CN113444321A - Polypropylene-based composite foaming base material and preparation method thereof - Google Patents
Polypropylene-based composite foaming base material and preparation method thereof Download PDFInfo
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- CN113444321A CN113444321A CN202110954461.2A CN202110954461A CN113444321A CN 113444321 A CN113444321 A CN 113444321A CN 202110954461 A CN202110954461 A CN 202110954461A CN 113444321 A CN113444321 A CN 113444321A
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- polypropylene
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- -1 Polypropylene Polymers 0.000 title claims abstract description 131
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 95
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 94
- 238000005187 foaming Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003365 glass fiber Substances 0.000 claims abstract description 91
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 229920001748 polybutylene Polymers 0.000 claims abstract description 24
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims description 26
- 229920001083 polybutene Polymers 0.000 claims description 23
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 14
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 13
- 239000008116 calcium stearate Substances 0.000 claims description 13
- 235000013539 calcium stearate Nutrition 0.000 claims description 13
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 claims description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 40
- 230000008018 melting Effects 0.000 abstract description 40
- 239000011159 matrix material Substances 0.000 description 13
- 238000005452 bending Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- 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
Landscapes
- 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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a polypropylene-based composite foaming base material and a preparation method thereof. The polypropylene-based composite foaming base material provided by the invention comprises the following raw materials: 58-90 parts of polypropylene, 3-20 parts of polybutylene alloy, 2-20 parts of modified short glass fiber, 1-8 parts of maleic anhydride grafted polypropylene, 0.05-0.5 part of antioxidant and 0.05-0.5 part of lubricant. The polypropylene-based composite foaming base material prepared from the raw materials has the advantages that the initial melting temperature and the melting temperature are reduced, the melting range is increased, the later foaming temperature is effectively reduced, and the mechanical property is more excellent.
Description
Technical Field
The invention relates to the field of foaming materials, in particular to a polypropylene-based composite foaming base material and a preparation method thereof.
Background
The polypropylene foaming product has higher tensile strength, higher elastic modulus, good thermal stability (usually, the foaming polypropylene can bear the high temperature of 130 ℃, and the polystyrene can generate softening deformation when reaching 105 ℃, and the polystyrene is only 80 ℃), good dimensional stability and environmental stress cracking resistance; in addition, due to the existence of methyl on the molecular chain of the polypropylene, the degradation performance of the polypropylene is superior to that of other foaming materials. The characteristics lead the polypropylene composite foaming material to be widely applied in the industries of automobiles, packaging and buildings.
Although polypropylene foams have the above advantages, ordinary polypropylene is a crystalline polymer, and its melt viscosity instantaneously decreases when its processing temperature exceeds the melting point. Therefore, the foaming temperature suitable for the common PP foaming material is higher, the foaming temperature range is narrower (about 4 ℃), and the foaming can be carried out only in the vicinity of the melting point range. In addition, after the polymer is foamed, the effective bearing area of the material is reduced, and under the condition of the same bearing area, cracks generated around large foam holes are easy to expand, so that the comprehensive mechanical property of a polymer foamed product is reduced, and the industrial application of the foamed polymer is limited. Therefore, the problem that needs to be solved by those skilled in the art is how to reduce the foaming temperature of the polypropylene material and widen the foaming temperature range without reducing the mechanical properties of the polypropylene.
Disclosure of Invention
In view of the above, the present invention aims to provide a polypropylene-based composite foamed base material and a preparation method thereof. The polypropylene-based composite foaming base material provided by the invention reduces the foaming temperature, widens the foaming temperature range and keeps higher mechanical property.
The invention provides a polypropylene-based composite foaming base material which is prepared from the following raw materials in parts by mass:
preferably, the polypropylene is homo-polypropylene and/or co-polypropylene;
the melt index of the polypropylene under the test conditions of 2.16kg load and 230 ℃ is 3-20 g/10 min; the weight average molecular weight of the polypropylene is 100000-800000.
