CN101875757B - Preparation method of polyethylene terephthalate/polyterephthalic glycol-1,4-cyclohexanedimethanol ester alloy - Google Patents
Preparation method of polyethylene terephthalate/polyterephthalic glycol-1,4-cyclohexanedimethanol ester alloy Download PDFInfo
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- CN101875757B CN101875757B CN200910083117XA CN200910083117A CN101875757B CN 101875757 B CN101875757 B CN 101875757B CN 200910083117X A CN200910083117X A CN 200910083117XA CN 200910083117 A CN200910083117 A CN 200910083117A CN 101875757 B CN101875757 B CN 101875757B
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Abstract
The invention relates to a preparation method of polyethylene terephthalate/polyterephthalic glycol-1,4-cyclohexanedimethanol ester polymer alloy. The method comprises the following steps of: drying polyterephthalic glycol-1,4-cyclohexanedimethanol ester in an electric heating air-blowing or vacuum dynamic mode at 70-75 DEG C for 10 hours, and drying bottle-grade polyethylene terephthalate chips at 120-125 DEG C for 10 hours; adding an ethylene-acetic acid ethylene copolymer which accounts for 2-10 wt% of the polyterephthalic glycol-1,4-cyclohexanedimethanol ester and polyethylene terephthalate; and blending the polyterephthalic glycol-1,4-cyclohexanedimethanol ester and the polyethylene terephthalate in a dual screw melting way to obtain the alloy, wherein the weight ratio of the polyterephthalic glycol-1,4-cyclohexanedimethanol ester to the polyethylene terephthalate is 30:70-50:50. The tensile property of the alloy is improved, and the elongation at break is enhanced to 116.4% from 3.8%.
Description
Technical field:
The invention belongs to the polymer alloy technology of preparing in the polymer modification, particularly relate to the preparation method of a kind of polyethylene terephthalate/poly terephthalic acid terepthaloyl moietie-1,4 cyclohexane dimethanol ester alloy.
Background technology:
Poly terephthalic acid terepthaloyl moietie-1; 4-cyclohexanedimethanoester ester (PETG copolyesters) is a kind of with pure terephthalic acid (PTA), terepthaloyl moietie (EG) and 1; 4-cyclohexanedimethanol (CHDM) is a basic raw material, a kind of new modified copolyester material that reaction makes through melt co-polycondensation.
The PETG copolyesters has the performance of a lot of excellences, is characterized in that the transparency is good, can be applicable to fields such as transparent plastics sheet material, sheet material, container bottle.At present, only there are U.S. Eastman company and Korea S SK company to have the production technology of this product in the world, and monopolized the whole market shares of China.Another approach that expansion PETG copolyester material is used in the plastics field is the operational path through melt blending, and preparation PETG polyblend is to satisfy the request for utilization of different application field plastics.In this regard, U.S. Eastman company had a lot of patent reports in the last few years, was main with the research and development of PETG/ polycarbonate (PC) alloy, and its main purpose is to improve the processing fluidity and the stress cracking resistance that improves the PC goods of PC.
Polyethylene terephthalate (PET) uses as engineering plastics, receives various restrictions for a long time.Because common processing mould temperature is in 70 ℃～110 ℃ scopes; The crystallization velocity of PET has caused crystallization imperfection and inhomogeneous too slowly; Cause prolong molding cycle, goods are prone to stick on the mould, and have produced shortcomings such as warpage, surface irregularity tarnish, shock-resistance and humidity resistance difference.
The superpolymer blending modification method is simple and easy to do; Very big advantage is arranged technically and economically, and it has not only kept the advantage of original superpolymer, owing to added new material; Give superpolymer new performance through changing aggregated structure, had certain theory and practical value.So blending and modifying is still nearly 2 years polymer modifications and uses one of maximum method, mainly for mechanical property, the particularly shock resistance etc. of the rheological property, crystal property and the material that improve co-mixing system.
