CN1834145A - Polypropylene composite material for automobile bumper and prepn. thereof - Google Patents
Polypropylene composite material for automobile bumper and prepn. thereof Download PDFInfo
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- CN1834145A CN1834145A CN 200510024469 CN200510024469A CN1834145A CN 1834145 A CN1834145 A CN 1834145A CN 200510024469 CN200510024469 CN 200510024469 CN 200510024469 A CN200510024469 A CN 200510024469A CN 1834145 A CN1834145 A CN 1834145A
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Abstract
This invention discloses a kind of polypropylene composite materials for automobile bumpers and its preparation method. This kind of materials comprises 93.3~56.5wt% polypropylene, 0.2~1.5wt% thermo-stabilizers, 0.3~1wt% photo-stabilizers, 0.2~1% auxiliary reagents, 1~20wt% activating and reinforcing masterbatches and 5~20wt% stuffing masterbatches. The product in this invention has high surface activity, low thermo expansion rate and high thermo expansion temperature. The surface tension is 40mN/m, the linear thermo expansion rate is 10 to the power -6 to 10 to the power -7 mm per mm per deg. C, the thermo deformation temperature is 55 deg. C and some other technological indices all reach or exceed current standards for automobile materials. Thanks to the high surface tension and strong paint-adhesion of the bumpers made of this kind of materials, paints can be directly sprayed rather than flame processing. The thermo expansion rate is low, and therefore, loosening due to significant deformation might not occur with large temperature variation. Besides, it also has the advantages of high the thermo resistant temperature, short baking time and high production efficiency.
Description
Technical field
The present invention relates to a kind of acrylic composite and preparation method thereof, be specifically related to high reactivity low-expansion heat-resisting polypropylene composite material that is used for by bumper and preparation method thereof.
Background technology
In the automotive material field, car is being represented current highest level with material.The bumper material of car is commonly the terpolymer EP rubber modified polypropene at present, and this material usage reaches more than 70% of the total consumption of bumper material.
No matter be external or domestic bumper material at present, though reached current automotive material standard, but still there is deficiency aspect some processing, needing to increase complete processing by automobile component manufacturer remedies, increase production cost, thereby can not fully satisfy the bumper material market requirement.Wherein the several representative problem is:
Collision bumper surfactivity by existing forming materials is low, and is poor with paint avidity, and collision bumper must be through the flame treating program before spraying.Flame treating is one key procedure in the collision bumper coating process, and under the normal condition of production, the substandard products that account for collision bumper total product amount 3% are owing to the defective generation of flame treating.Sometimes flame treating is improper, and then the application collision bumper will be scrapped by the gross, cause heavy losses.
Present bumper material thermal expansivity height, technique for fixing and size match requirement height for collision bumper, and cause collision bumper in use because variation of temperature and size changes causes the collision bumper distortion and produces internal stress, easily cause getting loose or destroying of collision bumper.
Collision bumper must be through the twice baking process in coating process, present bumper material thermotolerance is not high enough, for the Guarantee Insurance thick stick in bake process indeformable and paint completely solidified, storing temperature generally is set in about 80 ℃, the application of such collision bumper is rolled off the production line consuming time at 3～3.5 hours from reaching the standard grade to, production efficiency is low.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of polypropylene composite material for automobile bumper and preparation method thereof, to overcome the defective that prior art exists, satisfy the needs of car industrial development.
