CN116769254A - Low-density polypropylene material and preparation method thereof - Google Patents
Low-density polypropylene material and preparation method thereof Download PDFInfo
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- CN116769254A CN116769254A CN202211571792.9A CN202211571792A CN116769254A CN 116769254 A CN116769254 A CN 116769254A CN 202211571792 A CN202211571792 A CN 202211571792A CN 116769254 A CN116769254 A CN 116769254A
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- 239000000463 material Substances 0.000 title claims abstract description 91
- -1 polypropylene Polymers 0.000 title claims abstract description 61
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 60
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 230000003678 scratch resistant effect Effects 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 9
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 30
- 238000002347 injection Methods 0.000 claims description 28
- 239000007924 injection Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 15
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 230000001877 deodorizing effect Effects 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 12
- 239000010455 vermiculite Substances 0.000 description 11
- 229910052902 vermiculite Inorganic materials 0.000 description 11
- 235000019354 vermiculite Nutrition 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 235000002296 Ilex sandwicensis Nutrition 0.000 description 1
- 235000002294 Ilex volkensiana Nutrition 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WPUHLWYDTKIMGG-UHFFFAOYSA-L magnesium;2-hydroxyoctadecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCC(O)C([O-])=O.CCCCCCCCCCCCCCCCC(O)C([O-])=O WPUHLWYDTKIMGG-UHFFFAOYSA-L 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000002667 nucleating agent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012795 verification Methods 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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
A low-density polypropylene material relates to the technical field of high polymer materials, and comprises the following materials in parts by mass: heterophasic copolymerized high crystalline polypropylene: 60-80 parts of high-density polyethylene: 0-5 parts of high-melting high-impact polypropylene: 0-20 parts of inorganic mineral powder: 0-10 parts of toughening agent: 5-15 parts of scratch resistant agent: 1-3 parts of antioxidant, 0.1-0.5 part of deionized water: 1-3 parts of other auxiliary agents: 1-2 parts; the melt index of the multiphase copolymerization high-crystalline polypropylene is 40-100g/10min, the melt index of the high-melt high-impact polypropylene is 20-30g/10min, and the notch impact strength of the cantilever beam is as follows: 40-50Kj/m 2 The material can meet the requirements of light weight of automobiles, low odor and low VOC and meets the requirements ofThe performance requirements of various automobile interior parts are met, and the automobile interior part has stronger market competitiveness.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-density polypropylene material and a preparation method thereof.
Background
Polypropylene (PP), chemical formula (C) 3 H 6 ) n Is a polymer obtained by addition polymerization of propylene, and is a white wax-like material having a transparent and light appearance and a density of 0.89 to 0.91g/cm 3 Inflammable, melting point 189 deg.c, softening at 155 deg.c and use temperature range of-30-140 deg.c. Polypropylene is a thermoplastic synthetic resin with excellent performance, has chemical resistance, heat resistance, electrical insulation, high strength mechanical property, good high wear resistance processing property and the like, and is widely applied to the production fields of automobiles and the like.
At present, new energy automobiles become a development trend of the automobile industry, in the field of new energy automobiles, plastic materials gradually develop from original interior trim parts to exterior trim parts, engine peripheral parts and the like by virtue of the obvious advantages of low cost and high performance, the application range is gradually expanded, and the weight and the specific gravity of the plastic materials in the automobile materials are continuously improved. The application of the plastic material plays an important role in promoting the light weight of new energy automobiles and the production of special parts. Due to the stable increase of global automobile yield and the demand of automobile light weight, the use amount of modified plastics is increased, and automobiles become one of the fields with the fastest increase of plastic demands, and from the aspect of automobile modified plastics, modified polypropylene is the most widely applied subdivision type of automobile modified plastics and accounts for 46%.
The main aspects of automobile light weight in plastic materials are as follows: replacing metal with long glass fiber material; using a low-density material, a foaming material, a carbon fiber material, etc.; the thin wall design of the component material, the honeycomb plate structure design, etc. Meanwhile, on parts such as bumpers, automobile instrument panels, door panels, central channels, decorative columns and the like, mineral filled polypropylene materials are mainly adopted, the filling content is 15% -40%, and the mineral filled polypropylene materials effectively increase the rigidity and heat resistance of the materials, but also increase the density of the materials and increase the weight; the odor and the VOC volatility of the material are important to consider for the selection of the automotive interior material, so that the automotive interior material has the characteristics of low odor and low VOC while meeting the requirement of light weight of automobiles, and becomes a difficult problem for the production of the existing new energy automotive interior.