Preferably, the polybutylene alloy comprises the following structural units in mass ratio:
60% -95% of polybutylene structural units;
4.9 to 35 percent of polypropylene structural unit;
0.1 to 5 percent of polybutylene-polypropylene block copolymer structural unit.
Preferably, the melt index of the polybutylene alloy under the test conditions of 2.16kg load and 190 ℃ is 1-10 g/10 min; the weight average molecular weight of the polypropylene is 100000-800000.
Preferably, the modified short glass fiber is gamma-aminopropyltriethoxysilane modified short glass fiber;
in the modified short glass fiber, the diameter of the short glass fiber is 8-15 μm, and the length-diameter ratio is 5-10.
Preferably, the modified short glass fiber is prepared by the following preparation method:
s1, carrying out heat treatment on the short glass fiber to obtain the treated short glass fiber;
and S2, dipping the treated short glass fiber by utilizing a gamma-aminopropyltriethoxysilane solution, and drying to obtain the modified short glass fiber.
Preferably, the first and second liquid crystal materials are,
in the step S1:
the heat treatment comprises: sintering treatment and drying treatment;
the sintering treatment temperature is 300-600 ℃, and the time is 1-3 h;
the drying treatment temperature is 80-110 ℃, and the drying treatment time is 20-60 min;
in the step S2:
the volume concentration of the gamma-aminopropyl triethoxysilane solution is 0.5-2%;
the drying temperature is 80-120 ℃, and the drying time is 5-20 min.
Preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1330, antioxidant 3114, antioxidant 1076, antioxidant 626, antioxidant 168 and antioxidant 618;
the lubricant comprises one or more of zinc stearate, calcium stearate, stearic acid, polyethylene wax and chlorinated polyethylene.
Preferably, the antioxidant is 1010 and 168;
the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1: 0.5-2;
the lubricant is polyethylene wax and calcium stearate;
the mass ratio of the polyethylene wax to the calcium stearate is 1: 0.5-2.
The invention also provides a preparation method of the polypropylene-based composite foaming base material in the technical scheme, which comprises the following steps:
a) blending polypropylene, polybutylene alloy, modified short glass fiber, maleic anhydride grafted polypropylene, an antioxidant and a lubricant to obtain a premix;
b) and extruding and granulating the premix to obtain the polypropylene-based composite foaming base material.
The polypropylene-based composite foaming base material provided by the invention comprises the following raw materials: 58-90 parts of polypropylene, 3-20 parts of polybutylene alloy (PB-A), 2-20 parts of modified short glass fiber (modified SGF), 1-8 parts of maleic anhydride grafted polypropylene (PP-g-MAH), 0.05-0.5 part of antioxidant and 0.05-0.5 part of lubricant. Adding polybutylene alloy components to reduce the initial melting temperature and the melting temperature and widen the melting range, thereby widening the later processing window and reducing the foaming temperature; the short glass fiber is added, and due to the dual functions of surface modification treatment and introduction of maleic anhydride grafted polypropylene, the interface compatibility between the short glass fiber and matrix resin is enhanced, so that the short glass fiber is easier to be wrapped by the matrix, the dispersibility of the short glass fiber in the matrix is improved, the interaction between the short glass fiber and the matrix is enhanced, and the mechanical property of the polypropylene foam material is improved. Therefore, the chopped glass fiber reinforced polypropylene foaming material provided by the invention has the advantages of reduced initial melting temperature and melting temperature, widened melting range and excellent mechanical property.
Experimental results show that the polypropylene-based composite foaming base material provided by the invention has the initial melting temperature of below 116 ℃, the melting temperature of below 149.5 ℃ and the melting range of above 41.5 ℃; tensile strength of 23MPa or more, bending strength of 21MPa or more, bending modulus of 880MPa or more, and cantilever beam impact strength of 5.6kJ.m-2The above.
