CN115011058B - Reinforced polypropylene composite material and preparation method thereof - Google Patents
Reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN115011058B CN115011058B CN202210812216.2A CN202210812216A CN115011058B CN 115011058 B CN115011058 B CN 115011058B CN 202210812216 A CN202210812216 A CN 202210812216A CN 115011058 B CN115011058 B CN 115011058B
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- -1 polypropylene Polymers 0.000 title claims abstract description 92
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 86
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 13
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 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 9
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 28
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- 230000003678 scratch resistant effect Effects 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 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 5
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical group CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical group CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 claims description 3
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 2
- DKBCURTUXYMRFB-LXTVHRRPSA-N (2r,3r,4s,5r)-7-(3,4-dimethylphenyl)hept-6-ene-1,2,3,4,5,6-hexol Chemical compound CC1=CC=C(C=C(O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)C=C1C DKBCURTUXYMRFB-LXTVHRRPSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical group 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000001746 injection moulding Methods 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 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 2
- 230000009471 action Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- AMEDKBHURXXSQO-UHFFFAOYSA-N azonous acid Chemical compound ONO AMEDKBHURXXSQO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the field of polypropylene, and provides a reinforced polypropylene composite material and a preparation method thereof, aiming at the problem that the processability, toughness and strength of the existing reinforced polypropylene composite material can not meet the thinning requirement of an automobile material: the composite material comprises the following raw materials in parts by weight: 40-70 parts of grafting master batch A, 2-4 parts of catalytic master batch B, 0-10 parts of high impact polypropylene, 10-30 parts of toughening agent, 0-10 parts of linear low density polyethylene, 15-25 parts of talcum powder, 0.1-0.5 part of nucleating agent and 3-5 parts of other auxiliary agents. The prepared material has excellent toughness and high rigidity enhancement characteristics by adopting a two-step silane crosslinking process, and can meet the thin-wall development requirement of modern automobile parts; the grafting and crosslinking reactions are separated in the injection molding process, no moisture interference exists, and the requirement of long-flow rapid molding can be met in the extrusion injection molding process.
Description
Technical Field
The invention belongs to the field of polypropylene, and in particular relates to a reinforced polypropylene composite material and a preparation method thereof.
Background
The automobile instrument panel is used as the most important part of the automobile interior plastic parts, and has high requirements on the material properties. The area of the instrument board material is large, the illumination time is long, and the material is required to have very good rigidity and heat resistance so as to avoid the conditions of collapse, stress cracking, becoming sticky, color change and the like. Moreover, automobile instrument board products are increasingly thinned, the wall thickness is gradually changed from 3mm to 2.5mm or 1.8mm, and good melt fluidity is required for materials so as to ensure that the materials are filled in a die in the injection molding process; in addition, instrument panel parts also require low temperature airbag ignition experiments, which require materials with excellent low temperature toughness. In order to meet the requirements of automotive instrument panel parts, it is necessary to combine excellent flowability, toughness, rigidity, scratch resistance, low emission, tackiness resistance and the like.
The polypropylene has the advantages of excellent mechanical property, good heat resistance, high chemical stability, good processability and excellent electrical insulation, is a universal plastic with excellent comprehensive performance, and is widely applied to automobile instrument board parts. The polypropylene has good crystallization property due to higher regularity and proper flexibility. However, the polypropylene material cannot be crystallized in a hundred percent, the crystal structure is not perfect, the pure polypropylene material cannot meet the use requirements, and the reinforcing and toughening are required to be carried out through a modification technology.
The elastomer toughening plastic has good toughening effect and excellent balance between processability and mechanical properties, and external stress can trigger silver lines and shear bands in the impact process to obviously improve the toughness of the material, so that the elastomer toughening system becomes the toughening system most applied in plastic materials. However, the rigidity of the product is reduced after the elastomer toughening system is used, and the rigidity of the system is further improved mainly by adding filler so as to balance the rigidity and toughness of the material.
