CN115044139A - TPX polymer material and preparation method and application thereof - Google Patents
TPX polymer material and preparation method and application thereof Download PDFInfo
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- CN115044139A CN115044139A CN202210847847.8A CN202210847847A CN115044139A CN 115044139 A CN115044139 A CN 115044139A CN 202210847847 A CN202210847847 A CN 202210847847A CN 115044139 A CN115044139 A CN 115044139A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention particularly relates to a TPX polymer material and a preparation method and application thereof, belonging to the technical field of high polymer materials, wherein the method comprises the following steps: POE, HDPE and hydrophilic TPX polymer are blended and modified to form a blend, so that the TPX material is obtained; the preparation method of the hydrophilic TPX polymer comprises the following steps: carrying out plasma treatment on the TPX polymer, and then carrying out reduction treatment to obtain a hydrophilic TPX polymer; the TPX polymer is subjected to hydrophilization treatment to improve the compatibility with HDPE and POE, the TPX polymer subjected to hydrophilization treatment is subjected to blending modification with HDPE and POE, the HDPE can improve the elongation at break of the blend, and the notch impact strength of the blend can be improved by adding the HDPE. The addition of POE slightly lowers the melting and crystallization temperatures of the TPX polymer, and the reduction of the crystallization of the TPX polymer results in higher notch sensitivity and poorer fracture toughness of the polymer.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a TPX polymer material, and a preparation method and application thereof.
Background
TPX (poly-4-methyl-1-pentene) has the characteristics of high temperature resistance, high transparency and the like, and is widely applied to the field of electrical lighting equipment. With its good material properties, which is of great commercial value, poly-4-methyl-1-pentene is an irreplaceable component of optical materials as well as materials and films with high permeability to oxygen.
Although TPX has many advantages, its defects are not negligible, such as toughness, strength and flame retardant property. The application of TPX polymer, such as submarine cable and communication cable, has high requirement on the toughness of polymer material.
The existing methods for improving the performance of the TPX polymer material comprise a chemical method and a physical method, and the chemical modification and the physical method are adopted in industrial production, wherein the chemical modification mainly comprises the step of carrying out chemical grafting modification on the TPX polymer material; the physical method mainly comprises blending modification, blending TPX polymer and a plurality of high molecular materials by a double-screw extruder, such as adding rubber such as EPDM and SBS for toughening modification, and improving the interfacial adhesion between EPMD and TPX by a dynamic vulcanization method, but the generation of TPX/EPDM graft copolymer is found in the dynamic vulcanization process, so that the TPX polymer material has poor performance.
Disclosure of Invention
The application aims to provide a TPX polymer material, and a preparation method and application thereof, so as to solve the problem of poor performance of the conventional TPX polymer material.
The embodiment of the invention provides a preparation method of a TPX polymer material, which comprises the following steps:
POE, HDPE and hydrophilic TPX polymer are blended and modified to form a blend, so that the TPX material is obtained;
the preparation method of the hydrophilic TPX polymer comprises the following steps:
the TPX polymer is subjected to plasma treatment and then reduction treatment to obtain the hydrophilic TPX polymer.
Optionally, the plasma treatment time is 1-120 min.
Optionally, the reduction treatment is performed by using sodium borohydride, and the reduction treatment time is 1-5 h.
Optionally, the mass of the POE accounts for 15% to 30% of the mass of the TPX.
Optionally, the mass of the HDPE accounts for 5% -15% of the mass of the TPX.
Optionally, the blending modification is performed by using a twin-screw extruder.
Optionally, the rotation speed of the twin-screw extruder is 60-120 rpm.
Optionally, the temperature of the blending modification is 170-220 ℃.
Based on the same inventive concept, the embodiment of the invention also provides the TPX polymer material, and the material is prepared by the preparation method of the TPX polymer material.