The prior low-density polypropylene composite material can refer to the Chinese patent application document with the patent number of CN201911301956.4, discloses a low-density polypropylene composite material, talcum powder with different particle diameters and length-diameter ratios are used as filling materials, and the density of the prepared polypropylene composite material is as low as 0.92-1.00 g/cm 3 . Wherein, the median diameter D50 of the talcum powder T is 1.0 mu m-3.0 mu m, the length-diameter ratio is 3.1-4.8, the thickness of the lamellar layers is thinner, the number of the lamellar layers is more, the coverage range of the lamellar layers is wide, the median diameter D50 of the talcum powder K is 4.5 mu m-6.5 mu m, the length-diameter ratio is 1-2, and the talcum powder K is distributed in a rigid layer formed by the talcum powder T, and when the material is impacted, the talcum powder K with larger particle diameter can effectively prevent the development of cracks, thereby keeping the toughness of the material. The final result described by this modification is achieved in an ideal state, since the talc itself is incompatible with the polypropylene, the talc is mainly mixed into the polypropylene uniformly by the screw, the flaky talc T with a large aspect ratio is sheared by the twin screw in the screw, the structure is greatly destroyed, the described result is difficult to achieve, and the other talc K is added, and is difficult to be directionally dispersed in a certain sheet of material during extrusion.
The existing low-odor polypropylene composite material can refer to the Chinese patent application document with the patent number of CN201811491012.3, and discloses a low-odor polypropylene composite material and a preparation method thereof, wherein odor removal is carried out by adopting odor removal agent master batches, the volatility and intersolubility of an alcohol aqueous solution in the odor removal agent master batches are utilized in the high-temperature melt processing process of the material, and organic micromolecules in a carrying material are extracted under a certain vacuumizing condition; secondly, the use of the odor removing agent master batch has potential safety hazards, a large amount of alcohol volatilizes in the storage process and the use process, and the potential safety hazards of fire or deflagration exist; finally, industrial alcohol itself has a large pungent odor, and the use of such deodorizing master batches having a large odor itself for odor reduction makes it difficult to produce PP materials having excellent odor.
The prior low-density low-VOC scratch-resistant modified polypropylene composite material can refer to the Chinese patent application document with the patent number of CN201810505226.5, and discloses a low-density low-VOC scratch-resistant modified polypropylene composite material and a preparation method thereof, wherein after nano vermiculite and diatomite are baked for 4 hours at 80 ℃, the nano vermiculite and the diatomite are mixed in a high-speed mixer until the nano vermiculite is uniformly distributed in diatomite micropores, then a coupling agent is uniformly sprayed on the surface of the diatomite carrying the nano vermiculite for continuous mixing for 5 minutes, and then the coupling agent is uniformly mixed with an ethylene-octene copolymer (POE) and a compatilizer in the high-speed mixer, so as to obtain a toughening-VOC adsorption composite additive, the odor-reducing nature of the toughening-VOC adsorption composite additive is that the nano vermiculite is used as a small molecular substance generated in the VOC adsorbent adsorption extrusion process, the nano vermiculite is adsorbed by the nano vermiculite, and finally stays in the polypropylene composite material until the nano vermiculite is secondarily volatilized, and particularly when the nano vermiculite is used for injection molding, the nano vermiculite is high in the high-speed, and the nano vermiculite is high in speed again, so that the nano diatomite is high in quality and the nano VOC adsorption composite material is not volatilized, and the problem of high-quality is not easy to cause high-grade odor and the problem of the high-quality is caused when the nano VOC is injected and the nano-VOC adsorption composite material is high-stable.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a low-density polypropylene material and a preparation method thereof, which have the characteristics of low density, low odor and low VOC, and can improve the air quality of the whole inside of an automobile while meeting the light weight of the automobile.