Detailed Description
The invention provides a polypropylene-based composite foaming base material which is prepared from the following raw materials in parts by mass:
the polypropylene-based composite foaming base material provided by the invention is prepared by matching the raw materials according to a certain proportion, and adding the polybutylene alloy component to reduce the initial melting temperature and the melting temperature and widen the melting range, so that the later-stage processing window is widened and the foaming temperature is reduced; the short glass fiber is added, and due to the dual functions of the gamma-aminopropyltriethoxysilane coupling agent surface treatment and the maleic anhydride grafted polypropylene, the interface compatibility between the short glass fiber and the matrix resin is enhanced, so that the short glass fiber is easier to be wrapped by the matrix, the dispersibility of the short glass fiber in the matrix is improved, the interaction between the short glass fiber and the matrix is enhanced, and the mechanical property of the polypropylene foaming material is improved. Therefore, the chopped glass fiber reinforced polypropylene foaming material provided by the invention has the advantages of reduced initial melting temperature and melting temperature, widened melting range and excellent mechanical property.
In the present invention, the polypropylene is a matrix component, preferably homo-polypropylene and/or co-polypropylene. In order to enable the polypropylene foaming material to have better melt strength and mechanical property, the melt index of the polypropylene under the test conditions of 2.16kg load and 230 ℃ is 3-20 g/10min, and more preferably 5-10 g/10 min; the weight average molecular weight of the polypropylene is 100000-800000, and more preferably 250000-500000. In the invention, the content of the polypropylene is 58-90 parts, preferably 80-90 parts, and more preferably 85-90 parts; in some embodiments of the invention, the polypropylene is present in an amount of 81.9 parts, 83.7 parts, 85.5 parts, or 87.3 parts.
In the invention, the polybutylene alloy (also called PB-A) resin is a high molecular polymer and is mainly prepared by polymerizing butylene-1 and a second monomer in a kettle position. In the invention, the polybutylene alloy is a polymer comprising three structural units of polybutylene-polypropylene-polybutylene polypropylene block copolymer. In the invention, the polybutylene alloy comprises the following components: 60 wt% -95 wt% of polybutylene structural unit, 4.9 wt% -35 wt% of polypropylene structural unit and 0.1 wt% -5 wt% of polybutylene-polypropylene block copolymer structural unit. In the present invention, the content of the polybutene structural unit in the polybutene alloy may be specifically 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%; the content of the polypropylene structural unit may specifically be 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt% or 35 wt%; the content of the polybutene-polypropylene block copolymer structural unit may be specifically 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% by weight. In the invention, the ratio of the three structural units of the polybutylene alloy is controlled to be in the range, so that the product can obtain proper melting temperature and mechanical property, and if the ratio of the polybutylene to the block copolymer is increased, the mechanical property of the product is reduced; if the ratio of polybutene to block copolymer is decreased, the primary melting temperature of the product is increased. The source of the polybutene alloy is not particularly limited, and the polybutene alloy is commercially available.
In the invention, in order to enable the composite foaming material to have better melt strength and mechanical property, the melt index of the polybutylene alloy under the test conditions of 2.16kg load and 190 ℃ is 1-10 g/10min, and more preferably 2-8 g/10 min; the weight average molecular weight of the polybutene alloy is 100000-800000, and more preferably 250000-500000.
In the invention, the content of the polybutylene alloy is 3-20 parts, preferably 5-15 parts; in some embodiments of the invention, the polybutene alloy is present in an amount of 9.1 parts, 9.3 parts, 9.5 parts, or 9.7 parts.
In the invention, the polypropylene and the polybutylene alloy are granular materials. Preferably, the polypropylene and polybutene alloys have comparable molecular weights.
In the invention, the modified short glass fiber is gamma-aminopropyltriethoxysilane modified short glass fiber, namely, gamma-aminopropyltriethoxysilane is used as a modifier to modify the short glass fiber. Wherein the short glass fibers (i.e., SGF) preferably have the following dimensions: the diameter is 8-15 mu m, and the length-diameter ratio is 5-10; if the fiber size is too short or too long, the mechanical property of the product is not obviously enhanced.
