CN106147034A - A kind of PP composite material of low linear expansion coefficient and its preparation method and application - Google Patents
A kind of PP composite material of low linear expansion coefficient and its preparation method and application Download PDFInfo
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- 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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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
The invention discloses PP composite material of a kind of low linear expansion coefficient and its preparation method and application, this composite, is made up of the raw material of following weight percentage: polypropylene 50% 70%, thermoplastic elastomer (TPE) 1% 20%, Pulvis Talci 0% 30%, phlogopite powder 5% 30%, composite optothermal stabilizer 0.5% 5%, targeted nano synergistic function masterbatch 0.5% 3%, coloring agent 0 5%.The PP composite material of the low linear expansion coefficient of the present invention has the dimensional stability of excellence, prepared by employing double screw extruder, double screw extruder is divided into ten active sections by feed zone to head, can be used for preparing automobile interior exterior decorations product, be particularly applicable to superior automobile bumper, door sill protector, the isometric product of vent flap.
Description
Technical field
The present invention relates to PP composite material technical field, the polypropylene being specifically related to a kind of low linear expansion coefficient is multiple
Condensation material and its preparation method and application.
Background technology
Polypropylene is the general-purpose thermoplastic plastic of a kind of high comprehensive performance, have cheap, light weight, solvent resistant,
The feature such as easily reclaiming, nontoxic, be most important car light material, it can alleviate the quality of auto parts and components about 40%,
It is widely applied on automotive upholstery, such as instrument board, door-plate, column, bumper etc..But polypropylene also has easy warpage, receives afterwards
The shortcomings such as shrinkage is big, linear expansion coefficient is high, low-temperature flexibility difference, therefore have impact on its application on the big product of automobile, as protected
Danger thick stick, door sill protector, grid, door-plate etc. are desirable that product good stability of the dimension, and post-shrinkage ratio is little, and linear expansion coefficient is low.
At present, the linear expansion coefficient of material is mainly greatly lowered by adding the method such as glass fibre, Pulvis Talci
And shrinkage factor, but glass fibre modified polypropene can cause the easy warpage of product, and Pulvis Talci modified polypropene reduces material
Shrinkage factor and linear expansion coefficient effect are not clearly.Also have and reduce Material shrinkage rate and linear by elastomer, whisker
The coefficient of expansion, but the cost of elasticity of import body and whisker is the highest.
Application publication number is that the Chinese invention patent application of CN 101759934A (Application No. 200810207579.3) is public
Cloth a kind of high flowing, high tenacity, low-shrinkage filling modified polypropylene material, the preparation of raw material based on following percentage by weight
Become: 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%.This technical scheme improves mineral dispersibility by polyethylene powder, by calcium salt whisker
Be filled up to reduce shrinkage factor and improve material property way, but this polypropylene composite exist shrinkage factor reduce limited and
The problems such as low temperature impact properties is the highest.
The Chinese invention patent application of application publication number CN 105273301A (Application No. 201410251238.1) is announced
A kind of low-shrinkage PP composite material and preparation method thereof, this material is made up of the raw material of following mass fraction: 59.5-
The acrylic resin of 89.95 parts, the metallocene linear-low density polyethylene of 10～35 parts, the toughener of 1～5 part, 0.05～0.5
The Pulvis Talci of part.This technical scheme is mainly by metallocene linear-low density polyethylene, toughener and talcous mixing
Thing prepares with the polypropylene blending modified of low-shrinkage, and the PP composite material shrinkage factor obtained by this technical scheme is relatively low,
But poor rigidity, bending modulus is low, it is difficult to require the product having certain rigidity on automobile.
Summary of the invention
The invention provides PP composite material of a kind of low linear expansion coefficient and its preparation method and application, this is multiple
Condensation material has the dimensional stability of excellence, 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.
The PP composite material of a kind of low linear expansion coefficient, is made up of the raw material of following weight percentage:
In the present invention, the phlogopite by the high radius-thickness ratio of employing, 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 the dimensional stability, higher curved of excellence
Bent modulus, lower thermal linear expansion coefficient and lower warpage, obvious by adding targeted nano synergistic function masterbatch
Improve phlogopite powder dispersibility in composite system, and then improve the mechanical property of PP composite material,
Reduce linear expansion coefficient and the shrinkage factor of PP composite material.The present invention compounding by particular combination content, especially
It is the common effect each other of Pulvis Talci, targeted nano synergistic function masterbatch and phlogopite powder, it is possible to effectively reduce polypropylene
The linear expansion coefficient of composite and shrinkage factor, and ensure the mechanical property of the PP composite material of its excellence.
