CN1061056C - 热塑性聚酯的制备 - Google Patents
热塑性聚酯的制备 Download PDFInfo
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- CN1061056C CN1061056C CN95102733A CN95102733A CN1061056C CN 1061056 C CN1061056 C CN 1061056C CN 95102733 A CN95102733 A CN 95102733A CN 95102733 A CN95102733 A CN 95102733A CN 1061056 C CN1061056 C CN 1061056C
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- 238000000034 method Methods 0.000 claims abstract description 20
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
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- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
通过一种方法由二羟基化合物与二羧酯或它们的酯或成酯衍生物进行多阶段缩聚制备热塑性聚酯，在该方法中，至少有一个第一阶段，以每公斤聚酯1-10mmol(按照碱金属或碱土金属计算)的用量添加碱金属或碱土金属化合物，以及在至少一个其它阶段中进行固相缩合。
Description
本发明涉及由二羟基化合物与二羧酸或其酯或它们的成酯衍生物进行多阶段缩聚制备热塑性聚酯的方法。
上述类型的方法，尤其聚对苯二甲酸亚烷基酯的制备方法业已在全世界大规模工业化。
为了提高分子量，至少在反应的第二阶段常常进行固相后缩合。
针对这一目的所要求的长停留时间，以及该聚酯所遇到的相应热应力并导致生成不希望有的斑点和凝胶，需要对此加以改进。
为了提高聚酯的结晶度和结晶速率，在缩聚中碱金属化合物的存在是众所周知的，例如在EP-A 215 364和EP-A 29 285中有叙述。碱金属化合物的添加量根据EP-A 29 285，以聚酯为基础约为0．1-2％(重量)，或者为每公斤聚酯0．02-1mol(EP-215 364)。然而，如此大用量对于某些用处的最终产物来说是不利的。
本发明的目的是提供一种开头所述类型的聚酯的制备方法，该方法能获得基本上无斑点和无凝胶的产物，并且总体上需要较短的缩聚时间。
根据本发明，我们发现由二羟基化合物与二羧酸或其酯或它们的成酯衍生物进行多阶段缩聚制备热塑性聚酯的方法是能够实现。这一目的，在该方法中，至少有一个第一阶段，以每公斤聚酯1-10mmol(按照碱金属或碱土金属计算)的用量添加碱金属化合物或碱土金属化合物，以及在至少一个其它阶段中进行固相缩合。
在该新颖方法中，在较短的缩聚时间，尤其在固相缩合中，能够获得高分子量和基本上无斑点和无凝胶的聚酯。
脂族、芳族或环脂族二醇可用作二羟基化合物。
这些化合物最好具有2-20个、尤其2-12个碳原子，而具有2-12个、尤其2-6个碳原子的脂族二醇是特别优选的。
这些二元醇的实例是乙烷二醇(乙二醇)、1-3丙二醇、1，4-丁二醇、环己二醇、氢醌、间苯二酚和双酚A，它们当中乙二醇和1，4-丁二醇是特别优选的。
所用二羧酸可以优选具有4-20个、尤其4-12个碳原子的脂族和／或芳族二羧酸。
这类羧酸的例子是间苯二酸，邻苯二酸，对苯二酸，上述酸的烷基取代衍生物，2，6和2，7萘二羧酸，脂族二羧酸如琥珀酸、己二酸、癸二酸、壬二酸和癸烷二羧酸，它们当中间苯二酸和对苯二酸或其混合物是特别优选的。
从以上可清楚地看出，聚对苯二甲酸亚烷基酯或聚间苯二甲酸亚烷基酯或对苯二甲酸和间苯二甲酸作为酸组分的共聚酯能够特别理想地由该新颖的方法制备。
除了上述组分外，根据本发明制备的聚酯还含有较少量的，最好低于10mol％(以特定的单体组分为基础)的例如由羟基羧酸衍生而来的其它单元。
在该新颖方法中，在起始单体的反应过程中的第一阶段，以本身已知的方式每公斤聚酯添加1-10，优选2-7，尤其2．5-5mmol的碱金属化合物或碱土金属化合物(按照碱金属或碱土金属化合物计算)。
碱金属(优选Li、Na或K)的无机和有机化合物，特别优选Na化合物，原则上是适用的。
碱金属或碱土金属(优选钠)的适宜无机化合物的例子是相应的硅酸盐、磷酸盐、亚磷酸盐、硫酸盐，或优选碳酸盐、碳酸氢盐和氢氧化物。
碱金属和碱土金属(优选钠)的有机化合物包括具有最好至多30个碳原子和最好1-4个羧基的(环)脂族、芳脂族或芳族羧酸的相应盐类。这些盐的实例是甲酸、乙酸、丙酸、丁酸、异丁酸、辛酸、硬脂酸、环已烷羧酸、琥珀酸、己二酸、辛二酸、1，10-癸烷二羧酸、1，4-环己烷二羧酸、对苯二甲酸、1，2，3-丙烷三羧酸、1，3，5-环己烷三羧酸、偏苯三酸、1，2，3，4-环戊烷四羧酸、1，2，4，5-苯四酸、苯甲酸、取代苯甲酸、二聚酸和三聚酸的碱金属盐以及中性或部分中和的褐煤蜡盐或褐煤蜡酯盐类(褐煤酸酯(盐)类)。带有其它类酸根的盐，例如链烷烃磺酸碱金属盐，烯属磺酸碱金属盐以及芳基磺酸碱金属盐或酚盐和醇化物，如甲醇盐、乙醇盐或甘醇酸盐，根据本发明也可使用。优选使用碳酸钠，碳酸氢钠，氢氧化钠，单和多羧酸、尤其脂族的单和多羧酸(优选具有2-18个，尤其2-6个碳原子和至多4个，优选至多2个羧基的那些)的钠盐以及具有2-15个，尤其2-8个碳原子的醇钠。特别优选的例子是乙酸钠、丙酸钠、丁酸钠、草酸钠、丙二酸钠、琥珀酸钠、甲醇钠、乙醇钠和甘醇酸钠。甲醇钠是特别优选的，以2．5-5mmol的量(按照钠计算)使用尤为理想。还可使用不同碱金属和碱土金属化合物的混合物。
碱金属或碱土金属或碱金属化合物或碱土金属化合物可以在聚酯合成第一阶段的过程中的任何时间加进去，一般在酯化／缩聚过程时，但优选在酯基转移／缩聚过程时。当使用酯基转移／缩聚工艺时，在酯基转移作用开始时加入则是特别优选的。酯化／缩聚工艺和酯基转移作用／缩聚工艺是众所周知的，例如在UIImann′s Encykl opadie der thchnischen Chemie(第4版)：19(1980)，61-88页中有描述。
实施例
在通过酯基转移／缩聚工艺从对苯二甲酸二甲酯和1，4-丁二醇制备聚酯时，4mmol以甲醇钠形式的钠(以每公斤按完全化学计量反应中形成的聚酯为基础)在酯基转移过程中加入，并且在熔融态或在溶液中的第一次缩合之后，该产物在第二阶段进行固相缩合。
与没有使用甲醇钠而在其它相同条件下进行的反应相比较，观察到分子量显著快速提高，所得产物具有明显低的斑点和凝胶含量。
Claims (2)