In the present invention, the modified short glass fiber is preferably prepared by the following preparation method:
s1, carrying out heat treatment on the short glass fiber to obtain the treated short glass fiber;
and S2, dipping the treated short glass fiber by utilizing a gamma-aminopropyltriethoxysilane solution, and drying to obtain the modified short glass fiber.
Regarding step S1: the heat treatment comprises: sintering treatment and drying treatment. Wherein the sintering treatment temperature is 300-600 ℃, and preferably 500 ℃; the time of the sintering treatment is 1-3 h, preferably 2 h. The drying treatment is preferably a vacuum drying treatment. The drying temperature is 80-110 ℃, and preferably 100 ℃; the drying time is 20-60 min, preferably 40 min. Through the above treatment, the surface attachments of the short glass fibers are removed, and the treated short glass fibers are obtained.
Regarding step S2: the gamma-aminopropyl triethoxysilane solution is prepared by dissolving gamma-aminopropyl triethoxysilane (namely KH-550) in a solvent. The solvent is preferably one or more of absolute ethyl alcohol, methanol and acetone. The volume concentration of the gamma-aminopropyltriethoxysilane solution is 0.5-2%, preferably 1%. The temperature of the dipping treatment is not particularly limited, and the dipping treatment can be carried out at room temperature, wherein the room temperature can be specifically 15-30 ℃; the dipping time is 15-30 min, preferably 20 min. After the impregnation treatment, drying is performed, and the drying is preferably performed in an air atmosphere. The drying temperature is 80-120 ℃, and preferably 110 ℃; the drying time is 5-20 min, preferably 10 min. And (3) distilling and volatilizing the solvent on the surface of the short glass fiber through drying treatment, and uniformly dispersing the fiber to obtain the modified short glass fiber.
In the modified short glass fiber, the modifier accounts for 2-10% of the whole modified short glass fiber by mass.
In the invention, the content of the modified short glass fiber is 2-10 parts, preferably 2-8 parts, and specifically can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts.
In the present invention, the maleic anhydride grafted polypropylene (i.e., PP-g-MAH) is present in an amount of 1 to 8 parts, and in some embodiments, the maleic anhydride grafted polypropylene is present in an amount of 5 parts. The source of the maleic anhydride grafted polypropylene is not particularly limited in the invention, and the maleic anhydride grafted polypropylene can be a general commercial product or prepared according to a conventional preparation method in the field.
In the invention, the antioxidant is preferably one or more of antioxidant 1010, antioxidant 1330, antioxidant 3114, antioxidant 1076, antioxidant 626, antioxidant 168 and antioxidant 618; more preferably, the antioxidant 1010 and the antioxidant 168 are compounded. Wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is preferably 1: 0.5-2, and specifically can be 1: 0.5, 1:1, 1: 1.5 or 1: 2. In the invention, the content of the antioxidant is 0.05-0.5 part, and specifically can be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part.
In the invention, the lubricant comprises one or more of zinc stearate, calcium stearate, stearic acid, polyethylene wax and chlorinated polyethylene; more preferably a polyethylene wax and calcium stearate. The mass ratio of the polyethylene wax to the calcium stearate is preferably 1: 0.5-2, and specifically can be 1: 0.5, 1:1, 1: 1.5 or 1: 2. In the invention, the number average molecular weight of the polyethylene wax is preferably 2000-10000, and more preferably 3000-5000; the polymerization degree of the polyethylene wax is preferably 50-500, and more preferably 100-200; the density of the polyethylene wax is preferably 0.8-1.2 g/cm3More preferably 0.95g/cm3. In the present invention, the content of the lubricant is 0.05 to 2 parts, specifically 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 1.0 part, 1.5 parts, or 2.0 parts.