Further preferably, the PP composite material of described low linear expansion coefficient, by following weight percentage
Raw material is made:
Described polypropylene is COPP, and further preferably, this COPP is that Propylene-ethylene block copolymerization gathers
Propylene, wherein, acrylic molar content is 80%～90%, and vinyl molar content is 10%～20%.This kind of
The Propylene-ethylene block COPP of high-vinyl-content has good impact property at normal temperatures, can improve further
The impact property of polypropylene modified material.The melt flow rate (MFR) of described COPP is under the conditions of 230 DEG C × 2.16kg
For 10g/10min～100g/10min, more preferably 15g/10min～60g/10min.
The glass transition temperature of described thermoplastic elastomer (TPE) is less than-50 DEG C.By selecting glass transition temperature low
Such elastomer, the low temperature impact properties that COPP is material modified can be improved.The melt of described thermoplastic elastomer (TPE)
Flow rate is typically 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.
Described talcous particle diameter is 10 microns～50 microns, wherein SiO2Weight percentage is more than 60%, preferably
60%～99%.High mesh number talc powder filled polypropylene makes the degree of crystallinity of material improve, additionally, select SiO2Weight percent contains
The amount Pulvis Talci higher than 60% can further enhance the rigidity of polypropylene material.Described talcous weight percentage is
10%-20%.
Described phlogopite powder is preferably silane coupler modified phlogopite powder, has high radius-thickness ratio (50-for one
120) mineral, and the powder that surface processes through silane coupler.This phlogopite powder is the sheet knot of a kind of high radius-thickness ratio
Structure silicate mineral, can produce orientation effect in PP matrix so that PP composite material has the chi of excellence
Very little stability, high bending modulus, lower thermal linear expansion coefficient (CLTE) and lower warpage.
Described composite optothermal stabilizer one or two in thermal oxidation stabilizer commonly used in the art, light stabilizer
Kind.Described thermal oxidation stabilizer can be selected for phenolic antioxidant (such as: the Irganox1010 that Switzerland's Ciba produces), phosphorous acid
One or both in ester auxiliary antioxidant (such as: the Irganox168 that Switzerland Ciba produces).Described light stabilizer can
Select hindered amine light stabilizer (such as: Tinuvin770 and Chimassorb944 that Switzerland's Ciba produces).Thermal oxidation stability
Agent, light stabilizer all can be selected for commercially available prod.Polyacrylic weatherability is poor, degradable, for efficent use of resources, extends and gathers
In the propylene life-span, it is necessary for adding composite thermal stabilizer, and this composite optothermal stabilizer can prevent the fall expected in process of production
Solve, improve product thermostability, light resistance and discolouration in use simultaneously, and can effectively meet automobile decoration piece material
Weather resistance.
Described targeted nano synergistic function masterbatch is mainly composed of the Organic substance as carrier with polypropylene or polyethylene and becomes
Core agent and lubricant.I.e. described targeted nano synergistic function masterbatch is the polypropylene being loaded with Organic substance nucleator and lubricant
Or polyethylene master batch.The PP modification targeted nano synergistic function masterbatch produced such as Beijing new material Science and Technology Ltd. of Turner section
Nanopec M2005, for being loaded with the polypropylene agglomerate of Organic substance nucleator and lubricant.This masterbatch is applied to Pp System
In, the effect of molecule lubrication and molecule nucleation can be played, thus effectively eliminate intermolecular cohesion, it is achieved crystalling propylene shape
State is recombinated, and improves mineral etc. and fills the dispersibility and the compatibility strengthened with acrylic resin, thus improves the property of polypropylene product
Energy.
Described coloring agent is preferably 0.2%-2%, for improving the color of material.Described coloring agent can be as required
Select coloring agent generally in the art.
The preparation method of the PP composite material of described low linear expansion coefficient, uses double screw extruder, double spiral shells
Bar extruder is divided into ten active sections by feed zone to head, comprises the following steps:
(1) coloring agent polypropylene, composite optothermal stabilizer, thermoplastic elastomer (TPE) and selectivity added, mixing is all
Even, obtain mixed material A, add from the feed opening of the first active section；
By Pulvis Talci and targeted nano synergistic function masterbatch, mix homogeneously, obtain mixed material B, by the 5th active section
Feed opening adds；
By phlogopite powder and targeted nano synergistic function masterbatch, mix homogeneously, obtain mixed material C, by the 7th active section
Feed opening add；
(2) melt extrude in double screw extruder, cooled, dry, pelletizing, obtain poly-the third of low linear expansion coefficient
Alkene composite.
