CN107501714A - A kind of polypropene composition and preparation method thereof - Google Patents
A kind of polypropene composition and preparation method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 57
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 polypropylene Polymers 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 11
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000010702 perfluoropolyether Substances 0.000 claims description 4
- 239000000412 dendrimer Substances 0.000 claims description 3
- 229920000736 dendritic polymer Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 24
- 230000008859 change Effects 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 241000282376 Panthera tigris Species 0.000 abstract description 3
- 238000005452 bending Methods 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 241000555268 Dendroides Species 0.000 abstract 2
- 230000003628 erosive effect Effects 0.000 abstract 2
- 239000004925 Acrylic resin Substances 0.000 abstract 1
- 229920000178 Acrylic resin Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241001134446 Niveas Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 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 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of polypropene composition and preparation method thereof.The invention discloses a kind of polypropene composition, include the acrylic resin of 60 ~ 85 parts by weight；The high-density polyethylene resin of 5 ~ 10 parts by weight；The dendroid toughener of 5 ~ 20 parts by weight；The graphene of 1 ~ 5 parts by weight；The surface modifier of 3 ~ 5 parts by weight.The present invention uses dendroid toughener, and the good impact property of material can be maintained in the case of relatively low dosage, while is advantageous to improve polypropylene material chemical resistance；Add surface modifier and change material surface tension, can effectively weaken erosion of the chemicals to material surface；Add graphene and not only improve material bending modulus, and there is nanometer barrier effect to chemicals, it is suppressed that the erosion of chemicals.Acted synergistically in above-mentioned three, gained polypropylene material feed composition has excellent chemical resistance, maintains good rigidity-toughness balanced.In addition, having no any defect such as tiger fur line after gained polypropylene material injection molding, and there is special metallic luster.
Description
Technical Field
The invention relates to a high polymer material and technology, in particular to a polypropylene composition and a preparation method thereof.
Background
Polypropylene (PP) is a general plastic with wide source, low density and easy processing, and various filled, reinforced and toughened PP are widely applied to automobile parts, such as periphery of an engine, interior trim, exterior trim and the like. However, in different automobile application scenes, the automobile PP material can be corroded by different chemicals such as gasoline, engine oil, cosmetics, sweat, detergents and the like, so that the corrosion phenomena such as whitening, color change, even swelling and dissolution and the like can occur. Therefore, the PP material needs to be modified for a specific application scenario to meet the requirements of the application scenario on the material. On the other hand, host manufacturers place higher demands on the impact strength and appearance of automotive PP parts in view of safe and comfortable customer experience. Therefore, there is a need in the art to develop a good appearance, high impact resistance, and chemical resistance polypropylene composite for use in various application scenarios of automobiles.
The Chinese patent CN104987595A adopts the method that a polyurethane elastomer is added into PP to improve the wear resistance and oil resistance of the material, and a tetrafluoroethylene-hexafluoropropylene copolymer is added to improve the high temperature resistance and oil resistance. However, the production of the material needs multiple extrusion granulation and mixing, the steps are complex, the large-scale production is not facilitated, and the material is mainly used for cables and has a single use scene. Chinese patent CN106243484A adopts macromolecular silane or fluoropolymer to carry out blending modification with PP, and the prepared PP composition can resist corrosion of chemicals such as engine oil, cooling liquid and the like at high temperature. However, the material is mainly applied to the periphery of an engine, the use scene is single, and no further attention is paid to the improvement of mechanical property and appearance. The Chinese patent CN105602103A adopts silane coupling agent modified graphene as functional filler to endow PP material with antistatic performance and more excellent mechanical properties. However, the invention is not optimized for the chemical resistance of the material.
Disclosure of Invention
The invention aims to overcome the defects of difficult material processing, single use scene, insufficient comprehensive performance, poor appearance and the like in the prior art, and provides the polypropylene composition with simple production process, good appearance, excellent chemical corrosion resistance, good rigidity and toughness balance performance and more application scenes.
