CN1316457A - Composite polypropylene material filled by nm-class organized montmorillonite and inorganic spherical rigid particles and its preparing process - Google Patents
Composite polypropylene material filled by nm-class organized montmorillonite and inorganic spherical rigid particles and its preparing process Download PDFInfo
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Abstract
A polypropylene composition filled with nm-class organo-montmorillonite and inorganic spherical rigid particles is prepared from polypropylene (100 wt portions), nm-class organo-montmorillonite (1-25), inorganic spherical rigid particles (5-60) and antioxidizing agent (0.2-0.5) through spraying acetone solution onto said inorganic spherical rigid particles, mixing all components together, dual-screw extruding and fusion granulating. Its advantages include high modulus, good refractory nature, size stability and impact strength, and low cost.
Description
The present invention relates to polypropylene composite material, particularly collaborative polypropylene composite material of filling of nano organic montmorillonite and inorganic spherical rigid particles and preparation method thereof.
Polypropylene is as a kind of general-purpose plastics, because proportion is little, and good mechanical property, water-intake rate is low, has remarkable chemical stability, and is nonpoisonous and tasteless and have the advantage of the forming process of being easy to, and has been widely used in the every field of industrial production and daily life.The main drawback of polypropylene is that shrinking percentage is big, and the product size poor stability is easy to generate buckling deformation; And fragility is bigger under the low temperature, easily fracture.In addition, the plain polypropylene Young's modulus is low, poor heat resistance, weathering resistance are poor, rigidity deficiency, easy firing under the high temperature, thereby is difficult to directly as engineering plastics.In order to prolong polyacrylic work-ing life, the broadened application scope develops rapidly the study on the modification of polypropylene.At present polypropylene method of modifying commonly used is mainly contained: copolymerization, blend, filling strengthen, crosslinked, foaming, stretch, add suitable adjuvants etc.
Inorganics filled polypropylene composite material development rapidly, be because the adding of mineral filler has reduced the shrinking percentage of plastics, improved dimensional stability, overcome the buckling deformation of goods, thermotolerance, the rigidity of goods have also obtained improvement simultaneously, and have reduced cost.But because difference and both affinities of mineral filler and plastics self performance are poor, along with the adding of filler, the elongation at break of material, impelling strength and mobile can thereupon decline bring certain difficulty for the design of material and goods processing.Overcoming one of these difficult main method is the particle diameter that reduces the filler inorganic rigid particle, use spherical rigid particles hour at particle diameter, particularly reach micron order when following, under certain condition, inorganic spherical rigid particles can reach increases rigidity and simultaneously toughness reinforcing effect to polymkeric substance.As " modern plastics processed and applied " in April, 1998 number " ultra micro rigid inorganic rigid particles and filled plastics thereof " literary composition point out, the rigid particles radius is more little, toughness reinforcing effect is good more, but the rigid particles particle diameter is more little, then surfactivity is high more, easy more reunion the in the course of processing, can't be in matrix disperse well, thereby lose the purpose of enhancing, toughening polymer.So in actual applications, the ultra micro rigid particles is difficult in the matrix and fully disperses.
In various mineral fillers, fine inorganic spherical rigid particles often has toughness reinforcing effect.The toughening modifying mechanism of minute spherical inorganic rigid particle it is generally acknowledged to have following process: the existence of (1) inorganic spherical rigid particles produces stress concentration effect, and resin produces crack splitting around causing, and absorbs the certain deformation merit; (2) existence of inorganic spherical rigid particles makes the unlikely destructiveness cracking that develops into of tiny crack of matrix resin; (3) along with the miniaturization of filler, the specific surface area of inorganic spherical rigid particles increases, and filler and matrix contact area increase, and when material is hit, produces more crack splitting, and absorbs more striking energy.But if amount of filler is excessive, tiny crack easily develops into macroscopic view cracking, system degradation.The common layered silicate that has than big L/D ratio then is difficult to play the effect of increase flexible.