Wherein, double screw extruder is followed successively by by the temperature of feed zone to head: 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 is 220 DEG C-240 DEG C (preferably 230 DEG C).
Described 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 the dimensional stability of excellence, 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 have the advantage that
1, the present invention significantly improves phlogopite powder meeting material system by adding targeted nano synergistic function masterbatch
In dispersibility, and then improve the mechanical property of PP composite material, reduce the most swollen of PP composite material
Swollen coefficient and shrinkage factor.2, the phlogopite by the high radius-thickness ratio of employing, 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 the dimensional stability, higher curved of excellence
Bent modulus, lower thermal linear expansion coefficient and lower warpage.3, by the method for lateral feeding, phlogopite powder is added
Entering in extruder, it is to avoid undue screw rod shearing compromises the laminar structured of phlogopite powder, feeding interpolation in side makes Jin Yun
Female powder maintains original high thickness to diameter ratio characteristic, such competence exertion advantage of phlogopite powder, thus improves composite
Performance and reduction linear expansion coefficient.
The present invention uses specific raw material, mineral, auxiliary agent to prepare the polypropylene that can show low linear expansion coefficient
Material, good stability of the dimension, can be applicable to superior automobile bumper, door sill protector, the isometric product of vent flap, can substitute completely
Imported material, is automotive material production domesticization development trend, wide market.
Accompanying drawing explanation
Fig. 1 is the structural representation of ten active sections in double screw extruder in the present invention.
Detailed description of the invention
Embodiment 1～4 and comparative example 1～2
Double screw extruder is divided into ten active sections by feed zone to head, first active section the 1, second active section 2,
Three active section the 3, the 4th active section the 4, the 5th active section the 5, the 6th active section the 6, the 7th active section the 7, the 8th active section the 8, the 9th works
The section of work the 9, the tenth active section 10.
The coloring agent component that polypropylene, composite optothermal stabilizer, thermoplastic elastomer (TPE) and selectivity add is pressed in table 1
The proportioning of weight portion mix homogeneously in batch mixer, obtains mixed material A, the feed opening of the first active section 1 add.By Talcum
The proportioning of weight portion mix homogeneously in batch mixer in table 1 pressed by powder and targeted nano synergistic function masterbatch, obtains mixed material B,
Added by the feed opening of the 5th active section 5.Phlogopite powder and targeted nano synergistic function masterbatch are pressed the proportioning of weight portion in table 1
Mix homogeneously in batch mixer, obtains mixed material C, the feed opening of the 7th active section 7 add.
Double screw extruder is followed successively by by the temperature of feed zone to head: 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.
Shear through twin screw at a high speed (screw speed is 800r/min), mixing, by head extrusion, tie rod, air-cooled, cut
Grain, dry and packaging, prepare polypropylene modified material finished product.
Table 1
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| COPP 1 | 40Kg | 40Kg | 40Kg | 40Kg | 40Kg | 40Kg |
| COPP 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 |
| Pulvis Talci | 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 |
Embodiment 1～4 and comparative example 1～2 in raw material sources used and main performance index such as table 2:
Table 2
Performance test
By above-described embodiment 1～4 and the polypropylene modified material pellet for preparing of comparative example 1～2 by injection moulding mechanism
Standby one-tenth test bars.Linear expansion coefficient, is carried out by ISO 11359-2；Notch impact strength, by ISO179, uses I type sample
Carry out；Density, is carried out by ISO 1183；Bending modulus, by ISO 178, uses standard specimen, i.e. 80mm × 10mm × 4mm enters
OK；Hot strength, is carried out by ISO 527-2, uses I type sample to carry out；Shrinkage factor is passed judgment on by size of sample change, examination
Sample ruler cun 200*150*3mm.Carry out performance test, the results are shown in Table 3:
Table 3
Embodiment 1 owing to not adding Pulvis Talci, can as a comparison case 3, relative to comparative example 1～3, embodiment 2～4 all adds
Having entered phlogopite powder and targeted nano synergistic function masterbatch, the linear expansion coefficient (-30 DEG C～80 DEG C) of embodiment 2～4 is bright
Aobvious less than comparative example 1～3, there is lower thermal linear expansion coefficient, shrinkage factor is also significantly lower than comparative example 1～3, explanation simultaneously
Embodiment 2～4 good stability of the dimension, additionally, mechanical property is the most excellent, it is seen then that in the present invention, phlogopite powder and targeting are received
Rice synergistic function masterbatch can produce synergism.
