CN114539671B - High-melt-strength polypropylene composite material and preparation method and application thereof - Google Patents
High-melt-strength polypropylene composite material and preparation method and application thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 116
- -1 polypropylene Polymers 0.000 title claims abstract description 116
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 38
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 24
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims description 38
- 239000004033 plastic Substances 0.000 claims description 18
- 229920003023 plastic Polymers 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 239000013585 weight reducing agent Substances 0.000 abstract description 10
- 239000000945 filler Substances 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000007547 defect Effects 0.000 description 10
- 239000000454 talc Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- 235000012222 talc Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 241000218691 Cupressaceae Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000179970 Monarda didyma Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
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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
- C08L23/12—Polypropene
-
- 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
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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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a high melt strength polypropylene composite material, a preparation method and application thereof, and the high melt strength polypropylene composite material comprises the following components in parts by weight: 45-90 parts of polypropylene, 5-40 parts of talcum powder, 2-12 parts of hydrogenated styrene-butadiene block copolymer and 0.5-3 parts of modifier; the modifier is one or a combination of a phthalate ester coupling agent, an aminosilane coupling agent, an aluminum-titanium composite coupling agent, an epoxy silane coupling agent and a PP grafting modifier. The polypropylene composite material prepared by the invention has high melt strength, improves the compatibility of the filler and the matrix, effectively avoids the attenuation of mechanical properties, reduces environmental pollution, is suitable for preparing extruded and extruded foam parts, and can realize the weight reduction effect of 30% by melt extrusion after being mixed with a foaming agent.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high melt strength polypropylene composite material, and a preparation method and application thereof.
Background
Polypropylene is a universal plastic, has the advantages of high melting point, low density, good chemical stability, easy recovery, low price and the like, and has wide application prospect in the industries of automobiles, household appliances and the like. However, the conventional polypropylene material has low melt strength due to the linear structure of molecular chains and no strain hardening effect in a molten state, so that the application of polypropylene is greatly limited. Meanwhile, polypropylene is sheared by equipment in the melting process, molecular chains are broken, and the molecular weight is reduced. In addition, the softening point and the melting point of polypropylene are close, when the temperature is higher than the melting point, the melt strength and the viscosity of the polypropylene are sharply reduced, so that uneven wall thickness of a product is caused during thermoforming, edge curling shrinkage occurs during extrusion, and problems such as foam collapse or bulge occur during extrusion, blow molding and foaming.
To solve the above problems, the methods for preparing polypropylene with high melt strength in the prior art are generally classified into two types: firstly, polypropylene and other components are subjected to reaction modification, such as a ray irradiation method, a reaction extrusion method, a reaction crosslinking method and the like, but the method has high cost and low efficiency, is not suitable for industrial mass production, and has limited application. The other is blending modification of polypropylene and other high melt strength polymers, and the method is simple to operate, but the degree of high melt strength improvement depends on the matching property of a material system. The patent CN103834102B utilizes high-density polyethylene to improve the melt strength, but has poor compatibility with a system, and a compatilizer is additionally added to compensate the problem of mechanical property reduction caused by the improvement of the melt strength. Moreover, high melt polymers such as polyolefin elastomers, high melt strength polypropylene, polyethylene, etc. are expensive, which will increase raw material costs. In addition, non-environment-friendly polymers such as fluoride added in the blending modification process do not meet the requirements of green processing. For example, patent CN112724508a adds fluoride as an interpenetrating network forming agent. Fluoride is inevitably produced in the melt processing process as fluorine-containing toxic substances, which adversely affect the consumer and the material itself.
That is, the existing polypropylene material melt has the problems of poor compatibility with a polypropylene system, high price, low retention rate of mechanical properties, serious pollution in the modification process and the like in the process of improving the strength.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a polypropylene composite material with high melt strength, good compatibility, low cost, high mechanical property retention rate, environmental protection and preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: the high-melt-strength polypropylene composite material comprises the following components in parts by weight: 45-90 parts of polypropylene, 5-40 parts of talcum powder, 2-12 parts of hydrogenated styrene-butadiene block copolymer and 0.5-3 parts of modifier; the modifier is one or a combination of a phthalate ester coupling agent, an aminosilane coupling agent, an aluminum-titanium composite coupling agent, an epoxy silane coupling agent and a PP grafting modifier.