A kind of nanometer composite polyamide-clay material and preparation method thereof) and (on June 8th, 1999 laid-open U.S. Patents US5910523 adopt the intercalation composite methods layered silicate polynite can be scattered in the form of nanometer lamella and make composite nano polymer/clay material in the polymeric matrix (as disclosed Chinese patent CN 1206028 on January 27th, 1999:, Polyolefin nanocomposites), this nano composite material is under the less condition of inorganic content, can improve the intensity of polymer composites, rigidity, thermotolerance, barrier and processing characteristics etc., do not reduce simultaneously its impelling strength again, its behavior is different from general organic/inorganic composite material fully, is considered to high performance composite of new generation.Intercalation is compound generally dual mode, and monomer intercalation in advance aggregates into polymer then in the mineral filler of laminate structure, be called monomer intercalation polymeric composite method; Perhaps polymer is called direct intercalation compounding in montmorillonite layered silicate in solution or at direct intercalation under the polymer melt state.These two kinds of methods all must be handled montmorillonite layered silicate in advance, promptly pre-intercalation.Pre-intercalation is to utilize cation exchange reaction between montmorillonite layered silicate layer, the positively charged ion of organic molecule is inserted between montmorillonite layered silicate layer, and increase interlamellar spacing, improves the affinity of clay to polymkeric substance.
Adopt the different composite filled polymkeric substance of inorganic rigid particle can realize strengthening simultaneously toughness reinforcing, as Chinese invention patent CN1211591 (inorganic filler-toughened, Reinforced Polypropylene mixture and preparation method thereof, on March 24th, 1999 is open), process white and other mineral filler are constituted compounded mix, after its surface gives step-by-step processing with silane coupling agent and other coupling agent, play not only toughness reinforcing but also enhanced effect with acrylic resin is compound.The existing significant toughness of this polypropylene composite has favorable rigidity again; Also can become and have high workability and high tenacity concurrently, perhaps have the high filled polypropylene mixture of high tenacity.But because the autologous density of process white is higher, the proportion of polypropylene composite material that constitutes compounded mix preparation with other mineral filler is bigger, is unfavorable for reducing the weight of goods.
The object of the present invention is to provide collaborative polypropylene composite material of filling of nano organic montmorillonite and inorganic spherical rigid particles and preparation method thereof.In the polypropylene composite material of this collaborative filling, contain nano organic montmorillonite and minute spherical inorganic rigid particle simultaneously with good heat resistance.This nano organic montmorillonite with good heat resistance with polypropylene processing blend process in oxidative degradation less, and can in polypropylene matrix, disperse, under less content, can improve polyacrylic intensity, rigidity, thermotolerance, barrier and processing characteristics with the nanometer laminated structure unit; And the inorganic spherical rigid particles of filling simultaneously can be to polypropylene toughening, increase just, improve its dimensional stability, reduce the matrix material cost.Because the existence of nano organic montmorillonite, inorganic spherical rigid particles more can disperse in polymeric matrix well.By the synergy of laminar nano organic montmorillonoid and minute spherical inorganic rigid particle, realize the high performance of polypropylene composite material.
The component and the content following (weight part) of the collaborative polypropylene composite material of filling of nano organic montmorillonite of the present invention and inorganic spherical rigid particles:
100 parts of polypropylene
Nano organic montmorillonite 1-25 part
Surface-treated inorganic spherical rigid particles 5-60 part
Antioxidant 0.2-0.5 part
Polypropylene used in the present invention is for adopting isotatic polypropylene, syndiotactic polypropylene, Co-polypropylene or the modified polypropene of various polymerization process preparations, and wherein the effect of isotatic polypropylene is better.
Nano organic montmorillonite used in the present invention is the polynite mineral dust through heatproof organic molecule intercalation processing.Behind heatproof organic molecule intercalation, the distance between montmorillonite layer should be greater than 1.6 nanometers, even can be by 1.6 nanometers to about 7.0 nanometers.The polynite of this nano organic has good affinity to polypropylene, can disperse by the lamella with nanoscale in polypropylene matrix, and be difficult for oxidative degradation in recombination process.