The component and the weight percentage of polypropylene composite material for automobile bumper of the present invention comprise:
Polypropylene 56.5-93.3%
Thermo-stabilizer 0.2-1.5%
Photostabilizer 0.3-1%
Auxiliary agent 0.2-1%
Toner 0～5%
Activatory plasticizing mother particle 1-20%
Filler parent granule 5-20%
It is the polypropylene of 10-20 ten thousand that said polypropylene can be selected molecular weight for use;
Said thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester or a kind of or its mixture in the calixarene; As trade names is the thermo-stabilizer of Irganox 1010
Said photostabilizer is selected from hindered amines, as: poly--[6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazine-2, the 4-dimethyl] [2-(2-2,6, the 6-tetramethyl-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6, the 6-tetramethyl-piperidyl)]-and inferior amino class, N-alkylation class, piperazine ketone structurizing class or UV light absorber, as benzotriazole category, benzophenone, a kind of or its mixture in the triazine benzylidene malonic acid ester class; As trade names is the N-alkylation class photostabilizer (CIBA company) of TINUV 770;
Said auxiliary agent is selected from a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class, the amides etc., and it mainly acts on is to improve processing characteristics;
Said toner is selected from carbon black, a kind of or its mixture of titanium dioxide, and it mainly acts on is to make color articles;
Said activatory plasticizing mother particle is a kind of composition, is to adopt the raw material reaction of following parts by weight to extrude preparation:
Activated monomer 1-5 part, polypropylene 49-10 part, 50～80 parts of polyolefin elastomers;
Said activated monomer is selected from a kind of or its mixture of toxilic acid, vinylformic acid, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE glycine acrylate, glycine methyl acrylate, diallyl p phthalate, a phenyl dimaleimide, Ethylene glycol dimethacrylate etc.; All can obtain in special auxiliary agent producer or retailer's place's buying;
Polyolefin elastomer is selected from multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, hydrogenant ethylene-butadiene-styrene multipolymer, ethene-α-ethylene-octene copolymer, ethene and the acrylonitrile copolymer of alkene-alhpa olefin-octene terpolymer, vinylbenzene and divinyl, the multipolymer of acrylonitrile-butadiene-styrene (ABS) or a kind of or its mixture in ethylene-propylene diene copolymer or the urethane;
The spray paint of collision bumper comprises the number of chemical composition, and each composition is different with particular functional group's avidity.By polyfunctional group activation, form various active functional group at material surface, can be simultaneously with paint in various chemical ingredientss form physical adsorptions or chemical bonding, reach best spraying effect.
Synergistic effect between the multiple polyolefin elastomer can remedy the various defectives that only adopt unitary resilient body to be produced on material internal structure, macro property, as reduce rigidity loss, improve toughening efficiency, and improve and process rheological, reduce owing to the product surface defective that adopts unitary resilient body to produce, as ripple glaze, tiger fur line etc., the over-all properties of material is improved.Adopt multiple polyolefin elastomer composite toughening, can also improve the deployment conditions of elastomeric component, and form network IPN or Semi-IPN by dynamic crosslinking between elastomerics, improve the stress transmission, blushing etc. eliminates stress.
The component of said filler parent granule and parts by weight are:
Polypropylene powder 38.5-15.5 part, fibrous or emboliform mineral filler 60-80 part, initiator 0.1-1.0 part;
Said mineral filler is selected from a kind of or mixture in talcum powder, barium sulfate, lime carbonate, pure aluminium silicate whisker, Magnesium Silicate q-agent whisker, the magnesium sulfate crystal whisker;
Fibrous filler helps improving the intensity and the dimensional stability of material, emboliform filler then helps improving the toughness and the surface hardness of material, the both can improve the modulus and the heat-drawn wire of material, thereby both effective combinations can make material possess the excellent comprehensive performance.
The particle diameter of mineral filler is the 0.1-10 micron.
Initiator is selected from a kind of or its mixture in diaryl superoxide, alkyl aralkyl superoxide, two (t-butylperoxy sec.-propyl) benzene peroxyester, the diacyl peroxide etc.;
The preparation method of polypropylene composite material for automobile bumper of the present invention comprises the steps:
(1) preparation of activatory plasticizing mother particle: is that 40: 1 twin screw extruder reactivity is extruded with activated monomer, polypropylene and polyolefin elastomer in length-to-diameter ratio, and temperature of reaction is 190-250 ℃, and the reaction times is for being 10-60 second; The employing reactivity is extruded, and can activate polypropylene and elastomerics synchronously, with raising material surface activity, and between Reinforced Polypropylene and the elastomerics, and the interface binding power between the mineral filler that adds in polypropylene, elastomerics and the subsequent technique;
(2) preparation of filler parent granule:
Polypropylene powder, fibrous or emboliform mineral filler are pre-mixed, add initiator, in forcing machine, extrude then,, reach good distribution to reduce the reunion of filler.
(3) be that melting mixing is disperseed in 40: 1 the twin screw extruder with polypropylene, auxiliary agent, toner, activatory plasticizing mother particle, filler parent granule, thermo-stabilizer and photostabilizer in length-to-diameter ratio, extruding pelletization finally obtains product.
