CN102964576B - Modified polyester and preparation method thereof - Google Patents
Modified polyester and preparation method thereof Download PDFInfo
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- CN102964576B CN102964576B CN201210528292.7A CN201210528292A CN102964576B CN 102964576 B CN102964576 B CN 102964576B CN 201210528292 A CN201210528292 A CN 201210528292A CN 102964576 B CN102964576 B CN 102964576B
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- ethylene glycol
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Abstract
The invention provides modified polyester obtained by copolymerizing isophthalic acid, 1,4-cyclohexanedimethanol, terephthalic acid and ethylene glycol. The modified polyester has the beneficial effects that isophthalic acid and 1,4-cyclohexanedimethanol are taken as modifying agents to modify PET (polyethylene glycol terephthalate), that is, isophthalic acid, 1,4-cyclohexanedimethanol, terephthalic acid and ethylene glycol are taken as raw materials to undergo copolymerization to obtain a PET copolymer; by using isophthalic acid and 1,4-cyclohexanedimethanol as the modifying agents, not only can the shrinkage of the modified polyester be increased but also the fragility of the modified polyester can be reduced, so that the modified polyester can not be broken when serving as tags for bottles and the yield is increased; and results show that the shrinkage of the modified polyester film provided by the invention is over 60%, the longitudinal tensile strength is over 60MPa, the lateral tensile strength is over 200MPa, the longitudinal elongation at break is over 500% and the lateral elongation at break is over 50%.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of modified poly ester and preparation method thereof.
Background technology
Thermal shrink film label is that a kind of ink special that adopts is printed on film label on plastic film or plastics tubing.Along with getting prosperous with every passing day of bottled drink market, the demand of bottle thermal shrink film label constantly expands, and demand quality constantly promotes.At present, the heat-shrinkable film that can be used as shrink label is made primarily of polyvinyl chloride (PVC), polystyrene (PS) or polyester etc., wherein, polyvinyl chloride can cause environmental pollution, and polystyrene printing and less stable, the polyester with the excellent feature of environmental protection and heat-shrinkable becomes state-of-the-art shrink wrap material.
Modal polyester is polyethylene terephthalate (PET), it has excellent over-all properties, but the molecular chain arrangement of PET is comparatively regular, crystal property is better, no matter adopt which kind of method processing, the PET film obtained all is difficult to reach the requirement of shrinking and being greater than 50%, therefore, modification must be carried out to PET, destroy the ordered structure of its molecule, obtain unbodied PET multipolymer, thus use as heat-shrinkable film.
Prior art discloses the multiple method being prepared by PET modification to heat-shrinkable film, be used alone m-phthalic acid (IPA) as Japanese Patent 63-139725,7-53737,7-216107 etc. disclose or be used alone 1,4 cyclohexane dimethanol (CHDM) to carry out modification method to PET; SKC Limited of Korea S discloses the method using dicarboxylic acid and diol component copolymerization to prepare shrink film, wherein, dicarboxylic acid is selected from terephthalic acid (PTA) or ester, m-phthalic acid (IPA) or ester, 2, one or more in 6-naphthalic acid or ester, SA, toxilic acid, pentanedioic acid, glycol be selected from ethylene glycol (EG), 1,3-PD, glycol ether, hexylene glycol one or more.Although above-mentioned method of modifying all can prepare the PET film of high shrinkage, obtain PET film fragility comparatively large, produce or easily rupture as in the use procedure of bottle label, causing yield rate low.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of modified poly ester and preparation method thereof, and the modified poly ester that the present invention prepares has higher shrinking percentage and lower fragility.
The invention provides a kind of modified poly ester, obtained by m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol copolymerization.
Preferably, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92.
Preferably, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 8 ~ 12:10 ~ 15:88 ~ 92:85 ~ 90.
Present invention also offers a kind of preparation method of modified poly ester, comprise the following steps:
M-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol are mixed, at 240 DEG C ~ 280 DEG C, carries out esterification, obtain esterification products;
Described esterification products is warming up to 250 DEG C ~ 290 DEG C and carries out polycondensation, obtain modified poly ester.