In the composite material, polypropylene can provide effective melt strength and fluidity; the talcum powder can effectively inhibit the movement of a polypropylene chain segment, increase the viscosity of the material, improve the melt strength and improve the rigidity of polypropylene; the modifier can promote the dispersion of talcum powder in the polypropylene matrix, improve the binding force of talcum powder and the matrix, reduce the interface defect between powder and the matrix and promote the melt strength; more importantly, the inventor surprisingly found that the addition of the hydrogenated styrene-butadiene block copolymer can improve the dispersion of talcum powder in polypropylene, improve the binding force of talcum powder and polypropylene, reduce the interface defect between talcum powder and polypropylene, improve the melt strength of the finished product, and simultaneously maintain the high mechanical strength of the finished product. The polypropylene, talcum powder, hydrogenated styrene-butadiene block copolymer and modifier can play a synergistic role when used in a specific formula, so that the prepared polypropylene composite material has high melt strength, improves the compatibility of the filler and the matrix, effectively avoids the attenuation of mechanical properties, reduces environmental pollution, and is suitable for preparing extruded and extruded foamed plastic parts.
The content of each component is critical in the invention, and too high or too low content of the component can adversely affect the melt strength and mechanical properties of the high melt strength polypropylene composite material. Preferably, the weight part ratio of talcum powder to hydrogenated styrene-butadiene block copolymer is (25-35): (8-10). Under the condition, the hydrogenated styrene-butadiene segmented copolymer can well improve the dispersing effect of talcum powder in polypropylene, improve the binding force of talcum powder and polypropylene, reduce the interface defect between talcum powder and polypropylene, improve the melt strength of a finished product, and simultaneously keep the high mechanical strength of the finished product.
Preferably, the polypropylene has a melt mass flow rate of 0.3-2g/10min, measured according to ISO1133-2011 at 210 ℃ under a load of 2.16 kg. After a great number of creative test researches, the inventor discovers that the melt mass flow rate of the polypropylene is within the preferred range of the application, and can ensure that the prepared high-melt-strength polypropylene composite material has higher melt strength and fluidity.
Preferably, the hydrogenated styrene-butadiene block copolymer has a melt mass flow rate of 18 to 25g/10min, measured according to ISO1133-2011 at 230℃under a load of 5.0 kg. After a great number of creative experiments, the inventor discovers that the melt mass flow rate of the hydrogenated styrene-butadiene segmented copolymer can ensure that the prepared high melt strength polypropylene composite material has good fluidity and processability in the preferred range of the application, and meanwhile, the system compatibility can be improved, and the interface defect between talcum powder filler and polypropylene matrix can be reduced.
Preferably, the polypropylene is homo-polypropylene and/or co-polypropylene; the average particle size of the talcum powder is 800-5000 meshes.
More preferably, the talc has an average particle size of 1000 to 3000 mesh. The talcum powder has too small particle size and has insufficient limitation on the movement of the polypropylene chain segment; the higher the particle size of the talcum powder is, the stronger the shearing action generated in the processing process is, the more serious the polypropylene chain breakage is, and the lower the melt strength of the finished product is caused.
Preferably, the high melt strength polypropylene composite material further comprises 0-1 part of an auxiliary agent, wherein the auxiliary agent comprises one or more of a lubricant and an antioxidant.
Preferably, the lubricant is used in an amount of 0 to 0.5 parts, and the lubricant includes at least one of stearic acid amide, stearic acid metal salt, and silicone-based lubricant; the dosage of the antioxidant is 0-0.5 part, and the antioxidant comprises hindered phenol antioxidants and/or phosphite antioxidants.
