CN109721842A - A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof - Google Patents
A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof Download PDFInfo
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- CN109721842A CN109721842A CN201811635056.9A CN201811635056A CN109721842A CN 109721842 A CN109721842 A CN 109721842A CN 201811635056 A CN201811635056 A CN 201811635056A CN 109721842 A CN109721842 A CN 109721842A
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Abstract
The invention discloses a kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof, this PP composite material comprises the following raw materials by weight percent: polypropylene 33~90, ultra-fine inorganic filler 0~25, toughener 5~20, fully vulcanized powder rubber 1~15, compatilizer 0.5~3, antioxidant 0.1~1, light stabilizer 0.1~1, other auxiliary agents 0~2.The present invention introduces nanoscale fully vulcanized powder rubber in PP composite material system, and the reinforcing effect using fully vulcanized powder rubber to toughener elastomer cooperates with activeness and quietness PP composite material；Nanoscale fully vulcanized powder rubber and ultra-fine inorganic filler can form core-shell type structure in polypropylene matrix simultaneously, and gained composite material is while keeping higher toughness, intensity and rigidity with higher.Meanwhile fully vulcanized powder rubber can reduce the glossiness of composite system, play matt effect.
Description
Technical field
The present invention relates to a kind of PP composite materials, and in particular to a kind of automobile rigid plastic instrument board low gloss, Gao Gang
Property, high impact resistance polypropylene composite material and preparation method thereof, be a kind of simple process, PP composite material at low cost, tool
While having higher shock resistance, retain higher intensity and rigidity, while composite material has lower gloss etc. excellent
Point can fully meet the performance requirement of automobile interior decoration instrument board, belong to polymer modification and processing technique field.
Background technique
Recently as the fast development of auto industry, accounting of the plastic items in automobile interior exterior decorations is more and more.
As the fascia that carry driver side security performance, it is integrated with air bag, heading control loop, instrument and meter, it is empty
The components such as tuning acoustic system, structure is complicated, it is desirable that it has higher intensity and rigidity and higher shock resistance.
Especially when being acted on by foreign impacts, apparent rupture or sharp fragments, as far as possible protection driver and passenger will not be generated
Safety.Further, since instrument board face driver just has stronger light reflection, shadow if smooth surface glossiness is higher
Ring driver's sight safety.
Fascia material is broadly divided into two classes at present, and one kind is using PC/ABS or fiber glass reinforced polypropylene material as this
Body skeleton, thermoplastic elastomer (TPE), thermoplastic polyurethane or PVC foam to form the instrument of " sandwich " structure in skeleton surface slush moulding
Dash board ontology；But such instrument board is due to complex process, at high cost, only uses in the automobile at some slightly higher ends；In addition a kind of
It is the hard plastic instrument board ontology directly prepared by single injection-molded using PP composite material；Such instrument board technique letter
Single, easy to operate, at low cost, the demand in fascia is increasing.
Conventional hard plastic instrument board mainly uses inorganic filler and toughener to come filled modified polypropylene, gained polypropylene material
Ideal room temperature toughness can be obtained.But under cryogenic, especially under the maximum conditions such as -30 DEG C even -40 DEG C, gather
The higher glass transition temperature of propylene material determines that its low-temperature impact property is poor, can only pass through addition high level
Toughener elastomer improves, but will lead to the intensity and rigidity decline of material simultaneously, is unable to satisfy other test requirements documents, such as total
At detail rigidity test etc..In addition, conventional hard plastic instrument board lustrous surface is higher, pilot's line of vision is influenced, usually from consumer
It is denounced.Related patents study this, if publication number CN101173075 patent in PP composite material by adding
Enter silica to reduce the glossiness of composite material, but gloss reduces mechanical property that is limited, and influencing composite material；It is open
Number CN102807703B patent is improved by the way that powder nitrile rubber, graft polypropylene and silica are added in the composite
The gloss of material, but the toughness of material is affected.
Summary of the invention
For overcome the deficiencies in the prior art, the primary purpose of the present invention is that providing a kind of automobile rigid plastic instrument board with low
Gloss, high rigidity, high impact resistance polypropylene composite material.
It is a further object of the present invention to provide this automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene
The preparation method of composite material.
Modified polypropylene composite material of the present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material, by following weight percent
The raw material of ratio is configured to:
In the PP composite material system that the present invention is applicable in,
For the polypropylene under 230 DEG C, 2.16kg loading condiction, melt flow rate (MFR) is 10~70g/10min.
The polypropylene is homo-polypropylene or block copolymerization propylene；The crystallinity of the homo-polypropylene 70% or more, etc.
