CN111748154A - High-performance reinforced polypropylene composite material - Google Patents

High-performance reinforced polypropylene composite material Download PDF

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Publication number
CN111748154A
CN111748154A CN201910245653.9A CN201910245653A CN111748154A CN 111748154 A CN111748154 A CN 111748154A CN 201910245653 A CN201910245653 A CN 201910245653A CN 111748154 A CN111748154 A CN 111748154A
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polypropylene
rubber
nano
performance reinforced
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杨桂生
计娉婷
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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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
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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
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    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K3/34—Silicon-containing compounds
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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Abstract

The invention discloses a high-performance reinforced polypropylene composite material which is prepared from the following components in parts by weight: 33-95.8 parts of polypropylene, 1-30 parts of glass fiber, 2-10 parts of nano rubber, 1-5 parts of maleic anhydride grafted polypropylene, 0.1-1 part of antioxidant, 0.1-1 part of lubricant and 0-20 parts of filler. Wherein the nanometer rubber is rubber powder with the particle size of 10-100 nm. The high-performance reinforced polypropylene composite material prepared by the invention is added with the nano-scale rubber powder, and is used for improving the interfacial force between the glass fiber and the polypropylene base material, particularly improving the strength and toughness of the material under the low-temperature condition.

Description

High-performance reinforced polypropylene composite material
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a high-performance reinforced polypropylene composite material.
Background
Polypropylene (PP) is one of the most rapidly developed plastic varieties in the plastic industry, and has the advantages of good mechanical property, light specific gravity, no toxicity, easy processing, corrosion resistance and the like; and because the polypropylene has wide raw material sources and low price, the polypropylene has wide application in the fields of household appliances, automobiles, packaging and the like, and particularly has very wide application in the fields of automobiles, electric tools, household appliances and the like.
However, the properties of the composite material are not only related to the properties of the matrix and the reinforcing fibers, but also have a close relationship with the properties of the interface, and generally, the material failure process is that firstly, cracks are generated at the interface, the cracks gradually increase until the material is completely destroyed, and macroscopically, the strength and the toughness of the material are lower. The invention firstly proposes that the nano rubber particles are used for improving the interface acting force between the fiber and the base material, and particularly improving the strength and the toughness of the material under the low-temperature condition. Under the low temperature condition, the glass fiber and the matrix resin both shrink in volume, but the shrinkage conditions are different due to different thermal expansion coefficients of the glass fiber and the matrix resin, so that the surface tension of the interface joint of the glass fiber and the matrix resin is large, crack defects are easy to generate, and the impact resistance of the material is reduced under the low temperature condition. The nano-level rubber powder is added into the high-performance reinforced polypropylene composite material prepared by the invention, so that a layer of rubber is distributed between the fibers and the base material. At normal temperature, the rubber is in a high elastic state, so that the impact resistance of the material can be greatly improved; meanwhile, the nano rubber powder can improve the binding force between the glass fiber and the matrix, and can effectively bear external force, so that the strength is improved at the same time. The crystallinity of the base material is improved at low temperature, the cross-linked structure is more compact, the shape is not easy to change, the brittleness is increased, the combination between the matrix resin and the fiber can be more compact due to the nanometer rubber particles at the combination part of the base material and the glass fiber, and meanwhile, the nanometer particles can effectively block the capability of micro-crack expansion, so that the capability of bearing external load is improved, and the toughness and the rigidity of the material are obviously improved compared with the traditional glass fiber reinforced material at low temperature.
Disclosure of Invention
The invention aims to provide a high-performance reinforced polypropylene composite material.
The purpose of the invention can be realized by the following technical scheme:
a high-performance reinforced polypropylene composite material is prepared from the following components in parts by weight:
33-95.8 parts of polypropylene
1-30 parts of glass fiber
2-10 parts of nano rubber
1-5 parts of maleic anhydride grafted polypropylene
0.1 to 1 portion of antioxidant
0.1 to 1 portion of lubricant
0-20 parts of a filler;
wherein the nanometer rubber is rubber powder with the particle size of 10-100 nm.
In a further scheme, the polypropylene is one or a mixture of more of homo-polypropylene, co-polypropylene and random co-polypropylene; the melt flow rate of the solution is 0.5-100g/min under the condition of 2.16kg/230 ℃.
