CN104558837A - Scratching-resistant low-gloss polypropylene composite material and preparation method thereof - Google Patents
Scratching-resistant low-gloss polypropylene composite material and preparation method thereof Download PDFInfo
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- CN104558837A CN104558837A CN201410822039.1A CN201410822039A CN104558837A CN 104558837 A CN104558837 A CN 104558837A CN 201410822039 A CN201410822039 A CN 201410822039A CN 104558837 A CN104558837 A CN 104558837A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
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Abstract
The invention discloses a scratching-resistant low-gloss polypropylene composite material and a preparation method thereof. The scratching-resistant low-gloss polypropylene composite material is prepared from the following raw materials in percentage by weight: 40-93% of polypropylene, 0-30% of an inorganic filler, 1-5% of reaction type high polysiloxane, 5-20% of fully vulcanizated powdered rubber, 0.1-1% of an initiator, 0.1-1% of an antioxidant, 0.1-1% of a light stabilizer, and 0-2% of other auxiliaries. According to the preparation method disclosed by the invention, the reaction type high polysiloxane and the fully vulcanizated powdered rubber are added to the basic formula, so that when the scratching resistance of the polypropylene material is improved, the high gloss problem of the product caused by addition of polysiloxane can be solved; the obtained polypropylene composite material is low in surface gloss, good in light extinction effect, and suitable for automobiles, household appliances and other fields.
Description
Technical field
The present invention relates to a kind of mar-proof low-luster polypropylene composite material and preparation method thereof, be that a kind of technique is simple, cost is low, the polypropylene composite material of good combination property, is mainly used in automotive upholstery, belongs to polymer modification and processing technique field.
Background technology
Polypropylene because having good processing characteristics and physics, mechanics, chemical property, simultaneously light weight, be inexpensively thus widely used in inner and outer decorative parts of automobile, be the fastest universal thermoplastics of current rate of growth.But because polyacrylic surface hardness is low, the automotive upholstery be made up of polypropylene material is mar-proof poor-performing, surface is easy to scratch.If the glossiness of cab inside gadget is higher simultaneously, just has stronger light reflection, thus affect the comfortableness of navigating mate.Therefore how to improve its mar-proof performance and have low-luster concurrently and become this kind of material of exploitation urgent problem.
There are reports for the mar-proof performance of relevant raising polypropylene, proposes some solutions, fills and strengthen, improve polyacrylic degree of crystallinity, add some micromolecular amides lubricants, or add the method containing organo-siloxane as polypropylene.Japanese Patent Laid-Open 6-220270 is reported in polypropylene modification and improves surface hardness by adding nucleator, reaches the object improving mar-proof performance, finds that increasing rubber consumption also can improve mar-proof performance simultaneously.Chinese patent CN200810023328.X discloses a kind of scraping-resistant automobile inner fitting special-purpose material and preparation method thereof, adopts amide lubricant to improve the Marresistance energy of material.But amide lubricant molecular weight, have after being heated cause product surface separate out be clamminess affect product use risk.
The polysiloxane of high molecular has good surface lubrication effect, heat-resisting and weather resistance is excellent, not easily separates out generation and to be clamminess phenomenon, in recent years, is more and more used as scratch-proof aid and joins polypropylene material and improve mar-proof performance.But polysiloxane is while the mar-proof performance of raising polypropylene material, also causes the glossiness of material obviously to raise.US Patent No. 5585420 and US5731376 relate to the mar-proof performance that the method adding high molecular weight siloxane improves material.Chinese patent CN1580115A mentions and adopts rubber toughened technology, and adds high molecular weight silicone elastomerics and nucleant agent N A-21 makes the rigidity of material and toughness reach good balance, but does not all relate to the glossiness reducing material.
Therefore, one must be found to take into full account above-mentioned each side, while improving mar-proof performance, the glossiness reducing material, to meet the method for automobile special material high performance requirements, will have important actual application value.
Summary of the invention
The object of this invention is to provide a kind of mar-proof low-luster polypropylene composite material and preparation method thereof, to solve the problems referred to above of prior art.