Melting mixing is disperseed, and extrusion temperature is 180-240 ℃.
Product of the present invention has very high surfactivity, extremely low coefficient of thermal expansion and higher heat-drawn wire, and its surface tension 40mN/m (the contact horn cupping is measured), linear thermal expansivity is 10
-6～10
-7Mm/mm/ ℃ (ASTM D831), 55 ℃ (ISO75/1, the other technologies index meets or exceeds present automotive material standard to heat-drawn wire.Because the collision bumper surface tension height of this forming materials is strong with the bonding force of paint, can directly spray without flame treating; Coefficient of thermal expansion is low, and variation significantly that can Yin Wendu and obvious distortion takes place is difficult for getting loose or destroying; The heat resisting temperature height, storing time is short, the production efficiency height.
Embodiment
Embodiment 1
The preparation of activatory plasticizing mother particle: with phenyl dimaleimide between 2 kilograms of activated monomer, molecular weight is 70 kilograms of 26.5 kilograms of 110,000 polypropylene and polyolefin elastomer ethene-α-ethylene-octene copolymer in length-to-diameter ratio is that 1: 40 screw extrusion press reactivity is extruded, temperature of reaction is 230 ℃, and the reaction times is 30 seconds;
The preparation of filler parent granule: with molecular weight is that 120,000 27 kilograms of polypropylene powders, particle diameter are that 3 microns emboliform mineral filler lime carbonate and pure aluminium silicate whisker is pre-mixed 70 kilograms of things, and 0.2 kilogram of thermo-stabilizer Irganox 1010 (CIBA company) and 0.5 kilogram of initiator two (t-butylperoxy sec.-propyl) are extruded in forcing machine;
Is that melting mixing is disperseed in 1: 40 the twin screw extruder with 61.4 kilograms of polypropylene, 0.2 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 0.4 kilogram of N-alkylation class photostabilizer TINUV 770 (CIBA company), 1.0 kilograms of carbon blacks, 17 kilograms of activatory plasticizing mother particles, 20 kilograms of filler parent granules in length-to-diameter ratio, extrusion temperature is 215 ℃, extruding pelletization finally obtains product.
The said products has very high surfactivity, extremely low coefficient of thermal expansion and higher heat-drawn wire, and its surface tension 40mN/m (the contact horn cupping is measured), linear thermal expansivity is 10
-6Mm/mm/ ℃ (ASTM D831), 55 ℃ (ISO75/1, the other technologies index meets or exceeds present automotive material standard to heat-drawn wire.Performance is as follows:
| Performance | Unit | Testing standard | Test result |
| HDT(1.82MPa) | ℃ | ISO75/1-93 | 59 |
| Tensile strength | MPa | ISO527/2-93 | 18 |
| Elongation at break | ％ | ISO527/2-93 | 150 |
| Thermal linear expansion coefficient | mm/mm.℃ | ASTM D831 | 7×10 -6 |
| Flexural strength | MPa | ISO178-93 | 24 |
| Modulus in flexure | MPa | ISO178-93 | 1100 |
| Ball indentation hardness | N/mm2 | ISO2039/1-87 | 35 |
| Notched Izod impact strength | KJ/m2 | ISO180-93 | 45 |
| Unnotched impact strength | KJ/m2 | ISO180-93 | Do not rupture |
| Surface tension | mN/m | Solvent method | 42 |
Embodiment 2
(1) preparation of activatory plasticizing mother particle: with 2.5 kilograms of activated monomer Ethylene glycol dimethacrylate, molecular weight is 67.5 kilograms of 30 kilograms of 110,000 polypropylene and polyolefin elastomer ethene-α-ethylene-octene copolymer in length-to-diameter ratio is that 1: 40 screw extrusion press reactivity is extruded, temperature of reaction is 210 ℃, and the reaction times is 20 seconds;
(2) preparation of filler parent granule: with molecular weight is that 120,000 27 kilograms of polypropylene powders, particle diameter are that 3 microns emboliform mineral filler talcum powder and magnesium sulfate crystal whisker is pre-mixed 70 kilograms of things, and 0.2 kilogram of thermo-stabilizer Irganox 1010 and 0.5 kilogram of initiator diacyl peroxide are extruded in forcing machine;
(3) be that melting mixing is disperseed in 1: 40 the twin screw extruder with 68.9 kilograms of polypropylene, 0.2 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 0.4 kilogram of N-alkylation class photostabilizer TINUV 770 (CIBA company), 1.0 kilograms of carbon blacks, 12 kilograms of activatory plasticizing mother particles, 17.5 kilograms of filler parent granules in length-to-diameter ratio, extrusion temperature is 190 ℃, extruding pelletization finally obtains product.