Preferably, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92.
Preferably, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92.
Preferably, described esterification is carried out under the condition stirred.
Preferably, described polycondensation is carried out under vacuum.
Preferably, described polycondensation is carried out under the condition stirred.
Compared with prior art, the present invention with m-phthalic acid and 1,4 cyclohexane dimethanol for properties-correcting agent carries out modification to PET, namely with m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol for obtaining PET multipolymer after material copolymerization reaction.M-phthalic acid and 1,4 cyclohexane dimethanol can not only improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility, make it as during bottle label, the phenomenons such as fracture can not occur, and improve yield rate.Result shows, the shrinking percentage of modified poly ester film provided by the invention more than 60%, longitudinal tensile strength at more than 60MPa, transverse tensile strength at more than 200MPa, longitudinal fracture elongation more than 500%, transverse breakage elongation more than 50%.In addition, can reduce costs for properties-correcting agent carries out modification to PET with m-phthalic acid and 1,4 cyclohexane dimethanol.
Embodiment
The invention provides a kind of modified poly ester, obtained by m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol copolymerization.
In the present invention, m-phthalic acid and 1,4 cyclohexane dimethanol can not only improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility, make it as during bottle label, the phenomenons such as fracture can not occur, and improve yield rate.
In the present invention, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is preferably 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92, is more preferably 8 ~ 12:10 ~ 15:88 ~ 92:85 ~ 90.Specifically, described terephthalic acid and ethylene glycol are as the main ingredient of synthesizing PET, and its mol ratio is preferably 1 ~ 2:1 ~ 2; Described m-phthalic acid and 1,4 cyclohexane dimethanol are as properties-correcting agent, and its mol ratio is preferably 1 ~ 2:1 ~ 2; Described terephthalic acid and m-phthalic acid total mole and described 1, the ratio of total mole of 4-cyclohexanedimethanol and ethylene glycol is preferably 1:0.95 ~ 1.05, be more preferably 1:1, wherein, the mol ratio of described m-phthalic acid and terephthalic acid is preferably 5 ~ 15:85 ~ 95, is more preferably 8 ~ 12:88 ~ 92; The mol ratio of described 1,4 cyclohexane dimethanol and ethylene glycol is preferably 8 ~ 20:80 ~ 92, is more preferably 10 ~ 15:85 ~ 90.
The fusing point of described modified poly ester is preferably 180 DEG C ~ 220 DEG C, is more preferably 190 DEG C ~ 210 DEG C; The viscosity of described modified poly ester is preferably 0.6dl/g ~ 0.8dl/g.
Present invention also offers a kind of preparation method of modified poly ester, comprise the following steps:
M-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol are mixed, at 240 DEG C ~ 280 DEG C, carries out esterification, obtain esterification products;
Described esterification products is warming up to 250 DEG C ~ 290 DEG C and carries out polycondensation, obtain modified poly ester.
The present invention with terephthalic acid and ethylene glycol for raw material, with m-phthalic acid and 1,4 cyclohexane dimethanol for modified poly ester prepared by properties-correcting agent.First m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol mix by the present invention, at 240 DEG C ~ 280 DEG C, carry out esterification.After esterifying kettle is preferably warming up to 240 DEG C by the present invention, add m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol wherein, continue to be warming up to 240 DEG C ~ 280 DEG C, be preferably warming up to 255 DEG C ~ 265 DEG C and carry out esterification.In order to esterification is complete, the present invention preferably carries out esterification under the condition stirred, and the time of described esterification is preferably 1h ~ 4h, is more preferably 2h ~ 3h.
