CN112876774A - Polypropylene material and preparation method thereof - Google Patents

Polypropylene material and preparation method thereof Download PDF

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Publication number
CN112876774A
CN112876774A CN201911204077.XA CN201911204077A CN112876774A CN 112876774 A CN112876774 A CN 112876774A CN 201911204077 A CN201911204077 A CN 201911204077A CN 112876774 A CN112876774 A CN 112876774A
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polypropylene
parts
temperature
self
polypropylene material
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杨桂生
计娉婷
姚晨光
朱敏
廖雄兵
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Hefei Genius New Materials Co Ltd
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Hefei Genius New Materials Co Ltd
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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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a polypropylene material and a preparation method thereof, wherein the polypropylene material is prepared from 63-92.3 parts of polypropylene, 5-10 parts of a toughening agent, 0-20 parts of an inorganic filler, 2-5 parts of a self-repairing material, 0.2-1 part of an antioxidant and 0.5-1 part of a processing aid in parts by weight, wherein the self-repairing material is prepared from glycerol monomethacrylate, PP-G, boric acid and polypropylene powder through a hydrothermal reaction. Compared with the traditional material, the sensitivity of the polypropylene material prepared by the invention to machining gaps is obviously reduced, and the impact strength of the polypropylene material is close to that of the gaps of molding gaps, so that the application effect of the polypropylene material is improved, and the application field of the polypropylene material is expanded.

Description

Polypropylene material and preparation method thereof
Technical Field
The invention belongs to the field of modification of high polymer materials, and particularly relates to a polypropylene material and a preparation method thereof.
Background
Polypropylene is a thermoplastic synthetic resin with excellent performance, has the advantages of small specific gravity, no toxicity, easy processing, good impact strength, flexibility resistance, electric insulation performance and the like, and is widely used in automobiles, electronic appliances and household electrical appliances.
However, polypropylene has a large notch sensitivity, and when a sample strip or a product has a defect, the defect is easy to serve as a stress concentration point, and the product is broken continuously from the position, so that the impact resistance of the product with slight defects is greatly reduced, and the long-term application of the polypropylene material is limited.
Disclosure of Invention
In view of the above, the present invention needs to provide a polypropylene material and a preparation method thereof, wherein a self-made self-repairing material is added during a polypropylene modification process, so that the prepared polypropylene material can spontaneously form a cross-linked structure at a notch and a damaged part, and the bonding strength at the notch and the damaged part is improved, thereby improving the notch sensitivity resistance of the material, and solving the technical problem that polypropylene has large notch sensitivity in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the polypropylene material is characterized by being prepared from 63-92.3 parts of polypropylene, 5-10 parts of a toughening agent, 0-20 parts of an inorganic filler, 2-5 parts of a self-repairing material, 0.2-1 part of an antioxidant and 0.5-1 part of a processing aid in parts by weight, wherein the self-repairing material is prepared from glycerol monomethacrylate, PP-G, boric acid and polypropylene through a hydrothermal reaction.
Further, the polypropylene is one or a mixture of homo-polypropylene and co-polypropylene.
Further, the toughening agent is a polyolefin elastomer. It is understood that the polyolefin elastomer in the present invention refers to a kind of polyolefin material copolymerized by ethylene and propylene or other α -olefin (such as 1-butene, 1-hexene, 1-octene, etc.), which mainly includes two main types of ethylene-propylene copolymer and ethylene/α -olefin copolymer, and the polyolefin elastomer in the present invention is conventionally used in the art, such as EPM, EPDM, POE, OBC, etc. can be used in the present invention to achieve the purpose of the present invention, and is not exemplified herein.
Further, the inorganic filler is an inorganic material with an aspect ratio, and comprises one or a combination of more than two of talcum powder, wollastonite, whiskers, mica and barium sulfate.
Further, the antioxidant is selected from one of phenols, amines, phosphites, hindered phenols, complexes of acryloyl functional groups and thioesters, and calixarene.
Further, the processing aid comprises a lubricant, and the lubricant is selected from one of calcium stearate, zinc stearate or erucamide.