It is another object of the present invention to provide a process for the preparation of the polypropylene composition.
The invention is realized by the following technical scheme:
the polypropylene composition comprises the following components in parts by weight:
60-85 parts of polypropylene resin;
5-10 parts of high-density polyethylene resin;
5-20 parts of a dendritic toughening agent;
1-5 parts of graphene;
3-5 parts of a surface modifier.
The polypropylene resin is selected from one or more of homo-polypropylene resin or co-polypropylene resin, and the density range of the polypropylene resin is 0.894-0.914 g/cm3The melt mass flow rate is 1-100 g/10min at 190 ℃ under a load of 2.16 Kg.
The high-density polyethylene resin is extrusion-grade high-density polyethylene with the density of 0.948-0.958 g/cm3The melt mass flow rate is 5-10 g/10min at 190 ℃ under a load of 2.16 Kg.
The dendritic toughening agent is selected from dendritic polymers with flexible polyolefin long chain segments, and the density of the dendritic toughening agent is 0.935-0.955 g/cm3The melt mass flow rate is 0.4-5.4 g/10min at 190 ℃ under a load of 2.16 Kg.
The dendritic polymer with the flexible polyolefin long chain segment is selected from one or more of CYD-6000 and CYD-6100A.
The graphene is one or more selected from mechanically stripped graphene and chemically modified graphene, the number of the sheet layers is 1-5, the size of the sheet layers is 0.1-20 micrometers, and the stacking density of the sheet layers is 0.01-0.1 g/cm3. The mechanically exfoliated graphene is selected from KNG-G5; the chemically modified graphene is selected from TRGO prepared by a thermal expansion method.
The surface modifier is selected from fluorine-containing resin perfluoropolyether oil with molecular weight more than or equal to 80 ten thousand,Polytetrafluoroethylene with molecular weight of more than or equal to 80 ten thousand, tetrafluoroethylene-hexafluoropropylene copolymer with molecular weight of more than or equal to 80 ten thousand, and density of 0.9-2.0 g/cm3One or more fluorine-modified polysiloxanes; wherein the density is 0.9-2.0 g/cm3With the addition of the fluorine-modified polysiloxane, the polypropylene composition has the best chemical resistance.
The fluorine-containing resin perfluoropolyether oil with the molecular weight of more than or equal to 80 ten thousand is selected from JC 2000; the polytetrafluoroethylene with the molecular weight more than or equal to 80 ten thousand is selected from one or more of PTFE micro powder KTL-450 and F-201; the tetrafluoroethylene-hexafluoropropylene copolymer with the molecular weight more than or equal to 80 ten thousand is selected from NP-40; the density is 0.9-2.0 g/cm3The fluorine modified polysiloxane is selected from one or more of AF-600, MOK-2027 and HY-F-101.
The polypropylene composition further comprises 0-2 parts of pigment, and the pigment is selected from one or more of carbon black M717 or black master batch PE 2772.
The polypropylene composition further comprises 0-2 parts of an auxiliary agent, wherein the auxiliary agent is one or more selected from an antioxidant and a light stabilizer.
The antioxidant is hindered phenol and phosphite ester antioxidant, and is selected from one or more of 1010, 1076, 3114, 168 and PEP-36.
The light stabilizer is a hindered amine light stabilizer and is selected from one or more of UV-3808PP5, LA-402XP and LA-402 AF.
The preparation method of the polypropylene composition comprises the following steps:
a) putting polypropylene resin, high-density polyethylene resin, a dendritic toughening agent, graphene, a surface modifier, a pigment and an auxiliary agent into a high-speed stirrer and uniformly mixing;
b) adding the mixture into a double-screw extruder, carrying out melt mixing, extruding and granulating to obtain the polypropylene composition.
Wherein the melting and mixing temperature is 170-220 ℃, and the screw rotating speed is 350-450 r/m.