In recent years, the research of PET and other polymer blending modifications is also more and more.Mainly contain Vilaterm (PE), Vestolen PP 7052 (PP), PS (PS), polybutylene terephthalate (PBT), polyamide (PA), polycarbonate (PC) etc.
People (Polymer such as Christina P; 1997; 38:631) thermodynamic compatibility of PET/PETG binary alloy material and the intermolecular interaction between the two have been reported; The result shows that PET and PETG have certain thermodynamic compatibility, and the mass percent of PETG has better consistency greater than 50% in blend.
Summary of the invention:
The object of the invention provides a kind of preparation method of PET/PETG polymer alloy.In the preparation process, add the toughner of the 3rd component as polymer alloy material; Improve the mechanical property of PET/PETG polymer alloy; Thereby expansion PETG copolyesters improves value-added content of product in the Industrial Application field, for preparation high performance PE T engineering plastics new approach is provided simultaneously.
The present invention is a basic raw material with PETG copolyesters and bottle level PET section, and preparation PET/PETG polymer alloy method may further comprise the steps:
(1) drying treatment
The section of PETG copolyesters and bottle level PET is carried out drying treatment with electric heating forced air drying or dynamic vacuum drying mode, the PETG copolyesters 70～75 ℃ dry 10 hours down, the bottle level PET section 120～125 ℃ dry 10 hours down;
(2) double-screw melt blending
Dried PETG copolyesters, bottle level PET section and toughner are mixed in high-speed mixer with certain part by weight; Adding the twin screw extruder opening for feed then melt extrudes; Each section of control twin screw extruder temperature: body temperature: 195～220 ℃ in a district, 230～250 ℃ in two districts, 240～265 ℃ in three districts; 250～270 ℃ in four districts, 250～270 ℃ in five districts; 250～260 ℃ of head temperatures, melt extrusion is after the water-cooled pelletizing makes the PET/PETG polymer alloy;
Described toughner is ethane-acetic acid ethyenyl (EVA) multipolymer;
The add-on of described EVA is EVA in 2%～10% of PETG copolyesters and bottle level PET section gross weight, is preferably 3%～6% and is benchmark.The weight ratio of PETG copolyesters and bottle level PET section is 30: 70～50: 50.
The invention effect:
The present invention is a basic raw material with PETG copolyesters and bottle level PET section, has prepared the PET/PETG polymer alloy with better mechanical property.Main innovate point of the present invention is through adding the 3rd component toughner in preparation PET/PETG polymer alloy process; Improve the tensile property of former PET/PETG polymer alloy; Improve elongation at break, thereby expansion PETG copolyesters improves value-added content of product in the Industrial Application field.
Embodiment
Explain through concrete embodiment below, but do not limit the present invention because of concrete embodiment.
Adopt the TE-35 twin screw extruder of inferior plastics machinery ltd of Nanjing section, through melt blending process route, preparation PET/PETG polymer alloy material;
The mechanical property that the CMT6104 electronic universal experimental machine that adopts the Chengde XJU-22 of trier factory impact experiment machine and Shenzhen Sans Material Detection Co., Ltd to produce is tested the PET/PETG alloy material.
Embodiment 1:
The section of PETG copolyesters and bottle level PET is carried out drying treatment with electric heating forced air drying mode, the PETG copolyesters 70 ℃ dry 10 hours down, the bottle level PET section 120 ℃ dry 10 hours down.
Take by weighing 2.4 kilograms of dried PET bottle grade pet chips, 1.6 kilograms of PETG copolyesters, EVA multipolymer 80 grams; Above-mentioned starting material are mixed in high-speed mixer, add the twin screw extruder opening for feed then and melt extrude, each section of control twin screw extruder temperature: 200 ℃ in body temperature one district; 240 ℃ in two districts; 260 ℃ in three districts, 265 ℃ in four districts, 265 ℃ in five districts; 260 ℃ of head temperatures.Melt extrusion is after water-cooled is passed through the dicing machine pelletizing then.On injection moulding machine, process standard test specimen after the pellet drying, behind the sample injection, balance was carried out Mechanics Performance Testing in 24 hours.The Mechanics Performance Testing result of above-mentioned PET/PETG polymer alloy material is following: breaking tenacity 56.4MPa, Young's modulus 1373MPa, elongation at break 83.1%.