Further, the self-repairing material is prepared from 30-50 parts of glycerol monomethacrylate, 10-20 parts of PP-G, 10-20 parts of boric acid and 10-50 parts of polypropylene powder in parts by weight. In the preparation process of the material, the proportion of the raw materials also has great influence on the performance of the material, so that the proportion of the raw materials is optimized, the performance of the prepared self-repairing material is optimal, and the self-repairing effect of the self-repairing material is fully exerted.
Further, the preparation process of the self-repairing material comprises the following steps: and dissolving the glycerol monomethacrylate, the PP-G, the boric acid and the polypropylene powder in distilled water, carrying out hydrothermal reaction at 110-150 ℃ for 3-5h, and filtering and washing a product to obtain the self-repairing material. It can be understood that, in the process of the hydrothermal reaction, the temperature and the time of the reaction have certain influence on the performance, the yield and the like of the material, so that the invention optimizes the conditions of the hydrothermal reaction, optimizes the performance of the self-repairing material and more fully exerts the self-repairing effect of the self-repairing material.
The invention also provides a preparation method of the polypropylene material, which comprises the following steps:
uniformly mixing polypropylene, a toughening agent, an inorganic filler, an antioxidant, a self-repairing material and a processing aid according to a ratio, and then carrying out melt extrusion and granulation to obtain the polypropylene material. It should be understood that the term "uniformly mixing" herein generally means that the raw materials are uniformly mixed by mechanical blending, and the rotation speed, time, etc. of mixing can be adjusted as required as long as the purpose of uniform mixing can be achieved, and therefore, the present invention is not limited specifically herein.
Preferably, the melt extrusion and granulation adopt a twin-screw extruder, and the working temperature of each section of the twin-screw extruder is as follows: the temperature of the feeding section is 160-180 ℃, the temperature of the compression section is 170-190 ℃, the temperature of the plasticizing section is 180-190 ℃, the temperature of the homogenizing section is 190-200 ℃, and the temperature of the die orifice is 190-200 ℃. In the field of extrusion processing of polymer materials, the temperature of extrusion and the like can be adjusted according to different processing systems, and in some embodiments of the present invention, the above processing temperature is preferred, and it is understood that the temperature can be adjusted by a person skilled in the art according to different systems, and is not limited to the above parameters.
Compared with the prior art, the self-repairing material prepared from glycerol monomethacrylate, PP-G, boric acid and polypropylene powder through a hydrothermal reaction is added in the polypropylene modification process, on one hand, the glycerol monomethacrylate is subjected to surface grafting with the polypropylene powder through the PP-G, on the other hand, in the presence of the boric acid, the glycerol monomethacrylate molecules are bonded through a B atom, the bond is a dynamic ionic bond, the dynamic ionic bond has a dynamic reversible effect at room temperature, the dynamic reticular structure is dispersed in the polypropylene material, and a cross-linking structure can be spontaneously formed at a gap and a damaged part of the material, so that the bonding strength at the gap is improved, and the notch sensitivity resistance of the polypropylene material is improved, wherein the specific reaction formula of the glycerol monomethacrylate molecules bonded through the B atom is as follows:
Figure BDA0002296560150000031
compared with the traditional material, the sensitivity of the polypropylene material prepared by the invention to machining gaps is obviously reduced, and the impact strength of the polypropylene material is close to that of the gaps of molding gaps, so that the application effect of the polypropylene material is improved, and the application field of the polypropylene material is expanded.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
The compositions and proportions of the raw materials in this example are shown in the following table:
Figure BDA0002296560150000032
the preparation method of the self-repairing material in the embodiment comprises the following steps: dissolving 40 parts of glycerol monomethacrylate, 15 parts of PP-G, 15 parts of boric acid and 30 parts of polypropylene powder in distilled water according to the parts by weight, heating the mixture in a reaction kettle to 130 ℃, carrying out hydrothermal reaction for 4 hours, and filtering and washing the product to obtain the self-repairing material.
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 4min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 170 ℃, the temperature of the compression section is 180 ℃, the temperature of the plasticizing section is 185 ℃, the temperature of the homogenizing section is 195 ℃ and the temperature of the die orifice is 195 ℃.