The aim of the invention can be achieved by the following technical scheme: the low-density polypropylene material consists of the following materials in parts by weight:
heterophasic copolymerized high crystalline polypropylene: 60-80 parts of high-density polyethylene: 0-5 parts of high-melting high-impact polypropylene: 0-20 parts of inorganic mineral powder: 0-10 parts of toughening agent: 5-15 parts of scratch resistant agent: 1-3 parts of antioxidant, 0.1-0.5 part of deionized water: 1-3 parts of other auxiliary agents: 1-2 parts;
preferably, the inorganic mineral powder is talcum powder, wollastonite and mica, and the particle size of the inorganic mineral powder is D50 less than or equal to 3um; the toughening agent is a polyolefin elastomer, and the melt index of the polyolefin elastomer is 0.5-30g/10min; the scratch resistant agent is master batch which is prepared from polysiloxane and erucamide and takes PP as a carrier.
The invention provides a preparation method of a low-density polypropylene material, which comprises the following steps:
s1: the multiphase copolymerization high-crystalline polypropylene, the high-density polyethylene, the high-melting high-impact polypropylene, the toughening agent, the scratch resistant agent, the antioxidant and other auxiliary agents are simultaneously added into an extruder for blending through weightlessness weighing, so as to form a mixture I;
s2: adding inorganic mineral powder into an extruder from a side feeding port, and mixing with the first mixture to form a second mixture;
s3: injecting deionized water into an extruder, mixing with the mixture II to form a mixture III, then performing vacuum devolatilization on the mixture III, then injecting deionized water into the extruder again, mixing with the mixture III to form a mixture IV, and then performing vacuum devolatilization on the mixture IV;
s4: extruding the mixture four times by an extruder, cooling the extruded material strips to room temperature, granulating by a granulator, absorbing the material by negative pressure after granulating, entering a material drying and deodorizing system, drying the material for 5-8 hours at 130 ℃, and discharging after cooling.
Preferably, the extruder is a twin screw extruder, and the screw aspect ratio of the twin screw extruder is 40:1-56:1.
preferably, the twin-screw extruder has a screw aspect ratio of 44:1 or 48:1.
preferably, the twin-screw extruder has a screw aspect ratio of 48:1.
preferably, the step S1 is a feeding conveying section and an exhaust section, and the total of four temperature areas is specifically: a first section of 180 ℃; the second section is 200-220 ℃; three-stage 200-220 ℃; four sections of 200-220 ℃;
the step S2 is a side feeding section, and comprises three temperature areas, specifically: five sections of 200-220 ℃; 180-200 ℃ in six sections; seven sections of 180-200 ℃;
the step S3 is a first water injection section, a first vacuum section, a second water injection section and a second vacuum section, and comprises five temperature areas, specifically: eight sections of 180-200 ℃ and nine sections of 180-200 ℃; ten sections of 180-200 ℃; eleven sections 180-200 ℃; twelve sections 180-200 ℃;
preferably, the feed conveying section comprises 1 56/56A element, 3 96/96 elements, 3 72/72 elements, 1 56/56 element, 130 DEG/7/72 element, 1 45 DEG/5/56 element, 160 DEG/4/56 element and 1 56/28L element in sequence according to the raw material conveying path;
the exhaust section sequentially comprises 2 72/72 elements and 2 96/96 elements according to a raw material conveying path;
the side feeding section sequentially comprises 3 144/72 elements, 1 96/96 elements, 2 72/72 elements, 2 45 degrees/5/56 elements, 2 45 degrees/5/36 elements, 2 56/56 elements and 1 96/96 element according to a raw material conveying path;
the first water injection section sequentially comprises 1 72/72 element, 2 45 degrees/5/56 element, 160 degrees/4/56 element and 1 45 degrees/5/36L element according to a raw material conveying path;
the first vacuum section sequentially comprises 4 144/72 elements and 1 72/72 element according to a raw material conveying path;
the second water injection section sequentially comprises 1 56/56 element, 2 45 degrees/5/56 element, 1 90 degrees/5/36 element and 1 56/28L element according to the raw material conveying path;
the second vacuum section comprises, in order, 4 144/72 elements, 2 72/72 elements, and 3 56/56 elements in the feed path.
