CN104592645A - Low-density low-shrinkage high-impact polypropylene composite material and preparation method thereof - Google Patents
Low-density low-shrinkage high-impact polypropylene composite material and preparation method thereof Download PDFInfo
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- CN104592645A CN104592645A CN201410829067.6A CN201410829067A CN104592645A CN 104592645 A CN104592645 A CN 104592645A CN 201410829067 A CN201410829067 A CN 201410829067A CN 104592645 A CN104592645 A CN 104592645A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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Abstract
The invention discloses a low-density low-shrinkage high-impact polypropylene composite material and a preparation method thereof. The polypropylene composite material comprises the following raw materials in percentage by weight: 69%-85% of polypropylene, 5%-15% of high-property inorganic fillers, 10%-20% of elastomer toughening agents, 0.1%-2% of stabilizers and 0%-5% of other additives. The low-density low-shrinkage high-impact polypropylene composite material and the preparation method thereof have the advantages that 1, the polypropylene composite material with lower density and preferable toughness is obtained through the synergistic effect of the high-property inorganic fillers, the elastomer toughening agents and co-polypropylene; 2, in addition, the low-density high-impact polypropylene composite material with preferable comprehensive property is obtained through a process method in which the high-property inorganic fillers are added from a side feed opening.
Description
Technical field
The present invention relates to a kind of polypropylene composite material, be specially a kind of polypropylene composite material with low density, lower shrinkage, high-impact, with and preparation method thereof; Belong to polymer modification and manufacture field.
Background technology
Along with increasingly serious energy problem, Ge great automobile main frame maker is all carrying out the light-weighted trial of car load in recent years.For the raw material of plastic items, the density accounting for the pp material of larger proportion reduces, and effectively can alleviate the weight of product, thus makes a contribution for car load lightweight.In recent ten years, the research of target is turned to and related ends emerges in an endless stream with light weight, a lot of automobile factory or starting material producer have all carried out comparatively deep research to low density material, by high-performance superfine or the special process such as nano level is mineral-filled, microporous foam and the approach such as fiber-like is filling-modified, all make some progress in low density lightweighting materials field.
But for automobile component injection moulding producer, especially the large parts such as dashboard, door-plate, collision bumper, although low density lightweighting materials has obvious effect to car load loss of weight, the Design and manufacture for injection mold is had higher requirement.This is because low density material mostly with partial sacrifice rigidity or toughness for cost, concerning structural or functional details, more support or strengthening property structure must be increased in die design, the service requirements of the low density material of lower rigidity or toughness could be met.Even more serious problem is, because the shrinking percentage of polypropylene material self is larger, the low filling of low density will cause even more serious contraction, this just requires to use the mold shrinkage that compared with normal material is larger during die design, mean if car load lightweight will be done, must redesign the mould manufacturing all large-scale plastics articles, this is obviously unpractical for main engine plants and component factory.Therefore, the batch application of lightweighting materials on automobile is for many years very few.
In order to solve the problem, the present invention is by the synergy of research high-performance inorganic mineral, co-polypropylene and rubber elastomer, and by side feeding complete processing, obtain the polypropylene composite material of low density, lower shrinkage, high-impact, product alleviates except density, outside rigidity is not lost substantially, toughness improves, also has the shrinking percentage identical with orthodox material, the injection moulding of exterior trim component in Main Auto can be directly applied to easily, reach the effect of car load loss of weight.
Summary of the invention
The object of the invention is to develop a kind of low density, lower shrinkage, high impact resistance polypropylene composite material, for automobile or the common injection moulding component of household electric appliances.
Another object of the present invention is the preparation method in order to provide this polypropylene composite material.Object of the present invention can be achieved through the following technical solutions:
A kind of low density, lower shrinkage, high impact resistance polypropylene composite material, be made up of the raw material of following weight percents:
Wherein,
Described polypropylene is that under 230 DEG C × 2.16kg test condition, melt flow rate (MFR) is the co-polypropylene of 3-70g/10min, and wherein the comonomer of co-polypropylene is ethene, and its content is 4-10mol%.
