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High-heat-resistant amorphous polyester preparation method

An amorphous polyester, high heat resistance technology, applied in the field of polyester modification, can solve the problems of difficult production, low reactivity, difficult polymerization process, etc., to avoid yellowish hue, high intrinsic viscosity, and esterification effect. Good results

Inactive Publication Date: 2019-04-30
SINOPEC YIZHENG CHEM FIBER +1
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  • Abstract
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  • Application Information

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Problems solved by technology

However, these two modified monomers are all secondary carbon-based alcohols, that is, secondary alcohols, which have a large steric hindrance, and the activity of their hydroxyl groups is weaker than that of ethylene glycol. Therefore, a considerable amount of monomers do not participate in the polymerization during the polycondensation process. Being pumped into the vacuum system, the utilization efficiency of the monomer is relatively low
At the same time, since these two monomers are secondary carbon alcohols and have low reactivity, it is difficult to use these two monomers to carry out the polymerization process of modified polyester, and the production is difficult.
[0005] Chinese patent CN102264794A discloses the use of isosorbide to prepare heat-resistant polyester. As mentioned above, the isosorbide used is a secondary carbon-based alcohol, and the monomer utilization efficiency is low.
Chinese patent CN101679619 discloses the use of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol to prepare heat-resistant polyester. 2,2,4,4-Tetramethyl-1,3 cyclobutanediol monomer is a secondary carbon alcohol with low reactivity
[0006] U.S. Patent US2945008 uses titanium catalyst and spiro diol to prepare heat-resistant polyester. The polyester prepared by this method has high glass transition temperature and high heat resistance, but does not use special modified monomer 1,4-cyclohexane Dimethanol (CHDM), so the amorphousness of the polyester prepared by this cannot be guaranteed; and the titanium-based catalyst has hydrolysis phenomenon, which is very easy to react with the water generated in the reaction system to form hydrolyzate, which not only reduces the catalytic efficiency, but also the hydrolyzate It is easy to deposit and block the pipeline, which brings inconvenience to production
[0007] Chinese patent CN1424338 adopts PTA method, does not use esterification catalyst, prepares heat-resistant polyester with spirocyclic diol, because this method does not use esterification catalyst, so the reaction activity is low, and the output rate of polyester is low
Chinese patent CN102257031 uses a titanium catalyst as an esterification catalyst, or a tin compound as an esterification and polycondensation catalyst at the same time, and spiro diols are used to prepare heat-resistant polyester. As mentioned above, it does not use amorphous modified monomer 1,4-ring Hexane dimethanol (CHDM), so the polyester prepared by it is poor in amorphousness; and as mentioned above, the titanium-based catalyst used in it has hydrolysis phenomenon, and it is easy to react with the water generated in the reaction system to form hydrolyzed products, reducing the Catalytic efficiency

Method used

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  • High-heat-resistant amorphous polyester preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Add 350 grams of terephthalic acid, 65 grams of spiroglycol, 45 grams of 1,4 cyclohexanedimethanol, 163 grams of ethylene glycol, and 0.0175 monobutyltin oxide into a 2L reaction kettle. Esterification under the conditions of ~260°C and esterification pressure (gauge pressure) 2.5MPa. When the water output reaches the theoretical value, the esterification is terminated and released to normal pressure. Add 0.0261 g of phosphoric acid, continue stirring for 10 minutes, and add ethylene glycol After 0.13 grams of antimony, gradually increase the temperature and enter the low vacuum stage. After the low vacuum time is about 45 minutes, enter the high vacuum polycondensation stage (vacuum <100Pa), the polycondensation temperature is 270 ° C ~ 290 ° C, and the material is discharged when the stirring power reaches the rated value. Synthetic The modified polyester has a glass transition temperature of 107°C, an intrinsic viscosity of 0.862dL / g, a terminal carboxyl group of 28mo...

Embodiment 2

[0027] Add 350 grams of terephthalic acid, 90 grams of spirodiol, 48.5 grams of 1,4-cyclohexanedimethanol, 208 grams of ethylene glycol, and 0.070 monobutyltin oxide into a 2L reaction kettle. Esterification under the conditions of ~260°C and esterification pressure (gauge pressure) 2.5MPa. When the water output reaches the theoretical value, the esterification is terminated and released to normal pressure. Add 0.0175 grams of phosphoric acid, continue to stir for 10 minutes, and then add ethylene glycol After 0.13 grams of antimony, gradually increase the temperature and enter the low vacuum stage. After the low vacuum time is about 45 minutes, enter the high vacuum polycondensation stage (vacuum <100Pa), the polycondensation temperature is 270 ° C ~ 290 ° C, and the material is discharged when the stirring power reaches the rated value. Synthetic The modified polyester has a glass transition temperature of 117°C, an intrinsic viscosity of 0.810dL / g, a terminal carboxyl group ...

Embodiment 3

[0029] Add 350 grams of terephthalic acid, 65 grams of spirodiol, 30.5 grams of 1,4-cyclohexanedimethanol, 196 grams of ethylene glycol, and 0.044 monobutyltin oxide into a 2L reaction kettle. Esterification under the conditions of ~260℃ and esterification pressure (gauge pressure) 2.5MPa. When the water output reaches the theoretical value, the esterification is terminated and released to normal pressure. Add 0.035 g of phosphoric acid, continue stirring for 10 minutes, and add ethylene glycol After 0.13 grams of antimony, gradually increase the temperature and enter the low vacuum stage. After the low vacuum time is about 45 minutes, enter the high vacuum polycondensation stage (vacuum <100Pa), the polycondensation temperature is 270 ° C ~ 290 ° C, and the material is discharged when the stirring power reaches the rated value. Synthetic The modified polyester has a glass transition temperature of 100°C, an intrinsic viscosity of 0.895dL / g, a terminal carboxyl group of 23mol / t...

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Abstract

The invention provides a high-heat-resistant amorphous polyester preparation method, which comprises: using terephthalic acid and ethylene glycol as main reaction raw materials, adding modified monomers 1,4-cyclohexane dimethanol and spiro diol, and carrying out direct esterification by using a tin / phosphorus / antimony composite catalyst to prepare the high-heat-resistant amorphous polyester. According to the present invention, the tin compound is added as the esterification catalyst at the esterification stage, the phosphorus compound is added to passivate the tin catalyst after the esterification is completed, and the antimony-based catalyst is added as the condensation polymerization catalyst, such that the catalysis effect of the tin compound to the esterification reaction can be ensured, and the problems that the tin catalyst as the condensation polymerization catalyst can yellow the polyester to cause the poor thermal stability of the product can be avoided.

Description

technical field [0001] The invention relates to modification of polyester, in particular to a method for preparing polyethylene terephthalate (PET), especially a method for preparing a highly heat-resistant amorphous modified polyester. Background technique [0002] Polyester, a general term for polymers obtained by polycondensation of polyols and polybasic acids, mainly including polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyarylate (PAR) . Due to the characteristics of electrical insulation, creep resistance, fatigue resistance, friction resistance, high dimensional stability, and good physical and mechanical properties, PET has been expanded to bottle, film, engineering Plastics and other fields. [0003] Part of ethylene glycol in PET is replaced by 1,4-cyclohexanedimethanol (CHDM) to form a modified polyester PETG; when the molar content of CHDM is 20% to 30%, PETG does not crystallize at all. When extrusion, injection molding, blow moldi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G63/86C08G63/85C08G63/672
CPCC08G63/672C08G63/85C08G63/866
Inventor 戴志彬夏峰伟周倩常玉王余伟
Owner SINOPEC YIZHENG CHEM FIBER
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