Based on the same inventive concept, the embodiment of the invention also provides a cable, which comprises a wrapping layer, wherein the material of the wrapping layer is the TPX polymer material.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the preparation method of the TPX polymer material provided by the embodiment of the invention, the TPX polymer is subjected to hydrophilization treatment to improve the compatibility with HDPE and POE, the TPX polymer subjected to hydrophilization treatment is subjected to blending modification with HDPE and POE, the characteristics of high elongation at break, strong notch impact strength and the like of HDPE are utilized, the elongation at break of the blend can be improved by adding the HDPE, and the notch impact strength of the blend can also be improved by adding the HDPE. Meanwhile, by utilizing the characteristic that POE has lower melting and crystallization temperatures, the melting and crystallization temperatures of the TPX polymer are slightly reduced by adding the POE, and the reduction of the crystallization of the TPX polymer can lead to higher notch sensitivity and poorer fracture toughness of the TPX polymer.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a flow chart of a method provided by an embodiment of the invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The noun explains:
TPX: poly (4-methylpentene-1) monomer
HDPE: high density polyethylene
POE: polyolefin elastomer
EPR: ethylene propylene rubber
EPDM: ethylene propylene diene monomer
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
the applicant finds in the course of the invention that: TPX polymers have many good properties, such as good light transmission, very low density, resistance to organic reagents, high temperature resistance, and low electrical conductivity, and thus are used in many fields, such as electrical parts, drug separation materials, drug carriers, and the like. However, for many applications of TPX polymers, such as cables, flexibility, etc., is somewhat insufficient.
At present, a plurality of methods for improving the material performance through blending modification exist, for example, EPR is added into a TPX polymer, and the method finds that the EPR in the TPX polymer has poor dispersion, larger particles and poor toughening effect. The addition of EPDM to TPX polymers, while increasing the toughness of the TPX polymer, other properties of the material are affected to varying degrees such as tensile and flexural strength.
According to an exemplary embodiment of the present invention, there is provided a method of preparing a TPX polymer material, the method including:
s1, carrying out plasma treatment on a TPX polymer, and then carrying out reduction treatment to obtain a hydrophilic TPX polymer;
in some embodiments, the plasma treatment time is 1-120min, preferably 1-60min, and more preferably 1-30 min; the reduction treatment is carried out by sodium borohydride, and the reduction treatment time is 1-5h, preferably 1-2 h.
Specifically, in this example, the TPX polymer was treated with a plasma apparatus for a treatment time of 1 to 30 minutes; reducing the treated TPX polymer by using sodium borohydride for 1-3 hours; after treatment, the resulting mixture was rinsed with deionized water to obtain a hydrophilic TPX polymer.
S2, carrying out blending modification on POE, HDPE and hydrophilic TPX polymer to form a blend to obtain a TPX material;
in some embodiments, the mass of POE is 15% to 30%, preferably 15%, of the mass of TPX; the mass of HDPE accounts for 5% -15% of the mass of TPX, and the balance is hydrophilic TPX polymer and inevitable impurities.
In some embodiments, the blending modification is performed by using a twin-screw extruder; the rotating speed of the double-screw extruder is 60-120rpm, preferably 90 rpm; the temperature for blending modification is 170-220 ℃, preferably 200 ℃.
The speed of rotation of the twin-screw extruder determines the extrusion speed of the extruder. For accelerating the production process, when improving extrusion speed, for avoiding the material that extrudes not shaping scrap, corresponding cooling rate needs promote simultaneously, after considering comprehensively production process and present cooling scheme, the applicant finds that use twin screw extruder to carry out under the modified prerequisite of blending, control twin screw extruder's rotational speed can obtain better output and better quality for 60-120rpm, and the technical staff in the art can understand that, when cooling scheme has further development, can adopt faster cooling rate, and is corresponding, also can match faster rotational speed, reaches the purpose of accelerating production under the condition that does not influence the quality.