The beneficial effects of the invention are as follows:
(1) The low-density polypropylene material for the new energy automobile interior trim is characterized by low density, and the density range is 0.9-1.0 g/cm 3 The material has high rigidity and high toughness comprehensive mechanical property, meets scratch resistance requirements in appearance, has good formability, accords with the light weight trend of automobiles, can meet the requirements of almost all automobile interior parts on smell due to the characteristics of low smell and low VOC, has higher flowability and good comprehensive mechanical property, can reduce the wall thickness of a finished piece to a certain extent, further reduces weight through thinning on the basis of low density weight reduction, meets the performance requirements of various automobile interior parts, and has stronger market competitiveness.
(2) The preparation method of the low-density polypropylene material for the new energy automobile interior trim can treat the finished product after extrusion, so that the finished product meets the requirements of low odor and low VOC and the defect that raw material flowers and the like are generated in the subsequent injection molding process can not occur.
Drawings
FIG. 1 is a schematic diagram of a barrel layout and screw combination of a twin screw extruder of the present invention having a screw aspect ratio of 48:1.
FIG. 2 is a schematic diagram of a barrel layout and screw combination of a twin screw extruder of the present invention having a screw aspect ratio of 44:1.
FIG. 3 is a schematic diagram of a barrel layout and screw combination of a twin screw extruder of the present invention having a screw aspect ratio of 56:1.
FIG. 4 is a schematic diagram of a barrel layout and screw combination of a twin screw extruder of the present invention with a screw aspect ratio of 40:1.
FIG. 5 is a schematic flow chart of the method for preparing the low density polypropylene material of the present invention.
a-a feeding conveying section; b-an exhaust section; c-side feeding section; d-a first water injection section; e-a first vacuum section; f-a second water injection section; g-second vacuum stage
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The low-density polypropylene material consists of the following materials in parts by weight:
heterophasic copolymerized high crystalline polypropylene: 60-80 parts of high-density polyethylene: 0-5 parts of high-melting high-impact polypropylene: 0-20 parts of inorganic mineral powder: 0-10 parts of toughening agent: 5-15 parts of scratch resistant agent: 1-3 parts of antioxidant, 0.1-0.5 part of deionized water: 1-3 parts of other auxiliary agents: 1-2 parts;
wherein the melt index of the heterogeneous copolymerization high-crystalline polypropylene is 40-100g/10min.
The high density polyethylene (0.941 to 0.960g/cm 3 ) Common grade HDPE of various petrochemical manufacturers, such as 7260, 8008, etc.;
the high-melting high-impact polypropylene melt finger has the impact strength of a cantilever beam notch of 20-30g/10 min: 40-50Kj/m 2 。
The inorganic mineral powder comprises talcum powder, wollastonite and mica, wherein the particle size of the inorganic mineral powder is D50 less than or equal to 3um, and the molecular formula of the talcum powder is as follows: mg of 3 [Si 4 O 10 ](OH) 2 A powder having a white or white-like appearance and a fine, sand-free property; CAS NO:14807-96-6; specific gravity: 2.7 to 2.8, the invention selects the product with the talcum powder grain diameter D50 less than or equal to 3um measured by a laser particle sizer, and the silicon content is more than or equal to 60;
the toughening agent comprises a polyolefin elastomer, wherein the melt index of the polyolefin elastomer is 0.5-30g/10min;
the scratch-resistant agent comprises master batches which are prepared from polysiloxane and erucamide and take PP as a carrier;
the antioxidant comprises holly sciences S2225; the antioxidant comprises pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; n-stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; tris [2, 4-di-t-butylphenyl ] phosphite; DSTP thioesters, and the like.
The other auxiliary agents comprise a dispersion lubricant, a weather-proof agent and a nucleating agent, wherein the dispersion lubricant comprises ethylene bis-stearamide; a calcium stearate; zinc stearate; improved magnesium hydroxystearate; silicone wax; polysiloxanes, and the like.
