CN103570924A - Fast crystallized polyester and preparation method thereof - Google Patents
Fast crystallized polyester and preparation method thereof Download PDFInfo
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- CN103570924A CN103570924A CN201310620490.0A CN201310620490A CN103570924A CN 103570924 A CN103570924 A CN 103570924A CN 201310620490 A CN201310620490 A CN 201310620490A CN 103570924 A CN103570924 A CN 103570924A
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- zirconium boride
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Abstract
The invention relates to fast crystallized polyester which is characterized by containing nano zirconium boride with particle sizes ranging from 100 nm to 300 nm, wherein the weight content of the nano zirconium boride in the polyester accounts for 1%-5%. The fast crystallized polyester and the preparation method thereof have the advantages that the crystallization rate is high, the production and preparation process is not complicated, and superior physicochemical performance of the polyester can be maintained simultaneously.
Description
Technical field
The present invention relates to a kind of polyester with fast crystallization rate; Relate in particular to a kind of contain nanometer zirconium boride 99.5004323A8ure there is polyester of fast crystallization rate and preparation method thereof.
Background technology
Polyester is owing to having good mechanical property, wearability, creep resistant, and hardness is large, good rigidly, water-absorbent is little and good stability of the dimension, be widely used in fiber, film, sheet base and polyester bottles field, but also very limited as engineering plastics application, mainly to cause due to the slower crystallization rate of polyester and long shaping cycle, in addition the Tc of polyester is high, and its injection mould temperature reaches 150～180 ℃, so less economical.Under common molding processing temperature, crystallization rate is slow, and 160 ℃ of half-time of crystallization reach 62 seconds, has hindered its application in engineering plastics field.Make polyester successfully as engineering plastics, key is to accelerate the crystallization rate of polyester.
At present, the crystallization rate of quickening polyester mainly adopts following three kinds of methods: one, adopt the mode of blend in substrate polyester, to add nucleator and crystallization promoter; Two, adopt the mode of copolymerization in molecular chain, to access modified group; Three, in process of polyester synthesizing, add the materials such as Sodium Benzoate, polynite.But above three kinds of methods all have its weak point: method one nucleator and crystallization promoter are difficult to be uniformly dispersed, and in Blending Processes, can cause polyester degraded in matrix resin, affect the mechanical property of material; Method two is controlled and to be required highly polyester process, and after modified group access macromolecular chain, can change the physical and chemical performance of material, and the use range of material can be restricted; The additive of method three can reduce the rate of polymerization of polyester, and the limiting viscosity of gained polyester is generally difficult to reach service requirements.
Summary of the invention
For above-mentioned shortcoming, the object of the present invention is to provide a kind of fast crystallizing polyester, this anti-polyester had both had fast crystallization rate, and manufacture process is uncomplicated, can keep again the good physical and chemical performance of polyester itself simultaneously.
Technology contents of the present invention is: a kind of fast crystallizing polyester, and it is characterized by and in polyester, contain the nanometer zirconium boride 99.5004323A8ure that particle diameter is 100～300nm, the weight content of nanometer zirconium boride 99.5004323A8ure in polyester is 1～5%.
Another object of the present invention is to provide the preparation method of above-mentioned fast crystallizing polyester.