The invention also provides a preparation method of the high melt strength polypropylene composite material, which comprises the following steps:
(1) Mixing talcum powder, hydrogenated styrene-butadiene block copolymer and modifier in a mixer to obtain a mixture A;
(2) Adding the mixture A, polypropylene and an auxiliary agent into a mixer for mixing to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for melt extrusion, and granulating and cooling to obtain the high-melt-strength polypropylene composite material.
The invention combines talcum powder with hydrogenated styrene-butadiene segmented copolymer and modifier to prepare modified talcum powder filler, and then prepares polypropylene material after blending extrusion, granulation and cooling with other components. Talcum powder increases the viscosity of the material; the modifier improves the dispersibility of talcum powder and the interface combination of polypropylene, and reduces interface defects; the hydrogenated styrene-butadiene block copolymer further improves the compatibility of the talc powder with the polypropylene matrix. The prepared polypropylene material has higher melt strength and mechanical property, can be used in the processing procedures of extrusion, extrusion foaming and the like, and can realize the weight reduction effect of up to 30% through melt extrusion after being mixed with a foaming agent.
Correspondingly, the invention also provides application of the high-melt-strength polypropylene composite material in preparing extrusion foaming plastic parts.
Correspondingly, the invention also provides an extrusion foaming plastic part, which is obtained by mixing the high-melt-strength polypropylene composite material and a foaming agent and then carrying out melt extrusion. Preferably, the high melt strength polypropylene composite material and the foaming agent are mixed according to the weight ratio of 95-105:1, and the foamed plastic part is obtained after melt extrusion, and the obtained extruded foamed plastic part has good weight reduction effect.
Compared with the prior art, the invention has the beneficial effects that: the high melt strength polypropylene composite material prepared according to the formula of the invention has good system compatibility, low cost, high retention rate of mechanical properties and high melt strength, and is suitable for preparing extrusion and extrusion foaming plastic parts. Meanwhile, the invention also provides an extrusion foaming plastic piece, which is obtained by mixing the high melt strength polypropylene composite material and the foaming agent and then carrying out melt extrusion, and the obtained extrusion foaming plastic piece has good weight reduction effect.
Detailed Description
The technical solution of the present invention will be further described with reference to the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The starting materials used in the examples and comparative examples were commercially available and all used in the parallel experiments were the same.
The sources of the raw materials are as follows, but are not limited to:
Polypropylene:
random copolymer polypropylene, model: PP4220, manufacturer: the melt mass flow rate measured according to ISO1133-2011 under 210 ℃ and 2.16kg load is 0.3g/10min;
homo polypropylene, model: PP B1101, manufacturer: taiwan, the melt mass flow rate measured according to ISO1133-2011 under 210 ℃ and 2.16kg load is 0.7g/10min;
homo polypropylene, model: PP140HMS, manufacturer: the melt mass flow rate measured according to ISO1133-2011 at 210 ℃ under a load of 2.16kg is 2.0g/10min;
homo polypropylene, model: PPPPH-T03, manufacturer: zhenhai, melting, and measuring the mass flow rate of the melt at 210 ℃ and under the load of 2.16kg according to ISO1133-2011 to 3g/10min;
talc powder:
Model: t01, manufacturer: dandong Tianci with particle size of 1000 meshes
Model: TY90-13-C, manufacturer: dongguan III, the grain diameter is 1250 mesh;
model: TYT-777A, manufacturer: liaoning North sea with particle size of 3000 mesh;
And (3) a modifier:
aminosilane coupling agent, model: JH-A110, manufacturer: jiang Han fine chemical engineering;
phthalate ester coupling agent, model: TMC 931, manufacturer: the manufacturer raises the state;
aluminum-titanium composite coupling agent, model: HW-133, manufacturer: new material of Zhongjie;
epoxy silane coupling agent, model: KH-560, manufacturer: nanjing Chen worker;
PP grafting modifier, model: PC-1, manufacturer: the polymer material is prepared from the bergamot, the south China sea and the cypress.
Hydrogenated styrene-butadiene block copolymer:
Model: SEBS 1657, manufacturer: the melt mass flow rate was 22g/10min by Kraton Polymers, measured at 230℃under a 5.0kg load in accordance with ISO 1133-2011.
