CN104403206B - A kind of soft sense of touch polypropene composition and preparation method thereof of low smell, scratch-resistant - Google Patents
A kind of soft sense of touch polypropene composition and preparation method thereof of low smell, scratch-resistant Download PDFInfo
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- CN104403206B CN104403206B CN201410667370.0A CN201410667370A CN104403206B CN 104403206 B CN104403206 B CN 104403206B CN 201410667370 A CN201410667370 A CN 201410667370A CN 104403206 B CN104403206 B CN 104403206B
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- propylene
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 85
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 95
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000005977 Ethylene Substances 0.000 claims abstract description 90
- 229920001577 copolymer Polymers 0.000 claims abstract description 70
- -1 polypropylene Polymers 0.000 claims abstract description 61
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 58
- 239000003365 glass fiber Substances 0.000 claims abstract description 55
- 239000004611 light stabiliser Substances 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 235000006708 antioxidants Nutrition 0.000 claims description 57
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 238000012360 testing method Methods 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 238000005453 pelletization Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910000071 diazene Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 32
- 239000000463 material Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 15
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 229920005606 polypropylene copolymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 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 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical class CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to polypropene compositions, and in particular to a kind of low smell, scratch-resistant soft sense of touch polypropene composition and preparation method thereof.The polypropene composition includes the raw material of following weight percent：The copolymer 20~35% of polypropylene 30~60%, ethylene and propylene, glass fibre 10~30%, hyperbranched (ethylene and methyl acrylate) copolymer 5~10%, antioxidant 0.2~1%, light stabilizer 0.2~1%, additive 0.3~3%, the total amount of above-mentioned raw materials is 100%.The present invention also provides the production methods of this kind of product.Product of the present invention has the characteristics that strong high mechanical properties, impact resistance, high intensity, scratch-resistant, low smell, soft sense of touch and low linear expansion coefficient.
Description
Technical field
The present invention relates to polypropene compositions, and in particular to low smell, scratch-resistant soft sense of touch polypropene composition and its
Preparation method.
Background technology
In the prior art, mineral filled polypropylene is with density is relatively low, excellent in mechanical performance, corrosion-resistant, environmentally friendly, price is low
It is honest and clean and conducive to recycle the features such as, be widely used in inner and outer decorative parts of automobile.In recent years, the fast development of automobile industry is internal
Outer exterior material proposes increasingly higher demands；Such as instrument board, door-plate, column, bumper require high intensity, shock resistance, resistance to
The performances such as scraping, low smell, good stability of the dimension；Compared with mineral filled polypropylene, glass fiber reinforced polypropylene have compared with
High intensity, excellent scratch resistance and low linear expansion coefficient（Good stability of the dimension）.
CN102924806A discloses a kind of dedicated glass fiber reinforced polypropylene of bumper, resistance to high rigidity, height
The advantages of heat and good stability of the dimension.But it is different with automobile exterior, in order to assign the better appearance of product and feel, in automobile
Exterior material also needs to have soft sense of touch, and the hardness of glass fiber reinforced polypropylene is higher, does not have soft sense of touch；A kind of solution party
Method is to coat one layer by soft PVC in article surface（PVC）, the copolymer of PVC/ acrylonitrile-butadiene-styrene (ABS)s
（ABS）The covering of the material preparations such as alloy.But this not only results in complex procedures, cost increase, and flexible PVC, PVC/
ABS contains more plasticizer and heavy metal stabilizer, generates environmental protection and the problem recycled.
In order to improve drawbacks described above, US0242335 discloses a kind of glass fiber reinforced polypropylene of soft sense of touch, component packet
Include the polypropylene prepared by special metallocene catalyst catalysis propylene polymerization, 1~60% weight point of 40~99% weight fractions
Several glass fibres and compatilizer and auxiliary agent；In above-mentioned technical solution, although glass fibre can significantly increase it is poly-
The intensity of propylene material, scratch resistance, but its mobility can be seriously reduced, deteriorate the processing performance of material；In order to improve material
The mobility of material needs to add in a certain amount of peroxide to reduce polyacrylic molecular weight；But peroxide can cause material
The defects of material turns to be yellow, easy to aging and smell is larger；In addition, the compatilizer used in it is maleic anhydride inoculated polypropylene, itself has
Certain smell, and maleic anhydride homopolymers are easily remained, it can also influence the smell and performance of material.
JP510177 discloses a kind of reinforced polypropylene composition, and component includes the soft polypropylene of 5~90% weight fractions
Material, the mineral of 5-60% weight fractions or glass fibre and processing aid etc. have good scratch resistance and soft sense of touch.
In above-mentioned report, in order to improve the mobility of material, it is still desirable to add in a certain amount of peroxide；In addition, used is soft
Matter polypropylene material is the impact polypropylene of high rubber content, and not only proportion is high for EP rubbers（>70wt%）, and second third
Ethylene component in rubber is more（>40wt%）.This can cause material mechanical performance relatively low, EP rubbers and polypropylene matrix
The defects of compatibility is poor, and product is likely to occur point, bright print.
In conclusion the polypropene composition of the prior art has following defect：1）Do not have soft sense of touch or have soft touch
Sense still has environmental protection and recycles difficult problem；2）Jaundice, easy to aging, smell is big by 3）Poor fluidity, processing performance not enough 4）
There are the defects of point, bright print for material surface.
Invention content
The main object of the present invention be for above-mentioned deficiency of the prior art, provide a kind of low smell, scratch-resistant it is soft
Sense of touch polypropene composition and preparation method thereof is steady with high intensity, shock resistance, scratch-resistant, low smell, good fluidity, size
The advantages that qualitative good.Preparation method is simple, is conducive to promote and apply.