Inorganic spherical rigid particles used in the present invention is specially lime carbonate (comprising water-ground limestone, light calcium carbonate, activated calcium carbonate and rhombspar), silicon-dioxide (comprising precipitated silica, diatomite, silica powder and gas-phase silica) or titanium dioxide fine powder rigid particles.The granularity of inorganic rigid particle is a micron order, and they should be more than 1000 orders.
Antioxidant used in the present invention is at polyacrylic antioxidant, as four (β-(3,5-di-tert-butyl-4-hydroxy phenyl) propylamine) tetramethylolmethane (commercial disignation antioxidant 1010), (3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester (commercial disignation antioxidant 1076).The adding of antioxidant is in order to be reduced in polyacrylic oxidative degradation in the preparation composite material.
The preparation method of the collaborative polypropylene composite material of filling of nano organic montmorillonite of the present invention and inorganic spherical rigid particles is: with raw material (weight part)
100 parts of polypropylene
Nano imvite 1-25 part organises
Surface-treated inorganic spherical rigid particles 5-60 part
After antioxidant 0.2-0.5 part thorough mixing is even, on common double screw extrusion press or conical double screw extruder, melt extrude granulation with ordinary method, can make the collaborative polypropylene composite material of filling of nano organic montmorillonite and inorganic spherical rigid particles.This method is easy, easy handling, thereby cost of manufacture is lower.
For inorganic spherical rigid particles is dispersed in the polypropylene matrix uniformly, should adopt different surface treatment agents that it is carried out pre-treatment at different inorganic rigid particles, to improve the interface adhesion of inorganic rigid particle and polypropylene matrix.For lime carbonate fine powder rigid particles, use the calcium stearate treatment agent that is equivalent to processed particle weight 1-4% to handle; For the fine silica rigid particles, use siloxanes coupling agent γ-aminocarbonyl propyl triethoxyl silane (commercial disignation KH550) treatment agent that is equivalent to processed particle weight 0.5-1% to handle; For titanium dioxide fine powder rigid particles, use single alcoxyl phosphatic type titanic acid ester (commercial disignation NDZ-130) treatment agent that is equivalent to processed particle weight 0.5-2% to handle.Concrete surface treatment method is: the acetone soln that will contain weight percent and be the 1-15% treatment agent is sprayed on the processed inorganic spherical rigid particles powder, and thorough mixing is so that the treatment agent homodisperse, oven dry about 100 ℃ then.
The polypropylene composite material of the present invention's preparation has favorable rigidity, intensity, dimensional stability, shock resistance, thermotolerance and weathering resistance, can be used for injection moulding air conditioning machinery, dishwasher shell etc.
Below in conjunction with embodiment technical scheme of the present invention and effect are further described.But employed concrete grammar, prescription and explanation are not limitation of the present invention.
Embodiment 1
The calcium stearate that will be equivalent to pending weight of calcium carbonate 2.5% is mixed with the acetone soln of 5% (weight ratio), is sprayed on light calcium carbonate (1250 order) powder, and oven dry about 100 ℃ obtains handling light calcium carbonate behind the thorough mixing.
With 100 parts of polypropylene (the Hyundai petroleum chemistry H1500 of company), 2 parts of nano organic montmorillonites (interlamellar spacing 2.0 nanometers) are handled 5 parts of light calcium carbonates, and 0.2 part of antioxidant 1010 after high mixer mixes, adopts twin screw extruder to melt extrude.Screw rod parameter and processing conditions are: first section second section the 3rd section four zone screw rotating speed (mm) of screw rod parameter processing conditions screw diameter length-to-diameter ratio
(℃) (℃) (℃) (℃) (rpm) 30.0 27 150 220 220 225 50 extrudates made product (1#) in 6 hours 100 ℃ of oven dry after granulation.The fusing point of sample and Tc are measured on the DSC7 of Perkin-Elmer company with pellet, and mechanical property adopts U.S. ASTM method at room temperature to characterize, and the results are shown in table 1.