The Chinese patent application No. 201811494533.4 discloses a high-fluidity high-modulus high-impact modified filling polypropylene composite material for automobile thinning and a preparation method thereof, which consists of the following raw materials: polypropylene, polyethylene, POE, nucleating agent, filler, coupling agent, free radical scavenger, thermo-oxidative stabilizer and auxiliary agent. The modified filling polypropylene composite material is prepared by taking high-fluidity polypropylene as a matrix material, adding a nucleating agent and a filler and synergistic toughening of POE and high-density polyethylene. The melt flow rate of the prepared modified filling polypropylene composite material reaches 44g/10min,230 /2.16kg, the flexural modulus reaches 2434MPa, and the notch impact strength of the cantilever reaches 36KJ/m 2.
The technical scheme disclosed in the above patent application has the following problems:
1. After the coupling agent is added into the system, the system is easy to generate coupling reaction in the melt extrusion process to increase the viscosity and weaken the molding processability, and the melt flow rate of the prepared modified polypropylene system needs to be further improved to realize the requirement of a long process.
2. The effect of reinforcing and toughening in the system is mostly realized by physical mixing or nucleation crystallization in the extrusion process, the process has relatively short occurrence time (only completed in a single-step extrusion system), the performance improvement range is relatively low, and the possibility that the performance of the obtained product is further improved along with the water absorption of the product by graft coupling reaction is small, so that the reinforcing and toughening effect needs to be further improved.
Disclosure of Invention
Aiming at the problems that the processability, toughness and strength of the existing reinforced polypropylene composite material can not meet the thinning requirement of an automobile material, the invention provides the reinforced polypropylene composite material and the preparation method thereof, the composite material is toughened by POE/SEBS, the crystallinity is improved by linear low-density polyethylene, the two-step silane crosslinking process is adopted, the prepared reinforced polypropylene composite material has excellent toughness and high rigidity reinforcing characteristics, and can meet the thinning development requirement of modern automobile parts; the grafting and crosslinking reactions are separated in the injection molding process, no moisture interference exists, and the requirement of long-flow rapid molding can be met in the extrusion injection molding process.
In order to achieve the above purpose, in one aspect, the invention provides a reinforced polypropylene composite material, which comprises the following raw materials in parts by weight:
40-70 parts of grafting master batch A, 2-4 parts of catalytic master batch B, 0-10 parts of high impact polypropylene, 10-30 parts of toughening agent, 0-10 parts of Linear Low Density Polyethylene (LLDPE), 15-25 parts of talcum powder, 0.1-0.5 part of nucleating agent and 3-5 parts of other auxiliary agents, wherein the other auxiliary agents are one or a combination of more of scratch resistance agent, lubricant and self-crosslinking accelerator;
The grafting master batch A is obtained by mixing the following raw materials in parts by weight, and extruding the mixture after melt blending: 92-96 parts of high-rigidity high-fluidity polypropylene, 3-5 parts of silane crosslinking agent, 1-2 parts of initiator and 1-1.5 parts of antioxidant;
The catalytic master batch B is obtained by mixing the following raw materials in parts by weight, and extruding the mixture after melt blending: 96-100 parts of high-rigidity high-fluidity polypropylene, 0.5-1.5 parts of catalyst and 0.5-1.5 parts of antioxidant;
The toughening agent is a mixture of an ethylene-octene copolymer and a hydrogenated styrene-butadiene block copolymer (SEBS), and the weight ratio of the ethylene-octene copolymer to the hydrogenated styrene-butadiene block copolymer is 1:3-3:1;
the other auxiliary agent is one or a combination of more of scratch resistant agent, lubricant and self-crosslinking accelerator.
According to some embodiments of the invention, wherein the talc is 20 parts, the nucleating agent is 0.2 parts.
Wherein when the high impact polypropylene and the linear low density polyethylene are each independently 0 parts, this means that no such material is added.
According to some embodiments of the invention, the high impact polypropylene, when present, is present in an amount of 5 to 10 parts.
According to some embodiments of the invention, the linear low density polyethylene, when present, is 5 to 10 parts.
According to some specific embodiments of the invention, the grafting master batch A is obtained by mixing the following raw materials in parts by weight, melt blending and extruding: 94 parts of high-rigidity high-fluidity polypropylene, 4 parts of silane crosslinking agent, 1.5 parts of initiator and 0.5 part of antioxidant.
According to some specific embodiments of the invention, the catalytic masterbatch B is obtained by mixing the following raw materials in parts by weight, melt blending and extruding: 98 parts of high-rigidity high-fluidity polypropylene, 1 part of catalyst and 1 part of antioxidant.
