CN101709121A - Composite nucleating agent of polyethylene glycol terephthalate and preparation method thereof - Google Patents
Composite nucleating agent of polyethylene glycol terephthalate and preparation method thereof Download PDFInfo
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- CN101709121A CN101709121A CN200910309652A CN200910309652A CN101709121A CN 101709121 A CN101709121 A CN 101709121A CN 200910309652 A CN200910309652 A CN 200910309652A CN 200910309652 A CN200910309652 A CN 200910309652A CN 101709121 A CN101709121 A CN 101709121A
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Abstract
The invention provides a composite nucleating agent of polyethylene glycol terephthalate and a preparation method thereof. The composite nucleating agent comprises the following components in part by weight: 10 to 30 parts of superfine mineral powder, 10 to 40 parts of solid PEG, 20 to 50 parts of ionic bond polymer and 5 to 40 parts of sodium benzoate. After the composite nucleating agent provided by the invention is used, the effects of quick crystallization, low die temperature and high heat resistance of a PET material can be achieved.
Description
Technical field
The present invention relates to a kind of nucleator, relate to the composite nucleating agent of a kind of polyethylene terephthalate (PET) particularly.
Background technology
Nucleator is a kind of degree of crystallinity that is used for changing the imperfect crystal fluoropolymer resin, accelerate the processing modified adjuvant of its crystallization rate, its effect is by add some crystalline material of people in polymer melt, make melt heterogeneous nucleation under comparatively high temps, improve crystallization rate, make polymkeric substance at high temperature be easy to cure and demold simultaneously, thereby shorten the process-cycle, and improve quality of item.The application of nucleator in polymer processing can increase the occurrence probability of heterogeneous nucleation, improves processing characteristics, can improve the application performance of goods again simultaneously.
Polyethylene terephthalate (PET) plastics wide material sources, low price, so its usage quantity of excellent property increases year by year, owing to there being benzene ring structure to make its mobility relatively poor in the PET molecule, adding generally needs the adding softening agent to reduce second-order transition temperature man-hour, increases flowability, adds nucleator simultaneously to speed its crystallization rate, thereby improve the processing conditions of PET, the broadened application scope.
Domestic most of PET modified engineered plastic products are compared (as the FR530 of Du Pont) with external famous brand name at present, all there is the gap that differs in size at aspects such as fast crystallization, low mould temperature, thermotolerance, high tenacity and reclaimings, cause external product to occupy clear superiority in middle and high-end market, in recent years, domestic this situation was for a change carried out many research and development, but the performance lulu is quite rare in the product of market.This wherein major reason be that the nucleating systems of domestic PET is perfect not enough, with the certain gap of external existence.The nucleator kind of using is a lot of at present, and inorganic nucleator, organic nucleating agent and polymer nucleator are arranged, and they all have certain nucleating effect, but all exist deficiency to a certain extent.
Summary of the invention
The object of the present invention is to provide the composite nucleating agent of a kind of polyethylene terephthalate (PET), to solve the above-mentioned problems in the prior art.After adding composite nucleating agent provided by the invention, can reach the fast crystallization of PET material, low mould temperature, high heat-stable effect.
Another object of the present invention provides a kind of preparation method of above-mentioned composite nucleating agent.
Technical scheme provided by the invention is as follows:
The composite nucleating agent of a kind of polyethylene terephthalate (PET), it is characterized in that it comprises following components in portion by weight: 5～40 parts of 10～30 parts of super finely ground slags, 10～40 parts of solid polyethylene glycols (PEG), 20～50 parts of iolons and phenylformic acid sodium salts.
In the embodiment that recommends, described super finely ground slag is at least a in talcum powder, barium sulfate, Calucium Silicate powder or the Magnesium Silicate q-agent, and the maximum particle diameter of talcum powder, barium sulfate, Calucium Silicate powder or Magnesium Silicate q-agent is all smaller or equal to 10 μ m.
In the embodiment that recommends, described iolon is ethylene/methacrylic acid zinc salt ionomer, ethylene/methacrylic acid lithium salts ionomer or ethylene/propene acid sodium-salt ionomer.
In the embodiment that recommends, described phenylformic acid sodium salt is Sodium Benzoate, terephthalic acid methyl esters monocarboxylic acid sodium or P-hydroxybenzoic acid sodium.
In the embodiment that recommends, the molecular weight distribution of described polyoxyethylene glycol is between 2000～20000.
The preparation method of a kind of polyethylene terephthalate (PET) composite nucleating agent, it is characterized in that: after ball milling becomes uniform powder-like product in super finely ground slag, iolon, polyoxyethylene glycol and the phenylformic acid sodium salt adding ball mill of above-mentioned weight proportion, cross 100 eye mesh screens and obtain.