In the present invention, the total amount of the raw materials, i.e., the polypropylene, the polybutene alloy, the modified short glass fiber, the maleic anhydride-grafted polypropylene, the antioxidant and the lubricant, is preferably 100 parts by mass, i.e., the amount of the raw materials is in percentage.
The invention also provides a preparation method of the polypropylene-based composite foaming base material in the technical scheme, which comprises the following steps:
a) blending polypropylene, polybutylene alloy, modified short glass fiber, maleic anhydride grafted polypropylene, an antioxidant and a lubricant to obtain a premix;
b) and extruding and granulating the premix to obtain the polypropylene-based composite foaming base material.
With respect to step a):
the types, the use amounts and the like of the polypropylene, the polybutylene alloy, the modified short glass fiber, the maleic anhydride grafted polypropylene, the antioxidant and the lubricant are consistent with those in the technical scheme, and are not repeated herein. The blending is preferably performed at high speed using a high speed mixer. The stirring speed of the blending is 300-1800 r/min, and more preferably 500-1200 r/min; the blending time is 2-10 min, and more preferably 4-6 min. The materials are uniformly mixed by the blending treatment to obtain the premix.
With respect to step b):
the extrusion granulation is carried out by an extruder; the extruder is preferably a twin screw extruder. The extrusion granulation conditions are as follows: the temperature of a first zone of the extruder is preferably 180-195 ℃, the temperature of a second zone to a third zone is preferably 185-205 ℃, the temperature of a fourth zone to a fifth zone is preferably 190-210 ℃, the temperature of a sixth zone to a seventh zone is preferably 195-215 ℃, the temperature of an eighth zone to a ninth zone is preferably 200-210 ℃, the temperature of a tenth zone to a twelfth zone is preferably 195-220 ℃, and the temperature of a head is preferably 180-220 ℃; the diameter of a screw of the extruder is preferably 20-50 mm, and specifically can be 20mm, 25mm, 30mm, 35mm, 40mm, 45mm or 50 mm; the length-diameter ratio of a screw of the extruder is preferably 30-60, and specifically can be 30, 35, 40, 45, 48, 50, 55 or 60; the feeding frequency of the extruder is preferably 30-50 Hz. And extruding and granulating to obtain the polypropylene-based composite foaming base material.
The polypropylene-based composite foaming base material provided by the invention is a base material used for preparing a foaming material, and a foaming agent (such as supercritical carbon dioxide foaming) is added for foaming in the later foaming process to prepare a foaming product.
The polypropylene-based composite foaming base material provided by the invention comprises the following raw materials: 58-90 parts of polypropylene, 3-20 parts of polybutylene alloy (PB-A), 2-20 parts of modified short glass fiber (modified SGF), 1-8 parts of maleic anhydride grafted polypropylene (PP-g-MAH), 0.05-0.5 part of antioxidant and 0.05-0.5 part of lubricant. Adding polybutylene alloy components to reduce the initial melting temperature and the melting temperature and widen the melting range, thereby widening the later processing window and reducing the foaming temperature; the short glass fiber is added, and due to the dual functions of the gamma-aminopropyltriethoxysilane coupling agent surface treatment and the maleic anhydride grafted polypropylene, the interface compatibility between the short glass fiber and the matrix resin is enhanced, so that the short glass fiber is easier to be wrapped by the matrix, the dispersibility of the short glass fiber in the matrix is improved, the interaction between the short glass fiber and the matrix is enhanced, and the mechanical property of the polypropylene foaming material is improved. Therefore, the polypropylene-based composite foaming base material provided by the invention has the advantages that the initial melting temperature and the melting temperature are reduced, the melting range is increased, the later foaming temperature is effectively reduced, and the mechanical property is more excellent.
Experimental results show that the polypropylene-based composite foaming base material provided by the invention has the initial melting temperature of below 116 ℃, the melting temperature of below 149.5 ℃ and the melting range of above 41.5 ℃; tensile strength of 23MPa or more, bending strength of 21MPa or more, bending modulus of 880MPa or more, and cantilever beam impact strength of 5.6kJ.m-2The above.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, the short glass fibers have a diameter of 8 to 15 μm and an aspect ratio of 5 to 10.
