CN101230186B - Anti-static poly(ethylene terephthalate) material and preparation method thereof - Google Patents
Anti-static poly(ethylene terephthalate) material and preparation method thereof Download PDFInfo
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- CN101230186B CN101230186B CN2008100256633A CN200810025663A CN101230186B CN 101230186 B CN101230186 B CN 101230186B CN 2008100256633 A CN2008100256633 A CN 2008100256633A CN 200810025663 A CN200810025663 A CN 200810025663A CN 101230186 B CN101230186 B CN 101230186B
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Abstract
The invention discloses an antistatic polyethylene glycol terephthalate and a preparation method thereof. The antistatic polyethylene glycol terephthalate calculated according to the parts by weight comprises 96.8-89.5 parts of polyethylene glycol terephthalate, 3-10 parts of antistatic agent, and 0.2-0.5 part of antioxidant. The antioxidant is composed of [Beta-(3,5-di-tert-butyl-4-hydroxy-phenyl) methyl acetic acid] pentaerythritol ester and tri dimethylphenyl phosphate (2,4-di-tert-butyl-benzyl) according to the mol ratio of 1:2. The antistatic agent comprises water-soluble polymer sodium polystyrene sulfonate and nano-silver colloid with equal molar, and the preparation method comprises the following steps: the water-soluble polymer sodium polystyrene sulfonate and the nano-silver colloid with equal molar flow back in water for 5-6 hours, the coordination reaction happens between the molar water-soluble polymer sodium polystyrene sulfonate and the nano-silver colloid to cause the molar water-soluble polymer sodium polystyrene sulfonate and the nano-silver colloid to be combined together, and then the composition is dried and ground. The antistatic polyethylene glycol terephthalate has good antistatic performance, the preparation process is simple, and the preparation method is convenient and easy to be operated.
Description
Technical field
The present invention relates to the antistatic polyester field, specifically, relate to a kind of antistatic pet material and preparation method thereof.
Background technology
Polyethylene terephthalate is the polymkeric substance of highly crystalline, it has excellent physical and mechanical properties in wide temperature range, rub resistance, dimensional stability are all fine, and as the important engineering plastics, it is widely used in electronic apparatus, information communication, each field of daily necessities.But the polyethylene terephthalate structure is tight, and the degree of crystallinity height has hydrophobicity, and water absorbability is very poor, and than resistance height, friction voltage is big, easily produces static.Easier build up of electrostatic charge in the occasion of low humidity.After can causing dust suction, electric shock even produce spark, accumulation of static electricity causes serious accidents such as blast.As fiber, the static that electric part, auto parts, fiber produce in the course of processing can bring problems such as boundling difficulty to polyester in a large number, and the accumulation of static electricity of component results in hand cramps for processing and application.Antistatic polyethylene terephthalate always is an important research project.
Insulator surface is easily put aside the electric charge static electrification, and antistatic is exactly that the electric charge that insulator surface produces is in time discharged, thereby avoids the electric charge accumulation to cause electrostatic problem.Adding static inhibitor is to make polymer materials have the common method of static resistance.Static inhibitor is to prevent or chemical additive that the static charge that dissipates produces.Except lower molecular weight static inhibitor commonly used in the past, the researchist has developed various polymer base antistatic agents now.Can be divided into outside static inhibitor and inner static inhibitor again by the use-pattern static inhibitor.The lower molecular weight static inhibitor easily impacts and easily separates out from material the performance of material and do not have antistatic property, the easy frictionloss of outside static inhibitor and can not obtain permanent antistatic.
U.S. Pat 2007/0072974 A1 discloses a kind of hydrophobic permanent anti-static polyester.Thereby its preparation method obtains antistatic property for ionic conductive polymers, ion source or electrolytic solution, softening agent are compound in the polymeric matrix.Its antistatic polyester consists of the softening agent of vibrin, polyether-type ionic conductive polymer, ion source and polyether-type ionic conductive polymer.The antistatic polyester of this invention is mainly given the material static resistance by the polyether-type ionic conductive polymer and the ion source that add, but need to add the consistency that softening agent improves polyether type polymer and ion source and vibrin base material simultaneously, raw materials used complexity, and preparation process is loaded down with trivial details.