In the embodiment that recommends, the speed of ball mill ball milling is 30～450 rev/mins, and the ball milling time is 1～5 hour.
Compared with prior art, the present invention has following characteristics:
1) the PET composite nucleating agent of the present invention's preparation can be used for all PET matrix materials, comprises that PET adds the nucleating systems of materials such as fibre, PET fibre-added fire-retardant, PET/PBT alloy;
2) this composite nucleating agent has overcome the deficiency of single kind of nucleator, combines the advantage of all kinds of nucleators, has that nucleating effect is good, consumption is little, good dispersity, helps the raising of PET material property;
3) only need to add the composite nucleating agent that accounts for PET matrix material gross weight 0.5～1%, just can reach the fast crystallization of PET material, low mould temperature, high heat-stable effect.
Embodiment
Embodiment 1
Take by weighing talcum powder 20g, PEG-200010g, ethylene/propene acid sodium-salt ionomer (Dupont Surlyn 1601) 40g and the Sodium Benzoate 30g of maximum particle diameter less than 2 μ m, pour in the ball mill, after 2 hours, obtain powdered PET composite nucleating agent behind 100 eye mesh screens with 150 rev/mins of ball millings excessively at ball mill.
Embodiment 2
Take by weighing ultra-fine barium sulfate 30g, PEG-400020g, ethylene/methacrylic acid zinc salt ionomer (Dupont Surlyn8920) 20g and the terephthalic acid methyl esters monocarboxylic acid sodium 10g of maximum particle diameter less than 5 μ m, pour in the ball mill, after 1 hour, obtain powdered PET composite nucleating agent behind 100 eye mesh screens with 450 rev/mins of ball millings excessively at ball mill.
Embodiment 3
Take by weighing Calucium Silicate powder 20g, PEG-600020g, ethylene/propene acid sodium-salt ionomer (Dupont Surlyn 1601) 30g and the P-hydroxybenzoic acid sodium 40g of maximum particle diameter less than 10 μ m, after 4 hours, obtain powdered PET composite nucleating agent behind 100 eye mesh screens with 300 rev/mins of ball millings excessively at ball mill.
Embodiment 4
Take by weighing Magnesium Silicate q-agent 30g, PEG-1000010g, ethylene/methacrylic acid zinc salt ionomer (Dupont Surlyn8920) 40g and the terephthalic acid methyl esters monocarboxylic acid sodium 20g of maximum particle diameter less than 2 μ m, pour in the ball mill, after 1.5 hours, obtain powdered PET composite nucleating agent behind 100 eye mesh screens with 250 rev/mins of ball millings excessively at ball mill.
Embodiment 5
Take by weighing the Magnesium Silicate q-agent 10g of maximum particle diameter less than 2 μ m, PEG-2000 40g, ethylene/methacrylic acid zinc salt ionomer (Dupont Surlyn8920) 50g and Sodium Benzoate 5g, pour in the ball mill, after 5 hours, obtain powdered PET composite nucleating agent behind 100 eye mesh screens with 50 rev/mins of ball millings excessively at ball mill.
The test example
This test example has been investigated the effect of composite nucleating agent in the PET engineering plastics that makes among embodiment 1～embodiment 5:
The composite nucleating agent that makes among prescription consumption weighing PET resin, antioxidant 1010, oxidation inhibitor 168, Beijing glass and the embodiment 1～embodiment 5 by table 1, PET, antioxidant 1010, oxidation inhibitor 168 and composite nucleating agent after mixing, high-speed mixer are added in the TE-34 type twin screw extruder, add glass (glass usage quantity account for prescription gross weight 30%) back extruding pelletization from the glass mouth of forcing machine again, extrusion temperature is 240 ℃.Then gained material grain is injection molded into the standard batten through ST 125 type injection moulding machines, injection temperature is 250 ℃.The batten of gained is respectively No. 0 (not adding composite nucleating agent), No. 1 (adding embodiment 1 composite nucleating agent), No. 2 (adding embodiment 2 composite nucleating agents), No. 3 (adding embodiment 3 composite nucleating agents), No. 4 (adding embodiment 4 composite nucleating agents) and No. 5 (adding embodiment 5 composite nucleating agents).
Prescription/the g of table 1PET matrix material
Respectively 0～No. 5 batten is pressed ASTMD638 standard testing sample tensile strength, press ASTM D256 standard testing sample simply supported beam notched Izod impact strength, press ASTM790 standard testing sample modulus in flexure, press ASTM D648 standard testing heat-drawn wire, and 0～No. 5 sample is carried out DSC test, gained the results are shown in table 2.
