CN112646351B - PPE/PS alloy material and preparation method and application thereof - Google Patents

PPE/PS alloy material and preparation method and application thereof Download PDF

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Publication number
CN112646351B
CN112646351B CN202011558092.7A CN202011558092A CN112646351B CN 112646351 B CN112646351 B CN 112646351B CN 202011558092 A CN202011558092 A CN 202011558092A CN 112646351 B CN112646351 B CN 112646351B
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ppe
pentaerythritol
alloy material
film
resin
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CN112646351A (en
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江翼
黄险波
叶南飚
杨霄云
陆湛泉
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene
    • C08J2325/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12Polyphenylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02Homopolymers or copolymers of hydrocarbons
    • C08J2425/04Homopolymers or copolymers of styrene
    • C08J2425/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials

Abstract

The invention discloses a PPE/PS alloy material and a preparation method and application thereof, wherein the PPE/PS alloy material comprises the following components in parts by weight: 30-70 parts of PPE resin; 30-70 parts of PS resin; 0.3-3 parts of pentaerythritol ester. According to the invention, the pentaerythritol ester with an active-OH structure is added into a PPE/PS system, so that the processing film forming property of the PPE/PS alloy material can be obviously improved, the PPE/PS film is easy to form, the prepared PPE/PS film has high transparency and good flexibility, the application of the PPE/PS alloy in the field of food packaging is further widened, and the PPE/PS film is particularly suitable for the field of food flexible packaging.