Chinese patent CN1916102A discloses a kind of anti-static polyester film.This invention is coated by electrically conductive polymer resin, adhesive resin, bridging agent on the surface of polyester film and is contained the top coat liquid that fluorine is the silica dispersive composition, and makes polyester film have water tolerance solvent resistance and static resistance.The static resistance of polyester film is from the electrically conductive polymer resin in the coating liquid, and it plays the effect of static inhibitor.Obtain antistatic layer by surface coatings.Film in use since the frictionloss meeting of static inhibitor cause antistatic effect to weaken or disappear.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of antistatic property excellence, with polyphenyl dioctyl phthalate glycol ester consistency antistatic material good and that can be used for blending and modifying processing.
Another object of the present invention is to provide the preparation method of a kind of safety and environmental protection, the simple antistatic pet material of preparation method.
Purpose of the present invention can realize by following measure:
A kind of antistatic pet material is counted by weight, and this material is made up of 89.5～96.8 parts of polyethylene terephthalates, 3～10 parts of static inhibitor and 0.2～0.5 part of oxidation inhibitor; Described static inhibitor is made up of equimolar water-soluble polymers sodium polystyrene sulfonate and nano silver colloidal sol, preparation as follows: equimolar water-soluble polymers sodium polystyrene sulfonate and nano silver colloidal sol were refluxed in water 5～6 hours, then reaction product is dried, grind, get static inhibitor; Described oxidation inhibitor was made up of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in 1: 2 in molar ratio.
Be further to realize that the object of the invention, described oven dry are that to be decompressed to vacuum tightness at 80 ℃-100 ℃ be to dry under the 0.07MPa-0.09MPa condition.
Described grinding is to utilize mechanical grinder to grind, and being ground into particle diameter is 0.1-5 μ m.
Described static inhibitor is preferably 5～8 parts.
The preparation method of antistatic pet material comprises the steps and processing condition:
(1) preparation of static inhibitor: take by weighing equimolar sodium polystyrene sulfonate and nano silver colloidal sol; It was refluxed in water 5～6 hours; Then reaction product being decompressed to vacuum tightness at 80 ℃-100 ℃ is to dry under the 0.07MPa-0.09MPa condition, and being ground into particle diameter is 0.1-5 μ m;
(2) preparation of antistatic polyethylene terephthalate: take by weighing after 0.2～0.5 part in 3～10 parts in the static inhibitor of 96.8～89.5 parts of polyethylene terephthalates, step (1) preparation and oxidation inhibitor mixes, at 255～265 ℃ of following extruding pelletizations; Described oxidation inhibitor was made up of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in 1: 2 in molar ratio.
Described grinding is to utilize mechanical grinder to grind.
Described static inhibitor is preferably 5～8 parts.
Static inhibitor of the present invention is a polymer base antistatic agent, and polymeric matrix is selected hydrophilic sodium polystyrene sulfonate for use, nano silver colloidal sol and sodium polystyrene sulfonate generation complex reaction and combine.Antistatic property is mainly from the electroconductibility of nano silver colloidal sol, and the wetting ability of polymeric matrix sodium polystyrene sulfonate self also plays certain antistatic property.Described static inhibitor has certain polarity, and itself and polar polymer polyethylene terephthalate have consistency preferably.
Compared with prior art, the present invention has following characteristics:
The present invention combines as static inhibitor with the hydrophilic polymer sodium polystyrene sulfonate by adopting nano silver colloidal sol, obtained the antistatic polyethylene terephthalate of antistatic property excellence, and the preparation process of static inhibitor is simple, mild condition, with water is dispersion medium, safety and environmental protection, the gained static inhibitor is hydrophilic and certain polarity is arranged, and consumption is less and can consistency preferably be arranged with polyethylene terephthalate.
Embodiment
In order better to understand the present invention, the invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
The preparation of static inhibitor: taking by weighing with the Sodium styrene sulfonate group is that 1 mole sodium polystyrene sulfonate of benchmark and 1 mole nano silver colloidal sol refluxed 5 hours in 500ml water, being decompressed to vacuum tightness at 80 ℃ is to dry under the 0.09MPa condition, utilization utilizes mechanical grinder to grind, be milled to particle diameter 0.1-5 μ m, promptly make static inhibitor.
