CN101717548B - High-polarity polypropylene material and application thereof as inner and outer decorative parts of automobile - Google Patents
High-polarity polypropylene material and application thereof as inner and outer decorative parts of automobile Download PDFInfo
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Abstract
The invention discloses a high-polarity polypropylene material and the application thereof as inner and outer decorative parts of an automobile. The material is prepared from the following components in percentage by weight: 50-89 polypropylene, 5-25 flexibilizer, 0-30 mineral filler, 5-15 polar additives, 0.2-3 age resister and 0-0.5 colorant, and the components are premixed and then are extruded out by a double-screw extruder to prepare particles, thereby preparing the high-polarity modified polypropylene material. The surface tension of the material is as high as 37 dyne/cm<2>, dope-binding strength is high, an automobile bumper formed by the material can be coated without being pretreated, and when being used for preparing the inner decorative part for the automobile, the material has good property of binding other materials.
Description
Technical field
The invention belongs to material modified technical field, be specifically related to a kind of raising polar Vestolen PP 7052 (PP) matrix material and application thereof.
Background technology
Plastics satisfy that automobile is attractive in appearance, comfortable, safe, anticorrosion, lightweight and design freedom are big etc., and the aspect plays the irreplaceable effect of other material.Automobile with many macromolecular materials in, exploitation and the application of MODIFIED PP material on automobile is the focus that automotive industry and plastics industry are paid close attention to always.Can obtain to satisfy the MODIFIED PP material of various trolley part different function requirements through various modification processing means, its excellent cost performance in addition, make various toughness reinforcing, fill, strengthen the PP material and in each big assembly system of automobile, obtained widespread use.At present, the consumption of the bicycle PP of flourishing automotive industry country material reaches nearly 60kg, accounts for about 47% of car load plastic material application quantity, becomes on the automobile the maximum kind of consumption in all plastic materials.The PP material is because its wide material sources, density are little, harmonious good, the resistance to chemical attack of mechanics, be prone to processing and outstanding advantage such as cheap, thereby is widely used.
Collision bumper is used the MODIFIED PP material, not only needs good impact property, processing characteristics, but also needs good paint adhesion ability.The paint spraying rear bumper has good surface appearance, produces fine visual effect.Bumper material behind the paint spraying will be through experiments such as anti-gasoline, moisture-proof, water-fast and adherences.If the surface tension of bumper material is low, these tests can't be passed through.Because the PP material is non-polar material, surface energy is low, makes that its consistency with most polymers is poor, is difficult for soaking into, bonding and printing, and coating property is poor, and is low with the cohesive strength of coating, so will reach and can spray, and just needs its polarity of certain methods raising.Need bond with other material for automotive upholstery such as test board, also need good adhesive property.Usually plastics are in order to improve the surface tension on surface; Promptly improve PASS, before application, at first need carry out surface treatment; Eliminate antistatic and dust adsorbed greasy dirt through solvent; Carry out surface-treated with flame, corona discharge, tensio-active agent, gas plasma etc., improve the polar group on surface, enhancement coating sticking power.This type technological difficulties be should form uniform surface, again can not excessive handling, otherwise can cause the polymer chain fracture on surface, thus the performance of influence.
Flame method is to use comparatively general a kind of method, it contacts when making smooth surface with the oxydizing flame of flame part (being blue portion) with the PP material surface till, so that its surface oxidation increase polarity.The time is sprayed on hot oxygen flame temperature on the material surface up to 1100～2800 ℃, so must lack as far as possible.Distance at air-flow ratio, flame and the ground of using air and oxygen all can have influence on treatment effect.Since the special shape of collision bumper, flame often have processing less than the position produce, produce mass defect, the polarity that therefore improves the PP ground becomes an extremely attractive problem.