According to some embodiments of the invention, wherein the high stiffness high flow polypropylene is a copolymerized polypropylene having a melt flow rate of 30 to 80 g/min; the silane crosslinking agent is selected from one or a combination of more of methacryloxy silane and vinyl silane.
According to some embodiments of the invention, wherein the methacryloxy silane is 3-methacryloxypropyl trimethylsiloxane (VMMS); the vinyl silane is selected from one or more of Vinyl Triethoxysilane (VTES), vinyl Trimethoxysilane (VTMS) and vinyl tris (2-methoxyethoxy) silane (VTMES).
According to some embodiments of the invention, the initiator is a combination of one or more of peroxide initiators.
According to some embodiments of the invention, wherein the initiator is selected from the group consisting of dicumyl peroxide (DCP), benzoyl Peroxide (BPO), 2, 5-dimethylhexane- (di-tert-butyl) peroxide (DHBP), and di-tert-butyl peroxide (DTBP).
According to some embodiments of the invention, the catalyst is n-butyltin dilaurate and/or dodecylbenzenesulfonic acid.
According to some embodiments of the invention, wherein the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010) and/or tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168).
According to some embodiments of the invention, wherein the preparation of the grafting masterbatch a and the catalytic masterbatch B comprises:
Preparation of grafting masterbatch A: adding high-rigidity high-fluidity polypropylene, an initiator and an antioxidant into a double-screw extruder through a main feeding port, metering and adding a silane crosslinking agent through a liquid pump in a side feeding mode, extruding after melt blending, cooling with low-temperature nitrogen, granulating, drying to obtain a grafting master batch A, and preserving by vacuum nitrogen filling;
Preparation of catalytic masterbatch B: and (3) adding the high-rigidity high-fluidity polypropylene, the catalyst and the antioxidant into a double-screw extruder through a feeding port, extruding after melt blending, cooling with low-temperature nitrogen, granulating, drying to obtain a catalytic master batch B, and preserving under vacuum nitrogen filling.
The screw extruder extrusion for preparing the graft masterbatch A and the catalytic masterbatch B according to the invention can refer to conventional extrusion processes, while according to some embodiments of the invention, the screw extruder extrusion processes for preparing the graft masterbatch A and the catalytic masterbatch B respectively and independently comprise: the injection pressure is 4-6bar, the cooling time is 20-30s, and each section of the screw is 190 , 200 , 220 and 220 .
According to some embodiments of the invention, the low temperature nitrogen cooling temperatures for preparing the graft masterbatch A and the catalytic masterbatch B are each independently from 10 to 15 .
According to some embodiments of the invention, the drying temperatures for the preparation of the graft masterbatch A and the catalytic masterbatch B are each independently from 80 to 100 .
According to some embodiments of the invention, the high impact polypropylene is a copolymer polypropylene having a melt flow rate of 20 to 40 g/min.
The hydrogenated styrene-butadiene block copolymer has a density of 0.91-1.1g/cm3, a melt flow rate of 2.5-2.6g/min, and a weight average molecular weight of 7-22 ten thousand.
According to some embodiments of the invention, the mixture of ethylene-octene copolymer and hydrogenated styrene-butadiene block copolymer (SEBS) is 1:1 by weight.
According to some embodiments of the invention, wherein the ethylene-octene copolymer is an ethylene-octene random copolymer (POE) or an ethylene-Octene Block Copolymer (OBC).
According to some embodiments of the invention, wherein the POE and OBC have a density of 0.86 to 0.95g/cm3, respectively, and a melt flow rate of 5 to 10g/min, respectively.
According to some embodiments of the invention, the linear low density polyethylene is obtained by polymerizing ethylene with a small amount of alpha olefin, has a density of 0.918-0.935g/cm3, a melt flow rate of 5-20g/10min, a weight average molecular weight of 9-12 ten thousand, and a molecular weight distribution of 2.3-2.8.
According to some embodiments of the invention, the talc has a particle size of 3000 to 5000 mesh.
According to some embodiments of the invention, wherein the nucleating agent is a combination of one or more of sodium benzoate, dibenzylidene sorbitol, 3, 4-dimethylbenzylidene sorbitol, sodium 2, 2' -methylene-bis (4, 6-di-tert-butyl-phenyl) phosphate, dicyclohexyl-dinaphthyl dihydroxyamide nucleating agent.