In order to improve the mar-proof performance of polypropylene composite material, and solve because the interpolation of polysiloxane causes the problem of material high glossiness, technical scheme of the present invention adds response type height polysiloxane and fully vulcanized powder rubber in the basic components of polypropylene material, extruding in Blending Processes, response type height polysiloxane and polypropylene material are cross-linked, fully vulcanized powder rubber is dispersed in polypropylene and forms gel, forms uniform concaveconvex shape from product surface.While making polypropylene material have excellent mar-proof performance, also maintain the low-luster on surface.
This mar-proof low-luster polypropylene composite material, becomes by the preparation of raw material of following weight percent:
The present invention in the polypropylene composite material system that is suitable for,
Described polypropylene is the homo-polypropylene of melt flow rate (MFR) (test condition: 230 DEG C × 2.16kg) between 5 ~ 60g/10min or block copolymerization propylene, wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4 ~ 10mol%, the degree of crystallinity of homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
Described mineral filler is talcum powder, calcium carbonate, barium sulfate or their composition, and its particle size range is 1 ~ 10 micron.
Described initiator is tri-isopropyl benzene (TIPB).
Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can select hindered phenol or sulphur ester antioxidant as 3114,1010, DSTP wherein one or more; Auxiliary anti-oxidant can select phosphorite kind antioxidant as 618,168 etc.
Hindered amine light stabilizer selected by described photostabilizer, as the composition of one or both in 944 and 770.
Described response type polysiloxane is the polysiloxane containing vinyl reactive functional, and molecular weight is between 10000 ~ 30000, and the weight percent of its addition is 1 ~ 5%.
Described fully vulcanized powder rubber is fully sulfurized silicon rubber powder, median size 0.05 ~ 1 μm, and its gel content is 60wt% or higher.
Other described additives are color toner or Masterbatch.
The preparation method of above-mentioned mar-proof low-luster polypropylene composite material, its step is as described below:
(1) raw material is taken by weight ratio;
(2) polypropylene, talcum powder, response type height polysiloxane, fully vulcanized powder rubber, initiator, oxidation inhibitor, photostabilizer or other additives are mixed 3 ~ 15 minutes in super mixer;
(3) raw material of mixing is placed in dual-screw-stem machine, through melt extruding, granulation, its technique is: 190 ~ 200 DEG C, a district, two 200 ~ 210 DEG C, districts, three 210 ~ 220 DEG C, districts, four 205 ~ 215 DEG C, districts; The residence time of whole extrusion is 1 ~ 2 minute, and pressure is 12 ~ 18MPa, and purging vacuum degree reaches 5 ~ 20kPa, and single venting hole is positioned at the end of twin screw extruder.
Advantage of the present invention is:
1, the present invention uses appropriate response type polysiloxane in composite system, makes obtained polypropylene composite material have excellent mar-proof performance.
2, the polypropylene composite material obtained by the present invention while the mar-proof performance of raising, and solves the problem that the interpolation because of polysiloxane causes glossiness higher, and gained polypropylene composite material surface gloss is low, extinction effect is good.
3, the mar-proof and resistance to stress that the present invention proposes is turned white, and the preparation technology of polypropylene composite material is simple, production cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and comparative example composite-material formula, polypropylene used is the Co-polypropylene that oil of SPC is produced, and trade names are M2600R.Mineral filler is 5000 order talcum powder, and median size is 2.5 microns.The polysiloxane of response type polysiloxane self-control containing vinyl reactive functional used, molecular weight is between 10000 ~ 30000.Fully vulcanized powder rubber used is the fully sulfurized silicon rubber powder that Beijing Chemical Research Institute produces, and trade names VP-601 median size 0.05 ~ 1 μm, its gel content is 60wt% or higher.Initiator used is 1,3,5-tri-isopropyl benzene of Shanghai ethyl Chemical Co., Ltd., molecular formula C15H24, and molecule is 204.4.Primary antioxidant used is the DSTP that ICE company of Britain produces, and trade names are Negonox DSTP, and chemical name is thio-2 acid octadecyl ester, and 3114 of BASF AG's product, trade names are Irganox 3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of BASF AG's product, and trade names are Irgafos 168, and chemical name is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.Photostabilizer used is 944 of BASF AG's product, and chemical name is poly-{ [6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two support [(2,2,6,6-tetramethyl--4-piperidyl) imino-], and 770 of BASF AG's product, chemical name is two (2,2,6,6-tetramethyl-piperidyl) sebate.