The invention provides a preparation method of a low-density polypropylene material, which comprises the following steps:
s1: the multiphase copolymerization high-crystalline polypropylene, the high-density polyethylene, the high-melting high-impact polypropylene, the toughening agent, the scratch resistant agent, the antioxidant and other auxiliary agents are simultaneously added into an extruder for blending through weightlessness weighing, so as to form a mixture I;
s2: adding inorganic mineral powder into an extruder from a side feeding port, and mixing with the first mixture to form a second mixture;
s3: injecting deionized water into an extruder, mixing with the mixture II to form a mixture III, then performing vacuum devolatilization on the mixture III, then injecting deionized water into the extruder again, mixing with the mixture III to form a mixture IV, and then performing vacuum devolatilization on the mixture IV;
the method mainly comprises the steps of enabling deionized water to enter a barrel of a double-screw extruder and then be gasified instantly to form an azeotrope with materials in a molten state, fully mixing the material with micromolecule substances and the like generated by the materials in the molten state through a certain distance in the barrel, and then immediately devolatilizing the materials in the molten state through double vacuum to suck out gaseous water molecules and the micromolecule substances wrapped by the gaseous water molecules together, so that the micromolecule substances such as VOC are thoroughly removed, and the situation of secondary volatilization does not exist.
S4: extruding the mixture four times by an extruder, cooling the extruded material strips to room temperature, granulating by a granulator, absorbing the material by negative pressure after granulating, entering a material drying and deodorizing system, drying the material for 5-8 hours at 130 ℃, and discharging after cooling.
The extruded material strip is cooled to room temperature through a water tank, the water temperature in the water tank is 40 degrees, the material strip is cooled in the water at the water temperature of 40 degrees and then leaves the water, the water tank is kept clean, a drying fan operates normally, and the material strip is dried, so that the odor is further reduced, the residual moisture of the material can be removed, the injection molding quality problems of material flowers, air marks, silver wires and the like can not be generated, the surface pollution of the material particles is prevented, the water content is high, and the odor and the performance of the material are influenced.
The extruder is a double-screw extruder, and the length-diameter ratio of a screw rod of the double-screw extruder is 40:1-56:1.
the twin-screw extruder had a screw aspect ratio of 44:1 or 48:1.
as shown in fig. 1, the twin-screw extruder has a screw aspect ratio of 48:1.
the double-screw extruder is divided into twelve temperature areas, and the temperature of each temperature area is; a section of: 180 ℃; two sections: 200-220 ℃; three sections: 200-220 ℃; four sections: 200-220 ℃; five sections: 200-220 ℃; six sections: 180-200 ℃; seven sections: 160-180 ℃; eight sections: 160-180 ℃, nine sections: 180-200 ℃; ten sections: 180-200 ℃; eleven sections: 180-200 ℃; twelve sections: 180-200 ℃.
The step S1 is a feeding conveying section and an exhaust section, and comprises four temperature areas, namely: a first section of 180 ℃; the second section is 200-220 ℃; three-stage 200-220 ℃; four sections of 200-220 ℃;
the step S2 is a side feeding section, and comprises three temperature areas, specifically: five sections of 200-220 ℃; 180-200 ℃ in six sections; seven sections of 180-200 ℃;
the step S3 is a first water injection section, a first vacuum section, a second water injection section and a second vacuum section, and comprises five temperature areas, specifically: eight sections of 180-200 ℃ and nine sections of 180-200 ℃; ten sections of 180-200 ℃; eleven sections 180-200 ℃; twelve sections 180-200 ℃;
the low temperature of the first section is used for better blanking, so that partial materials are prevented from being fused at a blanking opening to block and bridge due to high temperature. The main reasons for the temperature setting of other areas are that if the temperature setting is low, insufficient melting of materials can be caused to influence dispersion and distribution mixing, if the temperature is too high, decomposition can be caused, odor and VOC content can be influenced by small molecules, and the set temperature is the optimal temperature range after verification.
The reason for the temperature decrease from the side feeding stage is: the front section material is conveyed to ensure that the material is melted, the temperature is slightly higher, and the rear section material is melted, so that the condition that micromolecular substances are generated by thermal decomposition of the material is reduced, and the temperature is properly reduced.
The screw of the double-screw extruder is sequentially divided into a feeding conveying section, an exhaust section, a side feeding section, a first water injection section, a first vacuum section, a second water injection section and a second vacuum section;
the feeding conveying section sequentially comprises 1 56/56A element, 3 96/96 elements, 3 72/72 elements, 1 56/56 element, 130 DEG/7/72 element, 1 45 DEG/5/56 element, 160 DEG/4/56 element and 1 56/28L element according to a raw material conveying path;
the 56/56A element represents a first section of screw thread block for blocking, so that the material in the blanking section can be effectively prevented from reversely leaking; the first 56 represents that the lead of the thread block is 56mm, which means the length from the start of the thread to the end of the turn, and the second 56 represents that the length of this thread block is 56mm; the letter L represents a reverse thread block, and mainly plays a role in preventing materials from advancing and building pressure.