The purpose of the present invention is achieved through the following technical solutions.
The soft sense of touch polypropene composition of a kind of low smell, scratch-resistant, the composition include following weight percent
Raw material：20~35 % of copolymer of 30~60 % of polypropylene, ethylene and propylene, 10~30 % of glass fibre, hyperbranched (ethylene
With methyl acrylate) copolymer 5~10 %, 0.2~1 % of antioxidant, 0.2~1 % of light stabilizer, 0.3~3 % of additive,
In, the total amount of above-mentioned raw materials is 100%.
The polypropylene is atactic copolymerized polypropene, and comonomer is ethylene, 2~10wt% of content, melting temperature（DCS
Method is tested）130~150 DEG C, under the test condition of 230 DEG C × 2.16kg, melt flow rate (MFR) is 10~50 g/10min.
In the ethylene and the copolymer of propylene, the content of ethylene is 10~5wt%, 80~130 DEG C of melting temperature,
Under the test condition of 190 DEG C × 2.16kg, 1~20g/10min of melt flow rate (MFR), 50~80 A of shore hardness.
The ethylene and the copolymer of propylene prepared preferably by metallocene catalyst, there is ethylene segment to be evenly distributed, with
The advantages of atactic copolymerized polypropene compatibility is good.
The ratio between melt flow rate (MFR) of copolymer of the atactic copolymerized polypropene and ethylene and propylene is less than 3；Ethylene
With 1~10wt% of difference of the ethylene contents of the copolymer and atactic copolymerized polypropene of propylene.On this condition, random copolymerization poly- third
Alkene is good with the compatibility of ethylene and the copolymer of propylene, and rubber phase is easily dispersed, and is conducive to improve impact resistance, the intensity of material
And dimensional stability.
The glass fibre be alkali-free short glass fiber, 2~15 mm of Length of Glass Fiber, 6-25 μm of diameter, the glass
Silanes, aluminate or titante coupling agent processing are passed through in the surface of glass fiber, to improve and polyacrylic compatibility.
Hyperbranched (the ethylene and methyl acrylate) copolymer byαDiimine palladium catalyst is catalyzed ethylene and propylene
Sour methyl esters copolymerization is prepared.
Described is hyperbranched（Ethylene and methyl acrylate）Copolymer refers to that the degree of branching is more than 60/1000C（It is 1000 i.e. every
Carbon atom at least contains 60 carbochains）Ethylene and methyl acrylate copolymer.It is hyperbranched（Ethylene and methyl acrylate）Altogether
Polymers can pass throughαDiimine palladium catalyst is catalyzed ethylene with methyl acrylate copoly to prepare.
It is describedαThe structural formula of diimine palladium catalyst is
。
αWhen diimine palladium catalyst is catalyzed ethylene with methyl acrylate copoly, there is unique " chain walking " behavior, energy
Hyperbranched polyethylene is enough efficiently obtained, and methyl acrylate is located at the end of polymer branch；Further, sinceαDiimine palladium
Catalyst cannot be catalyzed methyl acrylate polymerization, gained it is hyperbranched（Ethylene and methyl acrylate）Copolymer is free of polyacrylic acid
Acrylate homopolymer, smell are relatively low.
Described is hyperbranched（Ethylene and methyl acrylate）Copolymer preferable weight-average molecular weight 10~50 kg/mol, it is branched
Degree（90~130）/ 1000C, the weight fraction of methyl acrylate is 1.5~5%, hyperbranched（Ethylene and methyl acrylate）Copolymerization
It is transparent grease under its room temperature of object, hardness and melt viscosity are extremely low；In glass fiber reinforced polypropylene compositions, over-expense
Change（Ethylene and methyl acrylate）Copolymer there is flow ability modifying agent and compatilizer, extremely low melt viscosity can not only
The mobility of glass fiber reinforced polypropylene compositions is enough improved, contributes to each component melting mixing, is uniformly dispersed, and make it
Easily infiltration is in fiberglass surfacing；Methyl acrylate positioned at branch terminals can be anti-with the coupling agent of fiberglass surfacing
Should, the compatibility of raising glass fibre and polymer；It is in addition, hyperbranched（Ethylene and methyl acrylate）Extremely low hard of copolymer
Degree helps to reduce the case hardness of material, enhances soft sense of touch.
The antioxidant includes primary antioxidant and auxiliary anti-oxidant, and the primary antioxidant is one in Hinered phenols antioxidant
Kind or more than one combination, the auxiliary anti-oxidant are one or more kinds of groups in phosphite and esters antioxidant
It closes.
The primary antioxidant can select Hinered phenols antioxidant such as 1076, O310, one or more of 1010 group
It closes；Auxiliary anti-oxidant can select combination of one or more of phosphorite kind antioxidant such as 168, P-EPQ etc..
The light stabilizer is hindered amines, one or more kinds of groups in benzophenone, benzotriazole
It closes, such as the composition of one or both of 622 and UV-P；
The additive includes one or more kinds of compositions of color toner or Masterbatch.Preferably, the face
Color toner is black smoke.
A kind of low smell, scratch-resistant soft sense of touch polypropene composition preparation method, include the following steps：
A, the copolymer, hyperbranched of polypropylene, ethylene and propylene is weighed by weight ratio（Ethylene and methyl acrylate）Altogether
Polymers, antioxidant, light stabilizer and additive are then placed in 3~5 min of blending in high-speed mixer；
B, glass fibre is added to melt in double screw extruder together with the mixture as obtained by the feeding of side with step A and is mixed
Extruding pelletization is refined, extruding pelletization is divided into four melting mixing areas：One area's temperature be 190 DEG C -200 DEG C, two area's temperature for 200 DEG C -
210 DEG C, three area's temperature are 210 DEG C -220 DEG C, and four area's temperature are 190 DEG C -200 DEG C, and the residence time of entire extrusion is
Lmin-2min, pressure 21MPa-29MPa.
