CN109836704A - High scratch-resistant modified polypropylene material of low-density and preparation method thereof - Google Patents
High scratch-resistant modified polypropylene material of low-density and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high scratch-resistant modified polypropylene materials of a kind of low-density and preparation method thereof, the material uses the acrylic resin with ladder melt index to be blended, and using the toughener with specific structure, compatilizer carries out the modification in terms of toughness, the content of powder filled object is reduced by addition scratch resistance liniment, its unit mass can be substantially reduced on the basis of guaranteeing the toughness and scratch resistance of the polypropylene material, not only it is able to satisfy the requirement of automotive light weight technology, and pass through the promotion to its scratch performance, greatly extend its application field, with great realistic meaning and wide market application prospect.
Description
Technical field
The present invention relates to a kind of PP composite materials and preparation method thereof more particularly to a kind of high scratch-resistant of low-density to change
Property polypropylene material and preparation method thereof, belongs to polymer composite and its processing technology of preparing field.
Background technique
Polypropylene material has good mechanical property and processing performance, and it is excellent also to have that recyclable, light weight and cost is low etc.
Gesture, therefore be more and more applied in automobile especially automobile interior exterior decorations and other related fieldss.However polypropylene material
Scraping and wiping resistance performance it is poor, when this kind of polypropylene material is applied to the automotive interiors portions such as instrument board, console and door-plate epidermis
When part, poor scraping and wiping resistance performance becomes the most important factor of the appearance and service life that influence above-mentioned component, therefore significantly
Limit application of such material on automotive field.Although also there is poly- third improved regarding to the issue above on the market at present
Alkene material, but this kind of material is to increase its scratch-resistant by adding various powder filled objects in polypropylene matrix resin mostly
Performance, although effectively improving its scraping and wiping resistance performance in this way, the addition of powder considerably increases the close of such material
Degree, so that the weight of automotive upholstery greatly promotes, it is difficult to apply in the automotive field for having lightweight requirements.Therefore exploitation one
Polypropylene material of the kind with low-density and high scraping and wiping resistance performance has very important realistic meaning.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of high scratch-resistant modified polypropylene material of low-density and its systems
Preparation Method, the polypropylene material are capable of providing fabulous scratch-resistant effect on the basis of reducing unit of the product weight, meet and produce
Product functional requirement, and the preparation method of the alloy is simple and easy to operate.
The technical scheme is that
A kind of high scratch-resistant modified polypropylene material of low-density, including it is following by the high scratch-resistant modified polypropylene of the low-density
Following each components of material gross mass percentages:
Wherein the PP resin 1 is the polypropylene of melt index 20-30g/10min, and PP resin 2 is melt index 10-
The random copolymerization type polypropylene of 20g/10min, PP resin 3 are the polypropylene of melt index 1-5g/min；Above-mentioned melt index
Measuring method is GB/T 3682-2000, and the measuring method of all melt index involved in the application is the state
Measuring method described in mark standard.
The toughener is polymer electrolyte elastomer nitrile rubber NBR, hydrogenated styrene-butadiene block copolymer
At least one of SEBS, ethylene propylene diene rubber EPDM and polyolefin elastomer, preferably polyolefin elastomer, and should
The Mooney viscosity of polyolefin elastomer is 6-10 (ML 1+4,121 DEG C), preferably Mooney viscosity be 8 (ML 1+4,121 DEG C)
Polyolefin elastomer.
The filler is at least one of talcum powder, calcium carbonate, mica and montmorillonite, preferably partial size 5000-
The talcum powder of 5500 mesh.
The compatilizer is polypropylene grafted maleic anhydride copolymer, POE grafted maleic anhydride copolymer and silane coupled
At least one of agent, preferably polypropylene grafted maleic anhydride copolymer, and wherein the content of maleic anhydride is 0.5-
1.5wt.%, and the acid-base titration that the measuring method of the maleic anhydride content is well known to those skilled in the art.