The exhaust section sequentially comprises 2 72/72 elements and 2 96/96 elements according to a raw material conveying path;
the side feeding section sequentially comprises 3 144/72 elements, 1 96/96 elements, 2 72/72 elements, 2 45 degrees/5/56 elements, 2 45 degrees/5/36 elements, 2 56/56 elements and 1 96/96 element according to a raw material conveying path;
the first water injection section sequentially comprises 1 72/72 element, 2 45 degrees/5/56 element, 160 degrees/4/56 element and 1 45 degrees/5/36L element according to a raw material conveying path;
the 60/4/56 element mentioned above represents a shearing element, representing a threaded element consisting of 4 sheets, the centre line of which is at an angle of 60, the total length of the block being 56mm.
The first vacuum section sequentially comprises 4 144/72 elements and 1 72/72 element according to a raw material conveying path;
the second water injection section sequentially comprises 1 56/56 element, 2 45 degrees/5/56 element, 1 90 degrees/5/36 element and 1 56/28L element according to the raw material conveying path;
the second vacuum section comprises, in order, 4 144/72 elements, 2 72/72 elements, and 3 56/56 elements in the feed path.
As shown in FIG. 2, the length-diameter ratio of the screws of the double-screw extruder is 44:1
The screw of the double-screw extruder is sequentially divided into a feeding conveying section, an exhaust section, a side feeding section, a first water injection section, a first vacuum section, a second water injection section and a second vacuum section;
the feeding conveying section sequentially comprises 1 56/56A element, 3 96/96 elements, 3 72/72 elements, 1 56/56 element, 130 DEG/7/72 element, 1 45 DEG/5/56 element, 160 DEG/4/56 element and 1 56/28L element according to a raw material conveying path;
the exhaust section sequentially comprises 2 144/72 elements and 3 72/72 elements according to a raw material conveying path;
the side feeding section sequentially comprises 3 96/96 elements, 1 72/72 element, 1 45 degrees/5/56 element and 1 96/96 element according to a raw material conveying path;
the first water injection section sequentially comprises 1 72/72 element, 2 45 degrees/5/56 element, 160 degrees/4/56 element and 1 45 degrees/5/36L element according to a raw material conveying path;
the first vacuum section sequentially comprises 4 144/72 elements and 1 72/72 element according to a raw material conveying path;
the second water injection section sequentially comprises 1 56/56 element, 2 45 degrees/5/56 element, 1 90 degrees/5/36 element and 1 56/28L element according to the raw material conveying path;
the second vacuum section comprises, in order, 4 144/72 elements, 2 72/72 elements, and 3 56/56 elements in the feed path.
As shown in FIG. 3, the length-diameter ratio of the screw of the double-screw extruder is 56:1
The screw of the double-screw extruder is sequentially divided into a feeding conveying section, an exhaust section, a side feeding section, a first water injection section, a first vacuum section, a second water injection section and a second vacuum section;
the feeding conveying section sequentially comprises 1 56/56A element, 2 112/112SK elements, 1 96/96 element, 2 72/72 element, 1 56/56 element, 130 DEG/7/72 element, 1 45 DEG/5/56 element, 160 DEG/4/56 element, 1 56/56 element, 2 45 DEG/5/56 element, 1 45 DEG/5/56L element, 1 44/44 element, 1 45 DEG/5/56 element, 1 90 DEG/5/56 element and 1 56/28L element according to a raw material conveying path;
the exhaust section sequentially comprises 2 144/72 elements and 1 96/96 elements according to a raw material conveying path;
the side feeding section sequentially comprises 2 96/96 elements, 2 72/72 elements, 1 56/56 element, 2 45 degrees/5/56 element, 160 degrees/4/56 element, 1 56/56 element, 3 72/72 elements and 1 56/56 element according to a raw material conveying path;
the first water injection section sequentially comprises 1 56/56 element, 1 45 degrees/5/36 element, 1 90 degrees/5/36 element, 1 96/96 element and 1 56/28L element according to a raw material conveying path;
the first vacuum section sequentially comprises 3 144/72 elements, 1 96/96 elements, 1 72/72 element, 1 56/56 element, 2 45 degrees/5/56 element and 1 90 degrees/5/56 element according to a raw material conveying path;
