CN102964576A - Modified polyester and preparation method thereof - Google Patents
Modified polyester and preparation method thereof Download PDFInfo
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- CN102964576A CN102964576A CN2012105282927A CN201210528292A CN102964576A CN 102964576 A CN102964576 A CN 102964576A CN 2012105282927 A CN2012105282927 A CN 2012105282927A CN 201210528292 A CN201210528292 A CN 201210528292A CN 102964576 A CN102964576 A CN 102964576A
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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, relate in particular 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 the plastics tubing.Along with getting prosperous with every passing day of bottled drink market, bottle constantly enlarges with the demand of thermal shrink film label, and the demand quality constantly promotes.At present, the heat-shrinkable film that can be used as shrink label is mainly made by 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 good over-all properties, and still, the molecular chain of PET is arranged comparatively regular, crystal property is better, no matter adopt which kind of method processing, the PET film that obtains all is difficult to reach the requirement of shrinking greater than 50%, therefore, must carry out modification to PET, destroy the ordered structure of its molecule, obtain unbodied PET multipolymer, thereby use as heat-shrinkable film.
Prior art discloses that multiple modification prepares the method for heat-shrinkable film to PET, disclose independent use m-phthalic acid (IPA) or used separately 1,4 cyclohexane dimethanol (CHDM) that PET is carried out modification such as Japanese Patent 63-139725,7-53737,7-216107 etc.; Korea S SKC Limited discloses and has used dicarboxylic acid and diol component copolymerization to prepare the method for shrink film, wherein, dicarboxylic acid is selected from terephthalic acid (PTA) or ester, m-phthalic acid (IPA) or ester, 2, in 6-naphthalic acid or ester, SA, toxilic acid, the pentanedioic acid one or more, glycol is selected from one or more in ethylene glycol (EG), 1,3-PD, glycol ether, the hexylene glycol.Although above-mentioned method of modifying all can prepare the PET film of high shrinkage, it is larger to obtain PET film fragility, produces or conduct bottle easy fracture in the label use procedure, causes 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.
The present invention also provides a kind of preparation method of modified poly ester, may further comprise the steps:
M-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol are mixed, under 240 ℃ ~ 280 ℃, carry out esterification, obtain esterification products;
Described esterification products is warming up to 250 ℃ ~ 290 ℃ 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 that stirs.
Preferably, described polycondensation is carried out under vacuum condition.
Preferably, described polycondensation is carried out under the condition that stirs.
Compared with prior art, the present invention carries out modification take m-phthalic acid and 1,4 cyclohexane dimethanol as properties-correcting agent to PET, namely obtains the PET multipolymer take m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol as material copolymerization after the reaction.M-phthalic acid and 1,4 cyclohexane dimethanol not only can improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility, make its as bottle can fracture when the label etc. phenomenon, improve yield rate.The result shows, the shrinking percentage of modified poly ester film provided by the invention is more than 60%, longitudinal tensile strength more than 60MPa, transverse tensile strength more than 200MPa, the longitudinal fracture elongation more than 500%, the transverse breakage elongation is more than 50%.In addition, as carrying out modification to PET, properties-correcting agent can reduce cost take 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 not only can improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility, make its as bottle can fracture when the label etc. phenomenon, 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, more preferably 8 ~ 12:10 ~ 15:88 ~ 92:85 ~ 90.Particularly, described terephthalic acid and ethylene glycol are as the main ingredient of synthetic 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; Total mole of described terephthalic acid and m-phthalic acid is with described 1, total mole ratio of 4-cyclohexanedimethanol and ethylene glycol is preferably 1:0.95～1.05,1:1 more preferably, wherein, the mol ratio of described m-phthalic acid and terephthalic acid is preferably 5 ~ 15:85 ~ 95, more preferably 8 ~ 12:88 ~ 92; The mol ratio of described 1,4 cyclohexane dimethanol and ethylene glycol is preferably 8 ~ 20:80 ~ 92, more preferably 10 ~ 15:85 ~ 90.
The fusing point of described modified poly ester is preferably 180 ℃ ~ 220 ℃, more preferably 190 ℃ ~ 210 ℃; The viscosity of described modified poly ester is preferably 0.6dl/g ~ 0.8dl/g.
