CN115260661A - Low-CLTE high-modulus material free of flame treatment and preparation method and application thereof - Google Patents
Low-CLTE high-modulus material free of flame treatment and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 16
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 16
- 239000002667 nucleating agent Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract 2
- -1 polypropylene Polymers 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000000806 elastomer Substances 0.000 claims description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012764 mineral filler Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 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
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 229920005606 polypropylene copolymer Polymers 0.000 abstract description 14
- 229920005629 polypropylene homopolymer Polymers 0.000 abstract description 12
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007792 addition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QXKAIJAYHKCRRA-UHFFFAOYSA-N D-lyxonic acid Natural products OCC(O)C(O)C(O)C(O)=O QXKAIJAYHKCRRA-UHFFFAOYSA-N 0.000 description 1
- QXKAIJAYHKCRRA-FLRLBIABSA-N D-xylonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-FLRLBIABSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 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
- 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
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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)
Abstract
The invention relates to a high-modulus material with low CLTE (cyclic olefin sulfonate) and no flame treatment, and a preparation method and application thereof, belonging to the technical field of materials. The invention discloses a low CLTE high-modulus material free of flame treatment, which comprises the following raw materials in parts by weight: matrix resin: 50-75 parts of a toughening agent: 5-20 parts of mineral filling: 25-40 parts of surfactant: 1-10 parts of a nucleating agent: 0.2-1.5 parts of antioxidant: 0.2-1.5 parts of ultraviolet absorbent: 0.2-2 parts of lubricant: 0.1-0.3 part of dispersant: 0.05-0.1 part; the matrix resin accounts for 55-60% of the total mass of the raw materials, and specifically comprises the following components in percentage by mass (4-6): (1-1.5): 1, polypropylene copolymer, polypropylene homopolymer, and linear low density polyethylene. The invention discloses a preparation method and application thereof in the field of automobile parts.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a high-modulus material with low CLTE content and no flame treatment, and a preparation method and application thereof.
Background
At present, the usage amount of plastic parts in the fields of automobiles and household electrical appliances is continuously increasing, and especially, the usage amount of plastic parts with larger volume, complex size and structure and surface spraying is continuously increasing, such as: outer plate of automobile tail door, grid, periphery of bumper, shell of electric appliance and base of electric appliance. Because the functional requirements and the use environment of the parts require that the material has good dimensional stability, low linear expansion coefficient and high strength modulus, the cost is higher and the preparation process is complicated. The material in the prior art has large size and complex structure required by parts, so that the size change of the parts is large when the existing material is heated and cooled, and the assembly and subsequent use of the parts are influenced; and the strength of the material is not enough to ensure that the material still keeps the original properties when being stressed at high temperature or high strength. In addition, in order to enhance the appearance of the parts, the parts are usually required to be surface-sprayed, and the conventional spraying process is to perform flame or corona treatment before the parts are sprayed to increase the surface polarity of the partsThe steps are not beneficial to industrial production, and the efficient preparation of large-size and complex-structure plastic parts cannot be realized. Chinese patent application text (publication No. CN 103665544A) discloses an isotropic low linear expansion coefficient polypropylene composition and a preparation method thereof, wherein raw materials comprise 20-98% of polypropylene, 2-20% of whisker, 0-30% of mineral powder, 0-20% of toughening agent, 0-5% of compatilizer and 0-5% of other auxiliary agents; by adding different types and contents of three-dimensional structure whiskers, the surface appearance of the product is influenced to a certain extent, and the linear expansion coefficient of the prepared polypropylene composition is 3.2 multiplied by 10 to the lowest-5However, the cost of the whisker with a three-dimensional structure is too high, and low-cost raw materials are generally required to be adopted in order to adapt to industrial production. Chinese patent application text (publication No. CN 114507399A) discloses a polypropylene material, its preparation method and application, the raw materials include 60-70 parts of homopolymerized polypropylene, 10-15 parts of block copolymerization polypropylene, 10-30 parts of linear low density polyethylene, 0.2-0.5 part of beta-nucleating agent, 0.5-1 part of antioxidant and 0.1-1 part of light stabilizer; the prepared material has higher izod notched impact strength but lower flexural modulus, and the linear expansion coefficient of the material is not improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a composite material which has the advantages of low CLTE (linear expansion coefficient), no flame treatment, high strength modulus, high temperature and high pressure resistance and good dimensional stability.