Compared with prior art, the present invention it has the advantages that：
The present invention uses the atactic copolymerized polypropene of specific structure and ethylene and the copolymer of propylene, and the two compatibility is good,
Be conducive to improve impact resistance, intensity and the dimensional stability of material.The present invention uses hyperbranched（Ethylene and acrylic acid first
Ester）Copolymer has special dissaving structure, can improve the mobility of glass fiber reinforced polypropylene compositions, improves glass
The compatibility of glass fiber and polymer reduces the case hardness of composition, enhances soft sense of touch.The present invention is using hyperbranched（Ethylene
With methyl acrylate）Glass fiber reinforced polypropylene prepared by copolymer has the characteristics that low smell.In conclusion present invention tool
There is the features such as strong high mechanical properties, impact resistance, high intensity, scratch-resistant, low smell, soft sense of touch and low linear expansion coefficient.
It is an advantage of the invention that：
1st, the present invention is using the atactic copolymerized polypropene of specific structure and ethylene and the copolymer of propylene, random copolymerization poly- third
The ratio between alkene and the melt flow rate (MFR) of copolymer of ethylene and propylene are less than 3；The copolymer of ethylene and propylene gathers with random copolymerization
The difference of the ethylene contents of propylene is 1~10wt%.The two compatibility is good, is conducive to improve impact resistance, intensity and the size of material
Stability.
2nd, the present invention uses hyperbranched（Ethylene and methyl acrylate）Copolymer be byαIt is prepared by diimine palladium catalyst
, there is special dissaving structure, the degree of branching（90~130）/ 1000C, 10~50 kg/mol of weight average molecular weight, acrylic acid
1.5~5wt% of methyl ester content.Its shore hardness and melt viscosity are very low, have the function of flow ability modifying agent and compatilizer, can
The mobility of glass fiber reinforced polypropylene compositions is improved, improves the compatibility of glass fibre and polymer, reduces composition
Case hardness, enhance soft sense of touch.
3rd, the present invention is using hyperbranched（Ethylene and methyl acrylate）Glass fiber reinforced polypropylene tool prepared by copolymer
There is the characteristics of low smell.
4th, the present invention enhances soft sense of touch polypropylene using glass fibre, has high mechanical properties, scratch-resistant and low linear
The coefficient of expansion（Good stability of the dimension）The characteristics of.
Specific embodiment
With the following Examples and comparative example the invention will be further described.
Related data obtain embodiment according to following test method with comparative example：
1st, melt flow rate (MFR)（MFR）It is measured according to ISO1133, for polypropene composition, test temperature is 230 DEG C,
Load is 2.16 KG；For ethylene withα-Alkene（Propylene）Copolymer, test temperature be 190 DEG C, load be 2.16 KG.
2nd, tensile strength and elongation at break are measured according to ISO527, and test temperature is 23 DEG C.
3rd, bending modulus is measured according to ISO178, and test temperature is 23 DEG C.
4th, shore hardness D is measured according to ISO 868, and the residence time is 5 s.
5th, Izod notched impact strength is measured according to ISO 180, and test temperature is 23 DEG C.
6th, the PL-GPC220 types that weight average molecular weight and molecular weight distribution pass through Polymer Laboratories companies of Britain
High temperature gel chromatograph measures.Column temperature is 150 DEG C, mobile phase 1,2,4- trichloro-benzenes（Bis- uncles of antioxidant 2,6- containing 0.3 g/L
Butyl -4- methylphenols BHT）.
7th, the measure of the degree of branching：It is hyperbranched（Ethylene and methyl acrylate）The degree of branching of copolymer passes through nuclear magnetic resonance spectroscopy
（1H NMR）It measures.Test equipment is 300 MHZ type Nuclear Magnetic Resonance of Bruker AV, and solvent is deuterochloroform, test temperature
It is 23 DEG C.Degree of branching calculation formula is as follows：
,
Wherein SCH、SCH2And SCH3It represents respectively1Methine hydrogen atom in H NMR, methylene hydrogen atom and methyl hydrogen atom
Integral area.
8th, the measure of methyl acrylate content：It is hyperbranched（Ethylene and methyl acrylate）The methyl acrylate content of copolymer
Pass through nuclear magnetic resonance spectroscopy（1H NMR）It measures.Test equipment is 300 MHZ type Nuclear Magnetic Resonance of Bruker AV, and solvent is deuterium
For chloroform, test temperature is 23 DEG C.Calculation formula is as follows：
,
Wherein SCH、SCH2And SoCH3It represents respectively1Methine hydrogen atom, methylene hydrogen atom and methoxyl group hydrogen atom in H NMR
Integral area.
9th, smell is tested：It is tested according to lucky standard Q/JLY J711061-2009, experimental procedure is according to 5.2, by sample
It is put on tripod, is then placed in 1L odor bottles, 50 mL of deionized water is added in most backward bottle；Odor bottle is put into 70
DEG C constant temperature for 24 hours, is cooled to 65 DEG C of tests；Assessment identification is carried out by 5 smell persons, then takes arithmetic average, evaluation criterion is such as
Following table, numerical value is higher, shows that material smell is lower.Smell standards of grading are as follows：
10th, scratch-resistant is tested：It is tested according to PV 3952, laboratory apparatus 430-P1, pressure head diameter is 1 mm, and load is
10 N, scraping rate are 500 mm/min；Test sample size is 100 × 50 × 3 mm, dermatoglyphic patterns VW-K85；Pass through color
The L of sample before and after poor instrument test scrapes*Value difference is different（△L*）To weigh scraping and wiping resistance performance, △ L*It is smaller, represent the scratch-resistant of material
Performance is better.