Described high-performance inorganic filler is one or more the composition in talcum powder and mica, the talcum powder of preferred median size 0.5-2.5 μm.
Described elastic body toughening agent is one or more the composition in polybutadiene rubber, Ethylene-Propylene-Diene rubber (EPDM), ethylene-octene copolymer and ethylene-butene copolymer etc., optimal ethylene-butylene copolymer elastomerics, under 230 DEG C × 2.16kg test condition, melt flow rate (MFR) is 0.5-10g/10min.
Described stablizer is that those skilled in the art think required primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is hindered phenol or sulphur ester antioxidant, and auxiliary antioxidant is phosphorite kind antioxidant.
Other additive described comprises one or more the composition in tinting material, nucleator, whipping agent, tensio-active agent, softening agent, coupling agent, fire retardant, photostabilizer, processing aid, antistatic auxiliary, antimicrobial auxiliary agent and the lubricant that those skilled in the art think required.
The preparation method of above-mentioned low density, lower shrinkage, high impact resistance polypropylene composite material, its step is as follows:
1) raw material is taken by weight ratio;
2) by step 1) raw material is placed in super mixer and is dry mixed 3-15 minute, adds in twin screw extruder, cooling granulation after melt extruding by mixed raw material; Wherein in barrel, temperature is: a district 190-200 DEG C, two district 190-210 DEG C, three district 190-210 DEG C, four district 190-210 DEG C, head 190-220 DEG C, and twin screw extruder rotating speed is 100-1000 rev/min.
Another kind of preferred preparation method is: take raw material by weight ratio; Polypropylene, elastic body toughening agent, stablizer and other auxiliary agent are dry mixed in super mixer 3-15 minute obtained mixture A, mixture A is added twin screw extruder from the main spout of screw rod tail, high-performance inorganic filler adds twin screw extruder from screw rod medial side to spout, cooling granulation after melt extruding; Wherein in barrel, temperature is: a district 190-200 DEG C, two district 190-210 DEG C, three district 190-210 DEG C, four district 190-210 DEG C, head 190-220 DEG C, and twin screw extruder rotating speed is 100-1000 rev/min.
Advantage of the present invention is:
1, by the synergy of high-performance inorganic filler, elastic body toughening agent and co-polypropylene, obtain that density is lower, the better polypropylene composite material of toughness.
2, the processing method by being added from side spout by high-performance inorganic filler, obtains the better low density of over-all properties, high impact resistance polypropylene composite material.
3, by synergy and the side feeding production technique of each component, the low density of gained, High-impact Polypropylene have the low-shrinkage suitable with orthodox material and mechanical property, carry out material loss of weight under the prerequisite that can not make any adjustments in plastic paste mold shrinkage and structure, provide the lightweight approach comparatively easily realized to plastic paste.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.Scope of the present invention is not by the restriction of these embodiments, and scope of the present invention proposes in detail in the claims.
In the composite-material formula of embodiment and comparative example, polypropylene used is the block copolymerization propylene of melt flow rate (MFR) (230 DEG C × 2.16kg) 20-50/10min, wherein the comonomer of block copolymerization propylene is ethene, and its content is within the scope of 4-10mol%.
High-performance inorganic filler used is the superfine talcum powder of median size 0.5-2.5 μm.
Elastomerics used is the ethylene-butene copolymer 7487 of DOW company.
Stablizer used be the Negonox DSTP (chemical name be thio-2 acid stearic alcohol ester) of ICE company of Britain, BASF AG Irganox 1010 (chemical name is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester) and the Igrafos168 (chemical name is tricresyl phosphite (2,4-di-tert-butyl) ester) of BASF AG.