The glass fiber is chopped glass fiber with the diameter of 5-20 microns.
The nano rubber is at least one of nano cis-1, 4-polyisoprene rubber, nano butadiene styrene rubber and nano cis-1, 4-polybutadiene rubber.
The grafting rate of the maleic anhydride grafted polypropylene is 0.6-2.0 wt%.
The antioxidant is at least one of phosphite antioxidant and hindered phenol antioxidant.
The lubricant is at least one of stearic acid, amide and erucamide lubricants.
The filler is at least one of talcum powder, calcium carbonate and mica powder.
The invention has the beneficial effects that:
the invention firstly proposes that the nano rubber particles are used for improving the interface acting force between the glass fiber and the polypropylene base material, and particularly improving the strength and the toughness of the material under the low-temperature condition. Under the low temperature condition, the glass fiber and the matrix resin both shrink in volume, but the shrinkage conditions are different due to different thermal expansion coefficients of the glass fiber and the matrix resin, so that the surface tension of the interface joint of the glass fiber and the matrix resin is large, crack defects are easy to generate, and the impact resistance of the material is reduced under the low temperature condition. The high-performance reinforced polypropylene composite material prepared by the invention can ensure that a layer of rubber is distributed between the fiber and the base material by adding the nano-scale rubber powder. At normal temperature, the rubber is in a high elastic state, so that the impact resistance of the material can be greatly improved; meanwhile, the nano rubber powder can improve the binding force between the glass fiber and the matrix, and can effectively bear external force, so that the strength is improved at the same time. The crystallinity of the base material is improved at low temperature, the cross-linked structure is more compact, the shape is not easy to change, the brittleness is increased, the combination between the matrix resin and the fiber can be more compact due to the nanometer rubber particles at the combination part of the base material and the glass fiber, and meanwhile, the nanometer particles can effectively block the capability of micro-crack expansion, so that the capability of bearing external load is improved, and the toughness and the rigidity of the material are obviously improved compared with the traditional glass fiber reinforced material at low temperature.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Homo-polypropylene 1 (homo-PP 1): the melt flow rate was 60g/10min (230 ℃/2.16kg) and the density was 0.9g/cm3。
Homo-polypropylene 2 (homo-PP 2): the melt flow rate was 20g/10min (230 ℃/2.16kg) and the density was 0.9g/cm3。
Copolypropylene 1 (homopolypropylene 1): the melt flow rate was 15g/10min (230 ℃/2.16kg) and the density was 0.89g/cm3。
Copolypropylene 2 (homopolypropylene 2): the melt flow rate was 40g/10min (230 ℃/2.16kg) and the density was 0.89g/cm3。
Random copolymerized polypropylene: the Melt Flow Rate (MFR) was 5g/10min (230 ℃/2.16 kg).
Glass fiber: the chopped glass fiber has a diameter of 5-20 microns and is produced by Shandong Jushi glass fiber company.
Nano rubber powder: the grain diameter is 10-100 nanometers, and the manufacturers are China petrochemical Beijing chemical research institute.
The maleic anhydride grafted polypropylene has a grafting rate of 0.6-2.0wt%, and is synthesized by manufacturers in Guangzhou.
Talc powder: the particle size is 1-5 μm, and the manufacturer is Liaoning ai Hai.
Mica powder: the grain diameter is 5-15 μm, and the manufacturer is Tanshina mica material Co.
Calcium carbonate: particle size 1-15 μm, Shijiazhuanjin mining Co., Ltd.
Antioxidant 1010: the manufacturer is Nanjing Hua Li Ming chemical Co.
Antioxidant 168: the manufacturer is Nanjing Hua Li Ming chemical Co.
Calcium stearate: the manufacturer is Huaming Tai chemical materials Co., Ltd.
Examples 1 to 6:
the polypropylene materials of specific examples 1-6 were prepared according to the amounts of the components in table 1, and the preparation method thereof can adopt the conventional technical scheme in the art, specifically: weighing the components according to the dosage in the table 1, mixing the components in a high-speed mixer for 5min, and extruding and granulating by a double-screw extruder, wherein the corresponding process parameters are as follows: 190 ℃ in the first zone, 205 ℃ in the second zone, 220 ℃ in the third zone, 210 ℃ in the fourth zone, 210 ℃ in the head and 500 rpm in the speed of the twin-screw extruder.
And (3) carrying out related experimental tests on the obtained product, wherein the tensile strength test comprises the following steps: GB/T1040 test standard; notched impact strength test: GB/T1843 test Standard. The test results are shown in table 2.
Comparative examples 1 to 2:
the ingredients were weighed out in the amounts indicated in Table 1 and the preparation was as in example 1.
And (3) carrying out related experimental tests on the obtained product, wherein the tensile strength test comprises the following steps: GB/T1040 test standard; notched impact strength test: GB/T1843 test Standard. The test results are shown in table 2.
TABLE 1
Figure BDA0002010985810000051
TABLE 2
Figure BDA0002010985810000052
As can be seen from the test results of the specific examples 1-6 and the comparative examples 1-2 in the table 2, the rigidity and the toughness of the polypropylene composite material prepared by the invention are improved, the material can maintain higher toughness even under low temperature conditions, the application field of the polypropylene material is greatly expanded, and the polypropylene composite material has greater economic benefit when being applied to engineering parts and structural parts.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.

