CN106147034B - A kind of PP composite material and its preparation method and application of low linear expansion coefficient - Google Patents
A kind of PP composite material and its preparation method and application of low linear expansion coefficient Download PDFInfo
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a kind of PP composite materials and its preparation method and application of low linear expansion coefficient, the composite material is made of the raw material of following weight percentage: polypropylene 50%-70%, thermoplastic elastomer (TPE) 1%-20%, talcum powder 0%-30%, phlogopite powder 5%-30%, composite optothermal stabilizer 0.5%-5%, targeted nano synergistic function masterbatch 0.5%-3%, colorant 0-5%.The PP composite material of the low linear expansion coefficient of the present invention has excellent dimensional stability, it is prepared using double screw extruder, double screw extruder is divided into ten active sections by feed zone to head, it can be used for preparing automobile interior exterior decorations product, be particularly applicable to the isometric product of superior automobile bumper, door sill protector, vent flap.
Description
Technical field
The present invention relates to PP composite material technical fields, and in particular to a kind of polypropylene of low linear expansion coefficient is multiple
Condensation material and its preparation method and application.
Background technique
Polypropylene is a kind of general-purpose thermoplastic plastic of high comprehensive performance, have cheap, light weight, solvent resistant,
The features such as easily recycling, is nontoxic, is most important car light material, it can reduce the quality of auto parts and components about 40%,
It is widely applied on automotive upholstery, such as instrument board, door-plate, column, bumper.But polypropylene also has easy warpage, rear receipts
The disadvantages of shrinkage is big, linear expansion coefficient is high, and low-temperature flexibility is poor, therefore its application on the big product of automobile is affected, such as protect
Dangerous thick stick, door sill protector, grid, door-plate etc. require product good stability of the dimension, and post-shrinkage ratio is small, and linear expansion coefficient is low.
Currently, the linear expansion coefficient of material mainly is greatly lowered by the way that the methods of glass fibre, talcum powder is added
And shrinking percentage, but glass fibre modified polypropene will lead to product and be easy warpage, and talcum powder modified polypropene reduces material
Shrinking percentage and linear expansion coefficient effect are not apparent.Also having through elastomer, whisker reduces material shrinkage and linear
The coefficient of expansion, but the cost of elasticity of import body and whisker is very high.
Application publication number is that the Chinese invention patent application of CN 101759934A (application No. is 200810207579.3) is public
A kind of high flowing of cloth, high tenacity, low-shrinkage filling modified polypropylene material, the raw material based on following weight percent are prepared
At: polypropylene 45~80%, polyethylene powder 5~18%, inorganic filler 8~25%, calcium salt whisker 5~12%, antioxidant
0.1~1%, other auxiliary agents 0~2%.The technical solution improves mineral dispersibility by polyethylene powder, passes through calcium salt whisker
Be filled up to reduce shrinking percentage and improve material property method, but the polypropylene composite there are shrinking percentage reduce it is limited and
The problems such as low temperature impact properties are not high.
The Chinese invention patent application of application publication number CN 105273301A (application No. is 201410251238.1) is announced
A kind of low-shrinkage PP composite material and preparation method thereof, which is made of the raw material of following mass fraction: 59.5-
89.95 parts of acrylic resin, 10~35 parts of metallocene linear-low density polyethylene, 1~5 part of toughener, 0.05~0.5
The talcum powder of part.The technical solution is mainly to pass through the mixing of metallocene linear-low density polyethylene, toughener and talcum powder
Object and the polypropylene blending modified of low-shrinkage are made, and PP composite material shrinking percentage obtained by the technical solution is lower,
But poor rigidity, bending modulus are low, it is difficult to the product for having certain rigidity is required on automobile.
Summary of the invention
The present invention provides a kind of PP composite materials and its preparation method and application of low linear expansion coefficient, this is multiple
Condensation material has excellent dimensional stability, can be used for preparing automobile interior exterior decorations product, is particularly applicable to superior automobile insurance
The isometric product of thick stick, door sill protector, vent flap.
