CN102108151A - Polypropylene composition with high light aging resistant performance - Google Patents
Polypropylene composition with high light aging resistant performance Download PDFInfo
- Publication number
- CN102108151A CN102108151A CN 200910200858 CN200910200858A CN102108151A CN 102108151 A CN102108151 A CN 102108151A CN 200910200858 CN200910200858 CN 200910200858 CN 200910200858 A CN200910200858 A CN 200910200858A CN 102108151 A CN102108151 A CN 102108151A
- Authority
- CN
- China
- Prior art keywords
- polypropene composition
- resisting performance
- aging resisting
- polypropylene
- illumination aging
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polypropylene composition with high light aging resistant performance, which comprises the following raw materials in percentage by weight: 50 to 99 percent of polypropylene, 0 to 45 percent of inorganic filler, 0 to 15 percent of toughening agent POE, 0.1 to 0.8 percent of hindered phenol primary antioxygen, 0.1 to 0.6 percent of secondary antioxygen, 0.1 to 0.6 percent of oligomer hindered anime light stabilizer, and 0.1 to 4 percent of other assistant, wherein the hindered phenol primary antioxygen and the secondary antioxygen form an antioxygen, and the oligomer hindered anime light stabilizer serve as the light stabilizer. In the invention, because the hindered anime light stabilizer, which has a high molecular weight and low volatility, are added in the fundamental formula of the polypropylene composition, the polypropylene composition has high long-term light aging resistant performance.
Description
Technical field
The present invention relates to a kind of polypropene composition with excellent illumination aging resisting performance, more particularly by in the polypropene composition system, adding a kind of photostabilizer with high molecular, low volatility and excellent compatibility, improve the long-term illumination aging resisting performance of polypropene composition system, belong to polymer modification and manufacture field.
Background technology
Polypropylene has good, anti-gasoline of processing characteristics and the good advantage of pharmaceutical chemicals, while light weight, inexpensive, be widely used in the shell of inner and outer decorative parts of automobile, electronics and household electronic products etc., it is the fastest universal thermoplastics of present rate of growth, it is poor that but polyacrylic disadvantage is an illumination aging resisting performance, its degradation is a lot of behind the sunlight short irradiation, has therefore limited its Application Areas.
The illumination aging resisting performance of polypropene composition is mainly by adding various photostabilizers and heat-proof aging auxiliary agent and utilizing two kinds of synergies between auxiliary agent to realize at present.But most of light stabilization aid comprises that various photomask agent, UV light absorber, radical scavenger etc. all are lower organic compound of molecular weight or oligopolymer, and its speed to the material surface migration is very fast.When these auxiliary agents are added in the polypropylene, under high temperature or the long irradiation of UV-light, the trend of separating out to product surface is gradually arranged all.Particularly when the content of photostabilizer is big, the easier generation of this phenomenon of separating out to product surface, product surface even can produce the bloom phenomenon in the time of serious along with the prolongation of light application time.A lot of in addition photostabilizers such as UV 770 (chemical name is two (2,2,6, the 6-tetramethyl-piperidyl) sebates) itself is just very poor with the consistency of acrylic resin, and molecular weight less again (about about 400) more can aggravate the generation of transport phenomena.And the light stabilization aid is separated out the outward appearance and the surface property that not only can influence product from product surface, also can seriously reduce the long-term light aging resisting property of product.
At this problem, Lajos Avar etc. are at U.S. Pat P6, mention a kind of response type photostabilizer in 201,047, promptly this photostabilizer can and matrix material in base-material (as polypropylene) thus chemical bonding takes place reaches the effect that stops photostabilizer to move to material surface.But the molecular structure of this photostabilizer is more special, still is in the laboratory synthesis phase, so be not adapted at widespread use in the actual production at present.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, a kind of polypropene composition with excellent illumination aging resisting performance is provided.
A kind of polypropene composition with excellent illumination aging resisting performance, formulated by following weight percent proportion raw material:
Polypropylene 50～99
Mineral filler 0～45
Toughner POE 0～15
Photostabilizer 0.1～0.6
Primary antioxidant 0.1～0.8
Auxiliary anti-oxidant 0.1～0.6
Other auxiliary agents 0.1～4.
In the polypropene composition system that the present invention was suitable for:
Described polypropylene is different mobile homo-polypropylene and block copolymerization propylene; Wherein the comonomer of block copolymerization propylene is an 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%, polyacrylic melt flow rate (MFR) (test condition: 230 ℃ * 2.16kg) be 2～60g/10min.
