CN112876799A - Low-gloss high-toughness scratch-resistant polypropylene composite material and preparation method thereof - Google Patents
Low-gloss high-toughness scratch-resistant polypropylene composite material and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 69
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 55
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 54
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 18
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 18
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 239000004698 Polyethylene Substances 0.000 claims abstract description 14
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims abstract description 13
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 18
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 238000012661 block copolymerization Methods 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 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 description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 238000007790 scraping Methods 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000006120 scratch resistant coating Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 241001629511 Litchi Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 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 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
The invention discloses a low-gloss high-toughness scratch-resistant polypropylene composite material which is prepared from the following components in parts by weight: 46-90 parts of polypropylene; 2-10 parts of high-density polyethylene; 5-18 parts of a toughening agent; 0-25 parts of inorganic filler; 1-3 parts of a compatilizer; 1-4 parts of a scratch-resistant agent; 0.5-1.0 part of antioxidant; 0.1-0.5 part of processing aid. The scratch-resistant coating achieves the effect of preventing the surface from being scratched by adding the scratch-resistant agent; the glossiness of the material is reduced through the synergistic effect of GMA-g-PE and high-density polyethylene; the scraping resistance of the material is improved through the synergistic effect of GMA-g-PE, high molecular weight erucamide and high molecular weight polysiloxane; the interface bonding force between the PP matrix and the inorganic filler can be improved through GMA-g-PE, and the impact toughness of the material is improved; compared with a one-step mixing method, the material prepared by adopting a step-by-step mixing mode has better scratch resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-gloss high-toughness scratch-resistant polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) is a crystalline polymer with a regular structure, usually white granules or powder, tasteless, nontoxic, and light thermoplastic resin; the high-strength and high-flexibility composite material has the characteristics of easiness in processing, high impact strength, high flexibility, high electrical insulation and the like, has high chemical resistance, and is widely applied to the fields of automobile industry, household appliances, electronics, packaging, building materials, furniture and the like. Because the scratch resistance of the automotive interior parts is improved in recent years, and the PP material has low hardness and poor scratch resistance, the performance needs to be modified and optimized; on the other hand, currently, the sensory requirements for interior parts of automobiles are increasing, and in order to reduce the "plastic feeling" of interior parts such as instrument panels and door trim, low-gloss materials are required to be used in various major host factories, and new performance indexes are proposed for PP modified materials.
Chinese patent (CN 108384111A) discloses a spraying-free scraping-resistant polypropylene composite material for automobiles and a preparation method thereof, and the spraying-free scraping-resistant polypropylene composite material comprises the following raw materials in parts by weight: 50-85 parts of high-crystalline polypropylene, 10-22 parts of calcium carbonate, 5-10 parts of a toughening agent ethylene-octene copolymer, 1-4 parts of an organic silicon scratch-resistant agent, 0.5-4 parts of an aluminum pigment, 0.1-0.5 part of an organic phosphate nucleating agent, 0.3-0.8 part of a coupling agent alkyl modified polysiloxane, 0.2-0.8 part of a hindered amine light stabilizer, 0.2-0.8 part of an antioxidant and 0.3-0.8 part of an antistatic agent. The best cross scratch result for the scratch resistant polypropylene composite made in this patent is Δ L of 0.72. Chinese patent (CN 103524976B) is a high-strength scratch-resistant polypropylene modified resin, which comprises the following components in percentage by weight: 50-85% of polypropylene resin, 10-35% of filling agent, 1-10% of scratch-resistant auxiliary agent, 0.1-5% of cross-linking agent, 1-10% of compatilizer, 0.1-1% of antioxidant and 0.1-1% of processing aid. The patent discloses a high-strength scratch-resistant polypropylene modified resin with the best cross scratch result delta L being 0.96, wherein the scratch-resistant agent is one or more of organic silicon polymer, nano metal oxide and fatty acid amide, and the graft used in the high-strength scratch-resistant polypropylene modified resin is graft or copolymer polymer of polypropylene and unsaturated carboxylic acid or anhydride thereof. The cross scraping result of the polypropylene composition prepared by adding the components such as polypropylene, high-density polyethylene, toughening agent, inorganic filler, compatilizer, scraping-resistant agent, antioxidant, processing aid and the like into the low-gloss high-toughness scraping-resistant polypropylene composite material disclosed by the invention can be delta L-0.2, the scraping-resistant effect is very good, the low-gloss high-toughness scraping-resistant polypropylene composite material can be suitable for various skin marks of automobile interior parts, and the glossiness of the low-gloss high-toughness scraping-resistant polypropylene composite material is obviously reduced compared with that of a conventional material.