The preparation of antistatic pet material: count by weight, take by weighing polyethylene terephthalate 1936 grams, static inhibitor 60 grams of above-mentioned preparation, oxidation inhibitor 4 grams mix the back at 255 ℃ of following extruding pelletizations.Oxidation inhibitor was made up of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in 1: 2 in molar ratio.
Embodiment 2
The preparation of static inhibitor: taking by weighing with the Sodium styrene sulfonate group is that 1 mole sodium polystyrene sulfonate of benchmark and 1 mole nano silver colloidal sol refluxed 6 hours in 500ml water, being decompressed to vacuum tightness at 100 ℃ is to dry under the 0.08MPa condition, utilize the machinery method of grinding to be milled to particle diameter 0.1-5 μ m, promptly make static inhibitor.
The preparation of antistatic pet material: count by weight, take by weighing polyethylene terephthalate 1863 grams, static inhibitor 130 grams of above-mentioned preparation, oxidation inhibitor (with embodiment 1) 7 grams mix the back at 260 ℃ of following extruding pelletizations.
Embodiment 3
The preparation of static inhibitor: taking by weighing with the Sodium styrene sulfonate group is that 1 mole sodium polystyrene sulfonate of benchmark and 1 mole nano silver colloidal sol refluxed 5.5 hours in 500ml water, being decompressed to vacuum tightness at 90 ℃ is to dry under the 0.07MPa condition, utilize the machinery method of grinding to be milled to particle diameter 0.1-5 μ m, promptly make static inhibitor.
The preparation of antistatic pet material: count by weight, take by weighing polyethylene terephthalate 1790 grams, static inhibitor 200 grams of above-mentioned preparation, oxidation inhibitor (with embodiment 1) 10 grams mix the back at 265 ℃ of following extruding pelletizations.
In the foregoing description, the raw material sodium polystyrene sulfonate is a U.S. Aldrich company product; Nano silver colloidal sol is a Lekai company product; Oxidation inhibitor was made up of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in 1: 2 in molar ratio, and model is oxidation inhibitor B215, is Ciba company product.
The antistatic property of embodiment 1～3 is as shown in table 1:
Table 1
[0035]?
The test of antistatic property is carried out according to standard GB/T 1410-2006 " solid insulating material volume specific resistance and surface resistivity test method ".The antistatic property that obtains through 10 times the washing and 10 wipings, any variation does not take place.
It is generally acknowledged that the surface resistivity of material reaches 10
8-10
12Ω, volume specific resistance 10
4-10
11Ω cm reaches and promptly belongs to antistatic material.The general surface resistivity 10 of antistatic polyethylene terephthalate in the market
8-10
11Ω, volume specific resistance 10
8-10
11Between the Ω cm; And be generally surface-coated type antistatic material, or adopt the small molecules antistatic compound to carry out the commixed type antistatic material; Its antistatic property of the antistatic material that makes so mainly relies on moisture absorption type electrostatic dissipation mechanism, thus its not water-fastly wash, not anti-wiping, antistatic property is difficult to lastingly.Static inhibitor in the present invention adopts the composite nano silver colloidal sol conducting material of polar polymer sodium polystyrene sulfonate to make; Utilize its antistatic polyethylene terephthalate that makes can be from two aspects to antistatic property, the one, the moisture absorption type electrostatic dissipation mechanism of sodium polystyrene sulfonate itself, the 2nd, with the intrinsic conduction mechanism of the composite nanometer silver of sodium polystyrene sulfonate; This static inhibitor is owing to contain the polarity sodium group, thereby has good consistency with polyethylene terephthalate, helps the machine-shaping and the preparation comprehensive mechanical property excellent material of material; Static inhibitor is by its macromolecular characteristic in addition, and it is difficult for running off because of wiping or washing, thereby helps obtaining persistent antistatic effect.
Claims (7)
1. antistatic pet material is characterized in that: meter by weight, and this material is made up of 89.5～96.8 parts of polyethylene terephthalates, 3～10 parts of static inhibitor and 0.2～0.5 part of oxidation inhibitor; Described static inhibitor is made up of equimolar water-soluble polymers sodium polystyrene sulfonate and nano silver colloidal sol, preparation as follows: equimolar water-soluble polymers sodium polystyrene sulfonate and nano silver colloidal sol were refluxed in water 5～6 hours, then reaction product is dried, grind, get static inhibitor; Described oxidation inhibitor was made up of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in 1: 2 in molar ratio.