Model: SEBS ATPR 2040, manufacturer: aaron Industries Corp. Melt mass flow rate was 18g/10min, measured at 230℃under a 5.0kg load in accordance with ISO 1133-2011.
Model: SEBS KR13032, manufacturer: korrels b.v., melt mass flow rate of 25g/10min, measured at 230 ℃ under 5.0kg load according to ISO 1133-2011.
Model: SEBS 1653, manufacturer: the melt mass flow rate was 28g/10min by Kraton Polymers, measured at 230℃under a 5.0kg load in accordance with ISO 1133-2011.
Model: SEBS 1651, manufacturer: the melt mass flow rate was 16g/10min, measured according to ISO1133-2011 at 230℃under a load of 5.0 kg.
And (3) a lubricant: stearic acid-based lubricants, commercially available
An antioxidant: hindered phenol antioxidant Y-001, commercially available; phosphite antioxidant Y-002, commercially available.
The formulations (parts by weight) of the high melt strength polypropylene composites of examples 1-19 are shown in Table 1:
TABLE 1
Note that: in the table "-" indicates that the component was not added.
The polypropylene composite formulations (parts by weight) of comparative examples 1 to 8 are shown in table 2:
TABLE 2
Note that: in the table "-" indicates that the component was not added.
The polypropylene composites of examples 1 to 19 and comparative examples 1 to 8 were prepared as follows:
S1, weighing a modifier, a hydrogenated styrene-butadiene block copolymer and talcum powder, adding the weighed materials into a high-speed mixer for mixing, wherein the temperature of the high-speed mixer is 100 ℃, the mixing speed is 300r/min, and the mixing time is 6min, so as to obtain a mixture A;
s2, weighing polypropylene, an antioxidant and a lubricant, adding the mixture into a high-speed mixer together with the mixture A, wherein the mixing speed is 300r/min, and the mixing time is 5min, so as to obtain a mixture B;
s3, adding the mixture B into a double-screw extruder for melt extrusion, granulating and cooling to obtain the polypropylene composite material.
Performance testing
The polypropylene composites of examples 1 to 19 and comparative examples 1 to 8 were subjected to performance testing as follows:
(1) Melt strength test method: the polypropylene composite material prepared was extruded through a die having a diameter of 3mm at 200℃and 30r/min using a PolyLab OS type torque rheometer, and its melt strength was measured with Gottfert Rheotens.
(2) The test is carried out after the sample strip required for the mechanical property test is placed for 2 days in an environment with the temperature of 23 ℃ and the humidity of 50%. Tensile strength was tested according to ISO 527-2-2019, flexural strength was tested according to ISO 178-2019, and notched impact strength was tested according to ISO 179/1 eA-2010.
The prepared polypropylene composite material is calcined at 600-800 ℃ for 40min according to ISO 3451-2019, and the particle size of ash is tested by a laser particle sizer, and the average particle size of talcum powder in the composite material is the same as that of raw material talcum powder.
The polypropylene composites of examples 1 to 19 and comparative examples 1 to 8 above were mixed with a blowing agent in a weight ratio of 99.5:1 and then fed into a 40:1 single screw extruder and extruded at 190-200 ℃. The extruded bars were tested for density according to ISO 1183 and compared to composites without blowing agent and the weight loss ratio was calculated according to the formula (1-post-foaming density/pre-foaming density) ×100%.
Melt strength, mechanical properties and weight loss properties of the polypropylene composites of examples 1 to 19 and comparative examples 1 to 8 are shown in Table 3.
TABLE 3 Table 3
Analysis of results
As can be seen from comparing examples 1-14 with comparative examples 1-8: the polypropylene, talcum powder, hydrogenated styrene-butadiene block copolymer and modifier can play a synergistic effect under the specific formula condition provided by the invention, so that the prepared polypropylene composite material has good melt strength and mechanical property, is particularly suitable for preparing extrusion foaming plastic parts, and has obvious weight reduction effect.