A kind of PP composite material of low linear expansion coefficient, is made of the raw material of following weight percentage:
In the present invention, the phlogopite by using high radius-thickness ratio, tabular morphology is powder filled modified, so that phlogopite powder is poly-
Generation orientation effect in allyl resin matrix, so that PP composite material has excellent dimensional stability, higher curved
Bent modulus, lower thermal linear expansion coefficient and lower warpage, it is obvious by the way that targeted nano synergistic function masterbatch is added
Dispersibility of the phlogopite powder in composite system is improved, and then improves the mechanical property of PP composite material,
Reduce the linear expansion coefficient and shrinking percentage of PP composite material.The present invention passes through the compounding of specific combination content, especially
It is talcum powder, targeted nano synergistic function masterbatch and the mutual collective effect of phlogopite powder, can be effectively reduced polypropylene
The linear expansion coefficient and shrinking percentage of composite material, and guarantee the mechanical property of its excellent PP composite material.
Further preferably, the PP composite material of the low linear expansion coefficient, by following weight percentage
Raw material is made:
The polypropylene is copolymer polypropylene, and further preferably, which is that Propylene-ethylene block copolymerization is poly-
Propylene, wherein acrylic molar content is 80%~90%, and vinyl molar content is 10%~20%.It is this kind of
The Propylene-ethylene block copolymer polypropylene of high-vinyl-content has good impact property at normal temperature, can further improve
The impact property of polypropylene modified material.The melt flow rate (MFR) of the copolymer polypropylene is under the conditions of 230 DEG C × 2.16kg
For 10g/10min~100g/10min, further preferably 15g/10min~60g/10min.
The glass transition temperature of the thermoplastic elastomer (TPE) is lower than -50 DEG C.It is low by selection glass transition temperature
Such elastomer, the low temperature impact properties of copolymer polypropylene modified material can be improved.The melt of the thermoplastic elastomer (TPE)
Flow rate is generally 0.3g/10min~20g/10min under the conditions of 190 DEG C × 2.16kg, and density is generally 0.855g/cm3
~0.871g/cm3, bending modulus is generally 5MPa~12MPa.
The partial size of the talcum powder is 10 microns~50 microns, wherein SiO2Weight percentage is greater than 60%, preferably
60%~99%.High mesh number talc powder filled polypropylene improves the crystallinity of material, in addition, selection SiO2Weight percent contains
Talcum powder of the amount higher than 60% can further enhance the rigidity of polypropylene material.The weight percentage of the talcum powder is
10%-20%.
The phlogopite powder is preferably silane coupler modified phlogopite powder, has high radius-thickness ratio (50- to be a kind of
120) mineral, and the powder of silane coupling agent processing is passed through on surface.The phlogopite powder is a kind of sheet knot of high radius-thickness ratio
Structure silicate mineral can generate orientation effect in PP matrix, so that PP composite material has excellent ruler
Very little stability, high bending modulus, lower thermal linear expansion coefficient (CLTE) and lower warpage.
The composite optothermal stabilizer is selected from one of thermal oxidation stabilizer commonly used in the art, light stabilizer or two
Kind.Phenolic antioxidant (such as: the Irganox1010 of Switzerland's Ciba production), phosphorous acid can be selected in the thermal oxidation stabilizer
One or both of ester auxiliary antioxidant (such as: the Irganox168 of Switzerland's Ciba production).The light stabilizer can
Select hindered amine light stabilizer (such as: the Tinuvin770 and Chimassorb944 of Switzerland's Ciba production).Thermal oxidation stability
Commercial product can be selected in agent, light stabilizer.Polyacrylic weatherability is poor, degradable, for efficent use of resources, extends and gathers
The propylene service life, addition composite thermal stabilizer be it is necessary, this composite optothermal stabilizer can prevent from expecting drop in process of production
Solution, while heat resistance, light resistance and the discolouration of product in use are improved, and can effectively meet automobile decoration piece material
Weather resistance.