Described mineral filler is talcum powder, lime carbonate, barium sulfate or their mixture, and its particle size range is 1～20 micron.
Described toughner POE is linear ethylene-octene copolymer, and density is 0.88～0.90g/cm
3, melting index is 0.5～10g/10min (test condition: 190 ℃ * 2.16kg).
Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can select for use hindered phenol or thioesters kind antioxidant as 3114,1010, DSTP wherein one or more; Auxiliary anti-oxidant can select for use the phosphorite kind antioxidant as 618,168 etc.;
Photostabilizer of the present invention is a kind of hindered amines oligopolymer, and its chemical name is: alpha-olefin (C20-C24) maleic anhydride-4-amino-2,2,6,6-tetramethyl piperidine polymkeric substance.This photostabilizer has very high molecular weight (about 3500), and density is 0.99g/cm
3, softening temperature is 95-125 ℃, thermostability:＞300 ℃, its optimum addition is 0.1～0.6% by weight percentage.
Its molecular structural formula is:
Other auxiliary agents of the present invention comprise shades of colour and look mother.
Above-mentioned this preparation method with polypropene composition of excellent illumination aging resisting performance, its concrete steps are as described below:
(1) takes by weighing raw material by above-mentioned weight proportion;
(2) polypropylene, mineral filler, toughner, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3～5 minutes;
(3) raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: 190～200 ℃ in a district, 200～210 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1～2 minute, and pressure is 12～18MPa.
The present invention is by adding a kind of have high molecular, low volatility and the photostabilizer Uvinul 5050H of excellent compatibility in polypropene composition, make the illumination aging resisting performance that whole polypropene composition maintains a long-term stability.
Uvinul 5050H is a kind of oligomeric hindered amine class photostabilizer, light stability and weathering resistance for plastics are especially effective, distinctive molecular structure makes that its photostabilizer than other is more effective, has the consistency good with polyacrylic polymer, low volatility, high anti-extractibility and high thermostability.
Advantage of the present invention is:
1, the present invention makes prepared polypropene composition have excellent illumination aging resisting characteristic and low volatility by adding a kind of an amount of photostabilizer Uvinul 5050H.
2, the method preparation technology of the illumination aging resisting performance that improves polypropene composition of the present invention's proposition is very simple, production cost is low.
3, the prepared polypropene composition of the present invention is when guaranteeing that material has excellent illumination aging resisting performance, and every physical and mechanical property of material is unaffected.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite formula, polypropylene is the copolymerization PP of Shanghai petrochemical iy produced, and trade names are M2600R, and melt flow rate (MFR) is 25g/10min.Described mineral filler is the 5000 order talcum powder that haicheng talc powder factory produces, and median size is 2.5 microns.Described toughner POE is linear ethylene-octene copolymer that U.S. Dupont company produces, and trade names Engage 8180, and density is 0.863g/cm
3, melt flow rate (MFR) is 0.5g/10min.Described photostabilizer is to be that German BASF AG produces, and trade names are Uvinul 5050H, and its chemical name is: alpha-olefin (C20-C24) maleic anhydride-4-amino-2,2,6,6-tetramethyl piperidine polymkeric substance.Described primary antioxidant is the DSTP that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester, and Ciba company produce 3114, 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 Ciba company product, and trade names are Irgafos 168, and chemical name is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Be used for the Tinuvin 944 of the photostabilizer of Comparative Examples for Ciba company product in addition, chemical name is poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] }, and the Tinuvin 770 of Ciba company product, chemical name is two (2,2,6, the 6-tetramethyl-piperidyl) sebate.Used black masterbatch is the black masterbatch that Ke Laien produces, commodity by name 2014.
Resin and various additive do to mix in super mixer 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: 190～200 ℃ in a district, 200～210 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1～2 minute, and pressure is 12～18Mpa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 90～100 ℃ convection oven dry 2～3 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection moulding machine.
The melt flow rate (MFR) test is undertaken by ISO1133, and test condition is 230 ℃ * 2.16Kg; The tensile property test is undertaken by ISO527-2, and specimen size is 170 * 10 * 4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80 * 10 * 4mm, and rate of bending is 2mm/min, and span is 64mm; The simply supported beam notched Izod impact strength is undertaken by ISO 179, and specimen size is 80 * 6 * 4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO 75, and specimen size is 120 * 10 * 4mm, and load is 0.45MPa.The illumination ageing performance test is undertaken by the PV1303 standard, and periodicity of illumination was 5 cycles, and specimen size is 145 * 45 * 3.2mm, adopts Atlas Ci4000 water-cooled xenon lamp aging instrument to carry out the illumination ageing performance test.