1．一种由二羟基化合物与二羧酸或它们的酯或成酯衍生物进行多阶段缩聚制备热塑性聚酯的方法，其中，在至少一个第一阶段中，按照碱金属或碱土金属计算以每公斤聚酯1-10mmol的用量添加碱金属醇化物或碱土金属醇化物，以及在至少一个其它阶段中进行固相缩合。
2．按照权利要求1所要求的方法，其中使用甲醇钠。
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| Application Number | Priority Date | Filing Date | Title |
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| DE4401055A DE4401055A1 (de) | 1994-01-15 | 1994-01-15 | Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt |
| EP95100164A EP0663416B1 (de) | 1994-01-15 | 1995-01-07 | Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt |
| ES95100164T ES2139099T3 (es) | 1994-01-15 | 1995-01-07 | Procedimiento para la obtencion de poliesteres termoplasticos con un bajo contenido de grupos terminales carboxilo. |
| US08/370,985 US5496887A (en) | 1994-01-15 | 1995-01-10 | Preparation of thermoplastic polyesters having a low content of terminal carboxyl groups |
| CN95102733A CN1061056C (zh) | 1994-01-15 | 1995-02-21 | 热塑性聚酯的制备 |
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| DE4401055A DE4401055A1 (de) | 1994-01-15 | 1994-01-15 | Verfahren zur Herstellung von thermoplastischen Polyestern mit niedrigem Carboxylendgruppengehalt |
| CN95102733A CN1061056C (zh) | 1994-01-15 | 1995-02-21 | 热塑性聚酯的制备 |
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| DE3532033A1 (de) * | 1985-09-09 | 1987-03-19 | Hoechst Ag | Schnellkristallisierende polyestermassen und verfahren zu deren herstellung |
| DE3616431A1 (de) * | 1986-05-15 | 1987-11-19 | Hoechst Ag | Polyesterformmasse und verfahren zu ihrer herstellung |
| JPH039923A (ja) * | 1989-06-08 | 1991-01-17 | Dainippon Ink & Chem Inc | ポリエステルポリオールの製造法及びそれを用いたポリウレタンエラストマー |
| DE69225512T2 (de) * | 1991-02-28 | 1998-12-17 | Agfa-Gevaert N.V., Mortsel | Verfahren zur Herstellung von Polyestern mit erhöhter elektrischer Leitfähigkeit |
-
1994
- 1994-01-15 DE DE4401055A patent/DE4401055A1/de not_active Withdrawn
-
1995
- 1995-01-07 EP EP95100164A patent/EP0663416B1/de not_active Expired - Lifetime
- 1995-01-07 ES ES95100164T patent/ES2139099T3/es not_active Expired - Lifetime
- 1995-01-10 US US08/370,985 patent/US5496887A/en not_active Expired - Lifetime
- 1995-02-21 CN CN95102733A patent/CN1061056C/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54108898A (en) * | 1978-02-15 | 1979-08-25 | Nippon Ester Co Ltd | Preparation of polyester having high whiteness |
| US4654413A (en) * | 1984-12-28 | 1987-03-31 | Polyplastics Co., Ltd. | Manufacturing of high molecular weight polyester |
| EP0215364A2 (de) * | 1985-09-09 | 1987-03-25 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung schnellkristallisierender Polyestermassen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1129715A (zh) | 1996-08-28 |
| DE4401055A1 (de) | 1995-07-20 |
| EP0663416B1 (de) | 1999-10-27 |
| EP0663416A3 (de) | 1997-10-22 |
| US5496887A (en) | 1996-03-05 |
| ES2139099T3 (es) | 2000-02-01 |
| EP0663416A2 (de) | 1995-07-19 |
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