CN1566178A - Composite esterification and polycondensation catalyst for preparing poly trimethylene terephthalate - Google Patents
Composite esterification and polycondensation catalyst for preparing poly trimethylene terephthalate Download PDFInfo
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- CN1566178A CN1566178A CN 03141504 CN03141504A CN1566178A CN 1566178 A CN1566178 A CN 1566178A CN 03141504 CN03141504 CN 03141504 CN 03141504 A CN03141504 A CN 03141504A CN 1566178 A CN1566178 A CN 1566178A
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- esterification
- trimethylene terephthalate
- dioxide
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Abstract
The invention discloses a composite esterification and polycondensation catalyst for preparing poly trimethylene terephthalate, wherein the composite catalyst is a composition containing titanium dioxide, silicon dioxide and molybdenum trioxide. The prepared PTT product has very low end carboxyl content, ether content and rather high characteristic viscosity.
Description
Technical field
The present invention relates to a kind of being used for by terephthalic acid and 1, ammediol is made the esterification of Poly(Trimethylene Terephthalate) and the composite catalyst of polycondensation process, and this composite catalyst contains the mineral compound of titanium and the mineral compound of molybdenum.
Background technology
Poly(Trimethylene Terephthalate) (PTT) is a kind of by terephthalic acid (PTA) and 1, ammediol (PDO) is through esterification and polycondensation synthetic aromatic polyester, is to realize that suitability for industrialized production can become fine polyester macromolecule material after the polyethylene terephthalate fifties (PET) industrialization and the polybutylene terephthalate seventies (PBT) industrialization.Ptt fiber also has excellent elasticity recovery and response rate except the chemical resistance that possesses the PET fiber, its intrinsic pollution resistance, static resistance and colour fastness are also all very good.In addition, PTT also has a wide range of applications aspect fine non-, and as making container, film etc., purposes is very extensive.
PTT generally adopts direct esterification-melt phase polycondensation operational path to make, and esterification and polycondensation are carried out in the presence of catalyzer usually.Introduce to adopt titanium system or the tin based compound catalyzer as esterification and polycondensation as European patent 0547553A1, the maximum limiting viscosity of the PTT product that makes is 0.90dl/g, and color and luster b* value is 9.United States Patent (USP) 5,798, it is the catalyzer of esterification and polycondensation that titanium system and antimony series composite catalyst are adopted in 433 introductions, and the maximum limiting viscosity of the PTT product that makes is 0.91dl/g, and end carboxyl concentration is greater than 20mmol/kg.United States Patent (USP) 5,872,204 introductions are catalyst for esterification reaction with the titanium ethylene glycolate, with the antimony acetate is polycondensation catalyst, and the limiting viscosity of the PTT product that makes is at 0.65～0.91dl/g, and the end carboxyl is below 40meq/kg, form and aspect L* value is greater than 60, and the b* value is less than 9.
The defective that all these existing catalyzer exist is when it is used for corresponding preparation method, and the PTT product content of carboxyl end group that obtains is higher, and limiting viscosity is lower, is difficult to surpass 0.91dl/g usually.And we know that higher content of carboxyl end group will influence the thermostability of product.Limiting viscosity then is an important technology index of polyester product, studies show that, the PTT limiting viscosity reach 0.90dl/g when above macromolecular material just have higher physical strength, thereby spinning property is better, the fibre strength that makes can satisfy multi-purpose requirement.
Summary of the invention
The invention provides a kind of be used to the make esterification of Poly(Trimethylene Terephthalate) and the composite catalyst of polycondensation process, its technical problem to be solved is when this catalyzer is used for corresponding preparation method, can make the PTT product that makes have lower content of carboxyl end group and higher limiting viscosity.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind ofly be used to make the esterification of Poly(Trimethylene Terephthalate) and the composite catalyst of polycondensation process, this composite catalyst is the composition that contains titanium dioxide, silicon-dioxide and molybdic oxide.Wherein:
The mol ratio of titanium dioxide and silicon-dioxide is (7～10): 1, be preferably (8～9): 1;
The total amount of titanium dioxide and silicon-dioxide and the weight ratio of molybdic oxide are 280: (1～200) is preferably 280: (10～100).