The scratch resistance liniment is at least one of high molecular weight silicone, siloxanes and erucyl amide quasi polymer, preferably
It is at least 5000 high molecular weight silicone for weight average molecular weight.
The dispersing agent is at least one of stearic acid, stearate and vinyl bis-stearamides, preferably ethylene
Base bis-stearamides.
The composite antioxidant by [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of antioxidant four and
Antioxidant three (2,4- di-t-butyl) phenyl-phosphite is (1-2) in mass ratio: 1 is mixed to form.
The invention also discloses a kind of preparation method of above-mentioned high scratch-resistant modified polypropylene material of low-density, the preparation sides
Method includes the following steps:
(1) 1 30-60wt.%, PP resin of PP resin, 2 10-30wt.% and PP resin, 3 10-30wt.%, juxtaposition are weighed
3-5min is stirred in high speed mixing tank, obtains the first mixture；
(2) toughener 3-10wt.%, compatilizer 1-4wt.% and scratch resistance liniment 1-5wt.% are weighed and is thrown after mixing
Enter in above-mentioned first mixture and stir 3-5min, obtains the second mixture；
(3) filler 10-30wt.%, dispersing agent 0.1-1.0wt.% and composite antioxidant 0.1-1.0wt.% are weighed simultaneously
After mixing, it puts into above-mentioned second mixture and stirs 3-5min to uniform, obtain third mixture；
(4) the third mixture mixed is granulated using double screw extruder melting extrusion, wherein double screw extruder
Extrusion temperature be 180-230 DEG C, and third mixture in the screw rod of double screw extruder the residence time be 2-5min, squeeze out
Pressure is 5-12MPa.
The processing temperature in the area working process parameter Zhong Ge of double screw extruder in above-mentioned steps (4) are as follows: twin-screw extrusion
One 180-200 DEG C of area's temperature of machine, two 190-210 DEG C of area's temperature, three 200-220 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five
210-230 DEG C of area's temperature, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, head temperature
210-220 DEG C of degree.
The method have the benefit that: the high scratch-resistant modified polypropylene material of low-density uses, and there is ladder melting to refer to
Modification in terms of several acrylic resins is blended, and there is the toughener of specific structure, compatilizer to carry out toughness for use, by adding
Add scratch resistance liniment to reduce the content of powder filled object, it can be on the basis for the toughness and scratch resistance for guaranteeing the polypropylene material
On substantially reduce its unit mass, be not only able to satisfy the requirement of automotive light weight technology, but also pass through the promotion to its scratch performance, pole
The big application field for extending it has great realistic meaning and wide market application prospect.
Specific embodiment
In order to better understand the technical means of the present invention, it and can be implemented in accordance with the contents of the specification, below
In conjunction with specific embodiments, specific embodiments of the present invention will be described in further detail, and following embodiment is for illustrating this hair
It is bright, but be not intended to limit the scope of the invention.
Each raw material used in following specific embodiments and comparative example are as described below:
PP resin 1: melt index is the copolymer polypropylene of 20-30g/10min, selects Ningbo Tai Su company in following citings
The trade mark of production is the PP resin of PP 3204.
PP resin 2: melt index is the atactic copolymerized polypropene of 10-20g/10min, and platform modeling in Ningbo is selected in following citings
The PP resin that the trade mark of company's production is PP 5090T.
PP resin 3: melt index is the copolymer polypropylene of 1-5g/10min, selects Dushanzi petro-chemical corporation in following citings
The trade mark of production is the PP resin of K8003.
Toughener: at least one of polymer electrolyte elastomer NBR, SEBS, EPDM and POE；It is preferred that Mooney viscosity is 6-
The polyolefin elastomer of 10 (ML 1+4,121 DEG C), it is 875L's that the trade mark of South Korea SK company production is selected in following citings
Polyolefin elastomer, Mooney viscosity are 8 (ML1+4,121 DEG C), other toughener select common model on the market.