Comprehensive mechanical performance is passed judgment on by the numerical value of notched Izod impact strength, tensile strength, flexural strength and the modulus in flexure of test gained, resistance toheat is passed judgment on by the heat-drawn wire of test gained, the illumination aging resisting performance of material carries out the exposure experiment in 5 cycles according to the PV1303 standard code, passes judgment on the photostabilization grade according to the value of the colour-change scale Δ E of material surface behind the pre-irradiation.Specifically be divided into 5 grades: Δ E=0 ± 0.2 is 5 grades; Δ E=0.8 ± 0.2 is 4.5 grades; Δ E=1.7 ± 0.3 is 4 grades, and Δ E=2.5 ± 0.35 is 3.5 grades; Δ E=3.4 ± 0.4 is 3 grades; Δ E=4.8 ± 0.5 is 2.5 grades; Δ E=6.8 ± 0.6 is 2 grades; Δ E=9.6 ± 0.7 is 1.5 grades; Δ E=13.6 ± 1.0 are 1 grade.The numerical value of Δ E is more little, and the light aging resisting property of expression material is good more, and the photostabilization grade is also just high more.
Embodiment, Comparative Examples prescription and every The performance test results be Lie Gebiao as follows:
Table 1. embodiment 1-7 formula table (weight %)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Polypropylene | 70.25 | 70.05 | 69.85 | 63.05 | 78.05 | 58.05 | 98.05 |
| Mineral filler | 20 | 20 | 20 | 20 | 20 | 40 | - |
| Toughner POE | 8 | 8 | 8 | 15 | - | - | - |
| Photostabilizer Uvinul 5050H | 0.1 | 0.3 | 0.5 | 0.3 | 0.3 | 0.3 | 0.3 |
| Antioxidant 3114 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| Oxidation inhibitor DSTP | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Oxidation inhibitor 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Black masterbatch | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
Table 2. Comparative Examples 1-7 formula table (weight %)
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | Comparative Examples 7 | |
| Polypropylene | 70.35 | 69.95 | 69.55 | 62.95 | 77.95 | 57.95 | 97.95 |
| Mineral filler | 20 | 20 | 20 | 20 | 20 | 40 | - |
| Toughner POE | 8 | 8 | 8 | 15 | - | - | - |
| Photostabilizer 770 | - | 0.2 | 0.4 | 0.2 | 0.2 | 0.2 | 0.2 |
| Photostabilizer 944 | - | 0.2 | 0.4 | 0.2 | 0.2 | 0.2 | 0.2 |
| Antioxidant 3114 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| Oxidation inhibitor DSTP | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Oxidation inhibitor 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Black masterbatch | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
The test result of each prescription is referring to table 3, table 4
Table 3. embodiment 1-7 test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Melt flow rate (MFR) (g/10min) | 18.0 | 18.2 | 18.1 | 12.3 | 21.7 | 19.4 | 26.3 |
| Notched Izod impact strength (kJ/m 2) | 15.2 | 15.1 | 15.1 | 23.6 | 6.7 | 3.8 | 8.9 |
| Tensile strength (MPa) | 20.8 | 20.8 | 20.9 | 19.3 | 28.4 | 25.2 | 27.5 |
| Modulus in flexure (MPa) | 1760 | 1760 | 1756 | 1530 | 1950 | 2740 | 1260 |
| Heat-drawn wire (℃) | 102 | 103.7 | 103.6 | 101.8 | 112.6 | 121.8 | 99.6 |
| Fast light according to grade | 4.5 level | 5 grades | 5 grades | 5 grades | 5 grades | 5 grades | 5 grades |
Table 4 Comparative Examples 1-7 test result
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | Comparative Examples 7 | |
| Melt flow rate (MFR) (g/10min) | 18.0 | 18.2 | 18.1 | 12.2 | 21.9 | 19.1 | 26.2 |
| Notched Izod impact strength (kJ/m 2) | 15.2 | 15.1 | 15.1 | 23.7 | 6.7 | 3.8 | 8.9 |
| Tensile strength (MPa) | 20.8 | 20.7 | 20.9 | 19.2 | 28.5 | 25.2 | 27.4 |
| Modulus in flexure (MPa) | 1750 | 1760 | 1745 | 1520 | 1950 | 2740 | 1250 |
| Heat-drawn wire (℃) | 102 | 102.5 | 102.2 | 101.1 | 111.5 | 120.7 | 99.2 |
| Fast light according to grade | 1 grade | 4.5 level | 5 grades | 4.5 level | 4.5 level | 4 grades | 4.5 level |
Contrast as can be seen with the test result of Comparative Examples 1 from embodiment 1, the Uvinul 5050H of adding 0.1% can significantly improve the illumination aging resisting performance of material.Contrast as can be seen with the test result of Comparative Examples 2～6 from embodiment 2～6, no matter the polypropene composition of toughner POE and talcum powder filling or the polypropene composition that has only talcum powder to fill are arranged, the adding of photostabilizer Uvinul 5050H all has bigger help than other photostabilizer as 770,944 pairs of light aging resisting properties that improve material, and the fast light grade of shining all can reach 5 grades; Contrast as can be seen with the test result of Comparative Examples 7 from embodiment 7, the adding of Uvinul 5050H is also very obvious for the light aging resisting property that improves the virgin pp system.And can also find that from the contrast of the mechanical property of material the adding of Uvinul 5050H also can make the heat-drawn wire of material rise to some extent, thereby can improve the resistance toheat of composition.The consideration of comprehensive cost aspect simultaneously, in polypropene composition the addition of Uvinul 5050H be controlled at about 0.3% the most suitable.