Specifically, in this example, a twin-screw extruder TSSJ-25/03 was charged with appropriate amounts of POE and different amounts of HDPE and TPX polymers; adjusting the double-screw extruder to the rotating speed of 90 rpm; setting the temperature of a barrel pipe of a double-screw extruder at 200 ℃; the corresponding extrudate is drawn into a quench water tank before the trays. The dried mixture was molded using a K-TEC40 injection molding machine to form impact and tensile specimens with barrel temperature profile 180 ℃ and 230 ℃ and mold temperature maintained at 50 ℃.
According to another exemplary embodiment of the present invention, there is provided a TPX polymer material manufactured using the method for manufacturing a TPX polymer material as described above.
According to another exemplary embodiment of the present invention, a cable is provided, the cable comprising a wrapping layer, the material of the wrapping layer being the TPX polymer material as described above.
The TPX polymer material of the present application, its preparation method and application will be described in detail below with reference to examples, comparative examples and experimental data.
Example 1
A method of making a TPX polymeric material, the method comprising:
(1) hydrophilic modification
10g of TPX polymer was treated using a plasma apparatus for 20 minutes. And (3) carrying out reduction on the treated TPX polymer by using 0.2g of sodium borohydride for 2 hours, and cleaning by using deionized water after treatment to obtain the hydrophilic TPX polymer.
(2) Blending modification
TSSJ-25/03 was charged with 20% POE and 5% HDPE and 75% TPX polymer. The twin-screw extruder was adjusted to a speed of 90 rpm. The twin screw extruder barrel was set at a temperature of 200 ℃ and the corresponding extrudate was drawn into a quench water tank before the trays. The dried mixture was molded using a K-TEC40 injection molding machine to form impact and tensile specimens with barrel temperature profile 180 ℃ and 230 ℃ and mold temperature maintained at 50 ℃.
Example 2
A method of making a TPX polymeric material, the method comprising:
(1) hydrophilic modification
10g of TPX polymer was treated using a plasma apparatus for 30 minutes. And (3) reducing the treated TPX polymer by using 0.2g of sodium borohydride for 3 hours, and cleaning by using deionized water after treatment to obtain the hydrophilic TPX polymer.
(2) Blending modification
TSSJ-25/03 was charged with 20% POE and 15% HDPE and 70% TPX polymer. The twin-screw extruder was adjusted to a speed of 90 rpm. The twin screw extruder barrel was set at a temperature of 200 ℃ and the corresponding extrudate was drawn into a quench water tank before the trays. The dried mixture was molded using a K-TEC40 injection molding machine to form impact and tensile specimens with barrel temperature profile 180 ℃ and 230 ℃ and mold temperature maintained at 50 ℃.
Example 3
A method of making a TPX polymeric material, the method comprising:
(1) hydrophilic modification
10g of TPX polymer was treated using a plasma apparatus for 30 minutes. And (3) reducing the treated TPX polymer by using 0.2g of sodium borohydride for 3 hours, and cleaning by using deionized water after treatment to obtain the hydrophilic TPX polymer.
(2) Blending modification
TSSJ-25/03 was charged with 20% POE and 20% HDPE and 65% TPX polymer. The twin-screw extruder was adjusted to a rotation speed of 90 rpm. The twin screw extruder barrel was set at a temperature of 200 ℃ and the corresponding extrudate was drawn into a quench water tank before the trays. The dried mixture was molded using a K-TEC40 injection molding machine to form impact and tensile specimens with barrel temperature profile of 180 ℃ and 230 ℃ and mold temperature maintained at 50 ℃.
Example 4
A method of making a TPX polymeric material, the method comprising:
(1) hydrophilic modification
10g of TPX polymer was treated using a plasma apparatus for 30 minutes. And (3) reducing the treated TPX polymer by using 0.2g of sodium borohydride for 3 hours, and cleaning by using deionized water after treatment to obtain the hydrophilic TPX polymer.