Embodiment 2
The treatment process of light calcium carbonate (1250 order) is with embodiment 1.
With 100 parts of polypropylene (with embodiment 1), 2 parts of nano organic montmorillonites (interlamellar spacing 1.6 nanometers) are handled 15 parts of light calcium carbonates, and 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 2#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 3
The treatment process of light calcium carbonate (1250 order) is with embodiment 1.
With 100 parts of polypropylene (with embodiment 1), 2 parts of nano organic montmorillonites (interlamellar spacing 2.0 nanometers) are handled 30 parts of light calcium carbonates, and 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 3#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.Embodiment 4
The siloxanes coupling agent γ-aminocarbonyl propyl triethoxyl silane that will be equivalent to pending precipitated silica weight 1.0% is mixed with the acetone soln of 5% (weight ratio), be sprayed on silicon-dioxide (1250 order) powder, oven dry about 100 ℃ obtains handling silicon-dioxide behind the thorough mixing.
With 100 parts of polypropylene (with embodiment 1), 2 parts of nano organic montmorillonites (interlamellar spacing 2.0 nanometers) are handled 5 parts of silica 1s, and 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 4#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.Embodiment 5, Comparative Examples 1
With 100 parts of polypropylene (with embodiment 1), 1 part of nano organic montmorillonite (interlamellar spacing 2.0 nanometers), 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 5#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 6, Comparative Examples 2
With 100 parts of polypropylene (with embodiment 1), 2 parts of nano organic montmorillonites (interlamellar spacing 1.6 nanometers), 0.2 part of antioxidant adopts the method identical with embodiment 1 to process, and obtains product 6#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 7, Comparative Examples 3
With 100 parts of polypropylene (with embodiment 1), 4 parts of nano organic montmorillonites (interlamellar spacing 2.0 nanometers), 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 7#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 8, Comparative Examples 4
The treatment process of light calcium carbonate (1250 order) is with embodiment 1.
With 100 parts of polypropylene (with embodiment 1), handle 5 parts in lime carbonate, 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 8#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 9, Comparative Examples 5
The treatment process of light calcium carbonate (1250 order) is with embodiment 1.
With 100 parts of polypropylene (with embodiment 1), handle 15 parts in lime carbonate, 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 9#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 10, Comparative Examples 6
The treatment process of light calcium carbonate (1250 order) is with embodiment 1.
With 100 parts of polypropylene (with embodiment 1), handle 30 parts in lime carbonate, 0.2 part of antioxidant 1010 adopts the method identical with embodiment 1 to process, and obtains product 10#.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Embodiment 11
The treatment process of silicon-dioxide (1250 order) is with embodiment 4.
With 100 parts of propylene and ethylene block copolymers (Yanshan Petrochemical chemical industry two factories 1330), 2 parts of nano organic montmorillonites (interlamellar spacing 2.0 nanometers) are handled 5 parts of silica 1s, 0.2 part of antioxidant 1076, adopt the method identical to process, obtain product 11# with embodiment 1.Sample adopts the method sign identical with embodiment 1, the results are shown in table 1.
Each test data of comparison sheet 1 as seen, the Tc tool that contains the polypropylene composite material 1#-10# of filler is improved to some extent.In matrix material 5#-7#, owing to only added nano organic montmorillonite, 0# compares with virgin pp, and its tensile modulus, tensile strength all are improved, and tension set reduces less, but notched Izod impact strength is lower.In matrix material 8#-10#, owing to only added surface treatment inorganic spherical rigid particles lime carbonate, its notched Izod impact strength increases, and tensile modulus is improved less, and tension set reduces less, but tensile strength descends to some extent than virgin pp 0#.Added nano organic montmorillonite and surface treatment inorganic spherical rigid particles lime carbonate or silicon-dioxide simultaneously and make collaborative filled composite materials 1#-4# and 11# in polypropylene, the performance of material is comprehensively improved.