Comparative example 1:
Take the drying process identical with embodiment 1.
Take by weighing 2.4 kilograms of dried PET bottle grade pet chips, 1.6 kilograms of PETG copolyesters mix above-mentioned starting material in high-speed mixer; Adding the twin screw extruder opening for feed then melt extrudes; Each section of control twin screw extruder temperature: 200 ℃ in body temperature one district, 240 ℃ in two districts, 260 ℃ in three districts; 265 ℃ in four districts, 265 ℃ in five districts; 260 ℃ of head temperatures.Melt extrusion is processed standard test specimen after water-cooled is passed through the dicing machine pelletizing then on injection moulding machine after the pellet drying, behind the sample injection, balance was carried out Mechanics Performance Testing in 24 hours.The Mechanics Performance Testing result of above-mentioned PET/PETG polymer alloy material is following: breaking tenacity 59.4MPa, Young's modulus 2104MPa, elongation at break 3.8%.
Embodiment 2:
The section of PETG copolyesters and bottle level PET is carried out drying treatment with the dynamic vacuum drying mode, the PETG copolyesters 75 ℃ dry 10 hours down, the bottle level PET section 125 ℃ dry 10 hours down.
Take by weighing 2.0 kilograms of dried PET bottle grade pet chips, 2.0 kilograms of PETG copolyesters, EVA multipolymer 200 grams; Above-mentioned starting material are mixed in high-speed mixer, add the twin screw extruder opening for feed then and melt extrude, each section of control twin screw extruder temperature: 195 ℃ in body temperature one district; 230 ℃ in two districts; 240 ℃ in three districts, 250 ℃ in four districts, 250 ℃ in five districts; 250 ℃ of head temperatures.Melt extrusion is after water-cooled is passed through the dicing machine pelletizing then.On injection moulding machine, process standard test specimen after the pellet drying, behind the sample injection, balance was carried out Mechanics Performance Testing in 24 hours.The Mechanics Performance Testing result of above-mentioned PET/PETG polymer alloy material is following: breaking tenacity 52.6MPa, Young's modulus 1959MPa, elongation at break 116.4%.
Embodiment 3:
The section of PETG copolyesters and bottle level PET is carried out drying treatment with the dynamic vacuum drying mode, the PETG copolyesters 73 ℃ dry 10 hours down, the bottle level PET section 122 ℃ dry 10 hours down.
Take by weighing 2.8 kilograms of dried PET bottle grade pet chips, 1.2 kilograms of PETG copolyesters, EVA multipolymer 400 grams; Above-mentioned starting material are mixed in high-speed mixer, add two spiral shell Du forcing machine opening for feeds then and melt extrude each section of control twin screw extruder temperature: 220 ℃ in body temperature one district; 250 ℃ in two districts; 265 ℃ in three districts, 270 ℃ in four districts, 270 ℃ in five districts; 260 ℃ of head temperatures.Melt extrusion is processed standard test specimen after water-cooled is passed through the dicing machine pelletizing then on injection moulding machine after the pellet drying, behind the sample injection, balance was carried out Mechanics Performance Testing in 24 hours.The Mechanics Performance Testing result of above-mentioned PET/PETG polymer alloy material is following: breaking tenacity 47.7MPa, Young's modulus 1997MPa, elongation at break 37.4%.