Raising PP polar method commonly used has surface grafting method, surface-crosslinked method, surface coating modified method, adds polar material blending method etc.U.S. Pat 6153701 discloses a kind of wettable polypropene composition; Comprise Vestolen PP 7052 and the wetting ability polar compound that is selected from the functional group of hydroxyl, carboxyl, ether or ester moiety; This wetting ability polar compound is selected from Vestolen PP 7052, polyoxyethylene glycol (PEG), modified poly (ethylene glycol), Z 150PH (PVOH), the PVF (PVF) of maleic anhydride modified Vestolen PP 7052 (MAPP), acrylic acid modified Vestolen PP 7052, vinylformic acid glycol ester modified polypropene, grafted propylene acid sodium-salt, and this polypropene composition contact angle is less than or equal to 75 °; U.S. Pat 1950549 provides a kind of surface grafting that noncrystalline polypropylene articles of polar monomer and preparation method thereof is arranged, this patent with the Vestolen PP 7052 extrusion moulding after, cold in high temperature essence, carry to apply polar monomer; Patent CN2000410041378.2 discloses a kind of through in polypropylene matrix, adding polar compound (comprising vinylformic acid or its ester class, maleic anhydride), prepares and improves hydrophilic polypropylene material; Patent CN1182097 discloses a kind of method for preparing high-polarity modified polypropylene material; This preparation method is parent stock with the Vestolen PP 7052; Add a certain proportion of polarity unisexuality, cografting polar monomer and initiator, reacted 1-3 minute the high-polarity polypropylene material that makes at 170 ℃-220 ℃ down; Can improve the polarity of goods, improve the topcoating property of goods; Patent CN1230554 adds a certain proportion of maleic anhydride, cografting monomer and initiator, melt pelletization, and the high-polarity polypropylene material of preparation can improve the polarity of goods, improves the topcoating property of goods; Patent CN1238786 discloses the method for preparing polar modified polypropylene waxes, and through nonpolar HPP homopolymer polypropylene or copolymer waxes and,-undersaturated carboxylic acid or derivatives thereof reacts in the presence of radical, and the polarity PP wax polarity that makes is high; CN1858104 discloses a kind of Vestolen PP 7052, polyethylene treating agent; It is made up of following component: Chlorinated Polypropylene III, chlorinated rubber, toluene, Bing Xisuandingzhi, vinylbenzene, maleic anhydride, Lucidol, antioxidant BHT; React with Vestolen PP 7052; Has good stability, advantage such as avidity is strong.More than these methods can improve PP polarity, but these complex manufacturing.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of high polar polypropylene material is provided.
Another object of the present invention provides the application of above-mentioned high-polarity polypropylene in preparation car interior-exterior ornaments.
To achieve these goals, the present invention adopts following technical scheme:
A kind of high-polarity polypropylene material, form by the component of following weight percentage:
Vestolen PP 7052 50 ~ 70%
Toughner 14 ~ 20%
Polar additive 5 ~ 15%
Mineral filler 0 ~ 30%
Inhibitor 0.2 ~ 3%
Tinting material 0～0.5%.
In above-mentioned high-polarity polypropylene material, said Vestolen PP 7052 is a COPP, and it melts to refer to be 5 ~ 60g/min.
In above-mentioned high-polarity polypropylene material; Described toughner is elastomerics, adopts one or more mixing in ethene-hexene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-octene terpolymer, the hydrogenation of ethylene-BS.
In above-mentioned high-polarity polypropylene material, described polar additive is one or more mixing in TPU (TPU), maleic anhydride inoculated polypropylene, epoxy resin, ethylene-acrylate (EEA), ethylene vinyl acetate (EVA), polyetheramine, the polybutylenes polyvalent alcohol.
In above-mentioned high-polarity polypropylene material, described mineral filler is one or both mixing in talcum powder, lime carbonate, the permanent white.It surpasses 95% size distribution at 0.5-5 μ m, preferentially selects 0.5-1 μ m.
In above-mentioned high-polarity polypropylene material, described inhibitor is one or more mixing in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, metal passivator, benzophenone and the benzotriazole light stabilizer.