The present invention also provides a kind of preparation method of modified poly ester, may further comprise the steps:
M-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol are mixed, under 240 ℃ ~ 280 ℃, carry out esterification, obtain esterification products;
Described esterification products is warming up to 250 ℃ ~ 290 ℃ carries out polycondensation, obtain modified poly ester.
The present invention is take terephthalic acid and ethylene glycol as raw material, prepares modified poly ester take m-phthalic acid and 1,4 cyclohexane dimethanol as properties-correcting agent.The present invention at first mixes m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol, carries out esterification under 240 ℃ ~ 280 ℃.After the present invention preferably is warming up to 240 ℃ with esterifying kettle, to wherein adding m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol, continue to be warming up to 240 ℃ ~ 280 ℃, preferably be warming up to 255 ℃ ~ 265 ℃ and carry out esterification.Complete for esterification, the present invention preferably carries out esterification under the condition that stirs, and the time of described esterification is preferably 1h ~ 4h, 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, more preferably 8 ~ 12:10 ~ 15:88 ~ 92:85 ~ 90.Particularly, described terephthalic acid and ethylene glycol are as the main ingredient of synthetic 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; Total mole of described terephthalic acid and m-phthalic acid is with described 1, total mole ratio of 4-cyclohexanedimethanol and ethylene glycol is preferably 1:0.95 ~ 1.05,1:1 more preferably, wherein, the mol ratio of described m-phthalic acid and terephthalic acid is preferably 5 ~ 15:85 ~ 95, more preferably 8 ~ 12:88 ~ 92; The mol ratio of described 1,4 cyclohexane dimethanol and ethylene glycol is preferably 8 ~ 20:80 ~ 92, more preferably 10 ~ 15:85 ~ 90.
In order to control the color of the modified poly ester that obtains, the present invention preferably adds blue degree agent in the process of carrying out esterification.The present invention does not have particular restriction to add-on and the joining day of described blue degree agent, and joining day well known to those skilled in the art and add-on get final product.
After esterification is complete, the esterification products that obtains is continued to be warming up to 250 ℃ ~ 290 ℃ carry out polycondensation, obtain modified poly ester.Described polycondensation is preferably carried out under the condition of vacuum, stirring.Particularly, the present invention preferably imports polycondensation vessel with described esterification products by esterifying kettle, begins slowly to vacuumize after being warming up to 250 ℃, then is warming up to 250 ℃ ~ 290 ℃ and carries out polycondensation, and the temperature of described polycondensation is preferably 275 ℃ ~ 285 ℃.
In the present invention, when carrying out polycondensation, preferably stir according to following steps:
At first under the condition of 50HZ, 0.6kW, stir, during 2.1kW to be reached, reduce to 35HZ and continue to stir, during 2.0KW to be reached, reduce to 25HZ, when treating that stirring frequency reaches 1.8KW, stop to stir.
After polycondensation is complete, can obtain modified poly ester.The fusing point of described modified poly ester is preferably 180 ℃ ~ 220 ℃, more preferably 190 ℃ ~ 210 ℃; The viscosity of described modified poly ester is preferably 0.6dl/g ~ 0.8dl/g.
After polycondensation is complete, with nitrogen polycondensation vessel is boosted to discharging behind the 0.2MPa, with reaction product through water-cooled well known to those skilled in the art, pelletizing, drying after, obtain Modified polyester chips.
After obtaining Modified polyester chips, it is made film according to method well known to those skilled in the art, preferred masking in accordance with the following methods: modified poly ester is extruded by forcing machine through pre-crystallized, drying treatment, then slab moulding on sharp cooling roll, the slab that obtains is through vertical little stretching or do not stretch, rolling after the cross directional stretch, cut, and can obtain heat shrinkable polyester film.
After obtaining heat shrinkable polyester film, measure its shrinking percentage, tensile strength and elongation at break, the result shows, its shrinking percentage is more than 60%, longitudinal tensile strength is more than 60MPa, transverse tensile strength more than 200MPa, the longitudinal fracture elongation more than 500%, the transverse breakage elongation is more than 50%.
For the production of the bottle label, its yield rate is more than 99.8% with described heat shrinkable polyester film.