Further, it can be seen from comparative example 3 and comparative example 3 that: after the hydrogenated styrene-butadiene block copolymer is added, the melt strength and mechanical properties of the polypropylene composite material are obviously improved, the weight reduction effect of the obtained extruded foam plastic product is obvious, and the polypropylene, talcum powder, the hydrogenated styrene-butadiene block copolymer and the modifier can play a synergistic effect when being used in a specific formula, so that the prepared polypropylene composite material has high melt strength, the compatibility of the filler and the matrix is improved, and the attenuation of the mechanical properties is effectively avoided.
And, as can be seen from comparative examples 3 and 3 to 4, when the addition amount of the hydrogenated styrene-butadiene block copolymer is in the range of 2 to 12 parts, a polypropylene composite material having both melt strength and mechanical properties can be obtained, and when the addition amount of the hydrogenated styrene-butadiene block copolymer is too high in comparative example 4, the melt strength and mechanical properties of the polypropylene composite material are remarkably reduced, and the weight-reducing effect of the obtained extruded foam plastic product is reduced.
As can be seen from the comparison of example 3 and comparative example 5, comparative example 5 was free of modifier, the melt strength and mechanical strength of the finished product of comparative example 5 were significantly reduced, and the weight reduction ratio of the extruded foam plastic part made of the polypropylene composite material of comparative example 5 was significantly reduced. It follows that the modifier has a significant impact on the finished product properties. Meanwhile, as can be seen from comparative examples 3 and 9 to 11, the modifier can be one of phthalate ester coupling agents, aminosilane coupling agents, aluminum-titanium composite coupling agents, epoxy silane coupling agents and PP grafting modifying agents, and the performances of finished products obtained by using the modifying agents are similar.
As can be seen from comparative example 3 and comparative examples 7 to 8, comparative example 7 was free of talc, and the flexural modulus was significantly lowered, although the melt strength and notched impact strength of the final product were higher, and the weight reduction ratio of the extruded foam plastic part made of the polypropylene composite material of comparative example 7 was greatly lowered; comparative example 8 talc powder was excessively added, the notched impact strength impact of the polypropylene composite material was reduced, and the weight reduction ratio of the extrusion foamed plastic part made of the polypropylene composite material was greatly reduced. Therefore, in 10-35 parts of talcum powder of polypropylene, the prepared high-melt-strength polypropylene composite material can be ensured to have higher melt strength and fluidity, and the extrusion foaming plastic piece prepared from the high-melt-strength polypropylene composite material has better weight reduction effect.
In addition, it can be seen from comparing examples 3, examples 15 to 16 and examples 12 to 13: the melt mass flow rate of the hydrogenated styrene-butadiene block copolymer can ensure that the prepared high melt strength polypropylene composite material has good rigidity and mechanical property within the preferred range of the invention, and meanwhile, the system compatibility can be improved, and the interface defect between talcum powder filler and polypropylene matrix can be reduced. The hydrogenated styrene-butadiene block copolymer described in example 12 has a melt mass flow rate exceeding 25g/10min, resulting in an excessively large difference in flowability with the polypropylene matrix, resulting in reduced compatibility with the system, resulting in increased interfacial defects between the talc filler and the polypropylene matrix; the hydrogenated styrene-butadiene block copolymer described in example 13 has a melt mass flow rate of less than 18g/10min, resulting in an excessively large difference in flowability with the polypropylene matrix, resulting in reduced compatibility with the system, and in increased interfacial defects between the talc filler and the polypropylene matrix.
As can be seen from comparative examples 3, examples 6 to 7 and example 14: the melt mass flow rate of the polypropylene material in example 3 was 0.7g/10min, the melt mass flow rate of the polypropylene in example 6 was 0.3g/10min, the melt mass flow rate of the polypropylene in example 7 was 2g/10min, and the melt mass flow rate of the polypropylene in example 14 was 3g/10min. The inventor of the application discovers through a great number of creative tests that the melt mass flow rate of the polypropylene is within 0.3-2g/10min, and can ensure that the prepared high melt strength polypropylene composite material has higher melt strength and fluidity. The melt mass flow rate of the polypropylene in example 14 is out of range, such that the melt strength of the resulting polypropylene composite is greatly reduced.