A preparation method for fast crystallizing polyester, its step is as follows
(1), nanometer zirconium boride 99.5004323A8ure surface treatment
Methacryloxypropyl trimethoxy silane is mixed and made mixed solution with ethylene glycol, its mass ratio is 1:10～1:20, the nanometer zirconium boride 99.5004323A8ure that is 100～300nm by particle diameter again adds in homogenizer, high-speed stirring 5～20 minutes, then after the above-mentioned mixed solution making being heated to 50～80 ℃, with Sprayable, add in high-speed mixer, whole adition process is 1～3 hour, the quality of nanometer zirconium boride 99.5004323A8ure is 5～10 times of straying quatity of mixed solution, obtains the nanometer zirconium boride 99.5004323A8ure that surface treatment is good;
(2), polyester is synthetic
The polyester pulp preparing is first carried out to esterification and obtain carboxylate, the time of esterification is that 2～4 hours, temperature are that 260～275 ℃, pressure are 0.5～3MPa; After esterification finishes, the good nanometer zirconium boride 99.5004323A8ure of above-mentioned surface treatment is joined in carboxylate, normal pressure stirs after 5～20 minutes and carries out polycondensation, the weight content that add-on is zirconium boride 99.5004323A8ure in final polyester slice is 1～5%, and polycondensation reaction time is that 2～4 hours, temperature are that 275～285 ℃, pressure are 20～40Pa; Polycondensation finishes with nitrogen, material to be extruded afterwards, through water-cooled, pelletizing, obtains fast crystallizing polyester.
In the preparation method of above-mentioned fast crystallizing polyester, the technique of allocating oar material when the polyester oar material of preparation adopts conventional production polyester, this oar material is usingd diprotic acid and the dibasic alcohol unit as essentially consist, be added with catalyzer, thermo-stabilizer simultaneously, diprotic acid is as terephthalic acid, m-phthalic acid or NDA etc.; Dibasic alcohol is as ethylene glycol, neopentyl glycol, cyclohexanedimethanol or glycol ether etc.; Catalyzer is as antimony acetate etc.; Thermo-stabilizer is as polyphosphoric acid, trimethyl phosphite 99 etc.
Advantage of the present invention:
The present invention adopts nanometer zirconium boride 99.5004323A8ure particle as crystallization nucleating agent, due to this particle, specific surface area is large after treatment, surface can be high, after adding in process of polyester synthesizing, can be dispersed in polyester matrix, the dispersed nanometer zirconium boride 99.5004323A8ure particle that contains in the polyester making making, because nanometer zirconium boride 99.5004323A8ure does not participate in chemical reaction and addition is very little, therefore can not have influence on the rate of polymerization of polyester, prepared polyester has rapid crystallization performance and can keep the good physical and chemical performance of polyester itself; This fast crystallizing polyester can be widely used in the fields such as engineering plastics, packing.
Embodiment
In the following example, nanometer zirconium boride 99.5004323A8ure is the nanometer zirconium boride 99.5004323A8ure that the particle diameter that Hefei Kaier Nano Energy Source Science Co., Ltd produces is 100nm～300nm.
Example 1,1g methacryloxypropyl trimethoxy silane is mixed with 11.5g ethylene glycol, 100g nanometer zirconium boride 99.5004323A8ure is added in homogenizer, high-speed stirring 10 minutes, then after the above-mentioned mixed solution making being heated to 60 ℃, with Sprayable, add in high-speed mixer, whole adition process 1.5 hours, obtains the nanometer zirconium boride 99.5004323A8ure that surface treatment is good;
It is that 270 ℃, pressure are under 2MPa condition, to carry out esterification, 2.5 hours reaction times that pure terephthalic acid 8.5KG, ethylene glycol 3.8L, catalyst acetic acid antimony 5.6g, thermo-stabilizer polyphosphoric acid 0.4g are configured to after slurry in temperature; After esterification finishes, the good nanometer zirconium boride 99.5004323A8ure of above-mentioned surface treatment is joined in carboxylate, normal pressure stirred after 10 minutes, in temperature, was that 280 ℃, pressure are under 20～40Pa condition, to carry out polycondensation, and the reaction times is 3 hours; Polycondensation finishes with nitrogen, material to be extruded afterwards, through water-cooled, pelletizing, obtains fast crystallizing polyester.In fast crystallizing polyester, the weight content of nanometer zirconium boride 99.5004323A8ure is 1%; In the time of 160 ℃, the half-time of crystallization of this fast crystallizing polyester is 50 seconds.