Catalyzer should be added to when esterification feeds intake in the reaction system usually, and the add-on of catalyzer is a benchmark with terephthalic acid in the reaction system, and add-on is 50～500ppm, is preferably 100～300ppm.
Key of the present invention has provided a kind of new catalyst system, and other processing condition and the prior art of esterification and precondensation, polycondensation process are basic identical, and conventional additive such as toning agent, matting agent, lubricant, linking agent and stablizer etc. can add reaction system as required.The adding of stablizer can further reduce by-products content, thereby obtains higher-quality polyester product.Usually stablizer can be taken from one or more the mixture in triphenylphosphate, phosphorous acid or the trimethyl phosphite 99.All these are all known for those skilled in the art.
Compared with prior art, the invention has the advantages that the reaction times reduces to some extent when this composite catalyst is used to make the esterification of Poly(Trimethylene Terephthalate) and polycondensation process.The PTT product that particularly makes has lower content of carboxyl end group, ether content and has higher limiting viscosity, and limiting viscosity is more than 0.90dl/g generally speaking.
Below will the invention will be further described by embodiment and comparative example.
In embodiment and comparative example, each leading indicator testing method of PTT product is as follows:
Limiting viscosity (I.V.):
With 0.1250 gram polyester be dissolved in 25 milliliters of phenol and sym.-tetrachloroethane etc. in the solution of weight mixture, measure its limiting viscosities (I.V.) down in 25 ℃.
Content of carboxyl end group (COOH):
Adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds dibromothymolsulfonphthalein and make indicator, the ethanolic soln with the potassium hydroxide of 0.05N carries out titration then.
Ether content (DPG): vapor-phase chromatography.
Form and aspect b* value: measure by GB GB/T 14190-1993.
Reactor configurations whipping appts, rectifying column, condenser and pumped vacuum systems are carried out in being reflected in one 2 liters the stainless steel pressure reactor of embodiment and comparative example.
Embodiment
[embodiment 1～8]
Terephthalic acid and propylene glycol are dropped in the reactor, and molar ratio is a terephthalic acid: propylene glycol=1: (1.6～2.0), and the composite catalyst of adding aequum, system impose to stir carries out esterification.Temperature of reaction is 210～250 ℃, and reaction pressure is 0.1～0.3MPa, distillates the water of generation in the reaction process, and the reaction times is 120～150 minutes;
Get stablizer trimethyl phosphite 99 and an amount of 1, ammediol is mixed with solution and adds reaction system.The add-on of stablizer is a benchmark with terephthalic acid in the reaction system, and add-on is 15ppm.Reacted 10～30 minutes down in normal pressure;
Proceed prepolymerization reaction, temperature of reaction is 230～255 ℃, progressively reduce pressure during the reaction beginning, and be 0.3～1KPa absolute pressure until pressure, the reaction times is 30～90 minutes;
Above-mentioned reactant is proceeded polycondensation, and temperature of reaction is 250～280 ℃, and reaction pressure is 0.01～0.5KPa absolute pressure.Polycondensation finishes back resulting polymers Cast Strip pelletizing.
[comparative example 1～2]
Esterification begins to add different catalyzer in the forward direction system, and all the other are with embodiment 1～8.
The catalyzer that each embodiment and comparative example adopted, the add-on of catalyzer and concrete polycondensation reaction time see Table 1, and the main quality index that each embodiment and comparative example make the PTT product sees Table 2.
Table 1.