11st, linear expansion coefficient（CLTE）Test：With reference to ASTM D696, temperature range is -20 DEG C~80 DEG C, test side
To be parallel to flow direction；CLTE is smaller, shows that the dimensional stability of material is better.
12nd, sense of touch is evaluated：Use the sample that injection molding machine shot size is 100 × 50 × 3 mm, dermatoglyphic patterns VW-K85；
5 test mans touch dermatoglyph face with hand, give a mark, are averaged according to following standards of grading, and numerical value is higher, show touching for material
Sense is better.Sense of touch standards of grading are as follows：
Related raw material is as follows in the embodiment of the present invention and comparative example.
It is 1. hyperbranched（Ethylene and methyl acrylate）Copolymer 1（HBPE-1）：Under nitrogen protection, to the reaction kettle of 2L
Middle 850mL anhydrous methylene chlorides, the methyl acrylate of 91.6mL and the 15g of adding inαDiimine palladium catalyst（It is dissolved in 60mL
Anhydrous methylene chloride）.Ethylene gas is passed through to start to polymerize.23 DEG C of polymerization temperature, 0.1 MPa of polymerization pressure, 24 h of polymerization time.Add
Enter 5mL methanol and terminate polymerization, cross silicagel column and remove catalyst residue, solution is deposited to 800 mL's after vacuum distillation concentrates
In ethyl alcohol, the grease of precipitation is collected, 12h is dried in vacuo at 50 DEG C.The weight average molecular weight of HBPE-1 is 34.7kg/mol, point
Son amount distribution（M w/M n）It is 1.43, degree of branching 103/1000C, the weight fraction of methyl acrylate is 1.7 %.
It is 2. hyperbranched（Ethylene and methyl acrylate）Copolymer 2（HBPE-2）:HBPE-2's is produced similar to HBPE-1.
A concentration of 2.5 mol/L of methyl acrylate.The weight average molecular weight of HBPE-2 be 15.4kg/mol, molecular weight distribution（M w/M n）For
1.35, degree of branching 98/1000C, the weight fraction of methyl acrylate is 2.5 %
3. polypropylene 1 is the atactic copolymerized polypropene of CNOOC company production, product designation RP364R, melting temperature
145 DEG C, melt flow rate (MFR) is 25 g/10min, ethylene contents 5wt%（Infra-red sepectrometry is tested）；Polypropylene 2 is Yangtze petrochemical industry
The impact polypropylene of production, product designation YPJ-1220C, melt flow rate (MFR) are 19 g/10min, and EP rubbers is content
30wt%（Normal heptane extraction process is tested）, ethylene contents are 42wt% in EP rubbers（Infra-red sepectrometry is tested）.
4. the copolymer of ethylene and propylene is the Vistamaxx 6202 of Exxon Mobil, 12 wt% of ethylene contents, melt
9 g/10min of flow rate, 70 A of shore hardness.
5. the copolymer of ethylene and 1- octenes is the Engage 8150 of DOW Chemical.
6. glass fibre 1 is purchased from megalith group, product designation 502.Fibre length is 6.0mm, a diameter of 14 μm；Glass
Fiber 2 is purchased from Taishan glass fiber Ltd, product designation T438.Fibre length is 3.0mm, a diameter of 13 μm.
7. talcum powder is purchased from North Sea group, product designation KC-6300, mesh number is 2500 mesh.
8. polypropylene grafted maleic anhydride is purchased from the liter of Nantong day, product designation CMG9801.
9. primary antioxidant is the 1010 of BASF AG's production, product designation Irganox 1010, chemical name for four [β-
（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester.The P-EPQ that auxiliary anti-oxidant is produced for gram Lay benefactor department, commodity board
Number for Hostanox P-EPQ, chemical name is four-(2,4- di-tert-butyl-phenyl) -4, the double phosphorous esters of 4 '-xenyl.
10. light stabilizer is the UV-P, product designation Tinuvin P, chemical name 2- of BASF AG's production（2- hydroxyls
Base -5- aminomethyl phenyls）Benzotriazole and the 622 of BASF AG's production, product designation Tinuvin 622, chemical name are
Poly- [1-（2`- ethoxys）- 2,2,6,6- tetramethyl -4- hydroxy piperidine succinic acid fat].
Embodiment 1.
It is hyperbranched that 59wt% polypropylene 1, the copolymer of 25wt% ethylene and propylene, 5wt% are weighed by weight ratio（Ethylene with
Methyl acrylate）Copolymer 1,0.1wt% primary antioxidants 1010,0.1wt% auxiliary anti-oxidants P-EPQ, 0.5 wt% light stabilizers 622
With 0.3wt% black smokes, it is put into high-speed mixer and 3 min is blended, 1000 rpm of rotating speed, then 10wt% glass fibres 1 are passed through into side
Melting mixing in double screw extruder, extruding pelletization are added to together with feeding and said mixture.Its technique is：One 190 DEG C of area,
Two 210 DEG C of areas, three 220 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is l/min, pressure 21MPa.
Embodiment 2.
It is hyperbranched that 60wt% polypropylene 1, the copolymer of 20wt% ethylene and propylene, 5wt% are weighed by weight ratio（Ethylene with
Methyl acrylate）Copolymer 2,0.5wt% primary antioxidants 1010,0.5wt% auxiliary anti-oxidants P-EPQ, 0.5 wt% light stabilizers UV-
P, 0.5 wt% light stabilizers 622 and 3wt% black smokes are put into high-speed mixer and 3 min are blended, rotating speed 1000rpm, then will
10wt% glass fibres 2 by being added to melting mixing in double screw extruder together with side feeding and said mixture, make by extrusion
Grain.Its technique is：One 190 DEG C of area, two 210 DEG C of areas, three 220 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is l
Min, pressure 22MPa.