Description

PPE/PS alloy material and preparation method and application thereof
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a PPE/PS alloy material and a preparation method and application thereof.
Background
Polyphenylene Ether (PPE) is one of five engineering plastics, and has the defects of difficult processing and the like, and the practical application is limited, and the PPE is very excellent in heat resistance, chemical property, electrical property, dimensional stability and water resistance. At present, the processing performance is mainly improved by blending with Polystyrene (PS), thereby widening the application range. The PPE/PS alloy material has balanced rigidity and toughness required by food packaging, and has good application prospect in the field of food packaging. For example, GE plastics corporation in the United states has introduced a series of PPE resins that are blends of PPE and PS for use in the food packaging industry, which are suitable for a wide range of temperature applications from refrigerated storage to microwave ovens and can be used to make various food containers (dishes, trays, lids, etc.).
However, the PPE/PS alloy material has poor film forming property, has the problems of film cracking, film hardness and the like in the extrusion and film drawing process, cannot be made into a thin film grade material, can only be applied to hard packages such as food containers and the like at present, and is limited to be applied in the field of food flexible packages. The main research direction of the invention is how to improve the processing film forming property of the PPE/PS alloy material, prepare the PPE/PS film with high transparency and good flexibility, and widen the application of the PPE/PS alloy material in the field of food packaging.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a PPE/PS alloy material which is easy to process into a film and can be prepared into a film material with good flexibility and high transparency.
The invention also aims to provide a preparation method of the PPE/PS alloy material.
The invention is realized by the following technical scheme:
the PPE/PS alloy material comprises the following components in parts by weight:
30-70 parts of PPE resin;
30-70 parts of PS resin;
0.3-3 parts of pentaerythritol ester.
The pentaerythritol ester has 2 or more than 2 active-OH groups.
According to the invention, through research, pentaerythritol ester is selected to be added into the PPE/PS alloy material, and the end-capped hydroxyl group of the pentaerythritol ester has strong activity, so that the pentaerythritol ester can be well combined with matrix resin and uniformly dispersed on the surface of the matrix resin, the film forming property of the PPE/PS alloy material is obviously improved, and the PPE/PS film with good flexibility and high transparency can be prepared. Preferably, the pentaerythritol ester is selected from one or more of pentaerythritol stearate, pentaerythritol oleate or pentaerythritol laurate; more preferably, the pentaerythritol ester is selected from pentaerythritol stearate.
The pentaerythritol stearate is selected from one or more of pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate or pentaerythritol tetrastearate; the pentaerythritol oleate is selected from any one or more of pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate or pentaerythritol tetraoleate; the pentaerythritol laurate is selected from one or more of pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol trilaurate or pentaerythritol tetralaurate.
The addition amount of the pentaerythritol ester is too small, so that the film layer is not uniform, and the toughness of the film is insufficient; if the addition amount is too large, the film is too soft, the stiffness is not enough, and the wrinkling is easy. Preferably, the pentaerythritol ester accounts for 0.8-1.5 parts by weight.
The viscosity average molecular weight of the PPE resin adopted by the invention is 13000-60000, and the viscosity average molecular weight is calculated by a solution viscosity measured in a dichloromethane solvent at 25 ℃; the PPE resin has an excessively high viscosity-average molecular weight, which results in poor uniformity of the extruded film; preferably, the viscosity average molecular weight of the PPE resin is 30000-50000.
The number average molecular weight of the PS resin adopted by the invention is more than 20000. The PS resin has too low molecular weight and poor miscibility with the PPE resin, so that the film layer is not uniform and has defects.
The invention also provides a preparation method of the PPE/PS alloy material, which comprises the following steps: weighing the components according to the proportion, putting the components into a first section of feed opening of a double-screw extruder, heating and melting the components by the double-screw extruder, extruding the components into strips through a die orifice, cooling the strips by water, air-drying the strips, and dicing the strips to obtain the PPE/PS alloy material; wherein the temperature of the extruder is 240-290 ℃; the rotation speed is 250rpm to 600 rpm.
The PPE/PS alloy material can be prepared into a thin film material with the thickness of less than 0.35mm by an extrusion film-drawing process.
The invention also provides application of the PPE/PS alloy material, which can be used for preparing film materials and is particularly applied to the field of food flexible packaging.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, researches show that the processing film forming property of the PPE/PS alloy material can be obviously improved by adding pentaerythritol ester with an active-OH structure into the PPE/PS system, the PPE/PS film is easy to prepare into a film material, the prepared PPE/PS film has high transparency and good flexibility, the problem that the PPE/PS alloy material in the prior art cannot be prepared into a film material is solved, the application of the PPE/PS alloy in the field of food packaging is further widened, and the PPE/PS film is particularly suitable for the field of food flexible packaging.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
PPE resin 1: PX100L, Mitsubishi chemical industry, the viscosity average molecular weight is 40000-46000;
PPE resin 2: LXR050, Lanxing chemical Co., Ltd., viscosity average molecular weight 50000-56000;
PS resin 1: GPPS 818K, Taida chemical, number average molecular weight 170000-180000;
PS resin 2: GPPS 1441, Trinseo, number average molecular weight 95000-105000;
pentaerythritol distearate: purchasing in market;
pentaerythritol tetrastearate: purchasing in market;
pentaerythritol dioleate: purchasing in market;
n-butyl stearate: purchasing in market;
glycerol tristearate: purchasing in market;
803 a terpene resin: purchasing in market;
erucamide: is commercially available.
Preparation of PPE/PS alloy materials for examples and comparative examples:
weighing the components according to the proportion, putting the components into a first section of a feed opening of a double-screw extruder, heating and melting the components by the double-screw extruder, extruding the components into strips through a die opening, and then carrying out water cooling, air drying and grain cutting to obtain the PPE/PS alloy material. Wherein the temperature of the extruder is 240-290 ℃; the rotation speed is 250rpm to 600 rpm.
The PPE/PS alloy materials prepared in the above examples and comparative examples are extruded and drawn into films with the thickness of 0.3mm in a Haake rheometer, and the extrusion temperature is 270-300 ℃.
The related performance test method comprises the following steps:
(1) and (3) processing and film forming: evaluating the processing film-forming property of the material according to the film-discharging condition of the extruded and drawn film; the case where a thin film could not be made is denoted as XX; a film can be formed, but the case where the film cracks is represented as X; the case where a uniform film can be made is represented by O.
(2) Light transmittance: the higher the light transmission, the lower the haze, as determined by reference to the standard GB/T2410-2008 method, indicating the better the transparency of the material.
(3) Film softness: evaluating by adopting a touch rating mode, and dividing the evaluation into 5 grades (I grade, II grade, III grade, IV grade and V grade), wherein the lower the grade is, the harder the film is; a higher rating indicates a softer film.
(4) And (3) testing the impact resistance: the test was carried out according to method A in standard GB/T9639.1-2008. The better the impact resistance, the better the film toughness.
Table 1: specific proportions (by weight) of the components and performance test results in examples 1-7
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
PPE resin 1 50 50 50 60 65
PPE resin 2 50 55
PS resin 1 50 50 50 50 35
PS resin 2 40 45
Pentaerythritol distearate 1 0.3 2.5 1 0.8
Pentaerythritol Tetrastearate 1.5
PentaerythritolDioleic acid ester 3
Film forming property O O O O O O O
Light transmittance 85% 82% 82% 87% 80% 88% 83%
Softness of film
Impact resistance 150g 145g 140g 145g 160g 145g 135g
Table 2: the specific proportions (by weight) of the components in comparative examples 1-6 and the results of performance tests
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
PPE resin 1 50 50 50 50 50 50
PS resin 1 50 50 50 50 50 50
Pentaerythritol distearate 5
Stearic acid n-butyl ester 1
Glycerol tristearate 1
803 terpene resin 1
Erucamide 1
Film forming property O X O X XX XX
Light transmittance 87% / 70% / / /
Softness of film V / / / /
Impact resistance <120g / <120g / / /
The embodiment shows that the processing film forming property of the PPE/PS alloy material can be obviously improved by adding the pentaerythritol ester with an active-OH structure, and the prepared PPE/PS film has high light transmittance, excellent impact resistance and good flexibility. Comparative example 1, with an excess of pentaerythritol distearate, the PPE/PS films produced were too soft, had poor impact resistance, and had inadequate film toughness. Comparative example 2/3/4/5/6, no PPE/PS film with high clarity and good flexibility was obtained without the addition of pentaerythritol ester.