Example 1
1. Raw materials:
wherein:
the polypropylene was a copolymer polypropylene having a weight average molecular weight of 350000 and a melt index (2.16kg load, 230 ℃ C.) of 7g/10 min.
In the polybutene alloy, the polybutene content was 80 wt%, the polypropylene content was 18 wt%, the polybutene-polypropylene block copolymer content was 2 wt%, the weight average molecular weight was 750000, and the melt index (190 ℃, 2.16kg) was 1.26g/10 min.
The antioxidant is compounded by 1010 and 168 according to the mass ratio of 1: 1.
The lubricant is compounded by polyethylene wax (the number average molecular weight is 4500) and calcium stearate according to the mass ratio of 1: 1.
The modified short glass fiber is obtained by the following method:
a certain volume of silane coupling agent KH-550 and absolute ethyl alcohol are weighed to prepare a KH-550 solution with the volume concentration of 1%. Then weighing a certain mass of short glass fiber, treating for 2h at 500 ℃, and then putting the short glass fiber into a vacuum drying oven to dry for 40min at 100 ℃. And (3) soaking the treated short glass fiber in a prepared KH-550 solution for 20min at room temperature, and then drying in air at 110 ℃ for 10min to obtain the KH-550 modified short glass fiber. In the obtained modified short glass fiber, the KH-550 accounts for 5% of the total modified short glass fiber by mass.
2. Preparation:
s1, putting all the raw materials into a high-speed mixer, and blending at a high speed of 500r/min for 5min to obtain the premix.
S2, extruding and granulating the premix through a double-screw extruder under the following conditions: the temperature of the first zone of the extruder is 185 ℃, the temperature of the second zone to the third zone is 205 ℃, the temperature of the fourth zone to the fifth zone is 210 ℃, the temperature of the sixth zone to the seventh zone is 215 ℃, the temperature of the eighth zone to the ninth zone is 220 ℃, the temperature of the tenth zone to the twelfth zone is 225 ℃, the temperature of the head is 205 ℃, the diameter of the screw is 35mm, the length-diameter ratio of the screw is 48, and the feeding frequency is set to be 40 Hz. And (3) obtaining the polypropylene-based composite foaming base material through the treatment.
Example 2
1. Raw materials:
wherein:
the polypropylene was a copolymer polypropylene having a weight average molecular weight of 350000 and a melt index (2.16kg load, 230 ℃ C.) of 7g/10 min.
In the polybutene alloy, the polybutene content was 80 wt%, the polypropylene content was 18 wt%, the polybutene-polypropylene block copolymer content was 2 wt%, the weight average molecular weight was 750000, and the melt index (190 ℃, 2.16kg) was 1.26g/10 min.
The antioxidant is compounded by 1010 and 168 according to the mass ratio of 1: 1.
The lubricant is compounded by polyethylene wax (the number average molecular weight is 4500) and calcium stearate according to the mass ratio of 1: 1.
The modified short glass fiber is obtained by the following method:
a certain volume of silane coupling agent KH-550 and absolute ethyl alcohol are weighed to prepare a KH-550 solution with the volume concentration of 1%. Then weighing a certain mass of short glass fiber, treating for 2h at 500 ℃, and then putting the short glass fiber into a vacuum drying oven to dry for 40min at 100 ℃. And (3) soaking the treated short glass fiber in a prepared KH-550 solution for 20min at room temperature, and then drying in air at 110 ℃ for 10min to obtain the KH-550 modified short glass fiber. In the obtained modified short glass fiber, the KH-550 accounts for 5% of the total modified short glass fiber by mass.
2. Preparation: the same as in example 1.
Example 3
1. Raw materials:
wherein:
the polypropylene was a copolymer polypropylene having a weight average molecular weight of 350000 and a melt index (2.16kg load, 230 ℃ C.) of 7g/10 min.