Disclosure of Invention
In view of the limitations of the prior art, the present invention aims to provide a low-gloss high-toughness scratch-resistant polypropylene composite material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the low-gloss high-toughness scratch-resistant polypropylene composite material is prepared from the following components in parts by weight:
wherein the scratch-resistant agent is prepared by compounding high-molecular-weight erucamide and high-molecular-weight polysiloxane; the compatilizer is glycidyl methacrylate grafted polyethylene (GMA-g-PE).
According to a further scheme, the compounding ratio of the high molecular weight erucamide to the high molecular weight polysiloxane in the scratch-resistant agent is 1: 1; the grafting rate of the glycidyl methacrylate grafted polyethylene is 1-1.5%.
In a further scheme, the preparation method of the glycidyl methacrylate grafted polyethylene comprises the following steps:
(1) 5 parts of glycidyl methacrylate and 0.2 part of cumyl peroxide are stirred and mixed to obtain a compound;
(2) uniformly mixing 100 parts of high-density polyethylene, 10100.1 parts of antioxidant, 1680.2 parts of antioxidant and 0.1 part of lubricant EBS, adding the mixture into a double-screw extruder, uniformly adding the compound obtained in the step (1) from a side feeding port, wherein the temperature of each section of the extruder is 180-200 ℃, and extruding and granulating to obtain glycidyl methacrylate grafted polyethylene; wherein the melt index of the high-density polyethylene at 190 ℃ and under the condition of 2.16kg is 5g/10 min.
In a further scheme, the molecular weight of the high molecular weight erucamide is more than or equal to 10 ten thousand; the molecular weight of the high molecular weight polysiloxane is more than or equal to 50 ten thousand.
In a further scheme, the polypropylene is block copolymerization polypropylene, and the melt index of the block copolymerization polypropylene at 230 ℃ and 2.16kg is 30-80g/10 min; the melt index of the high-density polyethylene at 190 ℃ under the condition of 2.16kg is 5-15g/10 min.
In a further scheme, the toughening agent is one or a compound of two of an ethylene-octene copolymer and an ethylene-propylene copolymer; ethylene-octene copolymers (POE) are preferred.
In a further scheme, the inorganic filler is one or a compound of two of talcum powder, calcium carbonate, barium sulfate and mica powder.
According to a further scheme, the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant in a mass ratio of 2: 1; among them, the hindered phenol antioxidant is preferably 1076, and the phosphite antioxidant is preferably 168.
In a further scheme, the processing aid is Ethylene Bis Stearamide (EBS).