Embodiment 1
Take polypropylene 84.5% by weight percentage, high-performance inorganic filler 5%, elastomerics 10%, Irganox1010 be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, 5 minutes are dry mixed in super mixer, add in twin screw extruder again and melt extrude granulation, wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 2
Take polypropylene 79.5% by weight percentage, high-performance inorganic filler 10%, elastomerics 10%, Irganox1010 be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, 5 minutes are dry mixed in super mixer, add in twin screw extruder again and melt extrude granulation, wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 3
Take polypropylene 74.5% by weight percentage, high-performance inorganic filler 10%, elastomerics 15%, Irganox1010 be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, 5 minutes are dry mixed in super mixer, add in twin screw extruder again and melt extrude granulation, wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 4
Take polypropylene 69.5% by weight percentage, high-performance inorganic filler 10%, elastomerics 20%, Irganox1010 be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, 5 minutes are dry mixed in super mixer, add in twin screw extruder again and melt extrude granulation, wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 5
Take polypropylene 74.5% by weight percentage, high-performance inorganic filler 15%, elastomerics 10%, Irganox1010 be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, 5 minutes are dry mixed in super mixer, add in twin screw extruder again and melt extrude granulation, wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Embodiment 6
Take polypropylene 74.5% by weight percentage, elastomerics 15%, Irganox 1010 be 0.1%, Igrafos168 is 0.1%, Negonox DSTP is 0.3%, in super mixer, be dry mixed 5 minutes, obtained mixture A; Mixture A to be added in twin screw extruder to spout by screw rod medial side respectively by the main spout of screw rod tail, high-performance inorganic filler 10% and melt extrudes granulation; Wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, and head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Comparative example
Take polypropylene 69.5% by weight percentage, high-performance inorganic filler 20%, elastomerics 10%, Irganox1010 be 0.1%, Igrafos 168 is 0.1%, Negonox DSTP is 0.3%, 5 minutes are dry mixed in super mixer, add in twin screw extruder again and melt extrude granulation, wherein in barrel, temperature is: 200 DEG C, a district, two 210 DEG C, districts, three 210 DEG C, districts, four 210 DEG C, districts, head 220 DEG C, twin screw extruder rotating speed is 400 revs/min.Particle injection molding sample preparation on injection moulding machine after drying.
Performance evaluation mode:
Sample rate test is undertaken by ISO1183-1 standard; Bending property test is undertaken by ISO178 standard, and specimen size is 80 × 10 × 4mm, span 64mm, rate of bending 2mm/min; Charpy Impact performance test is undertaken by ISO179-1 standard, and specimen size is 80 × 10 × 4mm, and notch depth is 1/3rd of sample thickness; The test of material contracts rate is undertaken by the smooth plates being of a size of 150 × 100 × 3mm, places 48 hours after injection moulding under fixed temperature and humidity condition, measures flow direction model length (150mm side), and according to dimensional change shrinkage from mold dimensions.
Each embodiment and comparative example formula and the performance test results are shown in following each table:
Table 1 embodiment 1-6 and comparative example material prescription (% by weight)
Table 2 embodiment 1-6 and comparative example the performance test results
Embodiment 1,2,5 can be found out with comparing of comparative example, and along with the increase of extra fine talc powder content, the rigidity of material increases gradually, and toughness slightly declines, and shrinking percentage is downtrending substantially linearly.Embodiment 2-4 contrast can be found out, along with the increase of elastomer content, rigidity of material obviously declines, and toughness significantly improves, and shrinking percentage is downtrending linearly.Embodiment 5,6 relatively can be found out, by the technology mode that inorganic powder side feeding adds, can obtain the better material of over-all properties, and shrinking percentage also has a little decline simultaneously.All embodiments compare with comparative example respectively can be found out, embodiment 1,4 rigidity is too poor, embodiment 2 shrinking percentage is bigger than normal, embodiment 5 loss of weight ratio is not obvious, and embodiment 3 is comparatively close to comparative example performance, but rigidity and shrinking percentage still have certain difference, and the material property of embodiment 6 and comparative example are the most close, toughness is also significantly improved, and under the prerequisite that shrinking percentage is constant, material can loss of weight 7.5%, and the overall evaluation is optimum.