According to some embodiments of the invention, the self-crosslinking promoter is anhydrous aluminum chloride and/or aluminum hydroxide.
According to some embodiments of the invention, the scratch resistant agent is a silicone-based scratch resistant agent.
According to some embodiments of the invention, the lubricant is a combination of one or more of polyethylene wax, stearate, and ethylene bis-stearamide.
The invention also provides a preparation method of the reinforced polypropylene composite material, which comprises the following steps:
(1) Preparation of grafting masterbatch A: adding high-rigidity high-fluidity polypropylene, an initiator and an antioxidant into a double-screw extruder, adding a silane cross-linking agent in a side feeding mode, extruding after melt blending, cooling, granulating and drying to obtain a grafting master batch A, and preserving under vacuum nitrogen filling;
(2) Preparation of catalytic masterbatch B: adding high-rigidity high-fluidity polypropylene, a catalyst and an antioxidant into a double-screw extruder, extruding after melt blending, cooling, granulating and drying to obtain a catalytic master batch B, and preserving under vacuum nitrogen filling;
(3) Preparation of silane self-crosslinking polypropylene: adding a toughening agent, talcum powder, linear low-density polyethylene, a lubricant, a scratch resistant agent and a nucleating agent into the obtained grafting master batch A and catalytic master batch B, and uniformly mixing to obtain a mixture;
(4) Adding the mixture obtained in the step (3) into a double-screw extruder, adding a self-crosslinking accelerator in a side feeding mode, performing melt extrusion, and then cooling, granulating and drying to obtain the reinforced polypropylene composite material.
According to some embodiments of the invention, the method comprises the steps of:
(1) Preparation of grafting masterbatch A: adding high-rigidity high-fluidity polypropylene, an initiator and an antioxidant into a double-screw extruder through a main feeding port, metering and adding a silane crosslinking agent through a liquid pump in a side feeding mode, extruding after melt blending, cooling with low-temperature nitrogen, granulating, drying to obtain a grafting master batch A, and preserving by vacuum nitrogen filling;
(2) Preparation of catalytic masterbatch B: adding high-rigidity high-fluidity polypropylene, a catalyst and an antioxidant into a double-screw extruder through a feeding port, extruding after melt blending, cooling with low-temperature nitrogen, granulating, drying to obtain a catalytic master batch B, and preserving under vacuum nitrogen filling;
(3) Preparation of silane self-crosslinking polypropylene: adding the grafting master batch A and the catalytic master batch B into a charging barrel of a high-speed mixer, then adding high-impact polypropylene, a toughening agent, talcum powder, linear low-density polyethylene, a lubricant, a scratch-resistant agent and a nucleating agent, starting the high-speed mixer, and uniformly mixing to obtain a mixture;
(4) Adding the mixture obtained in the step (3) into a double-screw extruder through a main feeding port, metering in a self-crosslinking accelerator through a side feeding mode, and obtaining a product through melt extrusion, low-temperature nitrogen cooling, granulating and drying.
The screw extruder extrusion of step (4) of the present invention for preparing the reinforced polypropylene composite material may refer to a conventional extrusion process, and according to some embodiments of the present invention, the screw extruder extrusion process of step (4) for preparing the reinforced polypropylene composite material comprises: the injection pressure is 4-6bar, the cooling time is 20-30s, and each section of the screw is 190 , 200 ,220 and 220 .
According to some embodiments of the invention, the cooling temperature of step (4) of preparing the reinforced polypropylene composite is between 10 and 15 .
According to some embodiments of the invention, the drying temperature of step (4) of preparing the reinforced polypropylene composite is 80-100 .
Some embodiments of the present invention also provide methods of further improving the performance of reinforced polypropylene composite articles: placing the product in an environment with the temperature of 20-30 and the humidity of 25-45% for 24-72h, absorbing water by the material in the placing process, forming silanol by the system under the action of water and a crosslinking catalyst, and condensing hydroxyl and silanol groups to form Si-O-Si bonds for crosslinking, thereby achieving the purpose of self-enhancement.
The beneficial effects of the invention are as follows:
(1) The high impact reinforced polypropylene composite material obtained by the invention has excellent low-temperature impact resistance (-30 cantilever beam notch impact strength is 5.1-10.0 KJ/m 2), and the multiaxial impact performance of the material before and after modification is greatly improved.