the second water injection section sequentially comprises 1 56/56 element, 1 48/48 element, 1 44/44 element, 1 45 DEG 5/56 element, 1 90 DEG 5/56 element and 1 45 DEG/5/36 element according to a raw material conveying path;
the second vacuum section sequentially comprises 1 96/96 element, 1 56/28L element, 3 144/72 element, 2 72/72 element and 2 56/56 element according to the raw material conveying path;
as shown in fig. 4, the length-diameter ratio of the screw of the double screw extruder is 40:1
The screw of the double-screw extruder is sequentially divided into a feeding conveying section, an exhaust section, a side feeding section, a first water injection section, a first vacuum section, a second water injection section and a second vacuum section;
the feeding conveying section sequentially comprises 1 56/56A element, 3 96/96 elements, 3 72/72 elements, 1 56/56 element, 130 DEG/7/72 element, 1 45 DEG/5/56 element, 160 DEG/4/56 element and 1 56/28L element according to a raw material conveying path;
the exhaust section sequentially comprises 2 144/72 elements and 3 72/72 elements according to a raw material conveying path;
the side feeding section sequentially comprises 3 96/96 elements according to a raw material conveying path;
the first water injection section sequentially comprises 2 45 degrees/5/56 elements, 160 degrees/4/56 element and 1 45 degrees/5/36L element according to a raw material conveying path;
the first vacuum section sequentially comprises 4 144/72 elements and 1 72/72 element according to a raw material conveying path;
the second water injection section sequentially comprises 1 56/56 element, 2 45 degrees/5/56 element, 1 90 degrees/5/36 element and 1 56/28L element according to the raw material conveying path;
the second vacuum section comprises, in order, 4 144/72 elements, 3 72/72 elements, and 2 56/56 elements in the feedstock delivery path.
The test results of examples 1 to 7 of the present invention are shown in tables 1 to 3:
table 1 list of the component ratios of examples 1 to 7
Wherein, example 1 is the optimal proportion, and examples 2-7 are comparative examples.
Table 2 list of properties for examples 1-7
Table 3 examples 1-7 odor and VOC test profile
Remarks: VOC equipment detection limit 0.005mg/m 3 ND identifies that the device detection limit has not been reached.
From the above experimental data it is shown that: example 1 compared with examples 2 and 3, the talc powder of example 1 has the highest filling content, the best rigidity of the material, and the slightly lower impact of the material but can meet the use requirement (the impact strength requirement of normal materials is more than or equal to 25 Kj/m) 2 The strength of example 1 is fully compatible with the impact strength requirements of normal such materials), also the most cost-effective (talcThe price of the product is greatly lower than that of a polypropylene material, and the cost is lower like that of a talcum with high proportion in a formula system). Example 1 has a density of 0.98g/cm as compared with examples 4, 5, 6 and 7 3 However, the TVOC content of example 1 is far lower than examples 4 to 7, so that example 1 has the optimum odor and the lowest VOC, and can meet the requirements of automotive interior trim.
The low-density polypropylene material for the new energy automobile interior trim, which is prepared by the invention, has the characteristics of low density, the density range of 0.9-1.0 g/cm < 3 >, high rigidity and high toughness, comprehensive mechanical properties, scratch resistance requirements in appearance, good formability, and light weight trend of automobiles, and meanwhile, the odor grade of 2.0-2.5 of the material can meet the requirements of almost all automobile interior trim on odor due to the characteristics of low odor and low VOC, the higher fluidity and good comprehensive mechanical properties of the material can also reduce the wall thickness of a product to a certain extent, and on the basis of low density weight reduction, the weight is further reduced by thinning, the performance requirements of various automobile interior trim are met, and the material has stronger market competitiveness.
The invention has been described above with reference to preferred embodiments, but the scope of the invention is not limited thereto, and any and all technical solutions falling within the scope of the claims are within the scope of the invention. Various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict.