In the polybutene alloy, the polybutene content was 80 wt%, the polypropylene content was 18 wt%, the polybutene-polypropylene block copolymer content was 2 wt%, the weight average molecular weight was 750000, and the melt index (190 ℃, 2.16kg) was 1.26g/10 min.
The antioxidant is compounded by 1010 and 168 according to the mass ratio of 1: 1.
The lubricant is compounded by polyethylene wax (the number average molecular weight is 4500) and calcium stearate according to the mass ratio of 1: 1.
The modified short glass fiber is obtained by the following method:
a certain volume of silane coupling agent KH-550 and absolute ethyl alcohol are weighed to prepare a KH-550 solution with the volume concentration of 1%. Then weighing a certain mass of short glass fiber, treating for 2h at 500 ℃, and then putting the short glass fiber into a vacuum drying oven to dry for 40min at 100 ℃. And (3) soaking the treated short glass fiber in a prepared KH-550 solution for 20min at room temperature, and then drying in air at 110 ℃ for 10min to obtain the KH-550 modified short glass fiber. In the obtained modified short glass fiber, the KH-550 accounts for 5% of the total modified short glass fiber by mass.
2. Preparation: the same as in example 1.
Example 4
1. Raw materials:
wherein:
the polypropylene was a copolymer polypropylene having a weight average molecular weight of 350000 and a melt index (2.16kg load, 230 ℃ C.) of 7g/10 min.
In the polybutene alloy, the polybutene content was 80 wt%, the polypropylene content was 18 wt%, the polybutene-polypropylene block copolymer content was 2 wt%, the weight average molecular weight was 750000, and the melt index (190 ℃, 2.16kg) was 1.26g/10 min.
The antioxidant is compounded by 1010 and 168 according to the mass ratio of 1: 1.
The lubricant is compounded by polyethylene wax (the number average molecular weight is 4500) and calcium stearate according to the mass ratio of 1: 1.
The modified short glass fiber is obtained by the following method:
a certain volume of silane coupling agent KH-550 and absolute ethyl alcohol are weighed to prepare a KH-550 solution with the volume concentration of 1%. Then weighing a certain mass of short glass fiber, treating for 2h at 500 ℃, and then putting the short glass fiber into a vacuum drying oven to dry for 40min at 100 ℃. And (3) soaking the treated short glass fiber in a prepared KH-550 solution for 20min at room temperature, and then drying in air at 110 ℃ for 10min to obtain the KH-550 modified short glass fiber. In the obtained modified short glass fiber, the KH-550 accounts for 5% of the total modified short glass fiber by mass.
2. Preparation: the same as in example 1.
Comparative example 1
1. Raw materials:
in contrast to example 4, the modified short glass fibers were replaced by unmodified virgin short glass fibers and the maleic anhydride grafted polypropylene was replaced by other compatibilizer EVA.
2. Preparation: the same as in example 4.
Comparative example 2:
1. raw materials:
in contrast to example 4, the polybutene alloy was replaced with polybutene.
2. Preparation: the same as in example 4.
Example 7: performance testing
The initial melting temperature, the melting temperature and the melting range are tested according to GB/T19466-;
the tensile strength is tested according to the GB/T1040.1-2018 standard;
the bending strength and the bending modulus are tested according to GB/T9341-;
the cantilever beam impact strength was tested according to GB/T1843-2008.