The present invention carries out modification take m-phthalic acid and 1,4 cyclohexane dimethanol as properties-correcting agent to PET, namely obtains the PET multipolymer take m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol as material copolymerization after the reaction.M-phthalic acid and 1,4 cyclohexane dimethanol not only can improve the shrinking percentage of modified poly ester as properties-correcting agent, and can reduce its fragility, make its as bottle can fracture when the label etc. phenomenon, improve yield rate.
In order further to understand the present invention, below in conjunction with embodiment modified poly ester provided by the invention and preparation method thereof is elaborated.
Embodiment 1
With 91.2g terephthalic acid, 8.8g m-phthalic acid, 87.14g ethylene glycol and 12.86g1, the 4-cyclohexanedimethanol joins the slurry configurator, stirs, and obtains reaction mixture; Reaction kettle of the esterification is warming up to 250 ℃ backwardly wherein adds above-mentioned reaction mixture, heat up and start stirring, control still temperature adds blue degree agent between 240 ℃ ~ 280 ℃, slowly emit the esterification reaction product of generation; Described esterification reaction product is joined in the polycondensation vessel, being warming up to 260 ℃ of beginnings slowly vacuumizes, finally carry out the high vacuum polycondensation between 250 ℃ ~ 290 ℃, stir in the time of polycondensation, whipping process is as follows: at first stir under the condition of 50HZ, 0.6kW, during 2.1kW to be reached, reduce to 35HZ and continue to stir, during 2.0KW to be reached, reduce to 25HZ, when treating that stirring frequency reaches 1.8KW, stop to stir; With nitrogen the pressure of polycondensation vessel is risen to 0.2MPa, open the bleeder valve discharging, obtain modified poly ester, the fusing point of described modified poly ester is 190 ℃, 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 by forcing machine through pre-crystallized, drying treatment, then slab moulding on sharp cooling roll, the slab that obtains obtains heat shrinkable polyester film through vertical 0.5 times of stretching, horizontal 3.2 times of stretchings.
Shrinking percentage, tensile strength and elongation at break to described heat shrinkable polyester film are tested, and the result is referring to table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the invention and comparative example.
It is 99.9% that described heat shrinkable polyester film is used label, its yield rate as bottle.
Embodiment 2
With 87g terephthalic acid, 13g m-phthalic acid, 85g ethylene glycol and 15g1, the 4-cyclohexanedimethanol joins the slurry configurator, stirs, and obtains reaction mixture; Reaction kettle of the esterification is warming up to 250 ℃ backwardly wherein adds above-mentioned reaction mixture, heat up and start stirring, control still temperature adds blue degree agent between 240 ℃ ~ 280 ℃, slowly emit the esterification reaction product of generation; Described esterification reaction product is joined in the polycondensation vessel, being warming up to 260 ℃ of beginnings slowly vacuumizes, finally carry out the high vacuum polycondensation between 250 ℃ ~ 290 ℃, stir in the time of polycondensation, whipping process is as follows: at first stir under the condition of 50HZ, 0.6kW, during 2.1kW to be reached, reduce to 35HZ and continue to stir, during 2.0KW to be reached, reduce to 25HZ, when treating that stirring frequency reaches 1.8KW, stop to stir; With nitrogen the pressure of polycondensation vessel is risen to 0.2MPa, open the bleeder valve discharging, obtain modified poly ester, the fusing point of described modified poly ester is 195 ℃, 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 by forcing machine through pre-crystallized, drying treatment, then slab moulding on sharp cooling roll, the slab that obtains obtains heat shrinkable polyester film through vertical 0.3 times of stretching, horizontal 2.8 times of stretchings.
Shrinking percentage, tensile strength and elongation at break to described heat shrinkable polyester film are tested, and the result is referring to table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the invention and comparative example.
It is 99.8% that described heat shrinkable polyester film is used label, its yield rate as bottle.
Comparative example 1
84g terephthalic acid, 16g m-phthalic acid and 100g ethylene glycol are joined the slurry configurator, stir, obtain reaction mixture; Reaction kettle of the esterification is warming up to 250 ℃ backwardly wherein adds above-mentioned reaction mixture, heat up and start stirring, control still temperature adds blue degree agent between 240 ℃ ~ 280 ℃, slowly emit the esterification reaction product of generation; Described esterification reaction product is joined in the polycondensation vessel, be warming up to 260 ℃ of beginnings and slowly vacuumize, finally carry out the high vacuum polycondensation between 250 ℃ ~ 290 ℃, reaction 3h obtains modified poly ester under the condition of stirring.