Normality is greater than 99%；The comonomer of the block copolymerization polypropylene is ethylene, and vinyl monomer repetitive unit molar content is 4
~10%.
The inorganic filler that the ultra-fine inorganic filler is 0.05~1 μm of average particle size range, and then the ultra-fine inorganic
Filler is selected from one or both of talcum powder, calcium carbonate, barium sulfate, silica, mica, wollastonite and montmorillonite or more
Composition, preferably 0.5~2 μm of average grain diameter of talcum powder.
The toughener is the combination of ethylene-octene linear copolymer or Ethylene/Butylene linear copolymer or both,
Optimal ethylene-butylene linear copolymer, density are 0.88~0.90g/cm3, melt flow rate (MFR) is 0.5~10g/10min.
The fully vulcanized powder rubber is ultra-fine form of finely divided powder, mehtod butadiene-styrene rubber, and average grain diameter is 20~500nm.
The compatilizer is maleic anhydride grafted polyolefin propylene, acrylic acid-grafted polypropylene and maleic acid graft polypropylene
In any one.
The antioxidant includes primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is hindered phenol or sulphur ester antioxidant；It is auxiliary
Antioxidant is phosphorite kind antioxidant.
The primary antioxidant is one or more of 3114,1010 and DSTP mixing；Auxiliary anti-oxidant is 618 and 168
One or both of.
The light stabilizer is hindered amine light stabilizer.
Other auxiliary agents are various colors additive, antistatic agent, fire retardant, various esters or fatty acid lubrication
One of agent is a variety of.
Above-mentioned automobile rigid plastic instrument board low gloss, high rigidity, the preparation method of high impact resistance polypropylene composite material, tool
Steps are as follows for body:
(1) each component is weighed by claim 1 weight proportion；
(2) by polypropylene, ultra-fine inorganic filler, toughener, fully vulcanized powder rubber, compatilizer, antioxidant, light stabilizer
With other auxiliary agents dry-mixed 3~15 minutes in super mixer；
(3) raw material mixed is added twin-screw extrude, the cooling granulation after melting extrusion, technique are as follows: one
190~200 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 100-
1000r/min；The residence time of entire extrusion process is 1~2 minute, and pressure is 12~18MPa, purging vacuum degree reaches 5~
20kPa。
The invention has the advantages that
1, the present invention introduces nanoscale fully vulcanized powder rubber in the toughened system of PP composite material, utilizes full sulphur
Change reinforcing effect of the powdered rubber to toughener elastomer, coordination plasticizing PP composite material, more particularly to improve composite wood
The low-temperature flexibility of Material system, while playing reinforcing effect.
2, nanoscale fully vulcanized powder rubber and ultra-fine inorganic filler can form core-shell type knot in polypropylene matrix
Structure, gained composite material is while keeping higher toughness, intensity and rigidity with higher.
3, fully vulcanized powder rubber can reduce the glossiness of composite system, play surface matt effect.
4, preparation process of the invention is simple, at low cost, and gained composite material can fully meet automobile rigid plastic instrument board
The requirement of material.
Specific embodiment
Below with reference to embodiment, invention is further described in detail.The scope of the present invention is not by these embodiments
Limitation, the scope of the present invention propose in detail in the claims.
In the composite-material formula of embodiment and comparative example, polypropylene used is being total to for Exxon Mobil Corporation's production
Poly- polypropylene, trade name PP7555KNE2, melt flow rate (MFR) be 50g/10min (test condition: 230 DEG C ×
2.16kg).Talcum powder used is 10000 mesh, and average grain diameter is 1.2 μm.Toughener used is the ethylene-of DOW company
Octene copolymer Engage8150, density 0.868g/cm3, melt index be 0.5g/10min (test condition: 190 DEG C ×
2.16kg).Fully vulcanized powder rubber used is the form of finely divided powder, mehtod butadiene-styrene rubber of Beijing Chemical Research Institute's production, trade names
VP-108, average grain diameter about 100nm, gel content are 60wt% or higher.Compatilizer used is that maleic anhydride grafting is poly-
Propylene, grafting rate 1%.Primary antioxidant used is 3114 that BASF AG produces, and trade names are Irganox 3114, is changed
The DSTP that scientific name is known as 3,5- di-tert-butyl-4-hydroxyl benzyl diethyl phosphate and ICE company, Britain produces, trade names are
Negonox DSTP, chemical name are thio-2 acid octadecyl ester.Auxiliary anti-oxidant is 168 that BASF AG produces, and trade names are
Irgafos 168, chemical name are three (2,4- di-tert-butyl-phenyl) phosphite esters.Light stabilizer used is raw for BASF AG
Produce 944, chemical name be it is poly- [6- [(1,1,3,3- tetramethyl butyl) amino]] -1,3,5-triazines -2,4- it is bis- [(2,2,6,
6- tetramethyl-4-piperidyl) imino group] -1,6- oneself two supports [(2,2,6,6- tetramethyl -4- piperidyl) imino group] } and BASF
The 770 of company's production, chemical name are bis- (2,2,6,6- tetramethyl-piperidyl) sebacates.Other auxiliary agents used include various
Color additives, antistatic agent, fire retardant, various esters or fatty acid lubricant etc..