Above-mentioned high-polarity polypropylene material can be used to prepare automobile exterior spare, like collision bumper or rubbing strip or the like.Also can be used to prepare automotive upholstery, like parts or the like around glove box, test board, door-plate, column, back board putting things or the seat.
High-polarity polypropylene material provided by the invention is by said ratio feed composition to be carried out premix earlier, puts into twin screw extruder then and carries out the melt blending extruding pelletization by the common process condition and get final product.
Compared with prior art, the present invention has following beneficial effect:
1, through introducing high TPU, epoxy resin, ethylene-acrylate (EEA), ethylene vinyl acetate (EVA), the polyetheramine of polarity unipolarity; Significantly improve the surface polarity of PP, the surface energy of reduction PP; Improve dimensional stability; Make bumper material have good PASS, use the inside gadget such as exterior trimming parts such as collision bumper and test board of this forming materials.
2, do not need processing such as flame before high-polarity polypropylene material provided by the present invention sprays, save energy reduces CO2 emissions.
3, high-polarity polypropylene material material provided by the present invention through adding corresponding additive (oxidation inhibitor, photostabilizer, lubricant etc.), through double-screw melt blending, evenly spreads in the resin matrix auxiliary agent, excellent performance.
4, high-polarity polypropylene material material provided by the present invention adopts the high-molecular weight polar polymer, and is good with the PP consistency, is difficult for moving out, and can keep the high polarity of PP system for a long time.
Embodiment
Embodiment 1
Table 1 embodiment 1 formulation content
| Component | Manufacturer | Weight percentage |
| PP?EPC30R | Sinopec Maoming petrochemical industry branch office | 64％ |
| POE?8137 | DOW Chemical ltd | 20％ |
| Talcum powder | Extra large talcum powder ltd ends | 10％ |
| Epoxy resin | Yueyang petrochemical industry ltd of Ba Ling Huaxing | 5％ |
| Oxidation inhibitor: Irganox1010, | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Oxidation inhibitor: Irganox168 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Carbon black: 50L | The extraordinary chemical company of Degussa | 0.5％ |
With above-mentioned starting material by weight percentage polarity put into the super mixer that rotating speed is about 1000rpm earlier and mixed 3 minutes, and then put into twin screw extruder, temperature is controlled at: 200 ℃～215 ℃, extruding pelletization promptly gets under 450 rev/mins of conditions of screw speed.The product performance such as the table 2 that make:
Table 2 performance table
The material of embodiment 1 is processed collision bumper, observe behind the spraying frame.With the collision bumper that common PP processes, the laggard row of spraying frame relatively.The sticking power that can see the bumper material that the embodiment of the invention 1 provides is good, and surface effect is good after the cross frame method, and common PP obviously see peeling paint.
