensation manufacture of polyesters |
TW200526707A (en) * | 2003-12-04 | 2005-08-16 | Teijin Fibers Ltd | Polyester, process for production thereof, fiber and catalyst for polymerising the polyester |
US9777111B2 (en) | 2005-10-20 | 2017-10-03 | Grupo Petrotemex, S.A. De C.V. | PET polymer with improved properties |
CN101517124B (zh) * | 2006-09-26 | 2012-05-02 | 帝斯曼知识产权资产管理有限公司 | 一种金属化构件的方法 |
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US4356299A (en) * | 1982-02-04 | 1982-10-26 | Rohm And Haas Company | Catalyst system for a polyethylene terephthalate polycondensation |
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HUP9601490A2 (en) | 1997-04-28 |
TR199600450A2 (tr) | 1996-12-21 |
KR970001411A (ko) | 1997-01-24 |
HU9601490D0 (en) | 1996-07-29 |
EP0745629A2 (en) | 1996-12-04 |
HUP9601490A3 (en) | 1997-10-28 |
CZ157796A3 (en) | 1996-12-11 |
SK70896A3 (en) | 1997-04-09 |
PL314566A1 (en) | 1996-12-09 |
JPH0925338A (ja) | 1997-01-28 |
BR9602582A (pt) | 1998-10-06 |
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