Before use, weigh raw material according to said components and weight proportion, by polypropylene, ultra-fine inorganic filler, toughener, complete
Sulfide powder rubber, compatilizer, antioxidant, light stabilizer and other auxiliary agents are dry-mixed 3~15 minutes in super mixer；Then
The raw material mixed is added twin-screw extrude, the cooling granulation after melting extrusion, technique are as follows: an area 190~200
DEG C, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 100-1000r/min；Entirely
The residence time of extrusion process is 1~2 minute, and pressure is 12~18MPa, and purging vacuum degree reaches 5~20kPa.
Embodiment 1
PP composite material main component of the present invention includes 70.3% polypropylene, 15% talcum powder, 5% toughener, 5%
Fully vulcanized powder rubber, 2% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,
0.15% light stabilizer 944 and 0.15% light stabilizer 770,2% other auxiliary agents.
Embodiment 2
PP composite material main component of the present invention include 60.3% polypropylene, 20% talcum powder, 10% toughener,
5% fully vulcanized powder rubber, 2% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,
0.15% light stabilizer 944 and 0.15% light stabilizer 770,2% other auxiliary agents.
Embodiment 3
PP composite material main component of the present invention include 60.3% polypropylene, 20% talcum powder, 5% toughener,
10% fully vulcanized powder rubber, 2% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,
0.15% light stabilizer 944 and 0.15% light stabilizer 770,2% other auxiliary agents.
Embodiment 4
PP composite material main component of the present invention include 49.3% polypropylene, 25% talcum powder, 15% toughener,
5% fully vulcanized powder rubber, 3% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,
0.15% light stabilizer 944 and 0.15% light stabilizer 770,2% other auxiliary agents.
Embodiment 5
PP composite material main component of the present invention include 49.3% polypropylene, 25% talcum powder, 10% toughener,
10% fully vulcanized powder rubber, 3% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,
0.15% light stabilizer 944 and 0.15% light stabilizer 770,2% other auxiliary agents.
Embodiment 6
PP composite material main component of the present invention include 49.3% polypropylene, 25% talcum powder, 5% toughener,
15% fully vulcanized powder rubber, 3% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,
0.15% light stabilizer 944 and 0.15% light stabilizer 770,2% other auxiliary agents.
Comparative example 1
PP composite material main component of the present invention include 70.3% polypropylene, 15% talcum powder, 10% toughener,
2% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,0.15% light stabilizer 944 and
0.15% light stabilizer 770,2% other auxiliary agents.
Comparative example 2
PP composite material main component of the present invention include 60.3% polypropylene, 20% talcum powder, 15% toughener,
2% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,0.15% light stabilizer 944 and
0.15% light stabilizer 770,2% other auxiliary agents.
Comparative example 3
PP composite material main component of the present invention include 49.3% polypropylene, 25% talcum powder, 20% toughener,
3% compatilizer, 0.1% antioxidant 3114,0.1% antioxidant DSTP and 0.2% irgasfos 168,0.15% light stabilizer 944 and
0.15% light stabilizer 770,2% other auxiliary agents.
Examples 1 to 6 and 1~3 PP composite material main component mass percentage of comparative example are shown in Table 1.
1~3 material prescription table (weight %) of 1 Examples 1 to 6 of table and comparative example
Performance evaluation mode and implementation standard:
The particulate material that will be prepared according to the above method, it is 2~3 hours dry in 90~100 DEG C of air dry oven, then
Again by dried particle on injection molding machine injection molding sample.
Melt flow rate (MFR) test: being carried out by ISO 1133-1 standard, and test condition is 230 DEG C, 2.16kg.
Tensile property test: being carried out by ISO 527-2 standard, and specimen size is 170 × 10 × 4mm, and tensile speed is
50mm/min；
Bending property test: being carried out by 178 standard of ISO, and specimen size is 80 × 10 × 4mm, rate of bending 2mm/
Min, span 64mm；
Notch impact strength test: being carried out by ISO 179-1 standard, and specimen size is 80 × 10 × 4mm, and notch depth is
The one third of sample thickness；
The test of low temperature ball falling impact: being carried out by masses' PV3905 standard, and sample is the template of 70 × 70 × 3.2mm, sample
Aging temperature is -30 DEG C, and aging time is height of the fall ball 400mm for 24 hours；
Glossiness test: it is tested by standard GB8807 vancometer with 60 ° of angles.