In the present invention, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is preferably 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92, is more preferably 8 ~ 12:10 ~ 15:88 ~ 92:85 ~ 90.Specifically, described terephthalic acid and ethylene glycol are as the main ingredient of synthesizing PET, and its mol ratio is preferably 1 ~ 2:1 ~ 2; Described m-phthalic acid and 1,4 cyclohexane dimethanol are as properties-correcting agent, and its mol ratio is preferably 1 ~ 2:1 ~ 2; Described terephthalic acid and m-phthalic acid total mole and described 1, the ratio of total mole of 4-cyclohexanedimethanol and ethylene glycol is preferably 1:0.95 ~ 1.05, be more preferably 1:1, wherein, the mol ratio of described m-phthalic acid and terephthalic acid is preferably 5 ~ 15:85 ~ 95, is more preferably 8 ~ 12:88 ~ 92; The mol ratio of described 1,4 cyclohexane dimethanol and ethylene glycol is preferably 8 ~ 20:80 ~ 92, is more preferably 10 ~ 15:85 ~ 90.
In order to control the color of the modified poly ester obtained, the present invention preferably adds blue degree agent in the process of carrying out esterification.The present invention is not particularly limited the add-on of described blue degree agent and joining day, joining day well known to those skilled in the art and add-on.
After esterification, the esterification products obtained is continued be warming up to 250 DEG C ~ 290 DEG C and carry out polycondensation, obtain modified poly ester.Described polycondensation is preferably carried out under the condition of vacuum, stirring.Specifically, described esterification products is preferably imported polycondensation vessel by esterifying kettle by the present invention, starts slowly to vacuumize after being warming up to 250 DEG C, is then warming up to 250 DEG C ~ 290 DEG C and carries out polycondensation, and the temperature of described polycondensation is preferably 275 DEG C ~ 285 DEG C.
In the present invention, when carrying out polycondensation, preferably stir according to following steps:
First stir under the condition of 50HZ, 0.6kW, during 2.1kW to be achieved, reduce to 35HZ and continue to stir, during 2.0KW to be achieved, reduce to 25HZ, when frequency to be mixed reaches 1.8KW, stop stirring.
After polycondensation, modified poly ester can be obtained.The fusing point of described modified poly ester is preferably 180 DEG C ~ 220 DEG C, is more preferably 190 DEG C ~ 210 DEG C; The viscosity of described modified poly ester is preferably 0.6dl/g ~ 0.8dl/g.
After polycondensation, polycondensation vessel boosted to discharging after 0.2MPa with nitrogen, by reaction product after water-cooled well known to those skilled in the art, pelletizing, drying, obtain Modified polyester chips.
After obtaining Modified polyester chips, it is made film according to method well known to those skilled in the art, preferably masking in accordance with the following methods: modified poly ester is extruded through forcing machine after pre-crystallized, drying treatment, then on sharp cooling roll, slab is shaping, the slab that obtains is through longitudinal micro-stretching or do not stretch, rolling after cross directional stretch, to cut, and can obtain heat shrinkable polyester film.
After obtaining heat shrinkable polyester film, measure its shrinking percentage, tensile strength and elongation at break, result shows, its shrinking percentage is more than 60%, longitudinal tensile strength is at more than 60MPa, transverse tensile strength at more than 200MPa, longitudinal fracture elongation more than 500%, transverse breakage elongation more than 50%.
By described heat shrinkable polyester film for the production of bottle label, its yield rate is more than 99.8%.
The present invention with m-phthalic acid and 1,4 cyclohexane dimethanol for properties-correcting agent carries out modification to PET, namely with m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol for obtaining PET multipolymer after material copolymerization reaction.M-phthalic acid and 1,4 cyclohexane dimethanol can not only improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility, make it as during bottle label, the phenomenons such as fracture can not occur, and improve yield rate.
In order to understand the present invention further, below in conjunction with embodiment, modified poly ester provided by the invention and preparation method thereof is described in detail.
Embodiment 1
91.2g terephthalic acid, 8.8g m-phthalic acid, 87.14g ethylene glycol and 12.86g1,4-cyclohexanedimethanol are joined slurry configurator, stirs, obtain reaction mixture; Add above-mentioned reaction mixture wherein after reaction kettle of the esterification being warming up to 250 DEG C, heat up and start stirring, control still temperature between 240 DEG C ~ 280 DEG C, add blue degree agent, slowly release the esterification reaction product generated; Described esterification reaction product is joined in polycondensation vessel, be warming up to 260 DEG C of beginnings slowly to vacuumize, finally between 250 DEG C ~ 290 DEG C, carry out high vacuum polycondensation, stir while polycondensation, whipping process is as follows: first stir under the condition of 50HZ, 0.6kW, during 2.1kW to be achieved, reduce to 35HZ to continue to stir, during 2.0KW to be achieved, reduce to 25HZ, when frequency to be mixed reaches 1.8KW, stop stirring; With nitrogen, the pressure of polycondensation vessel is risen to 0.2MPa, open bleeder valve discharging, obtain modified poly ester, the fusing point of described modified poly ester is 190 DEG C, and viscosity is 0.75dl/g.
