CN1323853A - Rigid particle reinforced and flexibilized polypropylene material and its prepn. method - Google Patents
Rigid particle reinforced and flexibilized polypropylene material and its prepn. method Download PDFInfo
- Publication number
- CN1323853A CN1323853A CN 01113414 CN01113414A CN1323853A CN 1323853 A CN1323853 A CN 1323853A CN 01113414 CN01113414 CN 01113414 CN 01113414 A CN01113414 A CN 01113414A CN 1323853 A CN1323853 A CN 1323853A
- Authority
- CN
- China
- Prior art keywords
- rubber
- coupling agent
- polypropylene
- rigid particles
- rigid
- 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.)
- Granted
Links
Abstract
A rigid particle reinforced, flexibilized polypropylene material and its preparation method. It said material polymer having flexible chain is used to treat rigid particle there by forms strong mutual action between flexible chain polymer and rigid particle and introduces an interface flexible layer botween rigid particle and polypropylene matrix, so that the polypropylene composite material with increased strength, modulus and toughness is obtained.
Description
The present invention relates to a kind of modified polypropylene material, specifically, the rigid particles that relates to a kind of interface flexible layer that induces one strengthens, flexibilized polypropylene material, and this preparation methods.
Polypropylene is large commodity polymer material, owing to its wide material sources, better performances, in industrial sector widespread uses such as chemical industry, building, light industry, automobile making, household electrical appliances, packings.Development along with petrochemical industry, polyacrylic throughput has reached very big scale, and along with the development of industries such as aerospace, automobile, household electrical appliances, building, packing, requirement to material property is more and more higher, common polypropylene must pass through modification, give its high-performance, can satisfy the demand.At present, the unreasonable structure of polypropylene material product, in, low grade products is many, high-performance, high value added product are less, in order to satisfy the needs of industries such as the automobile develop rapidly, building materials, packing, household electrical appliances, developing many kinds, high-performance, high added value polypropylene material is a vital task.In addition, the exploitation high-performance poly olefin material that can replace engineering plastics has more special meaning.
By methods such as the change catalyzer of polyreaction and reaction conditions, adding comonomers, can synthesize the acrylic resin of better performances and different varieties, but this is very limited, and needs very big input.By new working method and to polypropylene fill, blend and enhancing modified, can make polypropylene reach high performance, the polypropylene of existing kind is carried out modification, be the development kind, improve the main path of performance.Adopt the filler filled polypropylene, can obviously improve the rigidity, hardness, heat-drawn wire, creep resistant, dimensional stability of material etc., also can significantly reduce cost, but can cause that usually the intensity of material, toughness descend.Elastomer blended with polypropylene and rubber-like, can improve the toughness of material effectively, but intensity, modulus and the thermotolerance etc. of material are descended significantly, this class system is carried out dynamic vulcanization, though can slow down these performance decrease, effect is also not obvious.In infill system, add a certain amount of rubber, can improve the toughness of material, but the intensity of material, modulus and thermotolerance significantly decrease all.The eighties is since mid-term, it is toughness reinforcing rigid particles to have occurred, polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) successively appearred, polycarbonate/(acrylonitrile-styrene), it is the inorganic rigid particle toughening polymer system of representative that polypropylene/organic rigid-particle toughening polymer systems such as (acrylonitrile-butadiene-styrene (ABS)s) reaches with lime carbonate, as: document is Kurauchi T 1., Ohta T.J.Mat.Sci., 1984,19:1699., 2. Ou Yuchun.ChineseJournal of Polymer Science, 1993,11 (1): 31., 3. appoint and show really, white orchid English, Wang Guiheng. Chinese plastics, 2000,14 (1): 22. and 4. Wu Wei, Xu plants moral. polymer journal, 2000, (1): 99. technology of being reported.For inorganic rigid particle toughening polymer system, mostly to be similar to globular lime carbonate, barium sulfate etc. as packing material, but this system has certain requirement to the character of matrix itself, the stretching of material, flexural strength significantly do not improve, and can not get can be used as the high-performance polypropylene material that engineering plastics use.The nano-particles filled polyolefine can improve the performance of material, but the dispersion of nanoparticle in polymkeric substance difficulty relatively for the Application Areas of being particular about material cost, does not reach practical degree as yet.People adopt the silane coupling agent of some belt length carbochains that mineral filler such as kaolin etc. is handled, and have introduced the interface flexible layer in compound system, because the deformation of flexible layer, improved compound system toughness, as document: Ou Yuchun, Fang Xiaoping. the polymer journal, 1996, (1): 59. and the Fang Xiao duckweed,, Ou Yuchun, Feng Yupeng, Li Liandi. polymer material science and engineering, 1996,12 (3): 50. technology of being reported.But owing to fail to form firm bonding (combining as chemical bond) between interface flexible layer and the matrix, the high rigidity of compound system that Inorganic Fillers Filled is given has also been lost in the deformation of interfacial layer.How introducing between flexible layer and weighting material and matrix structure and the performance that forms strong interactions such as chemical bond combines, controls the interface flexible layer, make balanced the increasing of intensity, modulus, toughness of infill system, be the focus of domestic and international macromolecular material circle research, the filled polyolefin material that acquisition has high strength, high-modulus, high tenacity simultaneously is the target that numerous material suppliers author pursues.