The second object of the present invention is to provide a method for preparing the low gloss, high toughness, scratch resistant polypropylene composite material, comprising the steps of:
(1) firstly, 46-90 parts of polypropylene, 2-10 parts of high-density polyethylene, 5-18 parts of toughening agent and 0-25 parts of inorganic filler; 1-3 parts of compatilizer, 0.5-1.0 part of antioxidant and 0.1-0.5 part of processing aid are put into a high-speed mixer and mixed for 3-8min at the temperature of 80-90 ℃ to obtain a mixture;
(2) adding 1-4 parts of scratch-resistant agent into the mixture, and continuously mixing for 1-3 min;
(3) adding the mixture prepared in the step (2) into a double-screw extruder with the temperature of 180-210 ℃ for extrusion granulation to obtain a target product
Compared with the prior art, the invention has the beneficial effects that:
1. the scratch-resistant agent is used as a surface modifier, and can reduce the friction force of the surface of a material in the processing process so as to achieve the effect of preventing the surface from being scratched. The scratch-resistant agent used in the invention is prepared by compounding high molecular weight erucamide and high molecular weight polysiloxane, the erucamide and siloxane materials with small molecular weight have the problems of surface stickiness, whitening and the like because the erucamide and siloxane materials with small molecular weight have short molecular chain, simple structure and more violent molecular motion and are easy to separate out on the surface of the materials, and the scratch-resistant agent with high molecular weight can avoid the problem of surface separation in the long-term use process of the materials.
2. GMA-g-PE used in the invention has a synergistic effect with high-density polyethylene, and in a double-screw extruder, the incomplete reaction of GMA component in the graft can cause PP and PE to generate side reaction to generate micro-crosslinking and form a polymer with a partial network structure, thereby reducing the glossiness of the material.
3. The GMA-g-PE used in the invention can improve the scratch resistance of the material through the synergistic effect with high molecular weight erucamide and high molecular weight polysiloxane.
4. The GMA-g-PE used in the invention can improve the interface bonding force between the PP matrix and the inorganic filler, and can reduce the influence of the inorganic filler on the impact toughness of the PP matrix, thereby improving the impact toughness of the material.
5. In the preparation method of the composition, the scratch-resistant agent is added in the step (2), and the purpose is to reduce the contact time of the inorganic filler and the scratch-resistant agent; in the inorganic filler modified polypropylene material, the inorganic filler has a large influence on the scratch resistance of the material, and when the scratch resistance agent and the inorganic filler are mixed, a part of the scratch resistance agent is absorbed by the inorganic filler, so that the scratch resistance effect is reduced; the mixing mode used by the invention can not reduce the using effect of the scratch-resistant agent.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The length to diameter ratio of the twin-screw extruder used in the examples of the present invention was 48: 1, the manufacturer is the company BraBEBDER, Germany.
The polypropylene used below is BX3900 of Korean SK company, the melt index is 60g/10min, the high-density polyethylene is 2908 smooth petrochemical, and the melt index is 8g/10 min;
the used toughening agent ethylene-octene copolymer (POE) is POE8150 of Dow company;
the used inorganic filler is talcum powder 3000 meshes, calcium carbonate 2500 meshes, barium sulfate 2000 meshes and mica powder 1250 meshes;
the molecular weight of the high molecular weight erucamide used in the scratch-resistant agent is 15 ten thousand, and the molecular weight of the high molecular weight polysiloxane is 100 ten thousand;
the antioxidant 1076, antioxidant 168 and EBS are commercially available.
The product of the invention adopts ISO standard to test, the extruded granules are molded by an injection molding machine to obtain a test sample strip, and the performance test is carried out after the test sample strip is stabilized for 24 hours under the conditions of 23 ℃ and 50 percent of relative humidity, and the physical and mechanical performance tests are carried out as follows:
impact strength of the simply supported beam notch: the sample preparation test is carried out according to ISO 179 standard, wherein: the sample strips are 80mm by 10mm, the thickness is (4 +/-0.2) mm, the A-shaped notches are formed, and the notch depth is 1/5; and (3) state adjustment: the sample strips are placed for 24 hours under the conditions of 23 +/-2 ℃ and 50 +/-5% RH and then tested;
cross scrub test conditions: test according to the PV3952 standard, load: 10N, needle diameter: 1 mm; examples 1-8, comparative examples 1-4 used dermatoglyph types: popular K3A (litchi grain); comparative example 5 used dermatoglyph type: popular K31 (frosted grain);
gloss: test according to ISO 2813 standard, dermatoglyph type: the general public K3A.