Claims (10)
1. low density, lower shrinkage, a high impact resistance polypropylene composite material, is characterized in that: be made up of the raw material of following weight percents:
2. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, it is characterized in that: described polypropylene is that under 230 DEG C × 2.16kg test condition, melt flow rate (MFR) is the co-polypropylene of 3-70g/10min, wherein the comonomer of co-polypropylene is ethene, and its content is 4-10mol%.
3. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, is characterized in that: described high-performance inorganic filler is one or more the composition in talcum powder and mica.
4. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, is characterized in that: described high-performance inorganic filler is the talcum powder of median size 0.5-2.5 μm.
5. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, is characterized in that: described elastic body toughening agent is one or more the composition in polybutadiene rubber, Ethylene-Propylene-Diene rubber (EPDM), ethylene-octene copolymer and ethylene-butene copolymer.
6. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, it is characterized in that: described elastic body toughening agent is ethylene-butene copolymer elastomerics, under 230 DEG C × 2.16kg test condition, melt flow rate (MFR) is 0.5-10g/10min.
7. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, it is characterized in that: described stablizer is that those skilled in the art think required primary antioxidant and auxiliary antioxidant, wherein primary antioxidant is hindered phenol or sulphur ester antioxidant, and auxiliary antioxidant is phosphorite kind antioxidant.
8. low density according to claim 1, lower shrinkage, high impact resistance polypropylene composite material, is characterized in that: other additive described comprises one or more the composition in tinting material, nucleator, whipping agent, tensio-active agent, softening agent, coupling agent, fire retardant, photostabilizer, processing aid, antistatic auxiliary, antimicrobial auxiliary agent and the lubricant that those skilled in the art think required.
9., according to the preparation method of one of any described low density of claim 1-8, lower shrinkage, high impact resistance polypropylene composite material, it is characterized in that: its step is as follows:
1) raw material is taken by weight ratio;
2) by step 1) raw material is placed in super mixer and is dry mixed 3-15 minute, adds in twin screw extruder, cooling granulation after melt extruding by mixed raw material; Wherein in barrel, temperature is: a district 190-200 DEG C, two district 190-210 DEG C, three district 190-210 DEG C, four district 190-210 DEG C, head 190-220 DEG C, and twin screw extruder rotating speed is 100-1000 rev/min.
10., according to the preparation method of one of any described low density of claim 1-8, lower shrinkage, high impact resistance polypropylene composite material, it is characterized in that:
1) raw material is taken by weight ratio;
2) polypropylene, elastic body toughening agent, stablizer and other auxiliary agent are dry mixed 3-15 minute obtained mixture A in super mixer, mixture A is added twin screw extruder from the main spout of screw rod tail, high-performance inorganic filler adds twin screw extruder from screw rod medial side to spout, cooling granulation after melt extruding; Wherein in barrel, temperature is: a district 190-200 DEG C, two district 190-210 DEG C, three district 190-210 DEG C, four district 190-210 DEG C, head 190-220 DEG C, and twin screw extruder rotating speed is 100-1000 rev/min.
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| CN105199218A (en) * | 2015-09-16 | 2015-12-30 | 深圳市西甫新材料股份有限公司 | High-tenacity low-contraction-rate inflaming retarding V2-stage polypropylene material and preparation method thereof |
| CN105254998A (en) * | 2015-10-12 | 2016-01-20 | 苏州亿馨源光电科技有限公司 | Low-voltage apparatus plastic material and preparation method thereof |
| CN105385088A (en) * | 2015-11-02 | 2016-03-09 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
| CN105524354A (en) * | 2015-12-30 | 2016-04-27 | 宁波科普特新材料有限公司 | A low-shrinkage low-specific-gravity PP material and a preparing method thereof |
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Application publication date: 20150506 |