As can be seen from comparing examples 17 to 19, the weight part ratio of talc to hydrogenated styrene-butadiene block copolymer described in example 17 and example 18 is (25-35): (8-10). The weight part ratio of talc to hydrogenated styrene-butadiene block copolymer described in example 19 was 5:1, not at (25-35): in the range of (8-10), it is found from the test results that the weight ratio of the talc to the hydrogenated styrene-butadiene block copolymer is (25-35): under the condition of (8-10), the hydrogenated styrene-butadiene segmented copolymer can well improve the dispersing effect of talcum powder in polypropylene, improve the binding force of talcum powder and polypropylene and reduce the interface defect between talcum powder and polypropylene, thereby improving the melt strength of the finished product and simultaneously keeping the high mechanical strength of the finished product.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The high melt strength polypropylene composite material is characterized by comprising the following components in parts by weight: 60 parts of polypropylene, 30-40 parts of talcum powder, 8.4-12 parts of hydrogenated styrene-butadiene block copolymer and 0.5-3 parts of modifier; the modifier is one or a combination of a phthalate coupling agent, an aminosilane coupling agent, an aluminum-titanium composite coupling agent, an epoxy silane coupling agent and PP grafted maleic anhydride; the melt mass flow rate of the polypropylene is 0.7g/10min, and the melt mass flow rate is measured according to ISO1133-2011 under the conditions of 210 ℃ and 2.16kg load; the hydrogenated styrene-butadiene block copolymer has a melt mass flow rate of 18 to 25g/10min, measured according to ISO1133-2011 at 230℃under a load of 5.0 kg.
2. The high melt strength polypropylene composite material according to claim 1, wherein the polypropylene is homo-and/or co-polypropylene; the average particle size of the talcum powder is 800-5000 meshes.
3. The high melt strength polypropylene composite of claim 1, further comprising 0-1 parts of an auxiliary agent, the auxiliary agent comprising one or more of a lubricant and an antioxidant.
4. The high melt strength polypropylene composite material according to claim 3, wherein the lubricant is used in an amount of 0 to 0.5 parts, including at least one of stearic acid amide, stearic acid metal salt, and silicone-based lubricant; the dosage of the antioxidant is 0-0.5 part, and the antioxidant comprises hindered phenol antioxidants and/or phosphite antioxidants.
5. The method for preparing a high melt strength polypropylene composite material according to any one of claims 3 to 4, comprising the steps of:
(1) Mixing talcum powder, hydrogenated styrene-butadiene block copolymer and modifier in a mixer to obtain a mixture A;
(2) Adding the mixture A, polypropylene and an auxiliary agent into a mixer for mixing to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder for melt extrusion, and granulating and cooling to obtain the high-melt-strength polypropylene composite material.
6. Use of a high melt strength polypropylene composite material according to any one of claims 1 to 4 for the preparation of extruded foam plastic parts.
7. An extrusion-foamed plastic article, characterized by being obtained by melt-extruding the high melt strength polypropylene composite material according to any one of claims 1 to 4 after mixing with a foaming agent.
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| US5543454A (en) * | 1993-08-10 | 1996-08-06 | Ube Industries, Ltd. | Reinforced polypropylene resin composition |
| CN114044968A (en) * | 2021-10-26 | 2022-02-15 | 江苏金发科技新材料有限公司 | High-melt-strength polypropylene material resistant to cyclic processing and preparation method and application thereof |
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| CN108178877A (en) * | 2017-12-19 | 2018-06-19 | 会通新材料股份有限公司 | A kind of automobile-used polypropylene chemical micro foaming composite material and preparation method thereof |
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| US5543454A (en) * | 1993-08-10 | 1996-08-06 | Ube Industries, Ltd. | Reinforced polypropylene resin composition |
| CN114044968A (en) * | 2021-10-26 | 2022-02-15 | 江苏金发科技新材料有限公司 | High-melt-strength polypropylene material resistant to cyclic processing and preparation method and application thereof |
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