Claims (8)
1. The low-density polypropylene material is characterized by comprising the following materials in parts by weight:
heterophasic copolymerized high crystalline polypropylene: 60-80 parts of high-density polyethylene: 0-5 parts of high-melting high-impact polypropylene: 0-20 parts of inorganic mineral powder: 0-10 parts of toughening agent: 5-15 parts of scratch resistant agent: 1-3 parts of antioxidant, 0.1-0.5 part of deionized water: 1-3 parts of other auxiliary agents: 1-2 parts.
2. The low-density polypropylene material according to claim 1, wherein the inorganic mineral powder is talcum powder, wollastonite and mica, and the particle size of the inorganic mineral powder is D50 less than or equal to 3um; the toughening agent is a polyolefin elastomer, and the melt index of the polyolefin elastomer is 0.5-30g/10min; the scratch resistant agent is master batch which is prepared from polysiloxane and erucamide and takes PP as a carrier.
3. The preparation method of the low-density polypropylene material is characterized by comprising the following steps of:
s1: the multiphase copolymerization high-crystalline polypropylene, the high-density polyethylene, the high-melting high-impact polypropylene, the toughening agent, the scratch resistant agent, the antioxidant and other auxiliary agents are simultaneously added into an extruder for blending through weightlessness weighing, so as to form a mixture I;
s2: adding inorganic mineral powder into an extruder from a side feeding port, and mixing with the first mixture to form a second mixture;
s3: injecting deionized water into an extruder, mixing with the mixture II to form a mixture III, then performing vacuum devolatilization on the mixture III, then injecting deionized water into the extruder again, mixing with the mixture III to form a mixture IV, and then performing vacuum devolatilization on the mixture IV;
s4: extruding the mixture four times by an extruder, cooling the extruded material strips to room temperature, granulating by a granulator, absorbing the material by negative pressure after granulating, entering a material drying and deodorizing system, drying the material for 5-8 hours at 130 ℃, and discharging after cooling.
4. A method of producing a low density polypropylene material according to claim 3, wherein said extruder is a twin screw extruder having a screw aspect ratio of 40:1-56:1.
5. the method of producing a low density polypropylene material according to claim 4, wherein said twin screw extruder has a screw aspect ratio of 44:1 or 48:1.
6. the method of producing a low-density polypropylene material according to claim 5, wherein said twin-screw extruder has a screw aspect ratio of 48:1.
7. the method for producing a low-density polypropylene material according to claim 6, wherein:
the step S1 is a feeding conveying section and an exhaust section, and comprises four temperature areas, namely: a first section of 180 ℃; the second section is 200-220 ℃; three-stage 200-220 ℃; four sections of 200-220 ℃;
the step S2 is a side feeding section, and comprises three temperature areas, specifically: five sections of 200-220 ℃; 180-200 ℃ in six sections; seven sections of 180-200 ℃;
the step S3 is a first water injection section, a first vacuum section, a second water injection section and a second vacuum section, and comprises five temperature areas, specifically: eight sections of 180-200 ℃ and nine sections of 180-200 ℃; ten sections of 180-200 ℃; eleven sections 180-200 ℃; twelve sections 180-200 ℃.
8. The method for producing a low-density polypropylene material according to claim 7, wherein:
the feeding conveying section sequentially comprises 1 56/56A element, 3 96/96 elements, 3 72/72 elements, 1 56/56 element, 130 DEG/7/72 element, 1 45 DEG/5/56 element, 160 DEG/4/56 element and 1 56/28L element according to a raw material conveying path;
the exhaust section sequentially comprises 2 72/72 elements and 2 96/96 elements according to a raw material conveying path;
the side feeding section sequentially comprises 3 144/72 elements, 1 96/96 elements, 2 72/72 elements, 2 45 degrees/5/56 elements, 2 45 degrees/5/36 elements, 2 56/56 elements and 1 96/96 element according to a raw material conveying path;
the first water injection section sequentially comprises 1 72/72 element, 2 45 degrees/5/56 element, 160 degrees/4/56 element and 1 45 degrees/5/36L element according to a raw material conveying path;
the first vacuum section sequentially comprises 4 144/72 elements and 1 72/72 element according to a raw material conveying path;
the second water injection section sequentially comprises 1 56/56 element, 2 45 degrees/5/56 element, 1 90 degrees/5/36 element and 1 56/28L element according to the raw material conveying path;
the second vacuum section comprises, in order, 4 144/72 elements, 2 72/72 elements, and 3 56/56 elements in the feed path.
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