The performance test results of 1~3 PP composite material of the embodiment of the present invention 1~6 and comparative example are shown in Table 2 respectively.
1~3 material property table of 2 Examples 1 to 6 of table and comparative example
It can be seen that from the performance test results of Examples 1 to 6 and comparative example 1~3 in conventional polypropylene composite bodies
After introducing fully vulcanized powder rubber in system, the impact property of composite material is improved, especially low temperature notched impact property, is said
Bright fully vulcanized powder rubber can improve the toughness of composite material, especially low-temperature flexibility.Meanwhile from embodiment and comparative example
It is also found that the stretching of composite material and bending property do not reduce, there is different degrees of promotion instead, illustrates to vulcanize powder entirely
Last rubber plays the role of reinforcement simultaneously in compound system.In addition, with the addition of fully vulcanized powder rubber, composite material
Gloss is substantially reduced, and glossiness even can achieve 1.6, and material surface has apparent matt effect, can expire completely
Performance requirement of the sufficient hard plastic instrument board for material low gloss, high-modulus and high-impact.
Claims (13)
1. a kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material, it is characterised in that: by with
The raw material of lower weight percent is made:
2. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: for the polypropylene under 230 DEG C, 2.16kg loading condiction, melt flow rate (MFR) is 10~70g/
10min。
3. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: the polypropylene is homo-polypropylene or block copolymerization propylene；The crystallinity of the homo-polypropylene 70% with
On, isotacticity is greater than 99%；The comonomer of the block copolymerization propylene is ethylene, vinyl monomer repetitive unit molar content
It is 4~10%.
4. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: the ultra-fine inorganic filler be talcum powder, calcium carbonate, barium sulfate, silica,
The composition of one or both of mica, wollastonite and montmorillonite or more.
5. a kind of automobile rigid plastic instrument board low gloss according to claim 4, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: its partial size average range of the ultra-fine inorganic filler is 0.05~2 μm.
6. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: the toughener is ethylene-octene linear copolymer or Ethylene/Butylene linear copolymer or both
Combination, density be 0.88~0.90g/cm3, melt flow rate (MFR) is 0.5~10g/10min.
7. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: the fully vulcanized powder rubber be ultra-fine form of finely divided powder, mehtod butadiene-styrene rubber, average grain diameter be 20-~
500nm。
8. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: the compatilizer is maleic anhydride grafted polyolefin propylene, acrylic acid-grafted polypropylene and maleic acid grafting
Any one in polypropylene.
9. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene composite wood
Material, it is characterised in that: the antioxidant includes primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is hindered phenol or thioesters class antioxygen
Agent；Auxiliary anti-oxidant is phosphorite kind antioxidant.
10. a kind of automobile rigid plastic instrument board low gloss according to claim 9, high rigidity, high impact resistance polypropylene are compound
Material, it is characterised in that: the primary antioxidant is one or more of 3114,1010 and DSTP mixing；
Auxiliary anti-oxidant is one or both of 618 and 168.
11. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene are compound
Material, it is characterised in that: the light stabilizer is hindered amine light stabilizer.
12. a kind of automobile rigid plastic instrument board low gloss according to claim 1, high rigidity, high impact resistance polypropylene are compound
Material, it is characterised in that: other auxiliary agents are various colors additive, antistatic agent, fire retardant, various esters or fat
One of acids lubricant is a variety of.
13. automobile rigid plastic instrument board low gloss, high rigidity, high impact poly described according to claim 1~any one of 12
The preparation method of acrylic composite, it is characterised in that: the specific steps of which are as follows:
(1) each component is weighed by claim 1 weight proportion；
(2) by polypropylene, ultra-fine inorganic filler, toughener, fully vulcanized powder rubber, compatilizer, antioxidant, light stabilizer and its
Its auxiliary agent is dry-mixed 3~15 minutes in super mixer；
(3) raw material mixed is added twin-screw extrude, the cooling granulation after melting extrusion, technique are as follows: an area 190
~200 DEG C, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 100-1000r/min；
The residence time of entire extrusion process is 1~2 minute, and pressure is 12~18MPa, and purging vacuum degree reaches 5~20kPa.
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| CN114989526A (en) * | 2022-04-08 | 2022-09-02 | 中国石油化工股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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Application publication date: 20190507 |