2. antistatic pet material according to claim 1 is characterized in that described oven dry is that to be decompressed to vacuum tightness at 80 ℃-100 ℃ be to dry under the 0.07MPa-0.09MPa condition.
3. antistatic pet material according to claim 1 is characterized in that described grinding is to utilize mechanical grinder to grind, and being ground into particle diameter is 0.1-5 μ m.
4. antistatic pet material according to claim 1 is characterized in that described static inhibitor is 5～8 parts.
5. the preparation method of the described antistatic pet material of claim 1 is characterized in that comprising the steps and processing condition:
(1) preparation of static inhibitor: take by weighing equimolar sodium polystyrene sulfonate and nano silver colloidal sol; It was refluxed in water 5～6 hours; Then reaction product being decompressed to vacuum tightness at 80 ℃-100 ℃ is to dry under the 0.07MPa-0.09MPa condition, and being ground into particle diameter is 0.1-5 μ m;
(2) preparation of antistatic pet material: take by weighing after 0.2～0.5 part in 3～10 parts in the static inhibitor of 89.5～96.8 parts of polyethylene terephthalates, step (1) preparation and oxidation inhibitor mixes, at 255～265 ℃ of following extruding pelletizations; Described oxidation inhibitor was made up of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in 1: 2 in molar ratio.
6. the preparation method of antistatic pet material according to claim 5 is characterized in that described grinding is to utilize mechanical grinder to grind.
7. the preparation method of antistatic pet material according to claim 5 is characterized in that described static inhibitor is 5～8 parts.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100256633A CN101230186B (en) | 2008-01-07 | 2008-01-07 | Anti-static poly(ethylene terephthalate) material and preparation method thereof |
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| CN2008100256633A CN101230186B (en) | 2008-01-07 | 2008-01-07 | Anti-static poly(ethylene terephthalate) material and preparation method thereof |
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| CN101230186A CN101230186A (en) | 2008-07-30 |
| CN101230186B true CN101230186B (en) | 2010-12-01 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993527B (en) * | 2010-10-20 | 2012-11-07 | 东华大学 | Preparation method and application of silver-containing PET based composite resin material |
| CN102020762B (en) * | 2010-10-20 | 2012-07-25 | 东华大学 | Novel silver-containing PET (polyethylene terephthalate)-based composite and in-situ assembly preparation method and application thereof |
| CN104086957B (en) * | 2014-07-15 | 2016-01-13 | 杭州华塑实业股份有限公司 | Anlistatig PET polyester film of a kind of high transparency and preparation method thereof |
| CN108623976B (en) * | 2018-05-30 | 2020-06-16 | 宁波科莱恩新材料科技有限公司 | Antistatic shading PET film and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN1346379A (en) * | 1999-02-10 | 2002-04-24 | 三洋化成工业株式会社 | Block polymer and antistatic agent comprising the same |
| CN1569931A (en) * | 2004-04-26 | 2005-01-26 | 东莞市正昱塑胶五金有限公司 | Fiber reinforced thermolplastic plastic preparation method |
| CN1670118A (en) * | 2005-03-11 | 2005-09-21 | 华南理工大学 | Polymer base antistatic agent and method for preparing same |
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2008
- 2008-01-07 CN CN2008100256633A patent/CN101230186B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346379A (en) * | 1999-02-10 | 2002-04-24 | 三洋化成工业株式会社 | Block polymer and antistatic agent comprising the same |
| CN1569931A (en) * | 2004-04-26 | 2005-01-26 | 东莞市正昱塑胶五金有限公司 | Fiber reinforced thermolplastic plastic preparation method |
| CN1670118A (en) * | 2005-03-11 | 2005-09-21 | 华南理工大学 | Polymer base antistatic agent and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| JP昭59－8731A 1984.01.18 |
| 郑敏等.纳米银原位掺杂导电碳浆的制备及对涤纶织物的抗静电整理.第七届功能性纺织品及纳米技术应用研讨会论文集.2007,78-83. * |
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