The purpose of the invention can be realized by the following technical scheme:
a high modulus material with low CLTE and no flame treatment comprises the following raw materials in parts by weight: matrix resin: 50-75 parts of a toughening agent: 5-20 parts of mineral filling: 25-40 parts of surfactant: 1-10 parts of a nucleating agent: 0.2-1.5 parts of antioxidant: 0.2-1.5 parts of ultraviolet absorbent: 0.2-2 parts of lubricant: 0.1-0.3 part of dispersant: 0.05-0.1 part; the matrix resin accounts for 55-60% of the total mass of the raw materials, and specifically comprises the following components in percentage by mass (4-6): (1-1.5): 1, a copolymer polypropylene, a homopolymer polypropylene, a linear low density polyethylene.
The copolymerized polypropylene has good impact property, relatively low shrinkage ratio and good dimensional stability, and simultaneously has good rigidity and toughness balance, relatively high proportion of the copolymerized polypropylene in the total content of the resin and better comprehensive effect. Homo-polypropylene has a higher modulus with a relatively low coefficient of linear expansion. The linear low-density polyethylene has higher crystallinity, reduces the linear expansion coefficient of the material, has higher impact resistance and plays a role in toughening. The three components act synergistically to make the matrix resin have better low linear expansion coefficient, high toughness and high stability.
Preferably, the mass ratio of the total mass of the co-polypropylene and the homo-polypropylene to the linear low density polyethylene is (6-7): 1.
preferably, the proportion of the copolymerized polypropylene in the matrix resin is 65-73%.
Preferably, the molecular weight of the polypropylene copolymer is 20-23 ten thousand, and the melt index is 30g/10min (230 ℃/2.16 kg); the molecular weight of the homopolymerized polypropylene is 15-20 ten thousand, and the melt index is 15g/10min (230 ℃/2.16 kg); linear Low Density Polyethylene (LLDPE) has a molecular weight of 10-15 ten thousand and a melt index of 2g/10min (230 ℃/2.16 kg).
Preferably, the mass ratio of the toughening agent to the nucleating agent is (9-11): 1.
preferably, the mass ratio of the matrix resin to the toughening agent is (5-100): 1.
Preferably, the toughening agent comprises one or more of ethylene octene copolymers, ethylene propylene diene monomer, hydrogenated styrene-butadiene block copolymers, thermoplastic polyurethane elastomers, thermoplastic vulcanizates.
Further preferably, when the toughening agent is an ethylene-octene copolymer, the mass ratio of the matrix resin to the toughening agent is (5-20): 1.
further preferably, when the toughening agent is a thermoplastic polyurethane elastomer, the mass ratio of the matrix resin to the toughening agent is (5-10): 1.
more preferably, when the mass ratio of the toughening agent is (0.5-2): (0.5-2) the mass ratio of the matrix resin to the toughening agent is (6-9): 1.
preferably, the surfactant comprises one or more of maleic anhydride, maleic anhydride graft, metal oxide and metal powder.
Further preferably, the metal powder includes one or more of iron powder, nickel powder, molybdenum powder, copper powder, and aluminum powder.
Still more preferably, the metal powder has a particle size of 1200 mesh.
Preferably, the mineral filler comprises one or more of calcium carbonate, talc, mica, wollastonite, barium sulfate whiskers.
More preferably, when the mineral filling is barium sulfate whisker, the mass ratio of the matrix resin to the barium sulfate whisker is (1-5): 1.
the addition of the surfactant and the mineral filler increases the hardness of the material and simultaneously reduces the impact property of the material, and the addition of the metal powder improves the surface activity of the material, so that the hardness of the material is increased and simultaneously the flexural modulus and the flexural strength of the material are increased.
Preferably, the nucleating agent comprises one or more of aliphatic carboxylic acid metal compounds, sorbitolidene derivatives, aromatic carboxylic acid metal compounds, organic phosphates, xylonic acid and derivatives thereof, sodium benzoate and bis (p-tert-butylbenzoic acid) aluminum carboxy.
Preferably, the nucleating agent comprises the following components in a mass ratio of (0.5-1): (0.5-1): (0.5-1) a mixture of a metal compound of a fatty carboxylic acid, a sorbitolidene derivative and an organic phosphate.
Further preferably, the nucleating agent is added in an amount of 0.8 to 1.8% of the matrix resin.
Preferably, the antioxidant comprises one or more of a phenolic antioxidant and a phosphite antioxidant.
More preferably, the antioxidant is a mixture of a phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-3) to 1.
Preferably, the ultraviolet absorber comprises one or more of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitriles and triazines.
Preferably, the lubricant comprises one or more of calcium stearate, zinc stearate, ethylene bis stearamide, and an organosilicon compound.
Preferably, the dispersant comprises one or more of white oil, mineral oil, paraffin oil, naphthenic oil.