Example 2. is mixed 2.5g methacryloxypropyl trimethoxy silane with 35g ethylene glycol, 300g nanometer zirconium boride 99.5004323A8ure is added in homogenizer, high-speed stirring 10 minutes, then after the above-mentioned mixed solution making being heated to 60 ℃, with Sprayable, add in high-speed mixer, whole adition process 2 hours, obtains the nanometer zirconium boride 99.5004323A8ure that surface treatment is good;
It is that 270 ℃, pressure are under 2MPa condition, to carry out esterification, 2.5 hours reaction times that pure terephthalic acid 8.3KG, ethylene glycol 3.7L, catalyst acetic acid antimony 5.6g, thermo-stabilizer polyphosphoric acid 0.4g are configured to after slurry in temperature; After esterification finishes, the good nanometer zirconium boride 99.5004323A8ure of above-mentioned surface treatment is joined in carboxylate, normal pressure stirred after 10 minutes, in temperature, was that 280 ℃, pressure are under 20～40Pa condition, to carry out polycondensation, and the reaction times is 3 hours; Polycondensation finishes with nitrogen, material to be extruded afterwards, through water-cooled, pelletizing, obtains fast crystallizing polyester.In fast crystallizing polyester, the weight content of nanometer zirconium boride 99.5004323A8ure is 3%; In the time of 160 ℃, the half-time of crystallization of this fast crystallizing polyester is 36 seconds.
Example 3: 5g methacryloxypropyl trimethoxy silane is mixed with 57.5g ethylene glycol, 500g nanometer zirconium boride 99.5004323A8ure is added in homogenizer, high-speed stirring 10 minutes, then after the above-mentioned mixed solution making being heated to 60 ℃, with Sprayable, add in high-speed mixer, whole adition process 2.5 hours, obtains the nanometer zirconium boride 99.5004323A8ure that surface treatment is good;
It is that 270 ℃, pressure are under 2MPa condition, to carry out esterification, 2.5 hours reaction times that pure terephthalic acid 8.1KG, ethylene glycol 3.7L, catalyst acetic acid antimony 5.6g, thermo-stabilizer polyphosphoric acid 0.4g are configured to after slurry in temperature; After esterification finishes, the good nanometer zirconium boride 99.5004323A8ure of above-mentioned surface treatment is joined in carboxylate, normal pressure stirred after 10 minutes, in temperature, was that 280 ℃, pressure are under 20～40Pa condition, to carry out polycondensation, and the reaction times is 3 hours; Polycondensation finishes with nitrogen, material to be extruded afterwards, through water-cooled, pelletizing, obtains fast crystallizing polyester.In fast crystallizing polyester, the weight content of nanometer zirconium boride 99.5004323A8ure is 5%; In the time of 160 ℃, the half-time of crystallization of this fast crystallizing polyester is 29 seconds.
Claims (2)
1. a fast crystallizing polyester, is characterized by and in polyester, contain the nanometer zirconium boride 99.5004323A8ure that particle diameter is 100～300nm, and the weight content of nanometer zirconium boride 99.5004323A8ure in polyester is 1～5%.