Embodiment 3.
It is hyperbranched that 37.1wt% polypropylene 1, the copolymer of 35wt% ethylene and propylene, 7wt% are weighed by weight ratio（Ethylene
With methyl acrylate）Copolymer 1,0.2wt% primary antioxidants 1010,0.2wt% auxiliary anti-oxidants P-EPQ, 0.1 wt% light stabilizers
UV-P, 0.1wt% light stabilizer 622 and 0.3wt% black smokes, which are put into high-speed mixer, is blended 4 min, rotating speed 1000rpm, then will
20wt% glass fibres 1 by being added to melting mixing in double screw extruder together with side feeding and said mixture, make by extrusion
Grain.Its technique is：One 200 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is 2
Min, pressure 24MPa.
Embodiment 4.
It is hyperbranched that 35wt% polypropylene 1, the copolymer of 35wt% ethylene and propylene, 7wt% are weighed by weight ratio（Ethylene with
Methyl acrylate）Copolymer 2,0.4wt% primary antioxidants 1010,0.4wt% auxiliary anti-oxidant P-EPQ, 0.1wt% light stabilizers UV-P,
0.1wt% light stabilizers 622 and 2wt% black smokes are put into high-speed mixer and 4 min are blended, rotating speed 1000rpm, then by 20wt% glass
Glass fiber 2 together with side feeding and said mixture by being added to melting mixing in double screw extruder, extruding pelletization.Its technique
For：One 190 DEG C of area, two 210 DEG C of areas, three 220 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is 2 min, pressure
For 25MPa.
Embodiment 5.
35.2wt% polypropylene 1, the copolymer of 30wt% ethylene and propylene, 8wt% are weighed by weight ratio（Hyperbranched ethylene
With methyl acrylate）Copolymer 1,0.3wt% primary antioxidants 1010,0.1wt% auxiliary anti-oxidants 168,0.2wt% light stabilizers UV-P,
0.2wt% light stabilizers 622 and 1wt% black smokes, which are put into high-speed mixer, is blended 4 min, rotating speed 1000rpm, then by 25wt% glass
Glass fiber 1 together with side feeding and said mixture by being added to melting mixing in double screw extruder, extruding pelletization.Its technique
For：One 200 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 190 DEG C of areas；The residence time of entire extrusion is 2 min, pressure
For 27MPa.
Embodiment 6.
It is hyperbranched that 36.5wt% polypropylene 1, the copolymer of 30wt% ethylene and propylene, 7.5wt% are weighed by weight ratio（Second
Alkene and methyl acrylate）Copolymer 2,0.2wt% primary antioxidants 1010,0.2wt% auxiliary anti-oxidant P-EPQ, 0.2wt% light stabilizers
UV-P, 0.2wt% light stabilizer 622 and 0.2wt% black smokes, which are put into high-speed mixer, is blended 4 min, 1000 rpm of rotating speed, then will
25%wt% glass fibres 2 by being added to melting mixing in double screw extruder together with side feeding and said mixture, make by extrusion
Grain.Its technique is：One 200 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 190 DEG C of areas；The residence time of entire extrusion is 2
Min, pressure 27MPa.
Embodiment 7.
It is hyperbranched that 29.7wt% polypropylene 1, the copolymer of 29wt% ethylene and propylene, 10wt% are weighed by weight ratio（Ethylene
With methyl acrylate）Copolymer 1,0.2wt% primary antioxidants 1010,0.2wt% auxiliary anti-oxidant P-EPQ, 0.3wt% light stabilizers UV-
P, 0.3wt% light stabilizers 622 and 0.3wt% black smokes, which are put into high-speed mixer, is blended 5 min, rotating speed 1000rpm, then will
30wt% glass fibres 1 by being added to melting mixing in double screw extruder together with side feeding and said mixture, make by extrusion
Grain.Its technique is：One 200 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 190 DEG C of areas；The residence time of entire extrusion is 2
Min, pressure 28MPa.
Embodiment 8.
It is hyperbranched that 32wt% polypropylene 1, the copolymer of 29wt% ethylene and propylene, 8wt% are weighed by weight ratio（Ethylene with
Methyl acrylate）Copolymer 2,0.2wt% primary antioxidants 1010,0.2wt% auxiliary anti-oxidant P-EPQ, 0.2wt% light stabilizers UV-P,
0.2wt% light stabilizers 622 and 0.2wt% black smokes, which are put into high-speed mixer, is blended 5 min, rotating speed 1000rpm, then by 30wt%
Glass fibre 2 together with side feeding and said mixture by being added to melting mixing in double screw extruder, extruding pelletization.Its work
Skill is：One 200 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 190 DEG C of areas；The residence time of entire extrusion is 2 min, is pressed
Power is 29MPa.
Comparative example 1.
It is hyperbranched that 69wt% polypropylene 1, the copolymer of 25wt% ethylene and propylene, 5wt% are weighed by weight ratio（Ethylene with
Methyl acrylate）Copolymer 1,0.1wt% primary antioxidants 1010,0.1wt% auxiliary anti-oxidants P-EPQ, 0.5 wt% light stabilizers 622
With 0.3wt% black smokes, it is put into high-speed mixer and 3 min is blended, rotating speed 1000rpm, then said mixture is added to twin-screw
Melting mixing in extruder, extruding pelletization.Its technique is：One 190 DEG C of area, two 210 DEG C of areas, three 220 DEG C of areas, four 200 DEG C of areas；It is whole
The residence time of a extrusion is l min, pressure 15MPa.