The invention also discloses a preparation method of the high-modulus material with low CLTE content and without flame treatment, which comprises the following steps: weighing the raw materials, adding the components except the powder in the raw materials into a high-speed mixer for premixing to obtain a premix, then adding the powder components for uniformly mixing, and then adding the premix into a double-screw extruder for melt blending extrusion, cooling, granulating and drying.
The invention also discloses application of the low CLTE flame-treatment-free high-modulus material in the field of automobile parts.
Preferably, the automobile parts include, but are not limited to, automobile tail door panels, grilles, bumper peripheries, appliance housings, and appliance mounts.
The material prepared by the invention has high strength, high modulus and low linear expansion coefficient, can be used in harsh environments with high temperature and high load, has small influence on the size change of parts due to the change of environmental temperature, and avoids the need of flame or corona treatment like the traditional spraying process; the production efficiency is improved while the cost is saved; can be widely applied to automobile tail door plates, grids, the periphery of bumpers, electric appliance shells, electric appliance bases and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, three types of resins of the polypropylene copolymer, the homo-polypropylene and the linear low-density polyethylene are simultaneously added into the raw materials, and other components are combined, so that the prepared material can have the performances of high strength, high modulus, high heat resistance, stable size and low linear expansion coefficient without adopting the traditional flame treatment.
2. The mass ratio of the three types of resins of the polypropylene copolymer, the polypropylene copolymer and the linear low-density polyethylene in the matrix resin is (4-6): (1-1.5): 1, wherein the proportion of the copolymerized polypropylene is 65-73%, so that the prepared material has better comprehensive performance.
3. The invention controls the content of the matrix resin to be 55-60% of the total mass of the raw materials so as to ensure the performance of the material.
4. Ratio of toughening agent to nucleating agent in the invention
5. The invention adds the surface active agent and the mineral filler to improve the mechanical property of the material, and especially can exert the optimal effect when the surface active agent is metal powder and the mineral filler is barium sulfate whisker.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
The raw materials comprise:
and (3) polypropylene copolymer: korean SK, BH3820;
homo-polypropylene: tai-Ning-Bo, 1124;
linear low density polyethylene: exxonfu, 1002KW;
the rest raw materials are conventional commercial products.
Example 1
The raw materials are weighed according to the following proportion, 40 parts of polypropylene copolymer, 10 parts of homopolymerized polypropylene, 8 parts of linear low-density polyethylene, 4 parts of thermoplastic polyurethane elastomer, 3 parts of ethylene-octene copolymer, 30 parts of barium sulfate whisker, 5 parts of metal powder (aluminum powder, 1200 meshes), 0.7 part of nucleating agent (NA 11), 0.2 part of phenol antioxidant (antioxidant 1010), 0.1 part of phosphite antioxidant (antioxidant 168), 0.3 part of ultraviolet absorbent (531), 0.2 part of lubricant (calcium stearate) and 0.05 part of dispersant (white oil).
Then adding the components except the powder in the raw materials into a high-speed mixer for premixing to obtain a premix, adding the powder components for uniformly mixing, adding the premix into a double-screw extruder for melt blending at the temperature of 160-220 ℃, and then extruding, cooling, granulating and drying. The properties are shown in Table 1.
Example 2
Compared with the embodiment 1, the difference is that the base resin comprises 38 parts of polypropylene copolymer, 12 parts of polypropylene homopolymer and 8 parts of linear low density polyethylene.
Example 3
Compared with the embodiment 1, the difference is that the base resin comprises 42 parts of polypropylene copolymer, 8 parts of polypropylene homopolymer and 8 parts of linear low density polyethylene.
Example 4
The difference compared to example 1 is that the toughening agent is only 7 parts of the ethylene octene copolymer.
Example 5
The difference compared to example 1 is that the toughening agent is only 7 parts of thermoplastic polyurethane elastomer.
Example 6
The difference compared to example 1 is that the toughening agent is only 7 parts of thermoplastic vulcanizate.
Example 7
The difference compared to example 1 is that the mineral filling is talc.
Example 8
The difference compared to example 1 is that the surfactant is maleic anhydride.
Example 9
The difference compared to example 1 is that the surfactant is a metal oxide (antimony trioxide).
Example 10
The difference from example 1 is that the nucleating agent was added in an amount of 0.5 part.
Example 11
The difference from example 1 is that the nucleating agent was added in an amount of 1 part.
Comparative example 1
The difference from example 1 is that the matrix resin is 40 parts of polypropylene copolymer and 10 parts of polypropylene homopolymer.
Comparative example 2
Compared with the embodiment 1, the difference is that the base resin comprises 10 parts of polypropylene copolymer, 40 parts of homo-polypropylene and 8 parts of linear low density polyethylene.