The targeted nano synergistic function masterbatch main component be using polypropylene or polyethylene as the organic matter of carrier at
Core agent and lubricant.I.e. the targeted nano synergistic function masterbatch, which is negative, is loaded with the polypropylene of organic matter nucleating agent and lubricant
Or polyethylene master batch.The modified targeted nano synergistic function masterbatch of PP produced such as Beijing new material Science and Technology Ltd. of Turner section
Nanopec M2005 is negative and is loaded with the polypropylene agglomerate of organic matter nucleating agent and lubricant.The masterbatch is applied to Pp System
In, molecule lubrication can be played the role of and be nucleated with molecule, to effectively eliminate intermolecular cohesion, realize crystalling propylene shape
State recombination, improves the dispersibility and compatibility of the fillings enhancings and acrylic resin such as mineral, to improve the property of polypropylene product
Energy.
The colorant is preferably 0.2%-2%, for improving the color of material.The colorant can be as needed
Select colorant generally in the art.
The preparation method of the PP composite material of the low linear expansion coefficient, using double screw extruder, double spiral shells
Bar extruder is divided into ten active sections by feed zone to head, comprising the following steps:
(1) polypropylene, composite optothermal stabilizer, thermoplastic elastomer (TPE) and the selectively colorant that adds, mixing is equal
It is even, mixed material A is obtained, is added from the feed opening of the first active section；
By talcum powder and targeted nano synergistic function masterbatch, it is uniformly mixed, mixed material B is obtained, by the 5th active section
Feed opening is added；
By phlogopite powder and targeted nano synergistic function masterbatch, it is uniformly mixed, mixed material C is obtained, by the 7th active section
Feed opening be added；
(2) poly- the third of low linear expansion coefficient is obtained through cooling, drying, pelletizing through melting extrusion in double screw extruder
Alkene composite material.
Wherein, double screw extruder by feed zone to head temperature successively are as follows: 190 DEG C -200 DEG C, 200 DEG C -220 DEG C,
210℃-230℃、220℃-230℃、220℃-230℃、220℃-230℃、220℃-230℃、220℃-230℃、220
DEG C -230 DEG C, 220 DEG C -230 DEG C, the temperature of die head are 220 DEG C -240 DEG C (preferably 230 DEG C).
The double screw extruder selects common apparatus commonly used in the art.
The PP composite material of the low linear expansion coefficient of the present invention has excellent dimensional stability, higher bending die
Amount, lower thermal linear expansion coefficient and lower warpage can be used for preparing automobile interior exterior decorations product, be particularly applicable to
The isometric product of superior automobile bumper, door sill protector, vent flap.
Compared with prior art, the invention has the advantages that
1, the present invention significantly improves phlogopite powder and is meeting material system by addition targeted nano synergistic function masterbatch
In dispersibility, and then improve the mechanical property of PP composite material, reduce the linear swollen of PP composite material
Swollen coefficient and shrinking percentage.2, the phlogopite by using high radius-thickness ratio, tabular morphology is powder filled modified, so that phlogopite powder is poly-
Generation orientation effect in allyl resin matrix, so that PP composite material has excellent dimensional stability, higher curved
Bent modulus, lower thermal linear expansion coefficient and lower warpage.3, by the method for lateral feeding, phlogopite powder is added
Enter into extruder, excessive screw rod shearing is avoided to compromise the laminar structured of phlogopite powder, side feed material adds so that golden cloud
Female powder maintains original high thickness to diameter ratio characteristic, such competence exertion advantage of phlogopite powder, to improve composite material
Performance and reduction linear expansion coefficient.
The polypropylene that can show low linear expansion coefficient has been made using specific raw material, mineral, auxiliary agent in the present invention
Material, good stability of the dimension can be applied to the isometric product of superior automobile bumper, door sill protector, vent flap, can substitute completely
Imported material is automotive material production domesticization development trend, wide market.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of ten active sections in double screw extruder in the present invention.
