CN101717548A - 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 PDF

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CN101717548A
CN101717548A CN200910193704A CN200910193704A CN101717548A CN 101717548 A CN101717548 A CN 101717548A CN 200910193704 A CN200910193704 A CN 200910193704A CN 200910193704 A CN200910193704 A CN 200910193704A CN 101717548 A CN101717548 A CN 101717548A
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polarity
polypropylene
polypropylene material
ethylene
material according
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CN101717548B (en
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杨燕
李永华
杨波
罗忠富
姚程
陈瑶
易庆锋
宁方林
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WUHAN JINFA TECHNOLOGY CO., LTD.
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MIANYANG DONGFANG SPECIAL ENGINEERING PLASTIC Co Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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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

High-polarity polypropylene material and as the application of inner and outer decorative parts of automobile
Technical field
The invention belongs to material modified technical field, be specifically related to a kind of raising polar polypropylene (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 by 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 kind of consumption maximum 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, easily processing and outstanding advantage such as cheap, thereby is widely used.
Collision bumper MODIFIED PP material not only needs good impact property, processing characteristics, but also needs good paint adhesion energy.The paint spraying rear bumper has good surface appearance, produces fine visual effect.Bumper material behind the paint spraying will be by 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, be difficult for soaking into, bonding with print, coating property is poor, and is low with the cohesive strength of coating, so will reach and can spray, and just needs certain methods to improve its polarity.Need bond with other material for automotive upholstery such as dashboard, 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 to carry out surface treatment, eliminate antistatic and dust adsorbed greasy dirt by solvent, carry out surface modification with flame, corona discharge, tensio-active agent, gas plasma etc., improve the polar group on surface, strengthen coating adhesion.These class 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.The distance of air-flow ratio, flame and the ground of air and oxygen all can have influence on treatment effect in application.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 polypropylene 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 selects Baima to come anhydride modified polypropylene (MAPP), acrylic acid modified polypropylene, vinylformic acid glycol ester modified polypropene, the polypropylene of grafted propylene acid sodium-salt, polyoxyethylene glycol (PEG), modified poly (ethylene glycol), polyvinyl alcohol (PVOH), polyvinyl formal (PVF), 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 polypropylene extrusion moulding after, cold in high temperature essence, carry to apply polar monomer; Patent CN2000410041378.2 discloses a kind of by add polar compound (comprising vinylformic acid or its ester class, maleic anhydride) in polypropylene matrix, 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 polypropylene, add a certain proportion of polarity unisexuality, cografting polar monomer and initiator, reacted 1-3 minute down at 170 ℃-220 ℃, the high-polarity polypropylene material that makes, can improve the polarity of goods, improve the surface daub on a wall 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 surface daub on a wall of goods; Patent CN1238786 discloses the method for preparing polar modified polypropylene waxes, and by nonpolar homopolymer polypropylene or copolymer waxes and, one undersaturated carboxylic acid or derivatives thereof reacts in the presence of free radical, the polarity PP wax polarity height that makes; CN1858104 discloses a kind of polypropylene, polyethylene treating agent, it is made of following component: Chlorinated Polypropylene III, chlorinated rubber, toluene, butyl acrylate, vinylbenzene, maleic anhydride, benzoyl peroxide, antioxidant BHT, react with polypropylene, 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 deficiencies in the prior art, a kind of high polar polypropylene material is provided.
Another object of the present invention provides the application in the ornaments inside and outside the preparation automobile of above-mentioned high-polarity polypropylene.
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:
Polypropylene 50～70%
Toughner 14～20%
Polar additive 5～15%
Mineral filler 0～30%
Antiaging agent 0.2～3%
Tinting material 0～0.5%.
In above-mentioned high-polarity polypropylene material, described polypropylene is a Co-polypropylene, 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-butadiene-styrene copolymer.
In above-mentioned high-polarity polypropylene material, described polar additive is one or more mixing in TPU(Thermoplastic polyurethanes) (TPU), maleic anhydride inoculated polypropylene, Resins, epoxy, ethylene-acrylate (EEA), ethylene vinyl acetate (EVA), polyetheramine, the polybutene polyvalent alcohol.
In above-mentioned high-polarity polypropylene material, described mineral filler is one or both mixing in talcum powder, lime carbonate, the barium sulfate.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 antiaging agent 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, as collision bumper or rubbing strip or the like.Also can be used to prepare automotive upholstery, as parts or the like around glove box, dashboard, 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, put into then twin screw extruder routinely processing condition carry out the melt blending extruding pelletization and get final product.
Compared with prior art, the present invention has following beneficial effect:
1, by introducing high TPU, Resins, epoxy, 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 inside gadgets such as the exterior trimming parts such as collision bumper of this forming materials and dashboard.
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 by 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 company limited ??20％
Talcum powder Extra large talcum powder company limited ends ??10％
Resins, epoxy Yueyang petrochemical industry company limited 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 under 450 rev/mins of conditions of screw speed.The product performance such as the table 2 that make:
Table 2 performance table
Figure G2009101937044D0000061
The material of embodiment 1 is made collision bumper, observe behind the spraying frame.With the collision bumper that common PP makes, 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 cross frame method rear surface is effective, 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 company limited ends ??20％
Ethylene-acrylate Elvaloy2112 AC DOW Chemical company limited ??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 International unit 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 company limited ??18％
Talcum powder Extra large talcum powder company limited 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 International unit 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％
??POE8137 DOW Chemical company limited ??20％
Talcum powder Extra large talcum powder company limited ends ??10％
??TPU Bayer chemical company ??3％
Oxidation inhibitor: Iranox1010 Vapour crust fine chemistry Industrial Co., Ltd ??0.25％
Oxidation inhibitor: Irganox168 Vapour crust fine chemistry Industrial Co., Ltd ??0.25％
Component Manufacturer Weight percentage
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 International unit 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 company limited ??76％
??POE?8137 DOW Chemical company limited ??3％
Resins, epoxy Yueyang petrochemical industry company limited of Ba Ling Huaxing ??10％
Polyetheramine BASF chemistry company limited ??10％
Oxidation inhibitor: Irganox1010 Vapour crust fine chemistry Industrial Co., Ltd ??0.25％
Component Manufacturer Weight percentage
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 International unit 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％
??POE8137 DOW Chemical company limited ??18％
Talcum powder Extra large talcum powder company limited ends ??10％
Resins, epoxy Yueyang petrochemical industry company limited of Ba Ling Huaxing ??10％
Component Manufacturer Weight percentage
Polyetheramine BASF chemistry company limited ??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 example 1.The properties of sample such as the table 12 that make:
Table 12 performance table
Performance Testing standard Test condition International unit 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 (9)