The objective of the invention is to disclose that a kind of rigid particles strengthens, flexibilized polypropylene material, and this preparation methods, the intensity that prior art exists is low to overcome, poor toughness defective.
Technical conceive of the present invention is such:
Rigid particles of the present invention strengthens, flexibilized polypropylene material, employing has the polymer treatment rigid particles of flexible chain, make the rubber polymer of flexible chain be coated on the surface of particle filled composite equably, by flexible-chain polymer and and rigid particles form the grafting between the coupling agent of mortise and the crosslinked flexible-chain polymer and the rigid particles formation strong interaction of making of polymkeric substance itself.The flexible chain coating layer can be higher in recombination process with substrate molecule chain occurrence degree molecular chain mutual diffusion mutually, dynamic vulcanization by the flexible layer polymkeric substance makes both molecular chains form grafting and interlocking structure, thereby has introduced one deck and both all have the interface flexible layer of mortise between rigid particles and polypropylene matrix.In matrix, add the functional poly propylene of grafting polar group simultaneously, with the interface bonding of further raising compound system.On the one hand, can bring into play the enhancement of rigid particles, on the other hand, because the existence of interface flexible layer, the endergonic ability of compound system will increase considerably, and the toughness of material increases.The character of research matrix properties, processing condition, introducing interfacial layer (modulus, molecular structure, with the consistency of matrix, with the bonding of weighting material) and the form of weighting material and the relation of matrix material morphological structure and mechanical property, optimize processing condition and interface structure, the thickness, modulus of control interfacial layer and with the bonding of particle filled composite, matrix etc. obtains intensity, modulus, the balanced inorganic rigid particle enhanced polypropylene compound system that increases of toughness.
Technical scheme of the present invention:
Polypropylene material of the present invention comprises that by weight percent 5.0～40.0% A and 60.0～95.0% B constitute.
Wherein:
Component and the weight percentage of A comprise:
Rigid particles 95～99%
Coupling agent 0.5～2.0%
Rubber 0.5～3.0%
Component and the weight percentage of B comprise:
Polypropylene 84～98%
The functional poly propylene 1.0～15% of graft modification
Oxidation inhibitor 0.05～1.0%
Component and the weight percentage of preferred B comprise:
Polypropylene 91.5～97.7%
The functional poly propylene 2.0～8.0% of graft modification
Oxidation inhibitor 0.3～0.5%
Said rigid particles is an inorganic rigid particle, comprises wollastonite, talcum powder, glass microballon, mica or short glass fiber and composition thereof etc.;
Said coupling agent is double bond containing silane coupling agent or a titanate coupling agent in the structure, can preferably adopt the silane coupling agent of two keys, the A-151 coupling agent that preferably adopt Shanghai to shine the strong waffle worker of KH-570 coupling agent or Nanjing company limited that magnificent Glass Co., Ltd. produces produces;
Said rubber is general synthetic rubber, as terpolymer EP rubber, cis-1,4-polybutadiene rubber, paracril, styrene-butadiene rubber(SBR), also can be natural rubber;
Said polypropylene is the universal product, can be homo-polypropylene, also can be Co-polypropylene, is the polypropylene of Y1600 and M700R as the trade mark that can adopt Shanghai petrochemical industry plastic section to produce;
The functional poly propylene of said graft modification the has been grafting polypropylene of polar group, comprise grafted maleic anhydride, graft acrylic acid, the modified polypropene of grafting methacrylic acid or grafted propylene acid butyl ester, the preparation method of the functional poly propylene of graft modification comprises solid phase grafting and fusion-grafting, can preferably adopt the modified polypropene of grafted maleic anhydride, this modified polypropene can adopt the commercially available prod, the trade mark that rises the production of novel material company limited as Shanghai day is the modified polypropene of CMG9801, preferably adopt U.S. Pat Patent5, the modified polypropene that 079,302 disclosed method is produced;
Said oxidation inhibitor is conventional product, as antioxidant 1010 and oxidation inhibitor DSTP etc.