Specific embodiment
Examples 1 to 4 and comparative example 1~2
Double screw extruder is divided into ten active sections, the first active section 1, the second active section 2, by feed zone to head
Three active sections 3, the 4th active section 4, the 5th active section 5, the 6th active section 6, the 7th active section 7, the 8th active section 8, the 9th work
Make section 9, the tenth active section 10.
By polypropylene, composite optothermal stabilizer, thermoplastic elastomer (TPE) and the selectively colorant component added by table 1
The proportion of parts by weight is uniformly mixed in batch mixer, obtains mixed material A, is added by the feed opening of the first active section 1.By talcum
Powder and targeted nano synergistic function masterbatch are uniformly mixed in batch mixer by the proportion of parts by weight in table 1, obtain mixed material B,
It is added by the feed opening of the 5th active section 5.Phlogopite powder and targeted nano synergistic function masterbatch are pressed to the proportion of parts by weight in table 1
It is uniformly mixed in batch mixer, obtains mixed material C, be added by the feed opening of the 7th active section 7.
Double screw extruder by feed zone to head temperature successively are as follows: 190 DEG C -200 DEG C, 200 DEG C -220 DEG C, 10 DEG C -
230℃、220℃-230℃、220℃-230℃、220℃-230℃、220℃-230℃、220℃-230℃、220℃-230
DEG C, 220 DEG C -230 DEG C, the temperature of die head is 230 DEG C.
By twin-screw high speed (screw speed 800r/min) shearing, be kneaded, by head extrusion, tie rod, it is air-cooled, cut
Grain, dry and packaging, are made polypropylene modified material finished product.
Table 1
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Copolymer polypropylene 1 | 40Kg | 40Kg | 40Kg | 40Kg | 40Kg | 40Kg |
| Copolymer polypropylene 2 | 21Kg | 21Kg | 21.8Kg | 21Kg | 22.3Kg | 22.3Kg |
| Elastomer POE8842 | 8Kg | 8Kg | 8Kg | 8Kg | 8Kg | 8Kg |
| Elastomer POE8180 | 8Kg | 8Kg | 8Kg | 8Kg | 8Kg | 8Kg |
| Phlogopite powder | 0 | 10Kg | 20Kg | 20Kg | 0 | 20Kg |
| Talcum powder | 20Kg | 10Kg | 0 | 0 | 20Kg | 0 |
| Targeted nano synergistic function masterbatch | 1.3Kg | 1.3Kg | 0.5Kg | 1.3Kg | 0 | 0 |
| Irganox1010 | 0.2Kg | 0.2Kg | 0.2Kg | 0.2Kg | 0.2Kg | 0.2Kg |
| Irganox168 | 0.3Kg | 0.3Kg | 0.3Kg | 0.3Kg | 0.3Kg | 0.3Kg |
| Tinuvin770 | 0.1Kg | 0.1Kg | 0.1Kg | 0.1Kg | 0.1Kg | 0.1Kg |
| Chimassorb944 | 0.1Kg | 0.1Kg | 0.1Kg | 0.1Kg | 0.1Kg | 0.1Kg |
| Black masterbatch | 1.0Kg | 1.0Kg | 1.0Kg | 1.0Kg | 1.0Kg | 1.0Kg |
Raw material sources used in Examples 1 to 4 and comparative example 1~2 and main performance index such as table 2:
Table 2
Performance test
By polypropylene modified material pellet made from above-described embodiment 1~4 and comparative example 1~2 by injection moulding mechanism
For at test bars.Linear expansion coefficient is carried out by ISO 11359-2；Notch impact strength, by ISO179, using I type sample
It carries out；Density is carried out by ISO 1183；Bending modulus, by ISO 178, using standard sample, i.e. 80mm × 10mm × 4mm into
Row；Tensile strength is carried out by ISO 527-2, is carried out using I type sample；Shrinking percentage is judged by size of sample variation, is tried
Sample ruler cun 200*150*3mm.It is tested for the property, the results are shown in Table 3:
Table 3
Embodiment 1 can be used as comparative example 3, relative to comparative example 1~3, embodiment 2~4 adds due to not adding talcum powder
Phlogopite powder and targeted nano synergistic function masterbatch are entered, the linear expansion coefficient (- 30 DEG C~80 DEG C) of embodiment 2~4 wants bright
It is aobvious to be lower than comparative example 1~3, there is lower thermal linear expansion coefficient, while shrinking percentage is also significantly lower than comparative example 1~3, explanation
2~4 good stability of the dimension of embodiment, in addition, mechanical property is also more excellent, it is seen then that in the present invention, phlogopite powder and targeting are received
Rice synergistic function masterbatch can generate synergistic effect.