Claims (10)
1. polypropene composition with excellent illumination aging resisting performance is characterized in that: formulated by following weight percent proportion raw material:
Polypropylene 50～99
Mineral filler 0～45
Toughner POE 0～15
Photostabilizer 0.1～0.6
Primary antioxidant 0.1～0.8
Auxiliary anti-oxidant 0.1～0.6
Other auxiliary agents 0.1～4.
2. a kind of polypropene composition with excellent illumination aging resisting performance according to claim 1 is characterized in that: described polypropylene is different mobile homo-polypropylene and block copolymerization propylene; Wherein the comonomer of block copolymerization propylene is an ethene, and its content is 4～10mol%, and the degree of crystallinity of homo-polypropylene is more than 70%, and degree of isotacticity is greater than 99%, and polyacrylic melt flow rate (MFR) is 2～60g/10min.
3. a kind of polypropene composition with excellent illumination aging resisting performance according to claim 1 is characterized in that: described mineral filler is talcum powder, lime carbonate, barium sulfate or their mixture, and its particle size range is 1～20 micron.
4. a kind of polypropene composition with excellent illumination aging resisting performance according to claim 1 is characterized in that: described toughner POE is linear ethylene-octene copolymer, and density is 0.88～0.90g/cm3, and melting index is 0.5～10g/10min.
5. a kind of polypropene composition according to claim 1 with excellent illumination aging resisting performance, it is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant is selected hindered phenol or thioesters kind antioxidant for use; Auxiliary anti-oxidant is selected the phosphorite kind antioxidant for use.
6. a kind of polypropene composition with excellent illumination aging resisting performance according to claim 5 is characterized in that: described oxidation inhibitor be 3114,1010 and DSTP in one or more, auxiliary anti-oxidant is 618 and/or 168.
7. a kind of polypropene composition according to claim 1 with excellent illumination aging resisting performance, it is characterized in that: described photostabilizer is a kind of hindered amines oligopolymer, its chemical name is: alpha-olefin (C20-C24) maleic anhydride-4-amino-2,2,6,6-tetramethyl piperidine polymkeric substance.
8. a kind of polypropene composition with excellent illumination aging resisting performance according to claim 7 is characterized in that:
This photostabilizer density is 0.99g/cm
3, softening temperature is 95-125 ℃, thermostability:＞300 ℃, its molecular structural formula is:
9. a kind of polypropene composition with excellent illumination aging resisting performance according to claim 7 is characterized in that: described other auxiliary agents comprise shades of colour and look mother.