The polypropylene composition has the following properties: the product has special luster similar to metal, good appearance, and no tiger skin line and other defects of a product obtained by injection molding; after being soaked in gasoline for 24 hours at the temperature of 23 ℃ and the relative humidity of 50 percent, the oil absorption rate is less than 13 percent, and the tensile strength attenuation rate is less than 30 percent; a certain amount of chemicals were dropped on the sample, and after 24 hours of storage at 23 ℃ under 50% relative humidity, no significant change in appearance was observed. Numerical value of notched impact Strength + numerical value of flexural modulus/10>140，70 kJ/m2>Notched impact strength>45 kJ/m2， 1100MPa>Flexural modulus>800MPa, meets the requirement.
Compared with the prior art, the invention has the following beneficial effects:
the dendritic toughening agent is adopted, so that the addition amount of the toughening agent is reduced, the good impact property is kept, and the dendritic toughening agent has good chemical resistance; the surface modifier is added to enrich the surface of the material, so that the corrosion of chemicals to the surface of the material is weakened; the added graphene not only improves the flexural modulus of the material, but also has a nano barrier effect on chemicals, and simultaneously enables the material to have similar metallic luster, and a workpiece obtained by injection molding has no defects such as tiger skin lines and the like, and has good appearance. The three components have synergistic effect, so that the polypropylene material composition has excellent chemical resistance, keeps good rigidity-toughness balance and has good appearance. Therefore, the polypropylene composition provided by the invention can be used for various automobile application scenes such as automobile engine periphery, automobile interior trim, exterior trim and the like. The invention can save the processes of spraying paint and the like, and has the characteristics of simple production process, low cost, reduction of environmental pollution and the like.
Detailed Description
The present invention will be further illustrated by the following specific embodiments, and the following examples are illustrative of the present invention and are not intended to limit the present invention.
The raw materials used in the examples and comparative experiments are, but not limited to, the following:
polypropylene resin: PP BX3920, available from SK in Korea, with a density of 0.899g/cm3The melt mass flow rate was 85 g/10min at 230 ℃ under a load of 2.16 Kg;
high density polyethylene: HDPE DMDA8008, from the Dushan petrochemical, having a density of 0.956g/cm3The melt mass flow rate is 7 g/10min at 190 ℃ under a load of 2.16 Kg;
dendritic flexibilizer: CYD-6100A, available from Waishaham molecular New materials, Inc.; the density is 0.945 +/-0.02 g/cm3The melt mass flow rate is 0.6-2.5 g/10min at 190 ℃ under 2.16Kg load;
dendritic flexibilizer: CYD-6700 was purchased from Waishaham molecular New materials, Inc.; the density is 0.945 +/-0.02 g/cm3The melt mass flow rate is 5.5-7.5 g/10min at 190 ℃ under a load of 2.16 Kg;
the toughening agent POE: POE 7447 available from Dow and having a density of 0.865g/cm3(ii) a The melt mass flow rate is 5 g/10min at 190 ℃ under a load of 2.16 Kg;
mechanically stripping graphene: KNG-G5 graphite powder is purchased from Xiamen Kaina graphene Co Ltd, the number of layers is 1-3, and the size is 5-10 microns; the bulk density is 0.01 to 0.1 g/cm3;
Fluorine-containing resin perfluoropolyether oil with molecular weight more than or equal to 80 ten thousand: JC2000, from Aiken chemical of Shanghai;
the polytetrafluoroethylene with the molecular weight more than or equal to 80 ten thousand is selected from PTFE micro powder: f-201, available from great metallurry;
tetrafluoroethylene-hexafluoropropylene copolymer with molecular weight not less than 80 ten thousand: NP-40, available from the great metallurry;
the density is 0.9 to 2.0g/cm3The fluorine-modified polysiloxane of (a): AF-600, available from Jiahua essence of Zhejiang, with a density of 0.97-1.25 g/cm3；
The density is 0.9 to 2.0g/cm3The fluorine-modified polysiloxane of (a): MOK-2027 available from Merck chemical of Germany having a density of 1.09 to 1.13 g/cm3；
Carbon black: m717, from cabot;
antioxidant 1010: purchased from basf;
antioxidant 168: purchased from basf;
light stabilizer UV-3808PP 5: purchased from cyanite.