Claims (8)
1. a kind of PP composite material of low linear expansion coefficient, which is characterized in that by the raw material of following weight percentage
It is made:
It is 110 that the phlogopite powder, which is selected from Sweden's power mine mining industry radius-thickness ratio, the phlogopite powder handled by silane coupling agent；
The targeted nano synergistic function masterbatch is selected from the modified target of PP of new material Science and Technology Ltd. of Beijing Turner section production
To nano-synergistic functional master batch Nanopec M2005.
2. the PP composite material of low linear expansion coefficient according to claim 1, which is characterized in that described poly- third
Alkene is copolymer polypropylene, which is Propylene-ethylene block copolymer polypropylene, wherein acrylic molar content
It is 80%~90%, vinyl molar content is 10%~20%.
3. the PP composite material of low linear expansion coefficient according to claim 1, which is characterized in that the copolymerization
Polyacrylic melt flow rate (MFR) is 10g/10min~100g/10min under the conditions of 230 DEG C × 2.16kg.
4. the PP composite material of low linear expansion coefficient according to claim 1, which is characterized in that the thermoplastic
Property elastomer melt flow rate (MFR) under the conditions of 190 DEG C × 2.16kg be 0.3g/10min~20g/10min.
5. the PP composite material of low linear expansion coefficient according to claim 1, which is characterized in that the talcum
The partial size of powder is 10 microns~50 microns, wherein SiO2Weight percentage is 60%~99%.
6. the PP composite material of low linear expansion coefficient according to claim 1, which is characterized in that described is compound
Optothermal stabilizer is one or both of thermal oxidation stabilizer, light stabilizer.
7. the preparation method of the PP composite material of described in any item low linear expansion coefficients according to claim 1~6,
It is characterized in that, using double screw extruder, double screw extruder is divided into ten active sections by feed zone to head, including following
Step:
(1) it by polypropylene, composite optothermal stabilizer, thermoplastic elastomer (TPE) and the selective colorant that adds, is uniformly mixed, obtains
To mixed material A, it is added from the feed opening of the first active section；
By talcum powder and targeted nano synergistic function masterbatch, it is uniformly mixed, mixed material B is obtained, by the blanking of the 5th active section
Mouth is added；
By phlogopite powder and targeted nano synergistic function masterbatch, it is uniformly mixed, mixed material C is obtained, by under the 7th active section
Material mouth is added；
(2) through melting extrusion in double screw extruder, through cooling, drying, pelletizing, the polypropylene for obtaining low linear expansion coefficient is multiple
Condensation material.
8. the PP composite material of described in any item low linear expansion coefficients is being prepared in automobile according to claim 1~6
Application in exterior trim product.
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| CN107266769A (en) * | 2017-07-21 | 2017-10-20 | 安徽江淮汽车集团股份有限公司 | It is a kind of by mica powder be high temperature resistant agent polyolefin |
| CN110628131B (en) * | 2019-09-26 | 2021-10-15 | 金发科技股份有限公司 | Polypropylene composite material with low shrinkage and low linear expansion coefficient and preparation method thereof |
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