Filler: at least one of talcum powder, calcium carbonate, mica and montmorillonite；Preferably partial size 5000-5500 purpose
Talcum powder selects the talcum powder that the trade names of Suzhou A Fanti company production are ECO9900, other fillers in following citings
Select common model on the market.
Compatilizer: in polypropylene grafted maleic anhydride copolymer, POE grafted maleic anhydride copolymer and silane coupling agent
It is at least one；Preferably polypropylene grafted maleic anhydride copolymer of the maleic anhydride content for 0.5-1.5wt.%, following citings
The polypropylene grafted maleic anhydride copolymer that the middle trade names for selecting the production of Shenyang Ke Tong Co., Ltd are KT-1, other are compatible
Common model on the market is selected in agent.
Scratch resistance liniment: at least one of high molecular weight silicone, siloxanes and erucyl amide quasi polymer；It is preferred that divide equally again
Son amount is at least 5000 high molecular weight silicone, and it is AS- that the trade names of EVONIK industrial group production are selected in following citings
100 scratch resistance liniment.
Dispersing agent: at least one of stearic acid, stearate and vinyl bis-stearamides；Preferably vinyl is double hard
Acyl amine selects Malaysia's EBS-SF spread powder in following citings.
Composite antioxidant: by [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of antioxidant four and resist
Oxygen agent three (2,4- di-t-butyl) phenyl-phosphite is (1-2) in mass ratio: 1 is mixed to form, wherein [the β-(3,5- of antioxidant four
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and antioxidant three (2,4- di-t-butyl) phenyl-phosphite be by Ciba
Refine company production, trade names are respectively Irganox 1010 and Irganox 168.
Prepare modified polypropylene material described in each specific embodiment.According to following table 1 and each specific reality of table 2Apply institute in example
It states formulation dosage and weighs each raw material, then will first weigh 1 30-60wt.%, PP resin of PP resin, 2 10-30wt.% and PP tree
3 10-30wt.% of rouge is placed in high speed mixing tank and stirs 3-5min (using 3min in following embodiments), it is mixed to obtain first
Close object；Toughener 3-10wt.%, compatilizer 1-4wt.% and scratch resistance liniment 1-5wt.% will be weighed again and will be put into after mixing
3-5min (using 5min in following embodiments) is stirred in above-mentioned first mixture, obtains the second mixture；Weigh filler 10-
It is mixed to put into above-mentioned second by 30wt.%, dispersing agent 0.1-1.0wt.% and composite antioxidant 0.1-1.0wt.% and after mixing
It closes in object and stirs 3-5min (in following embodiments using 5min) to uniform, obtain third mixture；The third that will be mixed
Mixture is granulated using double screw extruder melting extrusion, and wherein the extrusion temperature of double screw extruder is 200-250 DEG C, specifically
Are as follows: 210 DEG C of an area, 220 DEG C of 2nd area, 230 DEG C of 3rd area, 230 DEG C of 4th area, 230 DEG C of 5th area, 230 DEG C of 6th area, 230 DEG C of 7th area, 8th area
230 DEG C, 240 DEG C of head；And third mixture residence time in the screw rod of double screw extruder is 2-5min, extrusion pressure is
5-12MPa (uses 8MPa) in following embodiments.
Prepare modified polypropylene material described in each comparative example.It is weighed respectively according to formulation dosage described in the following table 2 comparative example
Raw material carries out according to above-mentioned specific embodiment preparation process during the preparation process, is not only added in an amount of zero in the corresponding stage
Component.
Dosage of each component (unit: mass percent) in 1 specific embodiment 1-10 of table
Dosage of each component (unit: mass percent) in table 2 specific embodiment 11-14 and comparative example 1-6
To be formulated according to above-mentioned Tables 1 and 2 prepare the high scratch-resistant modified polypropylene material of resulting low-density with
And commercial like product 1 and commercial like product 2 carry out density, notch impact strength measurement and scraping and wiping resistance performance measurement, survey
It is as described below to determine method:
Density is detected according to GB/T 1033-2008.