Claims (10)
1. the PP composite material of a low linear expansion coefficient, it is characterised in that by the raw material of following weight percentage
Make:
The PP composite material of low linear expansion coefficient the most according to claim 1, it is characterised in that by following weight
The raw material of percentage composition is made:
The PP composite material of low linear expansion coefficient the most according to claim 1 and 2, it is characterised in that described
Polypropylene is COPP, and this COPP is Propylene-ethylene block COPP, wherein, and acrylic Mole percent
Content is 80%～90%, and vinyl molar content is 10%～20%.
The PP composite material of low linear expansion coefficient the most according to claim 1, it is characterised in that described copolymerization
Polyacrylic melt flow rate (MFR) is 10g/10min～100g/10min under the conditions of 230 DEG C × 2.16kg.
The PP composite material of low linear expansion coefficient the most according to claim 1, it is characterised in that described thermoplastic
The melt flow rate (MFR) of property elastomer is 0.3g/10min～20g/10min under the conditions of 190 DEG C × 2.16kg.
The PP composite material of low linear expansion coefficient the most according to claim 1, it is characterised in that described Talcum
The particle diameter of powder is 10 microns～50 microns, wherein SiO2Weight percentage is 60%～99%.
The PP composite material of low linear expansion coefficient the most according to claim 1, it is characterised in that described golden cloud
Female powder is silane coupler modified phlogopite powder, and high radius-thickness ratio is 50-120.
The PP composite material of low linear expansion coefficient the most according to claim 1, it is characterised in that described is compound
Optothermal stabilizer is one or both in thermal oxidation stabilizer, light stabilizer.
9. according to the preparation method of the PP composite material of the low linear expansion coefficient described in any one of claim 1～8, its
Being characterised by, using double screw extruder, double screw extruder is divided into ten active sections by feed zone to head, including following
Step:
(1) coloring agent that polypropylene, composite optothermal stabilizer, thermoplastic elastomer (TPE) and selectivity are added, mix homogeneously,
To mixed material A, add from the feed opening of the first active section；
By Pulvis Talci and targeted nano synergistic function masterbatch, mix homogeneously, obtain mixed material B, by the blanking of the 5th active section
Mouth adds；
By phlogopite powder and targeted nano synergistic function masterbatch, mix homogeneously, obtain mixed material C, by under the 7th active section
Material mouth adds；
(2) melt extruding in double screw extruder, cooled, dry, pelletizing, the polypropylene obtaining low linear expansion coefficient is multiple
Condensation material.
10. according to the PP composite material of the low linear expansion coefficient described in any one of claim 1～8 within preparing automobile
Application in exterior trim product.
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| CN109486025A (en) * | 2018-10-24 | 2019-03-19 | 金发科技股份有限公司 | A kind of polypropene composition and preparation method thereof |
| CN111117060A (en) * | 2019-12-13 | 2020-05-08 | 中广核俊尔(浙江)新材料有限公司 | Continuous basalt fiber reinforced polypropylene composite material, preparation method and application |
| CN111371059A (en) * | 2020-03-23 | 2020-07-03 | 长安大学 | L-shaped composite cable groove component and preparation method thereof |
| WO2021057355A1 (en) * | 2019-09-26 | 2021-04-01 | 金发科技股份有限公司 | Polypropylene composite material with low shrinkage and low linear expansion coefficient, and preparation method |
| WO2023155573A1 (en) * | 2022-02-21 | 2023-08-24 | 金发科技股份有限公司 | Broad-temperature-range, low-shrinkage, strongly-acidic-electrolyte-resistant polypropylene composite material, preparation method therefor and use thereof |
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Cited By (7)
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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 |
| CN109486025A (en) * | 2018-10-24 | 2019-03-19 | 金发科技股份有限公司 | A kind of polypropene composition and preparation method thereof |
| WO2021057355A1 (en) * | 2019-09-26 | 2021-04-01 | 金发科技股份有限公司 | Polypropylene composite material with low shrinkage and low linear expansion coefficient, and preparation method |
| CN111117060A (en) * | 2019-12-13 | 2020-05-08 | 中广核俊尔(浙江)新材料有限公司 | Continuous basalt fiber reinforced polypropylene composite material, preparation method and application |
| CN111371059A (en) * | 2020-03-23 | 2020-07-03 | 长安大学 | L-shaped composite cable groove component and preparation method thereof |
| CN111371059B (en) * | 2020-03-23 | 2022-02-18 | 长安大学 | L-shaped composite cable groove component and preparation method thereof |
| WO2023155573A1 (en) * | 2022-02-21 | 2023-08-24 | 金发科技股份有限公司 | Broad-temperature-range, low-shrinkage, strongly-acidic-electrolyte-resistant polypropylene composite material, preparation method therefor and use thereof |
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