Glycidyl methacrylate grafted polyethylene (GMA-g-PE) was first prepared by the following method:
(1) 5 parts of glycidyl methacrylate and 0.2 part of cumyl peroxide are stirred and mixed to obtain a mixture;
(2) uniformly mixing 100 parts of high-density polyethylene, 10100.1 parts of antioxidant, 1680.2 parts of antioxidant and 0.1 part of lubricant EBS, adding the mixture into a double-screw extruder, uniformly adding the mixture obtained in the step (1) from a side feeding port, wherein the temperatures of a first zone to a ninth zone of the extruder are respectively 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃ and 195 ℃ and the head temperature is 195 ℃, and extruding and granulating to obtain the glycidyl methacrylate grafted polyethylene; wherein the melt index of the high-density polyethylene at 190 ℃ and under the condition of 2.16kg is 5g/10 min.
Then, the polypropylene composite material was prepared according to the following components in the following table 1, and the preparation steps were as follows (except for comparative example 3):
(1) firstly, putting polypropylene, high-density polyethylene, a toughening agent, an inorganic filler, a compatilizer, an antioxidant and a processing aid into a high-speed mixer, and mixing for 5min at 85 ℃ to obtain a mixture;
(2) adding scratch resistant agent into the mixture, and continuously mixing for 2 min;
(3) and (3) adding the mixture prepared in the step (2) into a double-screw extruder for extrusion granulation to obtain a target product, wherein the temperatures of an extrusion stage I area to an extrusion stage nine area are respectively 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ and the head temperature is 205 ℃.
The procedure for the preparation of comparative example 3 is as follows:
(1) putting 58 parts of polypropylene, 5 parts of high-density polyethylene, 15 parts of toughening agent, 20 parts of talcum powder, 2 parts of compatilizer, 0.6 part of antioxidant, 0.2 part of processing aid and 3 parts of scratch-resistant agent into a high-speed mixer, and mixing for 5min at the temperature of 85 ℃;
(2) adding the mixed material into a double-screw extruder for extrusion granulation to obtain the modified polypropylene material, wherein the temperatures from an extrusion grade I area to a extrusion grade nine area are respectively 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ and the head temperature is 205 ℃.
TABLE 1 ingredient amount design Table in each example or comparative example
TABLE 2 Performance test results
As can be seen from Table 2, the materials prepared from the components disclosed in the invention all have a notched impact strength of 25KJ/m2Above all, the results of the cross scratch DeltaL are below 0.5, and the popular K3A dermatoglyph is a dermatoglyph which is commonly used for interior decoration and is easy to have unqualified scratch (see K31 dermatoglyph in comparative example 5), so the composition of the invention can meet the requirements of most interior decoration dermatoglyphs.
Compared with the comparative example, the GMA-g-PE used in the invention can reduce the glossiness of the material through the synergistic effect with the high-density polyethylene; the scratch resistance of the material can be improved through the synergistic effect of the high molecular weight erucamide and the high molecular weight polysiloxane; can improve the impact toughness of the PP + inorganic filling system. In addition, the material prepared by the step-by-step material mixing method disclosed by the invention has better scratch resistance than a material prepared by a one-step material mixing method.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A low-gloss high-toughness scratch-resistant polypropylene composite material is characterized in that: the composition is prepared from the following components in parts by weight:
wherein the scratch-resistant agent is prepared by compounding high-molecular-weight erucamide and high-molecular-weight polysiloxane; the compatilizer is glycidyl methacrylate grafted polyethylene.
2. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the compounding ratio of the high molecular weight erucamide to the high molecular weight polysiloxane in the scratch resistant agent is 1: 1; the grafting rate of the glycidyl methacrylate grafted polyethylene is 1-1.5%.
3. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the preparation method of the glycidyl methacrylate grafted polyethylene comprises the following steps:
(1) 5 parts of glycidyl methacrylate and 0.2 part of cumyl peroxide are stirred and mixed to obtain a compound;
(2) uniformly mixing 100 parts of high-density polyethylene, 10100.1 parts of antioxidant, 1680.2 parts of antioxidant and 0.1 part of lubricant EBS, adding the mixture into a double-screw extruder, uniformly adding the compound obtained in the step (1) from a side feeding port, wherein the temperature of each section of the extruder is 180-200 ℃, and extruding and granulating to obtain glycidyl methacrylate grafted polyethylene; wherein the melt index of the high-density polyethylene at 190 ℃ and under the condition of 2.16kg is 5g/10 min.
4. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the molecular weight of the high molecular weight erucamide is more than or equal to 10 ten thousand; the molecular weight of the high molecular weight polysiloxane is more than or equal to 50 ten thousand.
5. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the polypropylene is block copolymerization polypropylene, and the melt index of the block copolymerization polypropylene is 30-80g/10min at 230 ℃ and under the condition of 2.16 kg; the melt index of the high-density polyethylene at 190 ℃ under the condition of 2.16kg is 5-15g/10 min.
6. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the toughening agent is one or a compound of two of ethylene-octene copolymer and ethylene-propylene copolymer.
7. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the inorganic filler is one or a compound of two of talcum powder, calcium carbonate, barium sulfate and mica powder.
8. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant in a mass ratio of 2: 1.
9. The low gloss, high toughness, scratch resistant polypropylene composite of claim 1 wherein: the processing aid is ethylene bis stearamide.
10. The process for the preparation of a low gloss high toughness scratch and mar resistant polypropylene composite as claimed in any one of claims 1 to 9, comprising the steps of:
(1) firstly, 46-90 parts of polypropylene, 2-10 parts of high-density polyethylene, 5-18 parts of toughening agent and 0-25 parts of inorganic filler; 1-3 parts of compatilizer, 0.5-1.0 part of antioxidant and 0.1-0.5 part of processing aid are put into a high-speed mixer and mixed to obtain a mixture;
(2) adding 1-4 parts of scratch-resistant agent into the mixture, and continuously mixing for 1-3 min;
(3) and (3) adding the mixture prepared in the step (2) into a double-screw extruder with the temperature of 180-210 ℃ in each zone for extrusion granulation to obtain the target product.
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| CN113321869A (en) * | 2021-06-03 | 2021-08-31 | 金发科技股份有限公司 | Scratch-resistant easy-spraying polypropylene composite material and preparation method and application thereof |
| CN113980386A (en) * | 2021-10-29 | 2022-01-28 | 金发科技股份有限公司 | HDPE-g-GMA modified polypropylene composite material and preparation method and application thereof |
| CN114716783A (en) * | 2022-04-13 | 2022-07-08 | 金发科技(印度)有限公司 | High-heat-resistance polypropylene material and preparation method and application thereof |
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| US20040072936A1 (en) * | 2000-12-22 | 2004-04-15 | Sok-Won Kim | Polyolefin resin composition |
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| US20040072936A1 (en) * | 2000-12-22 | 2004-04-15 | Sok-Won Kim | Polyolefin resin composition |
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| CN113321869A (en) * | 2021-06-03 | 2021-08-31 | 金发科技股份有限公司 | Scratch-resistant easy-spraying polypropylene composite material and preparation method and application thereof |
| CN113980386A (en) * | 2021-10-29 | 2022-01-28 | 金发科技股份有限公司 | HDPE-g-GMA modified polypropylene composite material and preparation method and application thereof |
| CN114716783A (en) * | 2022-04-13 | 2022-07-08 | 金发科技(印度)有限公司 | High-heat-resistance polypropylene material and preparation method and application thereof |
| CN114716783B (en) * | 2022-04-13 | 2024-03-15 | 金发科技(印度)有限公司 | High heat-resistant polypropylene material and preparation method and application thereof |
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