Notch impact strength is tested by 1043 standard of GB/T.Specimen types be I type, specimen size (mm): (80 ±
2)×(10.0±0.2)×(4.0±0.2)；Notch type is A class, and notch residue width is 8.0 ± 0.2mm.
Scraping and wiping resistance performance test is tested according to ISO 1518-1.
The above measurement result is referring to described in table 3 and table 4.Wherein comparative example 1-6 the performance test results are comparative example 1- in table 2
6 formula preparation institute properties of product, comparative example 7 be commercial like product 1 test gained performance, comparative example 8 be commercially available similar production
The test gained performance of product 2.
3 specific embodiment 1-10 the performance test results of table
4 specific embodiment 11-14 of table and comparative example 1-8 the performance test results
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of high scratch-resistant modified polypropylene material of low-density, it is characterised in that: press the high scratch-resistant of the low-density including following
Following each components of modified polypropylene material gross mass percentages:
Wherein the PP resin 1 is the polypropylene of melt index 20-30g/10min, and PP resin 2 is melt index 10-20g/
The random copolymerization type polypropylene of 10min, PP resin 3 are the polypropylene of melt index 1-5g/min；The toughener is macromolecule
Type elastomer nitrile rubber NBR, hydrogenated styrene-butadiene block copolymer SEBS, ethylene propylene diene rubber EPDM and polyolefin
At least one of elastomer POE；The compatilizer is polypropylene grafted maleic anhydride copolymer, POE grafted maleic anhydride is total
At least one of polymers and silane coupling agent；The scratch resistance liniment is that high molecular weight silicone, siloxanes and erucyl amide are birdsed of the same feather flock together
Close at least one of object；The dispersing agent is at least one of stearic acid, stearate and vinyl bis-stearamides.
2. the high scratch-resistant modified polypropylene material of low-density according to claim 1, it is characterised in that: the scratch resistance liniment
It is at least 5000 high molecular weight silicone for weight average molecular weight.
3. the high scratch-resistant modified polypropylene material of low-density according to claim 1, it is characterised in that: the dispersing agent is
Vinyl bis-stearamides.
4. the high scratch-resistant modified polypropylene material of low-density according to claim 1, it is characterised in that: the toughener is
Polyolefin elastomer, and the Mooney viscosity of the polyolefin elastomer is 6-10 (ML 1+4,121 DEG C).
5. the high scratch-resistant modified polypropylene material of low-density according to claim 1, it is characterised in that: the filler is
At least one of talcum powder, calcium carbonate, mica and montmorillonite.
6. the high scratch-resistant modified polypropylene material of low-density according to claim 5, it is characterised in that: the filler is
The talcum powder of partial size 5000-5500 mesh.
7. the high scratch-resistant modified polypropylene material of low-density according to claim 1, it is characterised in that: the compatilizer is
Polypropylene grafted maleic anhydride copolymer, and wherein the content of maleic anhydride is 0.5-1.5wt.%.
8. the high scratch-resistant modified polypropylene material of low-density according to claim 1, it is characterised in that: the compound antioxygen
Agent is by [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of antioxidant four and (2, the 4- bis- tertiary fourths of antioxidant three
Base) phenyl-phosphite is (1-2) in mass ratio: 1 is mixed to form.
9. the preparation side of the high scratch-resistant modified polypropylene material of low-density described in any claim in a kind of claim 1 to 8
Method, it is characterised in that: include the following steps:
(1) 1 30-60wt.%, PP resin of PP resin, 2 10-30wt.% and PP resin, 3 10-30wt.% is weighed, height is placed in
3-5min is stirred in fast mixing tank, obtains the first mixture；
(2) toughener 3-10wt.%, compatilizer 1-4wt.% and scratch resistance liniment 1-5wt.% are weighed and is put into after mixing
It states in the first mixture and stirs 3-5min, obtain the second mixture；
(3) filler 10-30wt.%, dispersing agent 0.1-1.0wt.% and composite antioxidant 0.1-1.0wt.% are weighed and is mixed
After uniformly, puts into above-mentioned second mixture and stir 3-5min to uniform, obtain third mixture；
(4) the third mixture mixed is granulated using double screw extruder melting extrusion, wherein double screw extruder is crowded
Temperature is 180-230 DEG C out, and third mixture residence time in the screw rod of double screw extruder is 2-5min, extrusion pressure
For 5-12MPa.