Examples 1 to 11 and comparative examples 1 to 9:
preparation method of polypropylene composition:
according to the formula shown in the table 1-table 3, the components are put into a high-speed stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt mixing at the temperature of 170-220 ℃ and the screw rotating speed of 350-450 rpm, and the mixture is extruded and granulated to obtain the polypropylene composition. The results of the mechanical property tests are shown in table 4; the chemical test results are shown in table 5.
Each performance evaluation method:
(1) chemical resistance appearance test: after the injection molded plaque sample was conditioned in a standard environment (23 ℃, 50% relative humidity) for 24h, 0.1mL of chemicals was dropped onto its surface and allowed to stand at 23 ℃ for 24 h. And lightly wiping the surface of the color plate by using gauze, washing the surface of the color plate by using deionized water if necessary, removing residual chemicals on the surface of the color plate, and observing the appearance change of the surface of the color plate. According to the corrosion degree of the appearance, 2-grade, 1.5-grade, 1-grade, 0.5-grade and 0-grade are set in sequence, and the color plate shows foaming swelling, severe whitening, slight whitening and slight imprinting (observed only by rotating the angle) after corrosion in sequence and has no obvious change. And the average value is taken as the final chemical appearance corrosion resistant grade through blind measurement by a plurality of professionals. Chemicals used for appearance test of chemical resistance comprise Nivea sun cream, LLC antifreeze solution, 95# gasoline, WWF washing solution and engine oil 5W-30.
(2) And (3) testing oil absorption rate: after the injection-molded ISO mechanical sample specimens have been conditioned for 24 hours in a standard environment (23 ℃, 50% relative humidity), the sample masses M are weighed0Soaking in appropriate amount of gasoline, standing at 23 deg.C for 24 hr, taking out mechanical sample strip to remove oil drop on surface, adjusting in standard environment (23 deg.C, 50% relative humidity) for 30min, and weighing sample mass Mi. The oil absorption is calculated according to the formula 1-1:
(formula 1-1)
(3) And (3) testing the tensile strength attenuation rate: the test was carried out in two groups, after conditioning the ISO mechanical bars after injection molding in a standard environment (23 ℃, 50% relative humidity) for 24h, performed according to the EN50342-5 standard. First set of tests for tensile Strength of samples before oil absorptionK 0 . Soaking the second group in gasoline, standing at 23 deg.C for 24 hr, taking out mechanical sample strips, removing oil drops on surface, adjusting in standard environment (23 deg.C, 50% relative humidity) for 30min, and testing tensile strength of the sample after absorbing oilK i . The attenuation ratio of tensile strength is calculated according to the formula 1-2
(formula 1-2)
Wherein,K 0performance test values before oil absorption;K i performance test values after oil absorption.
(4) And (3) testing mechanical properties: after injection molding, the samples were tested for tensile strength, flexural modulus and notched impact strength after conditioning the ISO mechanical specimens in a standard environment (23 ℃, 50% relative humidity) for 24 h.
Tensile strength was performed according to ISO 527 standard.
The bending strength and the bending modulus are performed according to the ISO178 standard.
Notched impact strength was performed according to the ISO180 standard.