Described modified poly ester is obtained Modified polyester chips after water-cooled, pelletizing, drying, described Modified polyester chips is extruded through forcing machine after pre-crystallized, drying treatment, then on sharp cooling roll, slab is shaping, the slab obtained, through longitudinal 0.5 times of stretching, laterally 3.2 times of stretchings, obtains heat shrinkable polyester film.
The shrinking percentage of described heat shrinkable polyester film, tensile strength and elongation at break are tested, result see table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the present invention and comparative example.
Described heat shrinkable polyester film is used as bottle label, and its yield rate is 99.9%.
Embodiment 2
87g terephthalic acid, 13g m-phthalic acid, 85g ethylene glycol and 15g1,4-cyclohexanedimethanol are joined slurry configurator, stirs, obtain reaction mixture; Add above-mentioned reaction mixture wherein after reaction kettle of the esterification being warming up to 250 DEG C, heat up and start stirring, control still temperature between 240 DEG C ~ 280 DEG C, add blue degree agent, slowly release the esterification reaction product generated; Described esterification reaction product is joined in polycondensation vessel, be warming up to 260 DEG C of beginnings slowly to vacuumize, finally between 250 DEG C ~ 290 DEG C, carry out high vacuum polycondensation, stir while polycondensation, whipping process is as follows: first stir under the condition of 50HZ, 0.6kW, during 2.1kW to be achieved, reduce to 35HZ to continue to stir, during 2.0KW to be achieved, reduce to 25HZ, when frequency to be mixed reaches 1.8KW, stop stirring; With nitrogen, the pressure of polycondensation vessel is risen to 0.2MPa, open bleeder valve discharging, obtain modified poly ester, the fusing point of described modified poly ester is 195 DEG C, and viscosity is 0.76dl/g.
Described modified poly ester is obtained Modified polyester chips after water-cooled, pelletizing, drying, described Modified polyester chips is extruded through forcing machine after pre-crystallized, drying treatment, then on sharp cooling roll, slab is shaping, the slab obtained, through longitudinal 0.3 times of stretching, laterally 2.8 times of stretchings, obtains heat shrinkable polyester film.
The shrinking percentage of described heat shrinkable polyester film, tensile strength and elongation at break are tested, result see table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the present invention and comparative example.
Described heat shrinkable polyester film is used as bottle label, and its yield rate is 99.8%.
Comparative example 1
84g terephthalic acid, 16g m-phthalic acid and 100g ethylene glycol are joined slurry configurator, stirs, obtain reaction mixture; Add above-mentioned reaction mixture wherein after reaction kettle of the esterification being warming up to 250 DEG C, heat up and start stirring, control still temperature between 240 DEG C ~ 280 DEG C, add blue degree agent, slowly release the esterification reaction product generated; Described esterification reaction product is joined in polycondensation vessel, is warming up to 260 DEG C of beginnings and slowly vacuumizes, finally between 250 DEG C ~ 290 DEG C, carry out high vacuum polycondensation, react 3h under the condition of stirring and obtain modified poly ester.
Described modified poly ester is obtained Modified polyester chips after water-cooled, pelletizing, drying, described Modified polyester chips is extruded through forcing machine after pre-crystallized, drying treatment, then on sharp cooling roll, slab is shaping, the slab obtained, through longitudinal 0.5 times of stretching, laterally 3.2 times of stretchings, obtains heat shrinkable polyester film.
The shrinking percentage of described heat shrinkable polyester film, tensile strength and elongation at break are tested, result see table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the present invention and comparative example.