2. a preparation method for fast crystallizing polyester, its step is as follows
(1), nanometer zirconium boride 99.5004323A8ure surface treatment
Methacryloxypropyl trimethoxy silane is mixed and made mixed solution with ethylene glycol, its mass ratio is 1:10～1:20, by particle diameter, be that 100～300nm nanometer zirconium boride 99.5004323A8ure adds in homogenizer again, high-speed stirring 5～20 minutes, then after the above-mentioned mixed solution making being heated to 50～80 ℃, with Sprayable, add in high-speed mixer, whole adition process is 1～3 hour, the quality of nanometer zirconium boride 99.5004323A8ure is 5～10 times of straying quatity of mixed solution, obtains the nanometer zirconium boride 99.5004323A8ure that surface treatment is good;
(2), polyester is synthetic
The polyester pulp preparing is first carried out to esterification and obtain carboxylate, the time of esterification is that 2～4 hours, temperature are that 260～275 ℃, pressure are 0.5～3MPa; After esterification finishes, the good nanometer zirconium boride 99.5004323A8ure of above-mentioned surface treatment is joined in carboxylate, normal pressure stirs after 5～20 minutes and carries out polycondensation, the weight content that add-on is zirconium boride 99.5004323A8ure in final polyester slice is 1～5%, and polycondensation reaction time is that 2～4 hours, temperature are that 275～285 ℃, pressure are 20～40Pa; Polycondensation finishes with nitrogen, material to be extruded afterwards, through water-cooled, pelletizing, obtains fast crystallizing polyester.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5138389A (en) * | 1974-09-30 | 1976-03-31 | Teijin Ltd | Horiesuteru no seizoho |
| CN1616518A (en) * | 2004-09-23 | 2005-05-18 | 上海交通大学 | Process for in-situ quiclely preparing crystalline polyester using nano silicon dioxide |
| CN101151314A (en) * | 2005-03-31 | 2008-03-26 | 伊士曼化工公司 | Polyester polymer and copolymer compositions containing particles of one or more transition metal compounds |
| CN101899201A (en) * | 2010-07-28 | 2010-12-01 | 江阴济化新材料有限公司 | Method for preparing PET (Polyethylene Terephthalate) engineering plastic particle of attapulgite fast crystallization |
| CN101948612A (en) * | 2010-10-18 | 2011-01-19 | 华润包装材料有限公司 | Antistatic polyester and preparation method thereof |
-
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- 2013-11-29 CN CN201310620490.0A patent/CN103570924B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5138389A (en) * | 1974-09-30 | 1976-03-31 | Teijin Ltd | Horiesuteru no seizoho |
| CN1616518A (en) * | 2004-09-23 | 2005-05-18 | 上海交通大学 | Process for in-situ quiclely preparing crystalline polyester using nano silicon dioxide |
| CN101151314A (en) * | 2005-03-31 | 2008-03-26 | 伊士曼化工公司 | Polyester polymer and copolymer compositions containing particles of one or more transition metal compounds |
| CN101899201A (en) * | 2010-07-28 | 2010-12-01 | 江阴济化新材料有限公司 | Method for preparing PET (Polyethylene Terephthalate) engineering plastic particle of attapulgite fast crystallization |
| CN101948612A (en) * | 2010-10-18 | 2011-01-19 | 华润包装材料有限公司 | Antistatic polyester and preparation method thereof |
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Address after: 213033 Jiangsu Changzhou City Xinbei District Chun Tong Town Comprehensive Industrial Park. Co-patentee after: Zhuhai Huarun Package Materials Co., Ltd. Patentee after: Huarun chemical Mstar Technology Ltd Address before: 213033 1 Xinyu East Road, Wei Tang Industrial Park, Xinbei District, Changzhou, Jiangsu Co-patentee before: Zhuhai Huarun Package Materials Co., Ltd. Patentee before: China Resources Packaging Materials Co., Ltd. |
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Address after: 213033 Jiangsu Changzhou City Xinbei District Chun Tong Town Comprehensive Industrial Park. Co-patentee after: ZHUHAI HUARUN PACKAGING MATERIALS Co.,Ltd. Patentee after: China Resources Chemical Materials Technology Co., Ltd Address before: 213033 Jiangsu Changzhou City Xinbei District Chun Tong Town Comprehensive Industrial Park. Co-patentee before: ZHUHAI HUARUN PACKAGING MATERIALS Co.,Ltd. Patentee before: CR CHEM-MAT TECHNOLOGY Co.,Ltd. |
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Address after: 213033 Jiangsu Changzhou City Xinbei District Chun Tong Town Comprehensive Industrial Park. Co-patentee after: Zhuhai Huarun Chemical Materials Technology Co.,Ltd. Patentee after: China Resources Chemical Materials Technology Co.,Ltd. Address before: 213033 Jiangsu Changzhou City Xinbei District Chun Tong Town Comprehensive Industrial Park. Co-patentee before: ZHUHAI HUARUN PACKAGING MATERIALS Co.,Ltd. Patentee before: China Resources Chemical Materials Technology Co.,Ltd. |
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