The said products has very high surfactivity, extremely low coefficient of thermal expansion and higher heat-drawn wire, and its surface tension 45mN/m (the contact horn cupping is measured), linear thermal expansivity is 8 * 10
-6Mm/mm/ ℃ (ASTM D831), 58 ℃ of heat-drawn wires (ISO75/1), other technologies index meet or exceed present automotive material standard.
Claims (6)
1. polypropylene composite material for automobile bumper is characterized in that component and weight percentage comprise:
Polypropylene 56.5-93.3%
Thermo-stabilizer 0.2-1.5%
Photostabilizer 0.3-1%
Activation plasticizing mother particle 1-20%
Processing aid 0.2-1%
Filler parent granule 5-20%
1) said thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester or a kind of or its mixture in the calixarene;
2) said photostabilizer is selected from hindered amines, is selected from poly--[6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazine-2, the 4-dimethyl] [2-(2-2,6, the 6-tetramethyl-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6, the 6-tetramethyl-piperidyl)]-inferior amino class, N-alkylation class, a kind of or its mixture in piperazine ketone structurizing class or the UV light absorber;
3) said activation plasticizing mother particle is that a kind of compound situ reaction is extruded polar polymer, is to adopt the starting material situ reaction of following weight percentage to extrude preparation:
50～80 parts of polyolefin elastomers are selected from multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, hydrogenant ethylene-butadiene-styrene multipolymer, ethene-α-ethylene-octene copolymer, ethene and the acrylonitrile copolymer of alkene-alhpa olefin-octene terpolymer, vinylbenzene and divinyl, the multipolymer of acrylonitrile-butadiene-styrene (ABS) or a kind of or its mixture in ethylene-propylene diene copolymer or the urethane;
Polypropylene 49-10 part, its molecular weight are 11-13 ten thousand;
Activated monomer 1-5 part is selected from a kind of or its mixture in toxilic acid, vinylformic acid, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE glycine acrylate, glycine methyl acrylate, diallyl p phthalate, a phenyl dimaleimide, the Ethylene glycol dimethacrylate;
Initiator 0.1-1.0 part is selected from a kind of or its mixtures of diaryl superoxide, alkyl aralkyl superoxide, two (t-butylperoxy sec.-propyl) benzene peroxyester, diacyl peroxide etc.;
Thermo-stabilizer 0.5-1.5 part, thermo-stabilizer are selected from the mixture class or the calixarene of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester;
Processing aid 1-3 part mainly is selected from a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class, the amides etc.;
4) component of said filler parent granule and weight percentage are:
Polypropylene powder 38.5-15.5 part, its molecular weight are 8-10 ten thousand;
Fibrous, sheet or granulous filler 60-80 part;
5) said processing aid is selected from a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class, the amides.
2. polypropylene composite material for automobile bumper according to claim 1 is characterized in that, it is the polypropylene of 10-20 ten thousand that said polypropylene is selected molecular weight for use.
3. polypropylene composite material for automobile bumper according to claim 1 is characterized in that, said mineral filler is selected from a kind of or mixture in talcum powder, barium sulfate, lime carbonate, pure aluminium silicate whisker, Magnesium Silicate q-agent whisker, the magnesium sulfate crystal whisker.
4. polypropylene composite material for automobile bumper according to claim 3 is characterized in that, the particle diameter of mineral filler is the 0.1-10 micron.
5. according to the preparation method of each described polypropylene composite material for automobile bumper of claim 1～4, it is characterized in that comprising the steps:
(1) preparation of activatory plasticizing mother particle: is that 40: 1 screw extrusion press reactivity is extruded with activated monomer, polypropylene and polyolefin elastomer in length-to-diameter ratio, and temperature of reaction is 190-250 ℃, and the reaction times is 10-60 second;
(2) preparation of filler parent granule:
Polypropylene powder, fibrous or emboliform mineral filler are pre-mixed, add initiator, in forcing machine, extrude then;
(3) with polypropylene, auxiliary agent, toner, activatory plasticizing mother particle, filler parent granule, be that melting mixing is disperseed in 40: 1 the twin screw extruder in length-to-diameter ratio, extruding pelletization finally obtains product.