Table 1: improved formula (parts by weight) of toughening agent
Table 2: improved formula (parts by weight) of graphene
Table 3: improved formula (weight portion) of surface modifier
TABLE 3
Table 4: performance test results of the Polypropylene composition
Table 5: chemical resistance appearance test results of the polypropylene compositions of examples and comparative examples
Numerical value of notched impact Strength + numerical value of flexural modulus/10>140，70 kJ/m2>Notched impact strength>45 kJ/m2，1100MPa>Flexural modulus>800MPa, meets the requirement. The comparison of the test results of mechanical property and chemical resistance of examples 1 to 11 and comparative examples 1 to 9 shows that: the dendritic toughening agent is used in an amount of 5-20 parts by weight, and the larger the amount is, the better the impact performance is, and the chemical resistance is always maintained at an excellent level. The impact property and chemical resistance of the polypropylene composition are general due to the addition of the dendritic flexibilizer CYD-6700. Therefore, the selection density range of the dendritic flexibilizer is 0.935-0.955 g/cm3The melt mass flow rate is 0.4 to 5.4 g/10min at 190 ℃ under a load of 2.16 Kg. Within the range of 1-5 parts, the more the graphene is used, the better the chemical resistance is. The reasonable amount range of the surface modifier is 3-5 parts by weight; wherein the addition density is 0.9-2.0 g/cm3The polypropylene composition of fluorine modified polysiloxane has the best chemical resistance and mechanical property.
Claims (9)
1. The polypropylene composition is characterized by comprising the following components in parts by weight:
60-85 parts of polypropylene resin;
5-10 parts of high-density polyethylene resin;
5-20 parts of a dendritic toughening agent;
1-5 parts of graphene;
3-5 parts of a surface modifier.
2. The polypropylene composition according to claim 1, wherein the polypropylene resin is one or more selected from homo-polypropylene resin and co-polypropylene resin, and the density is 0.894-0.914 g/cm3The melt mass flow rate is 1-100 g/10min at 190 ℃ under a load of 2.16 Kg.
3. The polypropylene composition as claimed in claim 1, wherein the high density polyethylene resin is an extruded high density polyethylene having a density of 0.948 to 0.958 g/cm3The melt mass flow rate is 5-10 g/10min at 190 ℃ under a load of 2.16 Kg.
4. The polypropylene composition of claim 1, wherein the dendritic toughening agent is selected from the group consisting of dendritic polymers having a long flexible polyolefin segment and a density of 0.935 to 0.955 g/cm3The melt mass flow rate is 0.4 to 5.4 g/10min at 190 ℃ under a load of 2.16 Kg.
5. The polypropylene composition according to claim 1, wherein the graphene is one or more selected from mechanically exfoliated graphene and chemically modified graphene, and has 1-5 lamellar layers, a size of 0.1-20 μm, and a bulk density of 0.01-0.1 g/cm3。
6. The polypropylene composition according to claim 1, wherein the surface modifier is selected from the group consisting of fluororesin perfluoropolyether oil having a molecular weight of 80 ten thousand or more, polytetrafluoroethylene having a molecular weight of 80 ten thousand or more, tetrafluoroethylene-hexafluoropropylene copolymer having a molecular weight of 80 ten thousand or more, and a density of 0.9 to 2.0g/cm3One or more fluorine-modified polysiloxanes; the preferred density is 0.9-2.0 g/cm3The fluorine-modified polysiloxane of (1).
7. The polypropylene composition according to claim 1, further comprising 0-2 parts of a pigment.
8. The polypropylene composition according to claim 1, further comprising 0 to 2 parts of an auxiliary agent.
9. A process for the preparation of a polypropylene composition according to any one of claims 1 to 8, comprising the steps of:
a) putting polypropylene resin, high-density polyethylene resin, a dendritic toughening agent, graphene, a surface modifier, a pigment and an auxiliary agent into a high-speed stirrer and uniformly mixing;
b) adding the mixture into a double-screw extruder, carrying out melt mixing, and carrying out extrusion granulation to obtain a polypropylene composition;
wherein the melting and mixing temperature is 170-220 ℃, and the screw rotating speed is 350-450 r/m.
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| CN107501714B (en) | 2018-12-07 |
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