Comparative example 2.
It is hyperbranched that 72.1wt% polypropylene 1,7wt% are weighed by weight ratio（Ethylene and methyl acrylate）Copolymer 1,
0.2wt% primary antioxidants 1010, the light stabilizer UV-P of 0.2wt% auxiliary anti-oxidants P-EPQ, 0.1wt%, 0.1 wt% light stabilizers
622 and 0.3wt% black smokes, which are put into high-speed mixer, is blended 4 min, rotating speed 1000rpm, then 20wt% glass fibres 1 are passed through side
Melting mixing in double screw extruder, extruding pelletization are added to together with feeding and said mixture.Its technique is：One 200 DEG C of area,
Two 200 DEG C of areas, three 210 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is 2 min, pressure 21MPa.
Comparative example 3.
Weigh by weight ratio 35.2wt% polypropylene 1, the copolymer of 30wt% ethylene and propylene, 25%wt% talcum powder,
8wt% is hyperbranched（Ethylene and methyl acrylate）Copolymer 1,0.3wt% primary antioxidants 1010,0.1wt% auxiliary anti-oxidants P-EPQ,
0.2wt% light stabilizer UV-P, 0.2wt% light stabilizer 622 and 1wt% black smokes are put into high-speed mixer and 4 min, rotating speed are blended
1000rpm.Said mixture is added to melting mixing in double screw extruder, extruding pelletization.Its technique is：One 200 DEG C of area,
Two 200 DEG C of areas, three 210 DEG C of areas, four 190 DEG C of areas；The residence time of entire extrusion is 2 min, pressure 22MPa.
Comparative example 4.
It is hyperbranched that 60wt% polypropylene 2, the copolymer of 20wt% ethylene and propylene, 5wt% are weighed by weight ratio（Ethylene with
Methyl acrylate）Copolymer 2,0.5wt% primary antioxidants 1010,0.5wt% auxiliary anti-oxidants P-EPQ, 0.5 wt% light stabilizers UV-
P, 0.5 wt% light stabilizers 622 and 3wt% black smokes are put into high-speed mixer and 3 min are blended, rotating speed 1000rpm, then will
10wt% glass fibres 2 by being added to melting mixing in double screw extruder together with side feeding and said mixture, make by extrusion
Grain.Its technique is：One 190 DEG C of area, two 210 DEG C of areas, three 220 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is l
Min, pressure 23MPa.
Comparative example 5.
It is hyperbranched that 35wt% polypropylene 1,35wt% ethylene and copolymer, the 7wt% of 1- octenes are weighed by weight ratio（Ethylene
With methyl acrylate）Copolymer 2,0.4wt% primary antioxidants 1010,0.4wt% auxiliary anti-oxidant P-EPQ, 0.1wt% light stabilizers UV-
P, 0.1wt% light stabilizers 770 and 2wt% black smokes are put into high-speed mixer and 4 min are blended, rotating speed 1000rpm, then by 20wt%
Glass fibre 2 together with side feeding and said mixture by being added to melting mixing in double screw extruder, extruding pelletization.Its work
Skill is：One 190 DEG C of area, two 210 DEG C of areas, three 220 DEG C of areas, four 200 DEG C of areas；The residence time of entire extrusion is 2 min, is pressed
Power is 24MPa.
Comparative example 6.
32wt% polypropylene 1, the copolymer of 29wt% ethylene and propylene, the polypropylene grafted Malaysias of 8wt% are weighed by weight ratio
Acid anhydrides, 0.2wt% primary antioxidants 1010,0.2wt% auxiliary anti-oxidant P-EPQ, 0.2wt% light stabilizer UV-P, 0.2wt% light stabilizers
622 and 0.2wt% black smokes, which are put into high-speed mixer, is blended 5 min, rotating speed 1000rpm, then 30wt% glass fibres 2 are passed through side
Melting mixing in double screw extruder, extruding pelletization are added to together with feeding and said mixture.Its technique is：One 200 DEG C of area,
Two 210 DEG C of areas, three 210 DEG C of areas, four 195 DEG C of areas；The residence time of entire extrusion is 2 min, pressure 30MPa.
Comparative example 7.
39.2wt% polypropylene 1, the copolymer of 29wt% ethylene and propylene, 0.5wt% dual-tert-butyl mistakes are weighed by weight ratio
Aoxidize diisopropylbenzene (DIPB), the primary antioxidant 1010 of 0.2wt%, 0.2wt% auxiliary anti-oxidant P-EPQ, 0.3wt% light stabilizers UV-P,
0.3wt% light stabilizers 622 and 0.3wt% black smokes, which are put into high-speed mixer, is blended 5 min, rotating speed 1000rpm, then by 30wt%
Glass fibre 1 together with side feeding and said mixture by being added to melting mixing in double screw extruder, extruding pelletization.Its work
Skill is：One 200 DEG C of area, two 200 DEG C of areas, three 210 DEG C of areas, four 190 DEG C of areas；The residence time of entire extrusion is 2 min, is pressed
Power is 34MPa.