Embodiment 2
Table 3 embodiment 2 formulation content
| Component | Manufacturer | Weight percentage |
| PP?CB5290 | Company of Korea S Kpic | 65％ |
| POE?5171 | Exxonmobil chemical company | 10％ |
| Talcum powder | Extra large talcum powder ltd ends | 20％ |
| Ethylene-acrylate Elvaloy2112 AC | DOW Chemical ltd | 4％ |
| Oxidation inhibitor: Irganox1010, | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Oxidation inhibitor: Irganox168 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Carbon black: 50L | The extraordinary chemical company of Degussa | 0.5％ |
Above-mentioned starting material are put into the super mixer that rotating speed is about 1000rpm earlier mixed 3 minutes, extruding and pelletizing process is seen embodiment 1.The properties of sample such as the table 4 that make:
Table 4 performance table
| Performance | Testing standard | Test condition | Iu | Test value |
| Melt mass flow rate | ISO1133-91 | 230℃，2.16Kg | g/10min | 24 |
| Tensile strength | ISO527/2-93 | 50mm/min | MPa | 19 |
| Elongation at break | ISO527/2-93 | 50mm/min | ％ | 100 |
| Flexural strength | ISO178-93 | 2mm/min | MPa | 21 |
| Modulus in flexure | ISO178-93 | 2mm/min | MPa | 1241 |
| The socle girder notched Izod impact strength | ISO180-93 | 4mm，23℃ | KJ/m 2 | 43 |
| Surface tension | Ford?Test Method | - | Dynes/cm | 41 |
Embodiment 3
Table 5 embodiment 3 formulation content
| Component | Manufacturer | Weight percentage |
| PPAW191 | Singapore polyolefine private limited partnership | 66％ |
| POE?8842 | DOW Chemical ltd | 18％ |
| Talcum powder | Extra large talcum powder ltd ends | 10％ |
| EVA | Exxonmobil chemical company | 5％ |
| Oxidation inhibitor: Irganox1010 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Oxidation inhibitor: Irganox168 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Carbon black: 50L | The extraordinary chemical company of Degussa | 0.5％ |
Above-mentioned starting material are put into the super mixer that rotating speed is about 1000rpm earlier mixed 3 minutes, extruding and pelletizing process is seen embodiment 1.The properties of sample such as the table 6 that make:
Table 6 performance table
| Performance | Testing standard | Test condition | Iu | Test value |
| Melt mass flow rate | ISO1133-91 | 230℃，2.16Kg | g/10min | 11.3 |
| Tensile strength | ISO527/2-93 | 50mm/min | MPa | 18 |
| Elongation at break | ISO527/2-93 | 50mm/min | ％ | 100 |
| Flexural strength | ISO178-93 | 2mm/min | MPa | 21 |
| Modulus in flexure | ISO178-93 | 2mm/min | MPa | 980 |
| The socle girder notched Izod impact strength | ISO180-93 | 4mm，23℃ | KJ/m 2 | 45 |
| Surface tension | Ford?Test Method | - | Dynes/cm | 41 |
Embodiment 4
Table 7 embodiment 4 formulation content
| Component | Manufacturer | Weight percentage |
| PPAW191 | Singapore polyolefine private limited partnership | 66％ |
| POE?8137 | DOW Chemical ltd | 20％ |
| Talcum powder | Extra large talcum powder ltd ends | 10％ |
| TPU | Bayer chemical company | 3％ |
| Oxidation inhibitor: Irganox1010 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Oxidation inhibitor: Irganox168 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Carbon black: 50L | The extraordinary chemical company of Degussa | 0.5％ |
Above-mentioned starting material are put into the super mixer that rotating speed is about 1000rpm earlier mixed 3 minutes, extruding and pelletizing process is seen embodiment 1.The properties of sample such as the table 8 that make:
Table 8 performance table
| Performance | Testing standard | Test condition | Iu | Test value |
| Melt mass flow rate | ISO1133-91 | 230℃，2.16Kg | g/10min | 11 |
| Tensile strength | ISO527/2-93 | 50mm/min | MPa | 18 |
| Elongation at break | ISO527/2-93 | 50mm/min | ％ | 100 |
| Flexural strength | ISO178-93 | 2mm/min | MPa | 22 |
| Modulus in flexure | ISO178-93 | 2mm/min | MPa | 1100 |
| The socle girder notched Izod impact strength | ISO180-93 | 4mm，23℃ | KJ/m 2 | 46 |
| Surface tension | Ford?Test Method | - | Dynes/cm | 42 |
Embodiment 5
Table 9 embodiment 5 formulation content
| Component | Manufacturer | Weight percentage |
| PP?EP200R | Ba Saier polyolefine ltd | 76％ |