| Catalyzer | ????TiO 2/SiO 2(mol ratio) | ????(TiO 2+SiO 2) ????/MoO 3(weight ratio) | Catalyzer add-on (ppm) | Polycondensation reaction time (min) | |
| Embodiment 1 | ??TiO 2/SiO 2/MoO 3 | ????7∶1 | ????280∶10 | ????100 | ????160 |
| Embodiment 2 | ??TiO 2/SiO 2/MoO 3 | ????8∶1 | ????280∶30 | ????100 | ????120 |
| Embodiment 3 | ??TiO 2/SiO 2/MoO 3 | ????10∶1 | ????280∶30 | ????100 | ????155 |
| Embodiment 4 | ??TiO 2/SiO 2/MoO 3 | ????8∶1 | ????280∶1 | ????100 | ????150 |
| Embodiment 5 | ??TiO 2/SiO 2/MoO 3 | ????8∶1 | ????280∶10 | ????50 | ????140 |
| Embodiment 6 | ??TiO 2/SiO 2/MoO 3 | ????8∶1 | ????280∶100 | ????100 | ????125 |
| Embodiment 7 | ??TiO 2/SiO 2/MoO 3 | ????8∶1 | ????280∶30 | ????300 | ????135 |
| Embodiment 8 | ??TiO 2/SiO 2/MoO 3 | ????8∶1 | ????280∶200 | ????500 | ????130 |
| Comparative example 1 | ??Ti(BuO) 4 | ????- | ????- | ????350 | ????220 |
| Comparative example 2 | ??SbO 3 | ????- | ????- | ????500 | ????300 |
Annotate: the add-on of catalyzer is a benchmark with terephthalic acid in the reaction system.
Table 2.
| Limiting viscosity (dl/g) | End carboxyl (mol/t) | Form and aspect (b* value) | ????DPG ????(mol％) | |
| Embodiment 1 | ????0.908 | ????15 | ????1 | ????1.30 |
| Embodiment 2 | ????0.962 | ????13 | ????0 | ????1.08 |
| Embodiment 3 | ????0.912 | ????15 | ????1 | ????1.15 |
| Embodiment 4 | ????0.922 | ????18 | ????2 | ????1.21 |
| Embodiment 5 | ????0.929 | ????15 | ????2 | ????1.25 |
| Embodiment 6 | ????0.941 | ????13 | ????1 | ????1.17 |
| Embodiment 7 | ????0.950 | ????15 | ????1 | ????1.15 |
| Embodiment 8 | ????0.935 | ????12 | ????3 | ????1.24 |
| Comparative example 1 | ????0.880 | ????25 | ????4 | ????1.52 |
| Comparative example 2 | ????0.821 | ????37 | ????7 | ????1.43 |
Claims (3)
1, a kind ofly be used to make the esterification of Poly(Trimethylene Terephthalate) and the composite catalyst of polycondensation process, this composite catalyst is the composition that contains titanium dioxide, silicon-dioxide and molybdic oxide, wherein:
The mol ratio of titanium dioxide and silicon-dioxide is 7～10: 1;
The total amount of titanium dioxide and silicon-dioxide and the weight ratio of molybdic oxide are 280: 1～200.
2, composite catalyst according to claim 1, the mol ratio that it is characterized in that described titanium dioxide and silicon-dioxide is 8～9: 1.
3, composite catalyst according to claim 1 is characterized in that the total amount of described titanium dioxide and silicon-dioxide and the weight ratio of molybdic oxide are 280: 10～100.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141504 CN1272360C (en) | 2003-07-09 | 2003-07-09 | Composite esterification and polycondensation catalyst for preparing poly trimethylene terephthalate |
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| CN 03141504 CN1272360C (en) | 2003-07-09 | 2003-07-09 | Composite esterification and polycondensation catalyst for preparing poly trimethylene terephthalate |
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| CN1566178A true CN1566178A (en) | 2005-01-19 |
| CN1272360C CN1272360C (en) | 2006-08-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127957A (en) * | 2013-02-19 | 2013-06-05 | 东南大学 | Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof |
| CN110437429A (en) * | 2018-05-02 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of preparation method of modified poly ester and preparation method thereof and its film |
| CN112920387A (en) * | 2019-12-05 | 2021-06-08 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing polytrimethylene terephthalate, preparation method and polytrimethylene terephthalate |
-
2003
- 2003-07-09 CN CN 03141504 patent/CN1272360C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127957A (en) * | 2013-02-19 | 2013-06-05 | 东南大学 | Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof |
| CN110437429A (en) * | 2018-05-02 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of preparation method of modified poly ester and preparation method thereof and its film |
| CN112920387A (en) * | 2019-12-05 | 2021-06-08 | 中国科学院成都有机化学有限公司 | Catalyst for synthesizing polytrimethylene terephthalate, preparation method and polytrimethylene terephthalate |
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| Publication number | Publication date |
|---|---|
| CN1272360C (en) | 2006-08-30 |
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