6. the preparation method of polypropylene composite material for automobile bumper according to claim 5 is characterized in that, melting mixing is disperseed, and extrusion temperature is 180-240 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510024469 CN1834145A (en) | 2005-03-18 | 2005-03-18 | Polypropylene composite material for automobile bumper and prepn. thereof |
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|---|---|---|---|
| CN 200510024469 CN1834145A (en) | 2005-03-18 | 2005-03-18 | Polypropylene composite material for automobile bumper and prepn. thereof |
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| CN101100593B (en) * | 2007-05-22 | 2010-05-26 | 深圳职业技术学院 | Environmental protection type SEBS thermoplastic elastic body sealing strip material and preparation method thereof |
| CN101190981B (en) * | 2007-11-29 | 2010-06-16 | 四川长虹电器股份有限公司 | Special-purpose material for automobile bumper and reclaiming utilizing method for waste printed circuit card |
| CN101845176A (en) * | 2010-06-09 | 2010-09-29 | 刘琳娇 | Automobile anticollision material |
| CN102050993A (en) * | 2010-12-10 | 2011-05-11 | 上海金发科技发展有限公司 | Flame-retardant PP/nylon corrugated tube composite material and preparation method thereof |
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| CN101100593B (en) * | 2007-05-22 | 2010-05-26 | 深圳职业技术学院 | Environmental protection type SEBS thermoplastic elastic body sealing strip material and preparation method thereof |
| CN101190981B (en) * | 2007-11-29 | 2010-06-16 | 四川长虹电器股份有限公司 | Special-purpose material for automobile bumper and reclaiming utilizing method for waste printed circuit card |
| CN101698736B (en) * | 2009-10-30 | 2011-10-05 | 华南理工大学 | Modification method for enhancing polarity and flowability of polypropylene |
| CN102206376A (en) * | 2010-03-31 | 2011-10-05 | 上海金发科技发展有限公司 | Polypropylene material filled with inorganic mineral powder, and its preparation method and application |
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| CN102453279B (en) * | 2010-10-22 | 2013-06-12 | 中国石油化工股份有限公司 | Polypropylene composition for producing bottle cap of carbonated beverage |
| CN102453279A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition for producing bottle cap of carbonated beverage |
| CN102050993B (en) * | 2010-12-10 | 2013-04-24 | 上海金发科技发展有限公司 | Flame-retardant PP/nylon corrugated tube composite material and preparation method thereof |
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| CN103113663A (en) * | 2011-11-17 | 2013-05-22 | 上海金发科技发展有限公司 | Scratch-resistant polypropylene compound with self-restoring function and preparation method thereof |
| CN103113663B (en) * | 2011-11-17 | 2016-06-15 | 上海金发科技发展有限公司 | A kind of damage resistant polypropylene composite with self-regeneration function and preparation method thereof |
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| CN108003478A (en) * | 2017-11-28 | 2018-05-08 | 安徽伟合电子科技有限公司 | A kind of automobile instrument PP composite material |
| CN110003572A (en) * | 2019-04-29 | 2019-07-12 | 上海金发科技发展有限公司 | A kind of polypropylene for thin-walled automobile product-alkali magnesium sulfate crystal whisker composite material |
| CN110498972A (en) * | 2019-09-26 | 2019-11-26 | 金发科技股份有限公司 | Purposes of the polyaluminosiloxane polymer as surface tension modifier |
| CN110498972B (en) * | 2019-09-26 | 2021-10-15 | 金发科技股份有限公司 | Use of polyaluminosiloxane polymers as surface tension modifiers |
| CN110591269A (en) * | 2019-09-29 | 2019-12-20 | 金发科技股份有限公司 | Use of polypropylene grafted sodium maleate polymer as surface tension modifier |
| CN110591269B (en) * | 2019-09-29 | 2022-03-08 | 金发科技股份有限公司 | Use of polypropylene grafted sodium maleate polymer as surface tension modifier |
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