The performance of table 1 polypropylene composite material
Illustrate: 0# is an isotatic polypropylene, is Hyundai petroleum chemistry company product, model H1500.
| Sample number into spectrum | Fusing point (℃) | Tc (℃) | Tensile strength (MPa) | Tensile modulus (MPa) | Tension set (%) | Izod notched Izod impact strength (KJ/m 2) |
| ????0# | ????165.8 | ????111.5 | ????31.9 | ?1300 | ?930.6 | ????3.38 |
| ????1# | ????166.1 | ????118.5 | ????32.7 | ?1819 | ?770.5 | ????3.00 |
| ????2# | ????165.9 | ????119.2 | ????32.9 | ?1824 | ?625.0 | ????3.65 |
| ????3# | ????165.5 | ????120.3 | ????29.9 | ?1851 | ?490.7 | ????2.98 |
| ????4# | ????166.5 | ????121.2 | ????33.2 | ?1900 | ?700.5 | ????3.80 |
| ????5# | ????166.5 | ????112.6 | ????35.6 | ?1545 | ?846.0 | ????2.70 |
| ????6# | ????167.0 | ????113.5 | ????35.0 | ?1573 | ?887.1 | ????2.90 |
| ????7# | ????164.9 | ????114.7 | ????37.6 | ?1774 | ?708.1 | ????3.25 |
| ????8# | ????166.4 | ????115.1 | ????25.6 | ?1143 | ?879.7 | ????2.88 |
| ????9# | ????167.3 | ????118.2 | ????30.8 | ?1657 | ?772.8 | ????3.78 |
| ???10# | ????164.9 | ????120.1 | ????29.6 | ?1749 | ?731.5 | ????3.63 |
| ???11# | ?????- | ?????- | ????30.0 | ?1200 | ?165 | ????11.5 |
| ???12# | ?????- | ?????- | ????23 | ?800 | ?200 | ????10 |
12# is propylene and ethylene block copolymer, is Yanshan Petrochemical chemical industry two factory's products, model 1330.
Claims (10)
1. the collaborative polypropylene composite material of filling of nano organic montmorillonite and inorganic spherical rigid particles is characterized in that component and content following (weight part):
100 parts of polypropylene
Nano organic montmorillonite 1-25 part
Surface-treated inorganic spherical rigid particles 5-60 part
Antioxidant 0.2-0.5 part.
2. nano organic montmorillonite as claimed in claim 1 and inorganic spherical rigid particles are worked in coordination with filling polypropylene composite material, it is characterized in that described polypropylene is isotatic polypropylene, syndiotactic polypropylene, Co-polypropylene or modified polypropene.
3. nano organic montmorillonite as claimed in claim 1 and inorganic spherical rigid particles are worked in coordination with filling polypropylene composite material, it is characterized in that described nano organic montmorillonite is that the distance between the montmorillonite layer behind the intercalation is more than 1.6 nanometers through the polynite mineral dust of organic molecule intercalation processing.
4. nano organic montmorillonite as claimed in claim 1 and inorganic spherical rigid particles are worked in coordination with filling polypropylene composite material, it is characterized in that described surface-treated inorganic spherical rigid particles is that granularity is more than 1000 orders, and the silicon-dioxide that the lime carbonate of handling through the calcium stearate that is equivalent to processed particle weight 1-4%, the siloxanes coupling agent γ-aminocarbonyl propyl triethoxyl silane that is equivalent to processed particle weight 0.5-1% are handled, or be equivalent to the titanium dioxide that single alcoxyl phosphatic type titanic acid ester treatment agent of processed particle weight 0.5-2% is handled.
5. nano organic montmorillonite as claimed in claim 4 and inorganic spherical rigid particles are worked in coordination with filling polypropylene composite material, it is characterized in that described lime carbonate is water-ground limestone, light calcium carbonate, activated calcium carbonate or rhombspar; Silicon-dioxide is precipitated silica, diatomite, silica powder or gas-phase silica.
6. nano organic montmorillonite as claimed in claim 1 and inorganic spherical rigid particles are worked in coordination with filling polypropylene composite material, it is characterized in that described antioxidant is four (β-(3,5-di-tert-butyl-4-hydroxy phenyl) propylamine) tetramethylolmethane or (3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester.