| POE?8137 | DOW Chemical ltd | 3％ |
| Epoxy resin | Yueyang petrochemical industry ltd of Ba Ling Huaxing | 10％ |
| Polyetheramine | BASF chemistry ltd | 10％ |
| Oxidation inhibitor: Irganox1010 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Oxidation inhibitor: Irganox168 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Carbon black: 50L | The extraordinary chemical company of Degussa | 0.5％ |
Above-mentioned starting material are put into the super mixer that rotating speed is about 1000rpm earlier mixed 3 minutes, extruding and pelletizing process is seen embodiment 1.The properties of sample such as the table 10 that make:
Table 10 performance table
| Performance | Testing standard | Test condition | Iu | Test value |
| Melt mass flow rate | ISO1133-91 | 230℃，2.16Kg | g/10min | 16 |
| Tensile strength | ISO527/2-93 | 50mm/min | MPa | 17.8 |
| Elongation at break | ISO527/2-93 | 50mm/min | ％ | 100 |
| Flexural strength | ISO178-93 | 2mm/min | MPa | 20 |
| Modulus in flexure | ISO178-93 | 2mm/min | MPa | 780 |
| The socle girder notched Izod impact strength | ISO180-93 | 4mm，23℃ | KJ/m 2 | 50 |
| Surface tension | Ford?Test Method | - | Dynes/cm | 41 |
Embodiment 6
Table 11 embodiment 6 formulation content
| Component | Manufacturer | Weight percentage |
| PP?HHP6 | Sinopec Maoming branch office | 56％ |
| POE?8137 | DOW Chemical ltd | 18％ |
| Talcum powder | Extra large talcum powder ltd ends | 10％ |
| Epoxy resin | Yueyang petrochemical industry ltd of Ba Ling Huaxing | 10％ |
| Polyetheramine | BASF chemistry ltd | 5％ |
| Oxidation inhibitor: Irganox1010, | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Oxidation inhibitor: Irganox168 | Vapour crust fine chemistry Industrial Co., Ltd | 0.25％ |
| Carbon black: 50L | The extraordinary chemical company of Degussa | 0.5％ |
Above-mentioned starting material are put into the super mixer that rotating speed is about 1000rpm earlier mixed 3 minutes, extruding and pelletizing process is seen instance 1.The properties of sample such as the table 12 that make:
Table 12 performance table
| Performance | Testing standard | Test condition | Iu | Test value |
| Melt mass flow rate | ISO1133-91 | 230℃，2.16Kg | g/10min | 18 |
| Tensile strength | ISO527/2-93 | 50mm/min | MPa | 19.7 |
| Elongation at break | ISO527/2-93 | 50mm/min | ％ | 100 |
| Flexural strength | ISO178-93 | 2mm/min | MPa | 19 |
| Modulus in flexure | ISO178-93 | 2mm/min | MPa | 1034 |
| The socle girder notched Izod impact strength | ISO180-93 | 4mm，23℃ | KJ/m 2 | 40 |
| Surface tension | Ford?Test Method | - | Dynes/cm | 42 |
Claims (7)
1. high-polarity polypropylene material is characterized in that being made up of the component of following weight percentage:
Described polar additive is a polyetheramine.
2. high-polarity polypropylene material according to claim 1; It is characterized in that: described toughner is elastomerics, adopts one or more mixing in ethene-hexene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-octene terpolymer, the hydrogenation of ethylene-BS.
3. high-polarity polypropylene material according to claim 1 is characterized in that: described mineral filler is one or both mixing in talcum powder, lime carbonate, the permanent white.
4. high-polarity polypropylene material according to claim 1 is characterized in that: described inhibitor is one or more mixing in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, metal passivator, benzophenone and the benzotriazole light stabilizer.
5. the application of the said high-polarity polypropylene material of claim 1 in preparation automobile exterior spare or automotive upholstery.
6. application as claimed in claim 5 is characterized in that said automobile exterior spare is collision bumper or rubbing strip.
7. application as claimed in claim 5 is characterized in that said automotive upholstery is parts around glove box, test board, door-plate, column, back board putting things or the seat.
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| CN101717548B true CN101717548B (en) | 2012-07-18 |
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