(2) The high toughening effect of the polypropylene composite material is realized by adjusting the proportion of POE to SEBS; the influence of POE/SEBS on PP crystallization performance is weakened by adding a small amount of LLDPE, so that the LLDPE/POE/SEBS core-shell structure is formed under the synergistic effect of the POE/SEBS core-shell structure to a certain extent, and the toughening effect is realized on the premise of ensuring the rigidity of a matrix.
(3) The silane cross-linking agent is used, grafting and cross-linking are separated through a two-step cross-linking process, and the two premixes are stored separately, so that the controllability of the production process is good and the equipment requirement is low; the material eliminates the interference of moisture in the processing process, and the mixed melt still has higher fluidity, so that the requirement of long-flow rapid forming in the product processing process can be met.
(4) After the product is processed and formed, the self-crosslinking reaction of the water in the self-absorbing environment can be further realized, so that the aim of enhancement is fulfilled.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1 to 9
The component contents of the formulations of examples 1 to 10 and comparative examples 1 to 3 of the high impact reinforced polypropylene composite are shown in Table 1.
Table 1 component content tables of the formulations of examples 1 to 10 and comparative examples 1 to 3
In the above table 1, the grafting master batch a is prepared from the following raw materials in parts by weight: 94 parts of high-rigidity high-fluidity polypropylene, 4 parts of silane crosslinking agent, 1.5 parts of initiator and 0.5 part of antioxidant; the catalytic master batch B is prepared from the following raw materials in parts by weight: 98 parts of high-rigidity high-fluidity polypropylene, 1 part of catalyst and1 part of antioxidant. Wherein the high-rigidity high-fluidity polypropylene is EP100 of Lanzhou petrochemical company, the silane crosslinking agent is U.S. Kang Daoning, and the model is Z-6011; the initiator dicumyl peroxide (DCP) is a product of Aizhu chemical technology Co., ltd, and the model is A69780; the antioxidant is antioxidant 1010, which is a synthetic chemical product of angel in Yixing city; the catalyst is n-butyltin dilaurate, which is manufactured by Anhui Zernike technology Co., ltd, and has the model number of C38269.
The high stiffness high flow polypropylene in table 1 above is EP100 from lanzhou petrochemical company; POE is 8677 of the dow chemical product; SEBS is YH-501 of Baling Yueyinylation company; linear Low Density Polyethylene (LLDPE) is YLF1802 from medium petrochemical yang; the high impact polypropylene is EA5073 from bassell, netherlands; the nucleating agent is NA-11, a product of Shandong Mole chemical industry Co., ltd; the aluminum hydroxide is AH-1 of the middle aluminum Shandong company, the talcum powder is Liaoning Ai Hai company, and the model is CP-5000; the scratch resistant agent is HM0221 of Guangzhou chemical industry Co; the lubricant is polyethylene wax, is a Shanghai Yi S product, and has the model number of R006519-35g.
The preparation method of each example in table 1 above is as follows:
(1) The first step: preparation of grafting masterbatch A: adding high-rigidity high-fluidity polypropylene, an initiator and an antioxidant into a double-screw extruder through a main feeding port according to a certain proportion, metering and adding a silane cross-linking agent through a liquid pump in a side feeding mode, extruding after melt blending, air-cooling with low-temperature nitrogen, granulating, drying, and obtaining a grafting master batch A, and preserving by vacuum nitrogen filling. The temperature of each section of the screw is 190 , 200 , 220 and the rotating speed of the screw is 350rpm.
Preparation of catalytic masterbatch B: and (3) adding the high-rigidity high-fluidity polypropylene, the catalyst and the antioxidant into a double-screw extruder through a feeding port according to a certain proportion, extruding after melt blending, carrying out low-temperature nitrogen air cooling, granulating, drying, thus obtaining the catalytic master batch B, and carrying out vacuum nitrogen filling preservation. The temperature of each section of the screw is 190 , 200 , 220 and the rotating speed of the screw is 350rpm.
(2) And a second step of: preparation of silane self-crosslinking polypropylene: adding the grafting master batch A and the catalytic master batch B into a charging barrel of a high-speed mixer according to a certain proportion, sequentially adding high-impact polypropylene, POE, SEBS, talcum powder, LLDPE, a lubricant, an anti-scratch agent and a nucleating agent according to a certain proportion, starting the high-speed mixer, and mixing for 10 minutes; the rotation speed was 800rpm.