Comparative example 3
Compared with the embodiment 1, the difference is that the base resin comprises 30 parts of polypropylene copolymer, 20 parts of polypropylene homopolymer and 8 parts of linear low density polyethylene.
Comparative example 4
Compared with the embodiment 1, the difference is that the matrix resin comprises 20 parts of polypropylene copolymer, 20 parts of polypropylene homopolymer and 8 parts of linear low density polyethylene.
Comparative example 5
The difference compared to example 1 is that no nucleating agent is added.
TABLE 1 Performance data Table
As can be seen from the data in the table, when the content of the matrix resin in examples 1 to 3 was 57.2%, the combination of the properties was higher than that in comparative example 1 in which the content of the matrix resin was 53.5%, and also higher than that in comparative examples 2 to 4 in which the proportions of the three resins were changed; the compounded toughening agent can obtain more excellent performances such as linear expansion coefficient and the like; the barium sulfate whisker is more suitable for preparing high-performance resin than the conventional mineral filling due to the characteristics of the barium sulfate whisker; when the metal powder is used as a surfactant, the properties such as bending strength and the like can be further improved; when the content of the nucleating agent is 0.8-1.8% of the matrix resin, better flexural modulus can be obtained without influencing the notch impact property.
In summary, the matrix resin in the invention accounts for 55-60% of the total mass of the raw materials, and simultaneously comprises three types of resins of polypropylene copolymer, polypropylene homopolymer and linear low density polyethylene, and combines other components, so that the prepared material can have the properties of high strength, high modulus, high heat resistance, stable size and low linear expansion coefficient without adopting the traditional flame treatment.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A low CLTE (cyclic vinyl acetate) flame-treatment-free high-modulus material is characterized by comprising the following raw materials in parts by weight: matrix resin: 50-75 parts of a toughening agent: 5-20 parts of mineral filling: 25-40 parts of surfactant: 1-10 parts of a nucleating agent: 0.2-1.5 parts of antioxidant: 0.2-1.5 parts of ultraviolet absorbent: 0.2-2 parts of lubricant: 0.1-0.3 part of dispersant: 0.05-0.1 part; the matrix resin accounts for 55-60% of the total mass of the raw materials, and the matrix resin is prepared from (4-6): (1-1.5): 1, a mixed resin of a copolymer polypropylene, a homopolymer polypropylene and a linear low density polyethylene.
2. The low CLTE, flame-free, high modulus material according to claim 1, wherein the mass ratio of the matrix resin to the toughening agent is (5-100): 1.
3. A low CLTE, flame-free, high modulus material according to claim 1 or 2, wherein said toughening agent comprises one or more of ethylene octene copolymer, ethylene propylene diene monomer, hydrogenated styrene-butadiene block copolymer, thermoplastic polyurethane elastomer, thermoplastic vulcanizate.
4. The low CLTE, flame-free, high modulus material according to claim 3, wherein when the toughening agent is a mixture of an ethylene octene copolymer and a thermoplastic polyurethane elastomer, the mass ratio of matrix resin to thermoplastic polyurethane elastomer is (6-9): 1.
5. the low CLTE, flame free, high modulus material according to claim 1, wherein said surfactant comprises one or more of maleic anhydride, maleic anhydride grafts, metal oxides, metal powders.
6. A low CLTE, flame-free treated high modulus material according to claim 1, wherein said mineral filler comprises one or more of calcium carbonate, talc, mica, wollastonite, barium sulfate whiskers.
7. The low CLTE, flame-safe, high modulus material of claim 1, wherein said nucleating agent comprises one or more of aliphatic carboxylic acid metal compounds, sorbitolidene derivatives, aromatic carboxylic acid metal compounds, organophosphates, wood acids and their derivatives, sodium benzoate, and bis (p-tert-butyl benzoic acid) aluminum carboxy.
8. A low CLTE, flame-free, high modulus material as claimed in claim 1, wherein said nucleating agent is added in an amount of 1-1.8% of the matrix resin.
9. A process for preparing a low CLTE, flame-free, high modulus material of claim 1, comprising: weighing the raw materials, adding the components except the powder in the raw materials into a high-speed mixer for premixing to obtain a premix, adding the powder components for uniformly mixing, adding into a double-screw extruder for melt blending extrusion, cooling, granulating and drying.
10. Use of a low CLTE, flame-free treated high modulus material of claim 1 in the automotive component area.
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| CN114181458A (en) * | 2021-12-16 | 2022-03-15 | 嘉兴学院 | Spraying-free polypropylene composite material, preparation method and application thereof |
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| EP2530117A1 (en) * | 2011-05-30 | 2012-12-05 | Borealis AG | Process for producing polypropylene compounds with low CLTE |
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