The preparation of above-mentioned polypropylene material comprises the steps:
(1) with coupling agent and the water mixed according to 1: 9, at room temperature stir with agitator, regulate pH to 2～6 of mixture with acid, mix, said acid is water-soluble organic acid, preferably adopts acetum;
(2) by said ratio, aqueous solution thorough mixing in super mixer with inorganic rigid particle and above-mentioned coupling agent, mixture is placed baking oven, in 80 ℃ to 120 ℃ oven dry down, making in the coupling agent molecule, the active group of the silicon hydroxyl of hydrolysis and inorganic rigid particle surface reacts, thereby between rigid particles and coupling agent, form strong interaction (combining), obtain a kind of inorganic rigid particle after coupling agent treatment as chemical bond;
(3) rubber is to the coating of rigid particles: terpolymer EP rubber and cis-1,4-polybutadiene rubber are dissolved in the solvent, be mixed with concentration and be 2～8% rubber solutions, add superoxide (account for rubber 1～3%) and vulcanization accelerator (account for rubber 1～2%), to place the super mixer mixing section according to aforementioned proportion through the rigid particles after the coupling agent treatment then, add rubber solutions, under 23～40 ℃, mix, place vacuum drying oven under 40～50 ℃ condition, to dry in the gained mixture, remove solvent;
Said solvent is a toluene, and said superoxide is a dicumyl peroxide, and said vulcanization accelerator is TMTD;
Paracril; styrene-butadiene rubber(SBR) and natural rubber adopt commercially available latex products; rubber latex is diluted with water to the emulsion of 10～30% rubber contents; add 0.5～2% (accounting for the percentage composition of rubber) vulcanizing agent; 0.05～1.5% (accounting for the percentage composition of rubber) vulcanization accelerator and 0.05～1.0% activator; mixture is stirred; will proportionally place the super mixer mixing section through the rigid particles after the coupling agent treatment then; add the mixture of rubber latex; under 23～40 ℃, mix; place vacuum drying oven under 40～50 ℃ condition, to dry in the gained mixture removal moisture;
Said vulcanizing agent is a colloid sulphur, and said vulcanization accelerator is TMTD, and said activator is a zinc oxide;
(4) rigid particles and polyacrylic compound:
Will be through the rigid particles and the polypropylene of step (3) processing, modified polypropene, oxidation inhibitor mixes according to aforementioned proportion, adopt double-screw extruding pelletizing, in extrusion, the rubber that is coated on the rigid particles surface is carried out dynamic vulcanization, promptly in the recombination process of system, pass through superoxide, the effect of vulcanizing agent and vulcanization accelerator, make the rubber layer that is coated on the rigid particles surface produce crosslinked, the molecular chain of rubber layer produces grafting with the double bond containing coupling agent in rigid particles surface on the one hand in cross-linking process, on the other hand with the chain formation grafting of matrix polypropylene molecule and the interlocking structure that contact, make the stronger bonding of formation between rubber molecular chain and rigid particles and matrix resin, thus the interface flexible layer of the bonds well that in rigid-particle filled polypropylene system, induces one all to have with two components.In conjunction with modified polypropene system interface bonded is further strengthened, promptly obtain rigid particles enhancing of the present invention, flexibilized polypropylene material.The material of gained can be used for various moulding processes, makes various goods.
Adopt the polypropylene material that aforesaid method obtained, can reduce polyacrylic cost, intensity, modulus and the toughness of filled polypropylene material all are significantly improved, obviously improve the thermotolerance and the creep resistance of material simultaneously.