Claims (8)

1. A high-performance reinforced polypropylene composite material is characterized in that: the composition is prepared from the following components in parts by weight:
33-95.8 parts of polypropylene
1-30 parts of glass fiber
2-10 parts of nano rubber
1-5 parts of maleic anhydride grafted polypropylene
0.1 to 1 portion of antioxidant
0.1 to 1 portion of lubricant
0-20 parts of a filler;
wherein the nanometer rubber is rubber powder with the particle size of 10-100 nm.
2. The high performance reinforced polypropylene composite of claim 1, wherein: the polypropylene is one or a mixture of more of homo-polypropylene, co-polypropylene and random co-polypropylene; the melt flow rate of the solution is 0.5-100g/min under the condition of 2.16kg/230 ℃.
3. The high performance reinforced polypropylene composite of claim 1, wherein: the glass fiber is chopped glass fiber with the diameter of 5-20 microns.
4. The high performance reinforced polypropylene composite of claim 1, wherein: the nano rubber is at least one of nano cis-1, 4-polyisoprene rubber, nano butadiene styrene rubber and nano cis-1, 4-polybutadiene rubber.
5. The high performance reinforced polypropylene composite of claim 1, wherein: the grafting rate of the maleic anhydride grafted polypropylene is 0.6-2.0 wt%.
6. The high performance reinforced polypropylene composite of claim 1, wherein: the antioxidant is at least one of phosphite antioxidant and hindered phenol antioxidant.
7. The high performance reinforced polypropylene composite of claim 1, wherein: the lubricant is at least one of stearic acid, amide and erucamide lubricants.
8. The high performance reinforced polypropylene composite of claim 1, wherein: the filler is at least one of talcum powder, calcium carbonate and mica powder.
CN201910245653.9A 2019-03-28 2019-03-28 High-performance reinforced polypropylene composite material Withdrawn CN111748154A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112538216A (en) * 2020-12-08 2021-03-23 武汉金发科技有限公司 Polypropylene composite material and preparation method thereof
CN113402872A (en) * 2021-07-29 2021-09-17 公牛集团股份有限公司 Spraying-free material with terrazzo effect and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112538216A (en) * 2020-12-08 2021-03-23 武汉金发科技有限公司 Polypropylene composite material and preparation method thereof
CN113402872A (en) * 2021-07-29 2021-09-17 公牛集团股份有限公司 Spraying-free material with terrazzo effect and preparation method thereof

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Application publication date: 20201009