The performance of table 26 kind of PET matrix material sample
As can be seen from Table 2:
Use the composite nucleating agent of the embodiment of the invention 1, the tensile strength of the PET matrix material that obtains improves 12.5%, shock strength improves 8.3%, modulus in flexure improves 11.8%, and heat-drawn wire improves 35 ℃, in the DSC data, the thermal crystalline temperature improves 25 ℃, the cold crystallization peak disappears, the high 0.44MW/mg of half-peak, and peak width at half height reduces 19.7 ℃.
Use the composite nucleating agent of the embodiment of the invention 2, the tensile strength of the PET matrix material that obtains improves 14.2%, shock strength improves 8.3%, modulus in flexure improves 14.3%, and heat-drawn wire improves 40 ℃, in the DSC data, the thermal crystalline temperature improves 30 ℃, the cold crystallization peak disappears, the high 0.42MW/mg of half-peak, and peak width at half height reduces 21.4 ℃.
Use the composite nucleating agent of the embodiment of the invention 3, the tensile strength of the PET matrix material that obtains improves 8.3%, shock strength improves 6.7%, modulus in flexure improves 10.1%, and heat-drawn wire improves 38 ℃, in the DSC data, the thermal crystalline temperature improves 32 ℃, the cold crystallization peak disappears, the high 0.33MW/mg of half-peak, and peak width at half height reduces 21.2 ℃.
Use the composite nucleating agent of the embodiment of the invention 4, the tensile strength of the PET matrix material that obtains improves 15.8%, shock strength improves 13.3%, modulus in flexure improves 20.1%, and heat-drawn wire improves 36 ℃, in the DSC data, the thermal crystalline temperature improves 36 ℃, the cold crystallization peak disappears, the high 0.51MW/mg of half-peak, and peak width at half height reduces 20.4 ℃.
Use the composite nucleating agent of the embodiment of the invention 5, the tensile strength of the PET matrix material that obtains improves 8.3%, shock strength improves 6.7%, modulus in flexure improves 11.7%, and heat-drawn wire improves 31 ℃, in the DSC data, the thermal crystalline temperature improves 31 ℃, the cold crystallization peak disappears, the high 0.43MW/mg of half-peak, and peak width at half height reduces 20.8 ℃.
Can sum up from the data of table 2, use PET composite nucleating agent of the present invention, can obviously improve the mechanical property of matrix material, and help the perfect of PET crystal property, thereby reach fast crystallization, low mould temperature, high heat-stable performance.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the composite nucleating agent of a polyethylene terephthalate is characterized in that, it comprises following components in portion by weight: 5～40 parts of 10～30 parts of super finely ground slags, 10～40 parts of solid polyethylene glycols, 20～50 parts of iolons and phenylformic acid sodium salts.
2. according to the composite nucleating agent of a kind of polyethylene terephthalate described in the claim 1, it is characterized in that: described super finely ground slag is at least a in talcum powder, barium sulfate, Calucium Silicate powder or the Magnesium Silicate q-agent, and the maximum particle diameter of talcum powder, barium sulfate, Calucium Silicate powder or Magnesium Silicate q-agent is all smaller or equal to 10 μ m.
3. according to the composite nucleating agent of a kind of polyethylene terephthalate described in the claim 2, it is characterized in that: described iolon is ethylene/methacrylic acid zinc salt ionomer, ethylene/methacrylic acid lithium salts ionomer or ethylene/propene acid sodium-salt ionomer.
4. according to the composite nucleating agent of a kind of polyethylene terephthalate described in the claim 3, it is characterized in that: described phenylformic acid sodium salt is Sodium Benzoate, terephthalic acid methyl esters monocarboxylic acid sodium or P-hydroxybenzoic acid sodium.
5. according to the composite nucleating agent of a kind of polyethylene terephthalate described in the claim 4, it is characterized in that: the molecular weight distribution of described polyoxyethylene glycol is between 2000～20000.
6. the preparation method of a polyethylene terephthalate composite nucleating agent, it is characterized in that: after ball milling becomes uniform powder-like product in super finely ground slag, iolon, polyoxyethylene glycol and the phenylformic acid sodium salt adding ball mill of weight proportion in the claim 1,2,3,4 or 5, cross 100 eye mesh screens and obtain.