Claims (6)

1. The PPE/PS alloy material is characterized by comprising the following components in parts by weight:
30-70 parts of PPE resin;
30-70 parts of PS resin;
0.3-3 parts of pentaerythritol ester;
the pentaerythritol ester is selected from one or more of pentaerythritol stearate, pentaerythritol oleate or pentaerythritol laurate;
the pentaerythritol ester has 2 or more than 2 active-OH;
the viscosity-average molecular weight of the PPE resin is 13000-60000;
the number average molecular weight of the PS resin is more than 20000.
2. The PPE/PS alloy material according to claim 1, wherein the pentaerythritol ester is 0.8-1.5 parts.
3. The PPE/PS alloy material according to claim 1, wherein the pentaerythritol stearate is selected from any one or more of pentaerythritol monostearate or pentaerythritol distearate; the pentaerythritol oleate is selected from one or more of pentaerythritol monooleate or pentaerythritol dioleate; the pentaerythritol laurate is selected from one or more of pentaerythritol monolaurate or pentaerythritol dilaurate.
4. The PPE/PS alloy material according to claim 1, wherein the viscosity average molecular weight of the PPE resin is 30000-50000.
5. The method for preparing the PPE/PS alloy material according to any one of claims 1 to 4, comprising the steps of: weighing the components according to the proportion, putting the components into a first section of a feed opening of a double-screw extruder, heating and melting the components by the double-screw extruder, extruding the components into strips through a die opening, cooling the strips by water, air-drying the strips, and cutting the strips into granules to obtain the PPE/PS alloy material; wherein the temperature of the extruder is 240-290 ℃; the rotation speed is 250rpm to 600 rpm.
6. The use of the PPE/PS alloy material according to any one of claims 1 to 4 in the field of food packaging.
CN202011558092.7A 2020-12-25 2020-12-25 PPE/PS alloy material and preparation method and application thereof Active CN112646351B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102712770A (en) * 2009-11-30 2012-10-03 帝人株式会社 High-insulating film
CN104169757A (en) * 2012-03-15 2014-11-26 日本瑞翁株式会社 Phase difference film laminate, method for producing phase difference film laminate, and method for producing phase difference film
CN109796717A (en) * 2018-12-27 2019-05-24 会通新材料股份有限公司 A kind of low-density PPE composite material and preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102712770A (en) * 2009-11-30 2012-10-03 帝人株式会社 High-insulating film
CN104169757A (en) * 2012-03-15 2014-11-26 日本瑞翁株式会社 Phase difference film laminate, method for producing phase difference film laminate, and method for producing phase difference film
CN109796717A (en) * 2018-12-27 2019-05-24 会通新材料股份有限公司 A kind of low-density PPE composite material and preparation method and application

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