Claims (1)
1. the preparation method of polyethylene terephthalate/poly terephthalic acid terepthaloyl moietie-1,4 cyclohexane dimethanol ester alloy, it is characterized in that: this method may further comprise the steps:
(1) drying treatment
With poly terephthalic acid terepthaloyl moietie-1; 4-cyclohexanedimethanoester ester and polyethylene terephthalate carry out drying treatment with electric heating forced air drying or dynamic vacuum drying mode; Poly terephthalic acid terepthaloyl moietie-1; The 4-cyclohexanedimethanoester ester 70～75 ℃ dry 10 hours down, the section of a bottle level polyethylene terephthalate 120～125 ℃ dry 10 hours down;
(2) double-screw melt blending
With dried poly terephthalic acid terepthaloyl moietie-1; 4-cyclohexanedimethanoester ester, polyethylene terephthalate and toughner mix in high-speed mixer with certain part by weight, add the twin screw extruder opening for feed then and melt extrude, each section of control twin screw extruder temperature: body temperature: 195～220 ℃ in a district; 230～250 ℃ in two districts; 240～265 ℃ in three districts, 250～270 ℃ in four districts, 250～270 ℃ in five districts; 250～260 ℃ of head temperatures, melt extrusion is after the water-cooled pelletizing makes polyethylene terephthalate/poly terephthalic acid terepthaloyl moietie-1,4 cyclohexane dimethanol ester polymer alloy;
Described toughner is ethene-vinyl acetate copolymer;
The ethene-vinyl acetate copolymer add-on is poly terephthalic acid terepthaloyl moietie-1,4 cyclohexane dimethanol ester copolyesters and 2～10% of bottle level polyethylene terephthalate section gross weight; Poly terephthalic acid terepthaloyl moietie-1,4 cyclohexane dimethanol ester is 30: 70～50: 50 with the weight ratio of bottle level polyethylene terephthalate section.
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| CN101875757B true CN101875757B (en) | 2012-05-30 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102399422A (en) * | 2011-12-29 | 2012-04-04 | 上海金发科技发展有限公司 | Toughened polyethylene terephthalate glycol (PETG) material and preparation method thereof |
| CN112135856A (en) * | 2018-05-18 | 2020-12-25 | Sabic环球技术有限责任公司 | Composition comprising polyester and polyolefin |
| CN109808269A (en) * | 2019-01-25 | 2019-05-28 | 深圳市蓝云新型材料有限公司 | A kind of novel GAG material and preparation method thereof |
| CN111073234B (en) * | 2019-12-30 | 2022-04-08 | 浙江新力新材料股份有限公司 | Heat-resistant flame-retardant PET composite material, preparation method thereof and application thereof in preparation of patch board |
| TWI805030B (en) * | 2021-10-15 | 2023-06-11 | 南亞塑膠工業股份有限公司 | Polyester composition and manufacturing method thereof |
| CN114376701B (en) * | 2021-12-21 | 2023-02-14 | 长春圣博玛生物材料有限公司 | High-strength screw |
| CN115716978A (en) * | 2022-11-24 | 2023-02-28 | 中船重工鹏力（南京）塑造科技有限公司 | Cold-resistant PET plastic cup and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142239A (en) * | 1994-02-28 | 1997-02-05 | 伊斯曼化学公司 | High impact strength articles made from polyester blends |
| CN1670078A (en) * | 2004-03-19 | 2005-09-21 | 陈明华 | PET resin composition |
| CN1807486A (en) * | 2005-12-06 | 2006-07-26 | 中国石油天然气股份有限公司 | Preparation method for modified copolyester for non-fiber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142239A (en) * | 1994-02-28 | 1997-02-05 | 伊斯曼化学公司 | High impact strength articles made from polyester blends |
| CN1670078A (en) * | 2004-03-19 | 2005-09-21 | 陈明华 | PET resin composition |
| CN1807486A (en) * | 2005-12-06 | 2006-07-26 | 中国石油天然气股份有限公司 | Preparation method for modified copolyester for non-fiber |
Non-Patent Citations (1)
| Title |
|---|
| Christina P.，et al..Compatibility behaviour of blends of poly(ethylene terephthalate) with an amorphous copolyester.《Polymer》.1997,第38卷(第3期),第631-637页. * |
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