The polypropylene-based composite foamed base materials obtained in examples 1 to 6 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in table 1:
table 1 results of performance testing
The test results in table 1 show that the polypropylene-based composite foamed base material obtained in the embodiments 1 to 4 of the present invention has a relatively low initial melting temperature and melting temperature, a relatively wide melting range, and relatively high tensile strength, bending modulus and impact strength, and it is proved that the polypropylene-based composite foamed base material provided by the present invention reduces the foaming temperature and widens the foaming temperature window on the basis of ensuring the mechanical properties. Compared with the effect of the comparative example 1, the melting range and the mechanical property of the material can be reduced if the short glass fiber is not modified and other compatilizers are adopted. Compared with the effect of the comparative example 2, the comparison proves that the melting range and the mechanical property of the material cannot be effectively improved if the polybutene component is singly adopted, and the melting range and the mechanical property of the material can be effectively improved only by adopting the polybutene alloy.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The polypropylene-based composite foaming base material is characterized by being prepared from the following raw materials in parts by mass:
2. the polypropylene-based composite foamed base material according to claim 1, wherein the polypropylene is homo polypropylene and/or co polypropylene;
the melt index of the polypropylene under the test conditions of 2.16kg load and 230 ℃ is 3-20 g/10 min; the weight average molecular weight of the polypropylene is 100000-800000.
3. The polypropylene-based composite foamed base material according to claim 1, wherein the polybutene alloy comprises the following structural units in mass ratio:
60% -95% of polybutylene structural units;
4.9 to 35 percent of polypropylene structural unit;
0.1 to 5 percent of polybutylene-polypropylene block copolymer structural unit.
4. The polypropylene-based composite foamed base material according to claim 1 or 3, wherein the polybutene alloy has a melt index of 1 to 10g/10min under a load of 2.16kg and at 190 ℃; the weight average molecular weight of the polypropylene is 100000-800000.
5. The polypropylene-based composite foamed base material according to claim 1, wherein the modified short glass fiber is a gamma-aminopropyltriethoxysilane modified short glass fiber;
in the modified short glass fiber, the diameter of the short glass fiber is 8-15 μm, and the length-diameter ratio is 5-10.
6. The polypropylene-based composite foam base material according to claim 5, wherein the modified short glass fiber is prepared by the following preparation method:
s1, carrying out heat treatment on the short glass fiber to obtain the treated short glass fiber;
and S2, dipping the treated short glass fiber by utilizing a gamma-aminopropyltriethoxysilane solution, and drying to obtain the modified short glass fiber.
7. The polypropylene-based composite foam base according to claim 6, wherein,
in the step S1:
the heat treatment comprises: sintering treatment and drying treatment;
the sintering treatment temperature is 300-600 ℃, and the time is 1-3 h;
the drying treatment temperature is 80-110 ℃, and the drying treatment time is 20-60 min;
in the step S2:
the volume concentration of the gamma-aminopropyl triethoxysilane solution is 0.5-2%;
the drying temperature is 80-120 ℃, and the drying time is 5-20 min.
8. The polypropylene-based composite foam base material as claimed in claim 1, wherein the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1330, antioxidant 3114, antioxidant 1076, antioxidant 626, antioxidant 168 and antioxidant 618;
the lubricant comprises one or more of zinc stearate, calcium stearate, stearic acid, polyethylene wax and chlorinated polyethylene.
9. The polypropylene-based composite foam base material as claimed in claim 1 or 8, wherein the antioxidant is antioxidant 1010 and antioxidant 168;
the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1: 0.5-2;
the lubricant is polyethylene wax and calcium stearate;
the mass ratio of the polyethylene wax to the calcium stearate is 1: 0.5-2.
10. The preparation method of the polypropylene-based composite foaming base material as set forth in any one of claims 1 to 9, characterized by comprising the following steps:
a) blending polypropylene, polybutylene alloy, modified short glass fiber, maleic anhydride grafted polypropylene, an antioxidant and a lubricant to obtain a premix;
b) and extruding and granulating the premix to obtain the polypropylene-based composite foaming base material.
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Effective date of registration: 20240606 Address after: Room 501, Building 21, Hexiang Technology Center, Xiasha Street, Qiantang New District, Hangzhou City, Zhejiang Province, China Patentee after: Zhejiang Jingbo Polyolefin New Material Co.,Ltd. Country or region after: China Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG CHAMBROAD PETROCHEMICALS Co.,Ltd. Country or region before: China |