7. as the preparation method of the collaborative filling polypropylene composite material of each described nano organic montmorillonite of claim 1-6 and inorganic spherical rigid particles: it is characterized in that with raw material (weight part)
100 parts of polypropylene
Nano organic montmorillonite 1-25 part
Surface-treated inorganic spherical rigid particles 5-60 part
After oxidation inhibitor 0.2-0.5 part thorough mixing is even, adopt ordinary method on twin screw extruder, to melt extrude granulation, promptly make the collaborative filling polypropylene composite material of nano organic montmorillonite and inorganic spherical rigid particles.
8. the preparation method of the collaborative filling polypropylene composite material of nano organic montmorillonite as claimed in claim 7 and inorganic spherical rigid particles, it is characterized in that described surface-treated inorganic spherical rigid particles is that granularity is more than 1000 orders, and process is equivalent to the lime carbonate of the calcium stearate processing of processed particle weight 1-4%, be equivalent to the silicon-dioxide of siloxanes coupling agent γ-aminocarbonyl propyl triethoxyl silane processing of processed particle weight 0.5-1%, or be equivalent to the titanium dioxide of single alcoxyl phosphatic type titanic acid ester treatment agent processing of processed particle weight 0.5-2%.
9. the preparation method of collaborative filling polypropylene composite material as claimed in claim 7, it is characterized in that described nano organic montmorillonite is that the distance between the montmorillonite layer after the intercalation processing is more than 1.6 nanometers through the polynite mineral dust of organic molecule intercalation processing.
10. the preparation method of collaborative filling polypropylene composite material as claimed in claim 8, it is characterized in that described surface treatment method is is that the acetone soln of 1-15% treatment agent is sprayed on the processed inorganic spherical rigid particles powder with containing weight percent, oven dry about 100 ℃ behind the thorough mixing.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040768B (en) * | 2009-10-13 | 2012-09-05 | 中国科学院化学研究所 | Polypropylene/calcium carbonate nanocomposite and preparation method thereof |
| CN104927283A (en) * | 2015-07-06 | 2015-09-23 | 蓝星（成都）新材料有限公司 | High-temperature-resistant polypropylene coloring master batch |
| CN104974423A (en) * | 2015-06-29 | 2015-10-14 | 北京化工大学 | Diatomite/polypropylene composite material and preparation method thereof |
| CN105820442A (en) * | 2016-05-19 | 2016-08-03 | 郑州航空工业管理学院 | High-temperature-resistant HPP basement membrane and preparing method thereof |
| CN114806015A (en) * | 2022-05-17 | 2022-07-29 | 深圳市酷彼伴玩具有限公司 | High-toughness polypropylene-based nano composite material and preparation method thereof |
-
2000
- 2000-04-03 CN CN 00105494 patent/CN1114657C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040768B (en) * | 2009-10-13 | 2012-09-05 | 中国科学院化学研究所 | Polypropylene/calcium carbonate nanocomposite and preparation method thereof |
| CN104974423A (en) * | 2015-06-29 | 2015-10-14 | 北京化工大学 | Diatomite/polypropylene composite material and preparation method thereof |
| CN104927283A (en) * | 2015-07-06 | 2015-09-23 | 蓝星（成都）新材料有限公司 | High-temperature-resistant polypropylene coloring master batch |
| CN105820442A (en) * | 2016-05-19 | 2016-08-03 | 郑州航空工业管理学院 | High-temperature-resistant HPP basement membrane and preparing method thereof |
| CN114806015A (en) * | 2022-05-17 | 2022-07-29 | 深圳市酷彼伴玩具有限公司 | High-toughness polypropylene-based nano composite material and preparation method thereof |
| CN114806015B (en) * | 2022-05-17 | 2024-03-22 | 深圳市酷彼伴玩具有限公司 | High-toughness polypropylene-based nanocomposite and preparation method thereof |
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| CN1114657C (en) | 2003-07-16 |
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