Resin and various additive are dry mixed 3 ~ 5 minutes in super mixer, then through melt extruding in twin screw extruder, granulation, its technique is: 190 ~ 200 DEG C, a district, two 200 ~ 210 DEG C, districts, three 210 ~ 220 DEG C, districts, four 205 ~ 215 DEG C, districts; The residence time of whole extrusion is 1 ~ 2 minute, and pressure is 12 ~ 18MPa, and purging vacuum degree reaches 5 ~ 20kPa, and single venting hole is positioned at the end of twin screw extruder.
performance evaluation mode and the standard of implementation:
By the particulate material prepared as stated above, drying 2 ~ 3 hours in the convection oven of 90 ~ 100 DEG C, and then dried particulate material is carried out injection molding sample preparation on injection moulding machine.
Mar-proof performance test: injection molding size of sample 150 × 100 × 3.2mm, be 10N with scratch hardness tester ERICHSEN430P-I load, nib diameter is that 1mm carries out scratch test at specimen surface, cut interval 2mm, vertical and horizontal each stroke of 20 lines, the color and luster change of grid material is drawn in the color test systems test adopting Japanese Minolta company to produce, and the Δ L value of recording materials, Δ L value is less shows that mar-proof performance is better.
Glossiness is tested: try with 60 ° of angular measurements by standard GB8807 vancometer.
Example formulations and the performance test results see the following form:
Table 1 embodiment 1-7 and comparative example 1-4 material prescription table (% by weight)
Table 2 embodiment 1-7 and comparative example 1-4 material property table
As can be seen from the contrast with comparative example 2 of the contrast of embodiment 1-3 and comparative example 1 and embodiment 4, response type polysiloxane effectively can improve the mar-proof performance of polypropylene composite material system, along with the increase of response type polysiloxane consumption, glossiness also increases gradually; Embodiment 5 and comparative example 3 and embodiment 6-7 and comparative example 4 contrast and can find out, polypropylene composite material is added after fully sulfurized silicon rubber powder, and its glossiness significantly reduces, and along with the increase of fully sulfurized silicon rubber powder consumption, the glossiness of matrix material also constantly reduces, and extinction effect is good.
Claims (13)
1. a mar-proof low-luster polypropylene composite material, is characterized in that: become by the preparation of raw material of following weight percent:
2. the mar-proof low-luster polypropylene composite material of one according to claim 1, is characterized in that: homo-polypropylene or the block copolymerization propylene of described polypropylene to be melt flow rate (MFR) be 5 ~ 60g/10min.
3. the mar-proof low-luster polypropylene composite material of one according to claim 2, is characterized in that: the comonomer of described block copolymerization propylene is ethene, and its content is 4 ~ 10mol%.
4. the mar-proof low-luster polypropylene composite material of one according to claim 2, is characterized in that: the degree of crystallinity of described homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
5. the mar-proof low-luster polypropylene composite material of one according to claim 1, it is characterized in that: described mineral filler is one or more mixtures in talcum powder, calcium carbonate, wollastonite, mica and barium sulfate, and its particle size range is 1 ~ 10 micron.
6. the mar-proof low-luster polypropylene composite material of one according to claim 1, is characterized in that: described response type height polysiloxane is the polysiloxane containing vinyl reactive functional, and molecular weight is between 10000 ~ 30000.
7. the mar-proof low-luster polypropylene composite material of one according to claim 1, is characterized in that: described fully vulcanized powder rubber is fully sulfurized silicon rubber powder, and median size 0.05 ~ 1 μm, its gel content is more than or equal to 60wt%.
8. the mar-proof low-luster polypropylene composite material of one according to claim 1, is characterized in that: described initiator is one or both in diisopropylbenzene(DIPB), tri-isopropyl benzene and toluene diisocyanate.