Embodiment 1
0.2 kilogram of coupling agent kh-570 and 1.8 kg of water are mixed in container, acetum with 8% is regulated the pH to 4 of mixture, with 9.6 kilograms of wollastonites (300 order) and coupling agent aqueous solution thorough mixing in super mixer, mixture is placed baking oven, in 110 ℃ of following dry for standby, with 0.2 kilogram of terpolymer EP rubber and 4 gram dicumyl peroxides, 4 gram TMTD are dissolved in 2.3 kilograms of toluene, wollastonite and rubber solutions with above-mentioned dry for standby places the super mixer mixing section then, under 25 ℃, mix, place vacuum drying oven under 45 ℃ condition, to dry in the gained mixture, remove solvent, and with solvent recuperation;
Polypropylene, 0.12 kilogram of antioxidant 1010 that rigid particles after will handling through above-mentioned steps and 37.8 kilograms of polypropylene Y1600,2 kilograms of solid phase graftings react the grafted maleic anhydride that makes, 0.08 kilogram kilogram oxidation inhibitor DSTP mixes, adopt double-screw extruding pelletizing, the twin screw extruder temperature is provided with: one section, and 120 ℃; Two sections, 180 ℃; Three sections, 190 ℃; Four sections, 200 ℃; Five sections, 205 ℃; Six sections, 205 ℃; Seven sections, 205 ℃; Eight sections, 205 ℃; Nine sections, 205 ℃; Ten sections, 200 ℃, driving screw rotating speed: 80 rev/mins; Charging conveying screw rod rotating speed: 15 rev/mins.Promptly obtain rigid particles enhancing of the present invention, flexibilized polypropylene material.Its mechanical property sees Table 1.
Embodiment 2
Adopt process and the processing condition identical with embodiment 1, rubber changes cis-1,4-polybutadiene rubber into.Its mechanical property sees Table 1.
Embodiment 3
Adopt process and the processing condition identical with embodiment 2, the cis-1,4-polybutadiene rubber consumption changes 0.1 kilogram into.Its mechanical property sees Table 1.
Embodiment 4
Adopt process and the processing condition identical with embodiment 3, rigid particles changes mica (325 order) into.Its mechanical property sees Table 1.
Embodiment 5
Adopt process and the processing condition identical with embodiment 3, rigid particles changes talcum powder (300 order) into.Its mechanical property sees Table 1.
Embodiment 6
Adopt process and the processing condition identical with embodiment 3, rigid particles changes glass microballon (300 order) into.Its mechanical property sees Table 1.
Embodiment 7
0.2 kilogram of coupling agent kh-570 and 1.8 kg of water are mixed in container, acetum with 8% is regulated the pH to 4 of mixture, with 9.6 kilograms of wollastonites (300 order) and coupling agent aqueous solution thorough mixing in super mixer, mixture is placed baking oven, in 110 ℃ of following dry for standby, with 1 kilogram of 20% natural rubber latex and 2 gram colloid sulphur, 1.6 gram TMTD and 1.0 gram zinc oxide mix, wollastonite and rubber latex with above-mentioned dry for standby places the super mixer mixing section then, under 25 ℃, mix, place vacuum drying oven under 45 ℃ condition, to dry in the gained mixture, remove moisture;
Rigid particles after will handling through above-mentioned steps and 37.8 kilograms of polypropylene Y1600,2 kilograms of polypropylene, 0.12 kilogram of antioxidant 1010s that react the grafted maleic anhydride that makes by solid phase grafting, 0.08 kilogram kilogram oxidation inhibitor DSTP mixes, adopt double-screw extruding pelletizing, the twin screw extruder temperature is provided with: one section, and 120 ℃; Two sections, 180 ℃; Three sections, 190 ℃; Four sections, 200 ℃; Five sections, 205 ℃; Six sections, 205 ℃; Seven sections, 205 ℃; Eight sections, 205 ℃; Nine sections, 205 ℃; Ten sections, 200 ℃, driving screw rotating speed: 80 rev/mins; Charging conveying screw rod rotating speed: 15 rev/mins.Promptly obtain rigid particles enhancing of the present invention, flexibilized polypropylene material.Its mechanical property sees Table 1.
Embodiment 8
Adopt process and the processing condition identical with embodiment 7, natural rubber latex changes nitrile rubber into.Its mechanical property sees Table 1.
Embodiment 9
Adopt process and the processing condition identical with embodiment 7, natural rubber latex changes styrene-butadiene latex into.Its mechanical property sees Table 1.
Embodiment 10
Adopt process and the processing condition identical with embodiment 1, used coupling agent changes A-151 into.Its mechanical property sees Table 1.
Embodiment 11
Adopt process and the processing condition identical with embodiment 1, used polypropylene changes M700R into.Its mechanical property sees Table 1.
Embodiment 12
Adopt process and the processing condition identical with embodiment 1, the modified polypropene of grafted maleic anhydride changes the modified polypropene of graft acrylic acid into.Its mechanical property sees Table 1.
Embodiment 13
Adopt process and the processing condition identical with embodiment 1, the modified polypropene that solid phase grafting reacts the grafted maleic anhydride that makes changes the modified polypropene of the graft acrylic acid that melting graft reaction makes into.Its mechanical property sees Table 1.