10. the preparation method of the high scratch-resistant modified polypropylene material of low-density according to claim 9, it is characterised in that: step
Suddenly in (4) area working process parameter Zhong Ge of double screw extruder processing temperature are as follows: one area temperature 180- of double screw extruder
200 DEG C, two 190-210 DEG C of area's temperature, three 200-220 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five area temperature 210-230
DEG C, six 210-230 DEG C of area's temperature, seven 210-230 DEG C of area's temperature, eight 210-230 DEG C of area's temperature, 210-220 DEG C of head temperature.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527263A (en) * | 2019-09-18 | 2019-12-03 | 合肥市和裕达塑业有限公司 | A kind of high scratch-resistant physical blowing squeezes out PET and PP composite material and preparation method |
| CN110951159A (en) * | 2019-12-11 | 2020-04-03 | 广东圆融新材料有限公司 | Polypropylene/polyamide/polyketone composition and preparation method thereof |
| CN112280166A (en) * | 2020-09-24 | 2021-01-29 | 句容市百事特复合材料有限公司 | Scratch-resistant long fiber reinforced polypropylene granule composition and preparation method thereof |
| CN112574505A (en) * | 2020-11-23 | 2021-03-30 | 宁波田丰日用品制造有限公司 | Modified PP material |
| CN114230958A (en) * | 2021-12-29 | 2022-03-25 | 上海普利特复合材料股份有限公司 | Low-density high-performance scratch-resistant polypropylene material for automobiles and preparation method thereof |
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| CN103694562A (en) * | 2013-12-10 | 2014-04-02 | 广州市聚赛龙工程塑料有限公司 | Spraying-free scrape-resistant polypropylene composite material for automobile interior trim parts and preparation method thereof |
| CN106366454A (en) * | 2016-08-26 | 2017-02-01 | 青岛海尔新材料研发有限公司 | Modified polypropylene material for high-performance thin-wall automobile door panel and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103694562A (en) * | 2013-12-10 | 2014-04-02 | 广州市聚赛龙工程塑料有限公司 | Spraying-free scrape-resistant polypropylene composite material for automobile interior trim parts and preparation method thereof |
| CN106366454A (en) * | 2016-08-26 | 2017-02-01 | 青岛海尔新材料研发有限公司 | Modified polypropylene material for high-performance thin-wall automobile door panel and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527263A (en) * | 2019-09-18 | 2019-12-03 | 合肥市和裕达塑业有限公司 | A kind of high scratch-resistant physical blowing squeezes out PET and PP composite material and preparation method |
| CN110951159A (en) * | 2019-12-11 | 2020-04-03 | 广东圆融新材料有限公司 | Polypropylene/polyamide/polyketone composition and preparation method thereof |
| CN110951159B (en) * | 2019-12-11 | 2022-04-15 | 广东圆融新材料有限公司 | Polypropylene/polyamide/polyketone composition and preparation method thereof |
| CN112280166A (en) * | 2020-09-24 | 2021-01-29 | 句容市百事特复合材料有限公司 | Scratch-resistant long fiber reinforced polypropylene granule composition and preparation method thereof |
| CN112574505A (en) * | 2020-11-23 | 2021-03-30 | 宁波田丰日用品制造有限公司 | Modified PP material |
| CN114230958A (en) * | 2021-12-29 | 2022-03-25 | 上海普利特复合材料股份有限公司 | Low-density high-performance scratch-resistant polypropylene material for automobiles and preparation method thereof |
| CN114230958B (en) * | 2021-12-29 | 2024-01-09 | 上海普利特复合材料股份有限公司 | Low-density high-performance scratch-resistant polypropylene material for automobiles and preparation method thereof |
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