9. the mar-proof low-luster polypropylene composite material of one according to claim 1, is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant is hindered phenol or sulphur ester antioxidant; Auxiliary anti-oxidant is phosphorite kind antioxidant.
10. the mar-proof low-luster polypropylene composite material of one according to claim 9, is characterized in that: primary antioxidant be 3114,1010 and DSTP in one or more mixing; Auxiliary anti-oxidant is one or both in 618 and 168.
The mar-proof low-luster polypropylene composite material of 11. one according to claim 1, is characterized in that: described photostabilizer is hindered amine light stabilizer, is selected from one or both the composition in 944 and 770.
The mar-proof low-luster polypropylene composite material of 12. one according to claim 1, is characterized in that, other described additives are color toner or Masterbatch.
The preparation method of 13. a kind of mar-proof low-luster polypropylene composite materials according to claim 1, is characterized in that: its concrete steps are as follows:
(1) raw material is taken by weight ratio;
(2) each raw material is placed in super mixer mixing 3 ~ 15 minutes;
(3) raw material of mixing is placed in dual-screw-stem machine, through melt extruding, granulation, its technique is: 190 ~ 200 DEG C, a district, two 200 ~ 210 DEG C, districts, three 210 ~ 220 DEG C, districts, four 205 ~ 215 DEG C, districts; The residence time of whole extrusion is 1 ~ 2 minute, and pressure is 12 ~ 18MPa, and purging vacuum degree reaches 5 ~ 20kPa, and single venting hole is positioned at the end of twin screw extruder.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348714A (en) * | 2015-11-27 | 2016-02-24 | 苏州润佳工程塑料股份有限公司 | Extinction modified polypropylene composite material |
| CN106700254A (en) * | 2016-12-15 | 2017-05-24 | 广东圆融新材料有限公司 | Polypropylene composition with low gloss, scratch resistance and high impact resistance and preparation method of polypropylene composition |
| CN107973976A (en) * | 2017-11-02 | 2018-05-01 | 上海日之升科技有限公司 | High impact high gloss exempts to spray PP/PETG alloy materials and preparation method thereof |
| CN109721842A (en) * | 2018-12-29 | 2019-05-07 | 浙江普利特新材料有限公司 | A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof |
| CN109880195A (en) * | 2019-02-22 | 2019-06-14 | 东莞市普凯塑料科技有限公司 | Plastics matt master and preparation method thereof and plastic products |
| CN112063053A (en) * | 2020-09-18 | 2020-12-11 | 鲁姣利 | Modified polypropylene wave crest double-wall pipe and preparation method of modified polypropylene material thereof |
-
2014
- 2014-12-22 CN CN201410822039.1A patent/CN104558837A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348714A (en) * | 2015-11-27 | 2016-02-24 | 苏州润佳工程塑料股份有限公司 | Extinction modified polypropylene composite material |
| CN105348714B (en) * | 2015-11-27 | 2018-08-31 | 苏州润佳工程塑料股份有限公司 | Delustring modified polypropylene composite material |
| CN106700254A (en) * | 2016-12-15 | 2017-05-24 | 广东圆融新材料有限公司 | Polypropylene composition with low gloss, scratch resistance and high impact resistance and preparation method of polypropylene composition |
| CN107973976A (en) * | 2017-11-02 | 2018-05-01 | 上海日之升科技有限公司 | High impact high gloss exempts to spray PP/PETG alloy materials and preparation method thereof |
| CN109721842A (en) * | 2018-12-29 | 2019-05-07 | 浙江普利特新材料有限公司 | A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof |
| CN109880195A (en) * | 2019-02-22 | 2019-06-14 | 东莞市普凯塑料科技有限公司 | Plastics matt master and preparation method thereof and plastic products |
| CN109880195B (en) * | 2019-02-22 | 2021-07-27 | 东莞市普凯塑料科技有限公司 | Extinction master batch for plastics, preparation method thereof and plastic product |
| CN112063053A (en) * | 2020-09-18 | 2020-12-11 | 鲁姣利 | Modified polypropylene wave crest double-wall pipe and preparation method of modified polypropylene material thereof |
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Application publication date: 20150429 |