(2) Blending modification
TSSJ-25/03 was charged with 25% POE and 25% HDPE and 55% TPX polymer. The twin-screw extruder was adjusted to a speed of 90 rpm. The twin screw extruder barrel was set at a temperature of 200 ℃ and the corresponding extrudate was drawn into a quench water tank before the trays. The dried mixture was molded using a K-TEC40 injection molding machine to form impact and tensile specimens with barrel temperature profile 180 ℃ and 230 ℃ and mold temperature maintained at 50 ℃.
Comparative example 1
A method of making a TPX polymeric material, the method comprising:
(1) blending modification
TSSJ-25/03 was charged with 20% POE and 5% HDPE and 75% TPX polymer. The twin-screw extruder was adjusted to a speed of 90 rpm. The twin screw extruder barrel was set at a temperature of 200 ℃ and the corresponding extrudate was drawn into a quench water tank before the trays. The dried mixture was molded using a K-TEC40 injection molding machine to form impact and tensile specimens with barrel temperature profile 180 ℃ and 230 ℃ and mold temperature maintained at 50 ℃.
Examples of the experiments
The TPX polymer materials obtained in examples 1-4 and comparative example 1 were subjected to property analysis, and the results are shown in the following table:
| Tm(℃) | D H m(W/g) | Tc(℃) | |
| comparative example 1 | 150 | 46 | 106 |
| Example 1 | 149.8 | 50 | 108 |
| Example 2 | 148.3 | 52 | 110 |
| Example 3 | 147.2 | 53 | 112 |
| Example 4 | 146.7 | 55 | 114 |
From the above table, comparative example 1 did not hydrophilically modify the TPX polymer, whereas example 1 hydrophilically modifies the polymer, it can be seen that there is a certain increase in Tc (c), indicating an increase in compatibility of the TPX polymer and the material.
In examples 2 to 4, the addition of HDPE improves the ductile fracture properties of the polymer. The addition of POE slightly reduces the melting and crystallization temperature of TPX polymer, and reduces the higher notch sensitivity and the poorer fracture toughness of the polymer caused by the crystallization of the TPX polymer.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
in the method provided by the embodiment of the invention, the hydrophilic modification of the polymer increases the compatibility of HDPE and POE with TPX polymer. The addition of DPE improves the ductile fracture properties of the polymer. The addition of POE slightly reduces the melting and crystallization temperature of TPX polymer, and reduces the higher notch sensitivity and the poorer fracture toughness of the polymer caused by the crystallization of the TPX polymer. The performance of the material is increased, and the method has important significance for the application of polymer materials.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method of making a TPX polymeric material, the method comprising:
POE, HDPE and hydrophilic TPX polymer are blended and modified to form a blend, so that the TPX material is obtained;
the preparation method of the hydrophilic TPX polymer comprises the following steps:
the TPX polymer is subjected to plasma treatment and then reduction treatment to obtain the hydrophilic TPX polymer.
2. The method of preparing a TPX polymer material according to claim 1, wherein the plasma treatment time is 1-120 min.
3. The method of preparing a TPX polymeric material of claim 1, wherein the reduction treatment is reduction with sodium borohydride.
4. The method for preparing a TPX polymer material according to claim 1 or 3, wherein the time of the reduction treatment is 1 to 5 hours.
5. The method for preparing TPX polymer material according to claim 1, wherein the POE accounts for 15-30% of the TPX.
6. The method of claim 1, wherein the HDPE comprises 5% to 15% by mass of the TPX.
7. The method for preparing TPX polymer material according to claim 1, wherein the rotation speed of the twin-screw extruder is controlled to be 60-120rpm on the premise that the twin-screw extruder is used for blending modification.
8. The method for preparing TPX polymer material as claimed in claim 1, wherein the temperature of blending modification is 170-220 ℃.
9. A TPX polymer material produced by the method of producing a TPX polymer material according to any one of claims 1 to 8.
10. A cable comprising a covering of the TPX polymer material of claim 9.
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2022
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