1. high-polarity polypropylene material is characterized in that being made up of the component of following weight percentage:
Polypropylene 50～70%
Toughner 14～20%
Polar additive 5～15%
Mineral filler 0～30%
Antiaging agent 0.2～3%
Tinting material 0～0.5%.
2. high-polarity polypropylene material according to claim 1 is characterized in that: described polypropylene is a Co-polypropylene, and it melts to refer to be 5～60g/min.
3. 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-butadiene-styrene copolymer.
4. high-polarity polypropylene material according to claim 1 is characterized in that: described polar additive is one or more mixing in TPU(Thermoplastic polyurethanes), maleic anhydride inoculated polypropylene, Resins, epoxy, ethylene-acrylate, ethylene vinyl acetate, polyetheramine, the polybutene polyvalent alcohol.
5. 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 barium sulfate.
6. high-polarity polypropylene material according to claim 1 is characterized in that: described antiaging agent is one or more mixing in suffocated amine antioxidant, Hinered phenols antioxidant, phosphite, metal passivator, benzophenone and the benzotriazole light stabilizer.
7. the application of the described high-polarity polypropylene material of claim 1 in preparation automobile exterior spare or automotive upholstery.
8. application as claimed in claim 7 is characterized in that described automobile exterior spare is collision bumper or rubbing strip.
9. application as claimed in claim 7 is characterized in that described automotive upholstery is parts around glove box, dashboard, door-plate, column, back board putting things or the seat.
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