Example 2
The compositions and proportions of the raw materials in this example are shown in the following table:
Figure BDA0002296560150000041
the preparation method of the self-repairing material in the embodiment comprises the following steps: dissolving 35 parts of glycerol monomethacrylate, 12 parts of PP-G, 12 parts of boric acid and 41 parts of polypropylene powder in distilled water according to the parts by weight, heating the mixture to 120 ℃ in a reaction kettle, carrying out hydrothermal reaction for 3.5 hours, and filtering and washing the product to obtain the self-repairing material.
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 4min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 170 ℃, the temperature of the compression section is 180 ℃, the temperature of the plasticizing section is 185 ℃, the temperature of the homogenizing section is 195 ℃ and the temperature of the die orifice is 195 ℃.
Example 3
The compositions and proportions of the raw materials in this example are shown in the following table:
Figure BDA0002296560150000042
Figure BDA0002296560150000051
the preparation method of the self-repairing material in the embodiment comprises the following steps: dissolving 45 parts of glycerol monomethacrylate, 16 parts of PP-G, 16 parts of boric acid and 23 parts of polypropylene powder in distilled water according to the parts by weight, heating the mixture in a reaction kettle to 140 ℃, carrying out hydrothermal reaction for 4.5 hours, and filtering and washing the product to obtain the self-repairing material.
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 3min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 175 ℃, the temperature of the compression section is 175 ℃, the temperature of the plasticizing section is 185 ℃, the temperature of the homogenizing section is 190 ℃ and the temperature of the die orifice is 195 ℃.
Example 4
The compositions and proportions of the raw materials in this example are shown in the following table:
Figure BDA0002296560150000052
the preparation method of the self-repairing material in the embodiment comprises the following steps: dissolving 30 parts of glycerol monomethacrylate, 10 parts of PP-G, 10 parts of boric acid and 50 parts of polypropylene powder in distilled water according to the parts by weight, heating the mixture in a reaction kettle to 110 ℃, carrying out hydrothermal reaction for 3 hours, and filtering and washing the product to obtain the self-repairing material.
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 3min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 160 ℃, the temperature of the compression section is 170 ℃, the temperature of the plasticizing section is 180 ℃, the temperature of the homogenizing section is 190 ℃, and the temperature of the die orifice is 190 ℃.
Example 5
The compositions and proportions of the raw materials in this example are shown in the following table:
Figure BDA0002296560150000061
the preparation method of the self-repairing material in the embodiment comprises the following steps: dissolving 50 parts of glycerol monomethacrylate, 20 parts of PP-G, 20 parts of boric acid and 10 parts of polypropylene powder in distilled water according to the parts by weight, heating the mixture in a reaction kettle to 140 ℃, carrying out hydrothermal reaction for 4.5 hours, and filtering and washing the product to obtain the self-repairing material.
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 3min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 180 ℃, the temperature of the compression section is 190 ℃, the temperature of the plasticizing section is 190 ℃, the temperature of the homogenizing section is 200 ℃, and the temperature of the die orifice is 200 ℃.
Comparative example 1
The compositions and proportions of the raw materials in this example are shown in the following table:
raw materials Specific components Parts by weight
Polypropylene copolymer PP EA5074 76.2
Inorganic filler Talcum powder 15
Toughening agent POE 8200 7
Antioxidant agent Irganox1010 0.6
Light stabilizers V703 0.6
Processing aid Calcium stearate 0.6
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 4min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 170 ℃, the temperature of the compression section is 180 ℃, the temperature of the plasticizing section is 185 ℃, the temperature of the homogenizing section is 195 ℃ and the temperature of the die orifice is 195 ℃.