Table 1：Embodiment material forms and proportioning.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Polypropylene 1 | 59 | 37.1 | 29.7 | 35.2 | 60 | 35 | 32 | 36.5 |
| The copolymer of ethylene and propylene | 25 | 35 | 29 | 30 | 20 | 35 | 29 | 30 |
| Glass fibre 1 | 10 | 20 | 30 | 25 | ||||
| Glass fibre 2 | 10 | 20 | 30 | 25 | ||||
| HBPE-1 | 5 | 7 | 10 | 8 | ||||
| HBPE-2 | 5 | 7 | 8 | 7.5 | ||||
| Primary antioxidant | 0.1 | 0.2 | 0.2 | 0.3 | 0.5 | 0.4 | 0.2 | 0.2 |
| Auxiliary anti-oxidant | 0.1 | 0.2 | 0.2 | 0.1 | 0.5 | 0.4 | 0.2 | 0.2 |
| Light stabilizer | 0.5 | 0.2 | 0.6 | 0.4 | 1 | 0.2 | 0.4 | 0.4 |
| Black smoke | 0.3 | 0.3 | 0.3 | 1 | 3 | 2 | 0.2 | 0.2 |
Table 2：The performance of embodiment.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Melt flow rate (MFR) g/10min | 18.2 | 13.5 | 11.3 | 12.6 | 19.3 | 14.1 | 12.2 | 13.7 |
| Tensile strength MPa | 23.9 | 30.5 | 38.6 | 33.4 | 20.4 | 28.6 | 34.5 | 31.7 |
| Elongation at break % | 11.8 | 8.5 | 4.7 | 7.3 | 10.8 | 7.2 | 4.5 | 6.8 |
| Bending modulus MPa | 1354 | 1630 | 2342 | 2013 | 1271 | 1528 | 2192 | 1884 |
| Shore hardness D | 47 | 58 | 67 | 63 | 50 | 55 | 64 | 61 |
| Heat distortion temperature | 95 | 114 | 128 | 121 | 92 | 110 | 123 | 117 |
| Notch impact strength KJ/m2 | 40.8 | 30.7 | 36.3 | 27.5 | 35.8 | 26.5 | 32.3 | 21.9 |
| △L* | 0.25 | 0.14 | 0.07 | 0.11 | 0.22 | 0.12 | 0.08 | 0.10 |
| CLTE | 48 | 37 | 25 | 31 | 52 | 39 | 27 | 36 |
| Oder levels | 7.5 | 7 | 7 | 7 | 8 | 7 | 7 | 7 |
| Sense of touch scores | 5 | 4 | 3.5 | 4 | 4.5 | 4 | 4 | 4 |
Table 3：The composition and proportioning of comparative example.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Polypropylene 1 | 69 | 72.1 | 39.2 | 35.2 | 35 | 32 | |
| Polypropylene 2 | 60 | 29 | |||||
| The copolymer of ethylene and propylene | 25 | 29 | 30 | 20 | |||
| The copolymer of ethylene and 1- octenes | 35 | ||||||
| Polypropylene grafted maleic anhydride | 8 | ||||||
| Glass fibre 1 | 20 | 30 | |||||
| Talcum powder | 25 | ||||||
| Glass fibre 2 | 10 | 20 | 30 | ||||
| HBPE-1 | 5 | 7 | 8 | ||||
| HBPE-2 | 5 | 7 | |||||
| DCP | 0.5 | ||||||
| Primary antioxidant | 0.1 | 0.2 | 0.2 | 0.3 | 0.5 | 0.4 | 0.2 |
| Auxiliary anti-oxidant | 0.1 | 0.2 | 0.2 | 0.1 | 0.5 | 0.4 | 0.2 |
| Light stabilizer | 0.5 | 0.2 | 0.6 | 0.4 | 1 | 0.2 | 0.4 |
| Black smoke | 0.3 | 0.3 | 0.3 | 1 | 3 | 2 | 0.2 |
Remarks：DCP is dual-tert-butyl cumyl peroxide, for improving the mobility of polypropylene material.
Table 4：The performance of comparative example.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| Melt flow rate (MFR) g/10min | 32.4 | 21.5 | 10.8 | 18.6 | 17.2 | 9.1 | 11.5 |
| Tensile strength MPa | 16.4 | 54.8 | 42.6 | 13.8 | 16.4 | 23.6 | 33.4 |
| Elongation at break % | 185 | 1.2 | 2.8 | 95 | 8.3 | 5.9 | 2.2 |
| Bending modulus MPa | 558 | 3705 | 2685 | 1203 | 1037 | 1426 | 1972 |
| Shore hardness D | 37 | 85 | 78 | 61 | 48 | 58 | 81 |
| Heat distortion temperature | 64 | 138 | 130 | 86 | 90 | 105 | 124 |
| Notch impact strength KJ/m2 | NB | 9.7 | 24.3 | NB | 32.4 | 23.5 | 13.9 |
| △L* | 0.48 | 0.34 | 0.27 | 2.58 | 0.47 | 0.32 | 0.15 |
| CLTE | 85 | 42 | 24 | 56 | 71 | 59 | 35 |
| Oder levels | 8 | 7 | 5.5 | 7.5 | 7 | 7 | 4 |
| Sense of touch scores | 5 | 2 | 2 | 4 | 4.5 | 4 | 2 |
It can be seen that by the comparison of embodiment 1 and comparative example 1 and glass fibre be introduced into polypropylene, it can be notable
Improve intensity, heat distortion temperature, scratch resistance and the dimensional stability of material in ground.
Can be seen that the copolymer of ethylene and propylene by the comparison of embodiment 2 and comparative example 2 can improve notch shock
Intensity significantly reduces case hardness, enhances soft sense of touch.
It can be seen that by embodiment 3 and the comparison of comparative example 3 containing hyperbranched（Ethylene and methyl acrylate）Copolymer
Glass fiber reinforced polypropylene not only mobility and soft sense of touch are good, but also have the characteristics that low smell.And utilize organic mistake
Oxide DCP improves the mobility of glass fiber reinforced polypropylene, can cause that smell is larger, and hardness is higher, and sense of touch is poor, unfavorable
In the application in automotive trim.