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder through a main feeding port, simultaneously metering in a self-crosslinking accelerator through a side feeding mode, and carrying out melt extrusion, low-temperature nitrogen cooling, granulating and drying to obtain a product, and carrying out vacuum nitrogen filling and preservation. The temperature of each section of the screw is 190 ,200 , 220 and the rotating speed of the screw is 350rpm.
The preparation method of each comparative example in table 1 above is as follows:
(1) Weighing the components according to the weight ratio of the formula;
(2) Adding high-rigidity high-fluidity polypropylene into a charging barrel of a high-speed mixer according to a certain proportion, sequentially adding POE, SEBS, talcum powder and lubricant according to a certain proportion, starting the high-speed mixer, and mixing for 5-20 minutes; the rotation speed was 800rpm.
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder through a main feeding port, and obtaining a product through melt extrusion, cooling, granulating and drying. The temperature of each section of the screw is 190 , 200 , 220 and the rotating speed of the screw is 350rpm.
Test case
The performance experiments of examples 1 to 10 and comparative examples 1 to 3 of the reinforced polypropylene composite material of the present invention are as follows:
performance evaluation mode and implementation standard:
Placing the plastic particles prepared by the method into an injection molding machine, injecting to prepare a primary sample, placing the primary sample into an air environment for standing for 48 hours at the injection temperature of 190 , 200 , 220 and 220 , and obtaining a standard sample.
The scratch resistance of the test specimens was tested according to U.S. standard GMW 14688; the U.S. standard ASTM D3763-2018 tests the multiaxial impact strength of the test specimens; odor rating of the test specimens according to U.S. standard GMW-3205; the tensile strength, the notched impact strength of the cantilever beam and the flexural modulus of the test samples were tested according to national standards.
The results of the above tests are shown in tables 2 and 3.
Table 2 comparative example test results comparison table
Table 3 example test results comparison table
TABLE 4 example 8 injection molded standard bars were tested after various days of storage (humidity: 25% -45%, temperature: 25 C.)
As can be seen, the tensile strength, flexural modulus, notched Izod impact strength (23 and-30 ) and multiaxial impact properties of the reinforced polypropylene composite material of the present invention are substantially improved as compared to the pure resin, i.e., the product produced by the scheme of comparative example 1. The method has the advantages that LLDPE and the POE/SEBS reinforcing and toughening system are used for generating a synergistic effect, so that the particle size of a disperse phase in the system is reduced, the phase interface between a continuous phase and the disperse phase is thickened, the compatibility between a PP phase and the POE/SEBS phase is enhanced, and the rigidity and the toughness of the composite material system are enhanced; in addition, the polypropylene grafting silane reaction and the cross-linking reaction of the grafted polypropylene material in the composite system are carried out step by step, the material is kept dry in the extrusion process and is protected in the whole nitrogen atmosphere, so that the condition that the viscosity of the system is greatly increased due to the occurrence of the cross-linking reaction in the extrusion process is greatly weakened (the melt flow rate is not obviously reduced).