Described heat shrinkable polyester film is used as bottle label, and its yield rate is 98.8%.
Comparative example 2
100g terephthalic acid, 82g ethylene glycol and 18g1,4-cyclohexanedimethanol are joined slurry configurator, stirs, obtain reaction mixture; Add above-mentioned reaction mixture wherein after reaction kettle of the esterification being warming up to 250 DEG C, heat up and start stirring, control still temperature between 240 DEG C ~ 280 DEG C, add blue degree agent, slowly release the esterification reaction product generated; Described esterification reaction product is joined in polycondensation vessel, is warming up to 260 DEG C of beginnings and slowly vacuumizes, finally between 250 DEG C ~ 290 DEG C, carry out high vacuum polycondensation, react 3h under the condition of stirring and obtain modified poly ester.
Described modified poly ester is obtained Modified polyester chips after water-cooled, pelletizing, drying, described Modified polyester chips is extruded through forcing machine after pre-crystallized, drying treatment, then on sharp cooling roll, slab is shaping, the slab obtained, through longitudinal 0.5 times of stretching, laterally 3.2 times of stretchings, obtains heat shrinkable polyester film.
The shrinking percentage of described heat shrinkable polyester film, tensile strength and elongation at break are tested, result see table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the present invention and comparative example.
The mechanical property of the modified poly ester film that table 1 embodiment of the present invention and comparative example provide
As shown in Table 1, modified poly ester provided by the invention has higher shrinking percentage, tensile strength and elongation at break.
Described heat shrinkable polyester film is used as bottle label, and its yield rate is 98.5%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (6)
1. a modified poly ester, by m-phthalic acid, 1,4-cyclohexanedimethanol, terephthalic acid and ethylene glycol copolymerization obtain, and the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92.
2. modified poly ester according to claim 1, is characterized in that, the mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 8 ~ 12:10 ~ 15:88 ~ 92:85 ~ 90.
3. a preparation method for modified poly ester, comprises the following steps:
M-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol are mixed, at 240 DEG C ~ 280 DEG C, carries out esterification, obtain esterification products;
Described esterification products is warming up to 250 DEG C ~ 290 DEG C and carries out polycondensation, obtain modified poly ester;
The mol ratio of described m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol is 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92.
4. preparation method according to claim 3, is characterized in that, described esterification is carried out under the condition stirred.
5. preparation method according to claim 3, is characterized in that, described polycondensation is carried out under vacuum.
6. preparation method according to claim 3, is characterized in that, described polycondensation is carried out under the condition stirred.
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| CN104231239B (en) * | 2014-09-01 | 2016-05-04 | 湖北鼎龙化学股份有限公司 | Polymer blend and manufacture method thereof, binder resin and toner for developing electrostatic latent image |
| CN105885024B (en) * | 2016-05-26 | 2017-10-20 | 江苏景宏新材料科技有限公司 | A kind of flexible polyester heat shrink films and its production method |
| CN117002863A (en) * | 2022-04-28 | 2023-11-07 | 康美包（苏州）有限公司 | Packaging film, use thereof and baled article |
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| US6765070B2 (en) * | 2001-05-18 | 2004-07-20 | Mitsubishi Chemical Corporation | Copolymerized polyester resin composition and stretched film |
| US6599994B2 (en) * | 2001-07-18 | 2003-07-29 | Eastman Chemical Company | Polyester blends and heat shrinkable films made therefrom |
| CN1266189C (en) * | 2004-05-18 | 2006-07-26 | 南亚塑胶工业股份有限公司 | Copolymerized ester and method for making heat-shrinkable double-pipe using same |
| CN1817938A (en) * | 2006-03-03 | 2006-08-16 | 四川大学 | Production of polyester materials for high-shrinkage thin-film |
| CN101134820A (en) * | 2006-09-01 | 2008-03-05 | 远东纺织股份有限公司 | Thermal contracting polyester film and method for preparing same |
| CN102898793B (en) * | 2007-11-19 | 2015-06-24 | 可隆工业株式会社 | Thermo-shrinkable polyester film |
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