10. method for preparing the described polypropene composition of claim 1, it is characterized in that: its concrete steps are as described below:
(1) weight proportion by claim 1 takes by weighing raw material;
(2) polypropylene, mineral filler, toughner, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3～5 minutes;
(3) raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: 190～200 ℃ in a district, 200～210 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time is 1～2 minute, and pressure is 12～18MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910200858 CN102108151A (en) | 2009-12-25 | 2009-12-25 | Polypropylene composition with high light aging resistant performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910200858 CN102108151A (en) | 2009-12-25 | 2009-12-25 | Polypropylene composition with high light aging resistant performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102108151A true CN102108151A (en) | 2011-06-29 |
Family
ID=44172442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910200858 Pending CN102108151A (en) | 2009-12-25 | 2009-12-25 | Polypropylene composition with high light aging resistant performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102108151A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345312A (en) * | 2011-07-15 | 2012-02-08 | 康泰塑胶科技集团有限公司 | Mute water discharging pipe |
| CN102675749A (en) * | 2012-05-22 | 2012-09-19 | 苏州新区华士达工程塑胶有限公司 | Formula of modified polypropylene |
| CN103102592A (en) * | 2013-02-04 | 2013-05-15 | 北京海科华昌新材料技术有限公司 | Modified polypropylene material for automotive bumper and preparation method thereof |
| CN105037944A (en) * | 2015-08-21 | 2015-11-11 | 天津市顺康科技发展有限公司 | Preparation method and application of soft foundation solidification component material |
| CN112538206A (en) * | 2019-09-23 | 2021-03-23 | 上海奉坤新材料有限公司 | Illumination-resistant modified PP material and preparation method thereof |
-
2009
- 2009-12-25 CN CN 200910200858 patent/CN102108151A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345312A (en) * | 2011-07-15 | 2012-02-08 | 康泰塑胶科技集团有限公司 | Mute water discharging pipe |
| CN102345312B (en) * | 2011-07-15 | 2014-06-25 | 康泰塑胶科技集团有限公司 | Mute water discharging pipe |
| CN102675749A (en) * | 2012-05-22 | 2012-09-19 | 苏州新区华士达工程塑胶有限公司 | Formula of modified polypropylene |
| CN103102592A (en) * | 2013-02-04 | 2013-05-15 | 北京海科华昌新材料技术有限公司 | Modified polypropylene material for automotive bumper and preparation method thereof |
| CN105037944A (en) * | 2015-08-21 | 2015-11-11 | 天津市顺康科技发展有限公司 | Preparation method and application of soft foundation solidification component material |
| CN105037944B (en) * | 2015-08-21 | 2017-06-20 | 天津市顺康科技发展有限公司 | The preparation method and application of soft base curing process construction material |
| CN112538206A (en) * | 2019-09-23 | 2021-03-23 | 上海奉坤新材料有限公司 | Illumination-resistant modified PP material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101759922B (en) | Light aging resistant polypropylene composition and preparation method thereof | |
| CN101759920B (en) | Polypropylene composite material with improved scraping and wiping resistance performance and preparation method thereof | |
| CN109370041B (en) | Polypropylene modified material with good rigidity and high elongation at break and preparation method thereof | |
| CN101759913A (en) | Novel scratch-proof polypropylene material and preparation method thereof | |
| CN102108152A (en) | Polypropylene (PP) composition with low dispersion property and excellent light ageing resistance | |
| CN103333409B (en) | Reinforced and toughened anti-ageing polypropylene composite material and preparation method thereof | |
| KR20210122267A (en) | Method for stabilizing halogen-free thermoplastic recyclables, plastic composition, stabilizer composition and use of stabilizer composition | |
| CN102181093A (en) | Anti-scratching polypropylene composite material and preparation method thereof | |
| KR101263983B1 (en) | Polymer alloy composition comprising poly-lactic acid for consumer plastic containers with excellent blow moldability and impact strength | |
| CN101759914A (en) | Mineral/whisker toughening-reinforcing polypropylene composition | |
| CN109679205A (en) | A kind of composite polyolefine material and preparation method thereof of high intensity that resist warping | |
| CN101759911A (en) | Polypropylene composite material with excellent rigid-tough balance and preparation method thereof | |
| KR101019261B1 (en) | Corrugated pipe for electrical cable using recycled polyethylene | |
| CN102108151A (en) | Polypropylene composition with high light aging resistant performance | |
| CN103756132A (en) | Wear-resisting polypropylene composite material and preparation method thereof | |
| CN114106532B (en) | Flame-retardant high-toughness PLA alloy material, and preparation method and application thereof | |
| CN101210097A (en) | ABS material with excellent light aging resisting property and preparing method thereof | |
| CN113912942A (en) | Environment-friendly odorless scratch-resistant polypropylene composite material and preparation thereof | |
| CN104559007A (en) | High-glossiness scratch-resistant polypropylene material and preparation method thereof | |
| CN101210088A (en) | Polypropylene composite material with excellent illumination aging resisting performance and preparing method thereof | |
| CN103073790A (en) | Polypropylene composite material resistant to surface friction damage and preparation method thereof | |
| CN102532692A (en) | Wollastonite modified polypropylene composite material | |
| CN109535563B (en) | Environment-friendly composite material and preparation method and application thereof | |
| KR102413843B1 (en) | Polyethylene resin composition for rotational molding | |
| TW202413529A (en) | Thermoplastic resin composition, method of preparing the same, and automotive interior part manufactured using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110629 |