Described modified poly ester is obtained Modified polyester chips after water-cooled, pelletizing, drying, described Modified polyester chips is extruded by forcing machine through pre-crystallized, drying treatment, then slab moulding on sharp cooling roll, the slab that obtains obtains heat shrinkable polyester film through vertical 0.5 times of stretching, horizontal 3.2 times of stretchings.
Shrinking percentage, tensile strength and elongation at break to described heat shrinkable polyester film are tested, and the result is referring to table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the invention and comparative example.
It is 98.8% that described heat shrinkable polyester film is used label, its yield rate as bottle.
Comparative example 2
With 100g terephthalic acid, 82g ethylene glycol and 18g1, the 4-cyclohexanedimethanol joins the slurry configurator, stirs, and obtains reaction mixture; Reaction kettle of the esterification is warming up to 250 ℃ backwardly wherein adds above-mentioned reaction mixture, heat up and start stirring, control still temperature adds blue degree agent between 240 ℃ ~ 280 ℃, slowly emit the esterification reaction product of generation; Described esterification reaction product is joined in the polycondensation vessel, be warming up to 260 ℃ of beginnings and slowly vacuumize, finally carry out the high vacuum polycondensation between 250 ℃ ~ 290 ℃, reaction 3h obtains modified poly ester under the condition of stirring.
Described modified poly ester is obtained Modified polyester chips after water-cooled, pelletizing, drying, described Modified polyester chips is extruded by forcing machine through pre-crystallized, drying treatment, then slab moulding on sharp cooling roll, the slab that obtains obtains heat shrinkable polyester film through vertical 0.5 times of stretching, horizontal 3.2 times of stretchings.
Shrinking percentage, tensile strength and elongation at break to described heat shrinkable polyester film are tested, and the result is referring to table 1, the mechanical property of the modified poly ester film that table 1 provides for the embodiment of the invention and comparative example.
The mechanical property of the modified poly ester film that table 1 embodiment of the 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.
It is 98.5% that described heat shrinkable polyester film is used label, its yield rate as bottle.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (9)
1. a modified poly ester is obtained by m-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol copolymerization.
2. method 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 5 ~ 15:8 ~ 20:85 ~ 95:80 ~ 92.
3. method according to claim 2 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.
4. the preparation method of a modified poly ester may further comprise the steps:
M-phthalic acid, 1,4 cyclohexane dimethanol, terephthalic acid and ethylene glycol are mixed, under 240 ℃ ~ 280 ℃, carry out esterification, obtain esterification products;
Described esterification products is warming up to 250 ℃ ~ 290 ℃ carries out polycondensation, obtain modified poly ester.
5. preparation method according to claim 4 is characterized in that, 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.
6. preparation method according to claim 5 is characterized in that, 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.
7. preparation method according to claim 4 is characterized in that, described esterification is carried out under the condition that stirs.
8. preparation method according to claim 4 is characterized in that, described polycondensation is carried out under vacuum condition.
9. preparation method according to claim 4 is characterized in that, described polycondensation is carried out under the condition that stirs.
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| CN104231239A (en) * | 2014-09-01 | 2014-12-24 | 湖北鼎龙化学股份有限公司 | Polyester composition and manufacturing method thereof, bonding resin and color matching agent for electrostatic charge image development |
| CN105885024A (en) * | 2016-05-26 | 2016-08-24 | 江苏景宏新材料科技有限公司 | Flexible polyester thermal contraction membrane and production method thereof |
| CN115491000A (en) * | 2021-06-18 | 2022-12-20 | 内蒙古伊利实业集团股份有限公司 | Low-temperature high-toughness polyester shrink film for heat-shrinkable label and preparation method and application thereof |
| WO2023206970A1 (en) * | 2022-04-28 | 2023-11-02 | 康美包（苏州）有限公司 | Packaging structure, packaging method, packaging device, and storage medium |
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| CN102964576B (en) | 2015-04-01 |
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