Meanwhile, after the materials are molded into products, the properties of the products can be further improved after the products are placed for different times. This is because the product absorbs water during the placement process, the system forms silanol under the action of water and a crosslinking catalyst, and then the hydroxyl groups condense with silanol groups to form Si-O-Si bonds to crosslink, thus achieving the purpose of self-reinforcement.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (9)
1. The reinforced polypropylene composite material is characterized by being prepared from the following raw materials in parts by weight: 40-70 parts of grafting master batch A, 2-4 parts of catalytic master batch B, 0-10 parts of high impact polypropylene, 10-30 parts of toughening agent, 0-10 parts of linear low density polyethylene, 15-25 parts of talcum powder, 0.1-0.5 part of nucleating agent and 3-5 parts of other auxiliary agents;
the grafting master batch A is obtained by mixing the following raw materials in parts by weight, and extruding the mixture after melt blending: 92-96 parts of copolymerized polypropylene with the melt flow rate of 30-80g/min, 3-5 parts of silane cross-linking agent, 1-2 parts of initiator and 1-1.5 parts of antioxidant;
The catalytic master batch B is obtained by mixing the following raw materials in parts by weight, and extruding the mixture after melt blending: 96-100 parts of copolymerized polypropylene with the melt flow rate of 30-80g/min, 0.5-1.5 parts of catalyst and 0.5-1.5 parts of antioxidant;
The toughening agent is a mixture of an ethylene-octene copolymer and a hydrogenated styrene-butadiene block copolymer, and the weight ratio of the ethylene-octene copolymer to the hydrogenated styrene-butadiene block copolymer is 1:3-3:1;
The other auxiliary agent is one or a combination of more of scratch resistant agent, lubricant and self-crosslinking accelerator;
The preparation method of the reinforced polypropylene composite material comprises the following steps:
(1) Preparation of grafting masterbatch A: adding copolymerized polypropylene with the melt flow rate of 30-80g/min, an initiator and an antioxidant into a double-screw extruder, adding a silane cross-linking agent in a side feeding mode, extruding after melt blending, cooling, granulating and drying to obtain a grafting master batch A, and preserving under vacuum nitrogen filling;
(2) Preparation of catalytic masterbatch B: adding the copolymerized polypropylene with the melt flow rate of 30-80g/min, the catalyst and the antioxidant into a double-screw extruder, extruding after melt blending, cooling, granulating and drying to obtain a catalytic master batch B, and preserving under vacuum nitrogen filling;
(3) Preparation of silane self-crosslinking polypropylene: adding high impact polypropylene, a toughening agent, talcum powder, linear low density polyethylene, a lubricant, a scratch resistant agent and a nucleating agent into the grafting master batch A and the catalysis master batch B, and uniformly mixing to obtain a mixture;
(4) Adding the mixture obtained in the step (3) into a double-screw extruder, adding a self-crosslinking accelerator in a side feeding mode, performing melt extrusion, and then cooling, granulating and drying to obtain the reinforced polypropylene composite material.
2. The reinforced polypropylene composite according to claim 1, wherein the silane cross-linking agent is selected from methacryloxy silane and/or vinyl silane.
3. The reinforced polypropylene composite according to claim 2, wherein the methacryloxy silane is 3-methacryloxypropyl trimethylsiloxane; the vinyl silane is selected from one or more of vinyl triethoxy silane, vinyl trimethoxy silane or vinyl tri (2-methoxyethoxy) silane.
4. The reinforced polypropylene composite according to claim 1, wherein the initiator is a peroxide initiator.
5. The reinforced polypropylene composite according to claim 1, wherein the initiator is selected from the group consisting of one or more of dicumyl peroxide, benzoyl peroxide, 2, 5-dimethylhexane- (di-tert-butyl) peroxide and di-tert-butyl peroxide.
6. The reinforced polypropylene composite according to claim 1, wherein the catalyst is n-butyltin dilaurate and/or dodecylbenzenesulfonic acid.
7. The reinforced polypropylene composite according to claim 1, wherein the antioxidant is pentaerythritol tetrakis [ - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and/or tris [2, 4-di-tert-butylphenyl ] phosphite.
8. The reinforced polypropylene composite of claim 1, wherein the nucleating agent is a combination of one or more of sodium benzoate, dibenzylidene sorbitol, 3, 4-dimethylbenzylidene sorbitol, sodium 2, 2' -methylene-bis (4, 6-di-tert-butyl-phenyl) phosphate.
9. The reinforced polypropylene composite according to claim 1, wherein the self-crosslinking promoter is anhydrous aluminum chloride and/or aluminum hydroxide; the scratch resistant agent is a silicone scratch resistant agent; the lubricant is one or a combination of more of polyethylene wax, stearate and ethylene bis-stearamide.
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| CN102070837A (en) * | 2010-12-31 | 2011-05-25 | 金发科技股份有限公司 | Cross-linked polypropylene composite material and preparation method thereof |
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| CN114292364A (en) * | 2021-12-21 | 2022-04-08 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
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| CN102070837A (en) * | 2010-12-31 | 2011-05-25 | 金发科技股份有限公司 | Cross-linked polypropylene composite material and preparation method thereof |
| CN103172937A (en) * | 2013-04-11 | 2013-06-26 | 杭州恒标管业有限公司 | Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof |
| CN114292364A (en) * | 2021-12-21 | 2022-04-08 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
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