The intensity of glass fiber reinforced polypropylene, thermal deformation temperature can be seen that by the comparison of embodiment 4 and comparative example 4
Degree, scratch resistance and dimensional stability are substantially better than mineral（Talcum powder）Filled polypropylene.
By the comparison of embodiment 5 and ratio 5 and embodiment 6 and comparative example 6 can be seen that atactic copolymerized polypropene with
The copolymer of ethylene and propylene has a synergistic effect, the high mechanical properties of the glass fiber reinforced polypropylene of gained, shock resistance, resistance to
Scraping and good stability of the dimension.And glass fibre can be influenced by introducing impact copolymer polypropylene and ethylene and the copolymer of 1- octenes
The mechanical property of reinforced polypropylene, hence it is evident that reduce its scratch-resistant and dimensional stability.
It can be seen that using polypropylene grafted maleic anhydride as compatilizer, can make by the comparison of embodiment 7 and comparative example 7
Larger into material smell, hardness is higher, and sense of touch is poor, is unfavorable for the application in automotive trim.And with hyperbranched（Ethylene and propylene
Sour methyl esters）Copolymer is compatilizer, and material has the characteristics that low smell, soft sense of touch, and mobility is also preferable.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of range is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Work as understanding, technical scheme of the present invention can be modified or replaced equivalently, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (4)
1. a kind of soft sense of touch polypropene composition of low smell, scratch-resistant, it is characterised in that：The composition includes following heavy
Measure the raw material of percentage：
The total amount of above-mentioned raw materials is 100%；
Wherein, the polypropylene is atactic copolymerized polypropene, and comonomer is ethylene, the content 5wt% of ethylene, melting temperature
145 DEG C, melt flow rate (MFR) is 25g/10min under the test condition of 230 DEG C × 2.16kg；
Wherein, in the copolymer of the ethylene and propylene, the content of ethylene is 10~5wt%, 80~130 DEG C of melting temperature,
Under the test condition of 190 DEG C × 2.16kg, 1~20g/10min of melt flow rate (MFR), 50~80A of shore hardness；
Wherein, the ratio between melt flow rate (MFR) of copolymer of the atactic copolymerized polypropene and ethylene and propylene is less than 3；Ethylene
With 1~10wt% of difference of the ethylene contents of the copolymer and atactic copolymerized polypropene of propylene；
Wherein, the glass fibre be alkali-free short glass fiber, 2~15mm of Length of Glass Fiber, 6-25 μm of diameter, the glass
Silanes, aluminate or titante coupling agent processing are passed through in the surface of glass fiber；
Wherein, hyperbranched (the ethylene and methyl acrylate) copolymer is catalyzed ethylene and propylene by alpha-diimine palladium catalyst
The copolymerization of sour methyl esters is prepared, and degree of branching 103/1000C, weight average molecular weight Mw are 34.7kg/mol, methyl acrylate content
1.7wt%；
Wherein, low smell, scratch-resistant soft sense of touch polypropene composition preparation method, include the following steps：
A, weigh by weight ratio the copolymer of polypropylene, ethylene and propylene, hyperbranched (ethylene and methyl acrylate) copolymer,
Antioxidant, light stabilizer and additive are then placed in 3~5min of blending in high-speed mixer；
B, glass fibre is added to melting mixing in double screw extruder together with the mixture as obtained by the feeding of side with step A to squeeze
Go out to be granulated, extruding pelletization is divided into four melting mixing areas：One area's temperature is 190 DEG C -200 DEG C, and two area's temperature are 200 DEG C -210
DEG C, three area's temperature are 210 DEG C -220 DEG C, and four area's temperature are 190 DEG C -200 DEG C, and the residence time of entire extrusion is lmin-
2min, pressure 21MPa-29MPa.
2. the soft sense of touch polypropene composition of a kind of low smell according to claim 1, scratch-resistant, it is characterised in that：Institute
The antioxidant stated includes primary antioxidant and auxiliary anti-oxidant, the primary antioxidant be one kind in Hinered phenols antioxidant or it is a kind of with
On combination；The auxiliary anti-oxidant is one or more kinds of combinations in phosphite and esters antioxidant.
3. the soft sense of touch polypropene composition of a kind of low smell according to claim 1, scratch-resistant, it is characterised in that：Institute
The light stabilizer stated is hindered amines, one or more kinds of combinations in benzophenone, benzotriazole.
4. the soft sense of touch polypropene composition of a kind of low smell according to claim 1, scratch-resistant, it is characterised in that：Institute
State the compositions for the one or more that additive is included in color toner, Masterbatch.
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| CN106280016A (en) * | 2016-08-29 | 2017-01-04 | 合肥会通新材料有限公司 | Low-density bionical PP composite material of super sub-light and preparation method thereof |
| CN106751002A (en) * | 2016-12-27 | 2017-05-31 | 上海普利特复合材料股份有限公司 | A kind of low VOC, soft sense of touch glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN106916358A (en) * | 2017-04-12 | 2017-07-04 | 浙江胜钢新材料有限公司 | A kind of high durable flowing glass dipping Polyolefin Formation high and preparation method thereof |
| CN109627591A (en) * | 2018-12-25 | 2019-04-16 | 金旸（厦门）新材料科技有限公司 | A kind of high antimicrobial form polypropylene modified material of soft sense of touch and preparation method thereof |
| CN109749243A (en) * | 2018-12-29 | 2019-05-14 | 江苏和伟美科技发展有限公司 | A kind of high glaze, it is resistance to be precipitated, low warpage enhancing halogen-free polypropylene flame redardant and preparation method thereof |
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