Comparative example 2
The compositions and proportions of the raw materials in this example are shown in the following table:
raw materials Specific components Parts by weight
Polypropylene copolymer PP EA5074 80.8
Inorganic filler Whisker 10
Toughening agent POE 8842 8
Antioxidant agent Irganox1010 0.4
Light stabilizers V703 0.4
Processing aid Zinc stearate 0.4
Adding the components into a high-speed mixer according to the proportion in the table, dry-mixing for 4min, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the polypropylene material, wherein the working temperature of each section of the double-screw extruder is as follows: the temperature of the feeding section is 170 ℃, the temperature of the compression section is 180 ℃, the temperature of the plasticizing section is 185 ℃, the temperature of the homogenizing section is 195 ℃ and the temperature of the die orifice is 195 ℃.
The polypropylene materials prepared in examples 1-5 and comparative examples 1-2 were subjected to a relevant mechanical property test, wherein the machining notch impact property test is a test result after the post-machining state was adjusted for 88 hours, and the specific data results are shown in table 1:
TABLE 1 Performance test results for Polypropylene materials of examples 1-5 and comparative examples 1-2
Test items Impact strength of simply supported beam notch (Molding) Simply supported beam gapMouth impact strength (machining)
Standard of merit ISO 179 ISO 179
Condition 23℃,4.0mm 23℃,4.0mm
Unit of kJ/m2 kJ/m2
Example 1 26 25.4
Example 2 18.3 18.1
Example 3 22.5 21.4
Example 4 12.4 12
Example 5 8.2 8
Comparative example 1 8.5 4.2
Comparative example 2 13.2 7.6
As can be seen from the above table, the notch sensitivity of the notch-sensitive-resistant polypropylene material prepared by the invention is obviously reduced compared with the traditional material, and the notch impact strength performance of the notch-sensitive-resistant polypropylene material is close to that of a molding notch, so that the application effect and the application field of the polypropylene material are improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The polypropylene material is characterized by being prepared from 63-92.3 parts of polypropylene, 5-10 parts of a toughening agent, 0-20 parts of an inorganic filler, 2-5 parts of a self-repairing material, 0.2-1 part of an antioxidant and 0.5-1 part of a processing aid in parts by weight, wherein the self-repairing material is prepared from glycerol monomethacrylate, PP-G, boric acid and polypropylene powder through a hydrothermal reaction.
2. The polypropylene material of claim 1, wherein the polypropylene is a mixture of one or both of homo-polypropylene and co-polypropylene.
3. The polypropylene material of claim 1, wherein the toughening agent is a polyolefin elastomer.
4. The polypropylene material of claim 1, wherein the inorganic filler is an inorganic material having an aspect ratio comprising one or a combination of two or more of talc, wollastonite, whiskers, mica, and barium sulfate.
5. The polypropylene material of claim 1, wherein the antioxidant is selected from the group consisting of phenols, amines, phosphites, hindered phenols, complexes of acryloyl functional groups and thioesters, calixarenes.
6. The polypropylene material of claim 1, wherein the processing aid comprises a lubricant selected from one of calcium stearate, zinc stearate, or erucamide.
7. The polypropylene material of claim 1, wherein the self-repairing material is prepared from 30-50 parts by weight of glycerol monomethacrylate, 10-20 parts by weight of PP-G, 10-20 parts by weight of boric acid and 10-50 parts by weight of polypropylene powder.
8. The polypropylene material of claim 1, wherein the self-healing material is prepared by a process comprising: and dissolving the glycerol monomethacrylate, the PP-G, the boric acid and the polypropylene powder in distilled water, carrying out hydrothermal reaction at 110-150 ℃ for 3-5h, and filtering and washing a product to obtain the self-repairing material.
9. A process for the preparation of a polypropylene material according to any one of claims 1 to 8, comprising the steps of:
uniformly mixing polypropylene, a toughening agent, an inorganic filler, an antioxidant, a self-repairing material and a processing aid according to a ratio, and then carrying out melt extrusion and granulation to obtain the polypropylene material.
10. The method of claim 9, wherein the molten base and the pellets are produced by a twin-screw extruder, and the operating temperature of each section of the twin-screw extruder is as follows: the temperature of the feeding section is 160-180 ℃, the temperature of the compression section is 170-190 ℃, the temperature of the plasticizing section is 180-190 ℃, the temperature of the homogenizing section is 190-200 ℃, and the temperature of the die orifice is 190-200 ℃.
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Application publication date: 20210601