7. according to the preparation method of a kind of polyethylene terephthalate composite nucleating agent described in the claim 6, it is characterized in that: the speed of described ball mill ball milling is 30～450 rev/mins, and the ball milling time is 1～5 hour.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020756A (en) * | 2010-11-15 | 2011-04-20 | 北京大学 | PET nucleating agent, preparing method thereof and PET modifying method |
| CN102491883A (en) * | 2011-12-16 | 2012-06-13 | 东华大学 | Polyethylene glycol magnesium and preparation method and application thereof |
| CN102775616A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for improving dispersibility of sodium benzoate nucleating agent in polypropylene |
| CN103102475A (en) * | 2011-11-11 | 2013-05-15 | 合肥杰事杰新材料股份有限公司 | Talcum powder-polyester composite material and preparation method thereof |
| CN106947226A (en) * | 2017-03-24 | 2017-07-14 | 杭州本松新材料技术股份有限公司 | A kind of PET composite material |
| CN109721765A (en) * | 2018-12-17 | 2019-05-07 | 南京工业大学 | Preparation method of PET organic-inorganic composite nucleating agent |
| CN109749370A (en) * | 2018-12-21 | 2019-05-14 | 广州华新科智造技术有限公司 | A kind of PET composite nucleating agent and preparation method thereof |
| CN110885540A (en) * | 2019-12-11 | 2020-03-17 | 宁波华腾首研新材料有限公司 | PET composite material and preparation method and application thereof |
| CN112679921A (en) * | 2021-03-18 | 2021-04-20 | 中广核高新核材科技（苏州）有限公司 | Ionomer composite nucleating agent for PET extrusion foaming and preparation method and application thereof |
| CN113651953A (en) * | 2021-08-19 | 2021-11-16 | 山东科华赛邦新材料股份有限公司 | Reactive nucleating additive and preparation method and application thereof |
| CN117603103A (en) * | 2023-12-15 | 2024-02-27 | 太原科技大学 | Synthesis method of PET flame retardant/nucleation auxiliary agent and application of PET flame retardant/nucleation auxiliary agent in PET recovery |
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| TWI823663B (en) * | 2022-11-04 | 2023-11-21 | 南亞塑膠工業股份有限公司 | Polyethylene terephthalate composite material containing glass fiber and method for manufacturing the same |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020756A (en) * | 2010-11-15 | 2011-04-20 | 北京大学 | PET nucleating agent, preparing method thereof and PET modifying method |
| CN102775616A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for improving dispersibility of sodium benzoate nucleating agent in polypropylene |
| CN102775616B (en) * | 2011-05-13 | 2014-06-04 | 中国石油天然气股份有限公司 | Method for improving dispersibility of sodium benzoate nucleating agent in polypropylene |
| CN103102475A (en) * | 2011-11-11 | 2013-05-15 | 合肥杰事杰新材料股份有限公司 | Talcum powder-polyester composite material and preparation method thereof |
| CN103102475B (en) * | 2011-11-11 | 2016-05-04 | 合肥杰事杰新材料股份有限公司 | A kind of talcum powder-polyester composite and preparation method thereof |
| CN102491883A (en) * | 2011-12-16 | 2012-06-13 | 东华大学 | Polyethylene glycol magnesium and preparation method and application thereof |
| CN102491883B (en) * | 2011-12-16 | 2014-01-08 | 东华大学 | Polyethylene glycol magnesium and preparation method and application thereof |
| CN106947226B (en) * | 2017-03-24 | 2019-02-05 | 杭州本松新材料技术股份有限公司 | A kind of PET composite material |
| CN106947226A (en) * | 2017-03-24 | 2017-07-14 | 杭州本松新材料技术股份有限公司 | A kind of PET composite material |
| CN109721765A (en) * | 2018-12-17 | 2019-05-07 | 南京工业大学 | Preparation method of PET organic-inorganic composite nucleating agent |
| CN109749370A (en) * | 2018-12-21 | 2019-05-14 | 广州华新科智造技术有限公司 | A kind of PET composite nucleating agent and preparation method thereof |
| CN110885540A (en) * | 2019-12-11 | 2020-03-17 | 宁波华腾首研新材料有限公司 | PET composite material and preparation method and application thereof |
| CN112679921A (en) * | 2021-03-18 | 2021-04-20 | 中广核高新核材科技（苏州）有限公司 | Ionomer composite nucleating agent for PET extrusion foaming and preparation method and application thereof |
| CN113651953A (en) * | 2021-08-19 | 2021-11-16 | 山东科华赛邦新材料股份有限公司 | Reactive nucleating additive and preparation method and application thereof |
| CN113651953B (en) * | 2021-08-19 | 2023-07-11 | 山东科华赛邦新材料股份有限公司 | Reactive nucleation additive and preparation method and application thereof |
| CN117603103A (en) * | 2023-12-15 | 2024-02-27 | 太原科技大学 | Synthesis method of PET flame retardant/nucleation auxiliary agent and application of PET flame retardant/nucleation auxiliary agent in PET recovery |
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