Comparative Examples 1
10 kilograms of wollastonites and 39.8 kilograms of polypropylene Y1600,0.12 kilogram of antioxidant 1010,0.08 kilogram of kilogram oxidation inhibitor DSTP mixes, and adopts double-screw extruding pelletizing, and the expressing technique condition is with embodiment 1.
Comparative Examples 2
Adopt process and the processing condition identical with Comparative Examples 1, wollastonite makes mica into.Its mechanical property sees Table 1.
Comparative Examples 3
Adopt process and the processing condition identical with Comparative Examples 1, polypropylene Y1600 makes M700R into.Its mechanical property sees Table 1.
Table 1
| Material | Tensile strength (MPa) | Tensile modulus (MPa) | Flexural strength (MPa) | Modulus in flexure (MPa) | Notched izod shock strength (J/m) |
| Virgin pp Y1600 | ????32.73 | ????1379 | ????52.86 | ????1394 | ????21.67 |
| Virgin pp M700R | ????23.25 | ????995 | ????36.89 | ????1037 | ????68.42 |
| Comparative Examples 1 | ????28.16 | ????2018 | ????58.94 | ????2116 | ????18.39 |
| Comparative Examples 2 | ????28.79 | ????2071 | ????59.28 | ????2109 | ????18.72 |
| Comparative Examples 3 | ????21.76 | ????1502 | ????44.37 | ????1687 | ????62.54 |
| Example one | ????33.15 | ????2154 | ????62.75 | ????2541 | ????26.27 |
| Example two | ????34.02 | ????2208 | ????62.30 | ????2216 | ????26.39 |
| Example three | ????34.87 | ????2245 | ????63.56 | ????2592 | ????27.63 |
| Example four | ????35.14 | ????2342 | ????65.14 | ????2651 | ????29.43 |
| Example five | ????33.98 | ????2274 | ????64.13 | ????2630 | ????29.36 |
| Example six | ????33.28 | ????2193 | ????60.32 | ????2169 | ????24.50 |
| Example seven | ????33.76 | ????2230 | ????63.18 | ????2460 | ????27.87 |
| Example eight | ????33.07 | ????2216 | ????62.91 | ????2514 | ????27.64 |
| Example nine | ????33.19 | ????2209 | ????62.18 | ????2537 | ????27.81 |
| Example ten | ????33.68 | ????2176 | ????63.15 | ????2530 | ????26.94 |
| Example 11 | ????27.59 | ????1635 | ????51.32 | ????1816 | ????137.65 |
| Example 12 | ????32.94 | ????2103 | ????61.18 | ????2351 | ????27.39 |
| Example 13 | ????32.89 | ????2116 | ????61.95 | ????2478 | ????26.97 |
Claims (10)
- A rigid particles strengthen, flexibilized polypropylene material, it is characterized in that this material comprises that by weight percent 5.0～40.0% A and 60.0～95.0% B constitute, wherein:Component and the weight percentage of A comprise:Rigid particles 95～99%Coupling agent 0.5～2.0%Rubber 0.5～3.0%Component and the weight percentage of B comprise:Polypropylene 84～98%The functional poly propylene 1.0～15% of graft modificationOxidation inhibitor 0.05～1.0%Said rigid particles is an inorganic rigid particle;Said coupling agent is double bond containing silane coupling agent or a titanate coupling agent in the structure;Said rubber is terpolymer EP rubber, cis-1,4-polybutadiene rubber, paracril, styrene-butadiene rubber(SBR) or natural rubber;The functional poly propylene of said graft modification the has been grafting polypropylene of polar group.
- 2. material as claimed in claim 1 is characterized in that, component and the weight percentage of B comprise:Polypropylene 91.5～97.7%The functional poly propylene 2.0～8.0% of graft modificationOxidation inhibitor 0.3～0.5%.
- 3. material as claimed in claim 1 or 2 is characterized in that, said rigid particles is wollastonite, talcum powder, glass microballon, mica or short glass fiber and composition thereof.
- 4. material as claimed in claim 1 or 2 is characterized in that, said coupling agent is a double bond containing silane coupling agent in the structure.
- 5. material as claimed in claim 4 is characterized in that, said coupling agent is the Shanghai A-151 coupling agent that the strong waffle worker of KH-570 coupling agent or Nanjing company limited that magnificent Glass Co., Ltd. produces produces of shining.
- 6. material as claimed in claim 1 is characterized in that, the functional poly propylene of said graft modification is the modified polypropene of grafted maleic anhydride, graft acrylic acid, grafting methacrylic acid or grafted propylene acid butyl ester.
- 7. material as claimed in claim 6 is characterized in that, the functional poly propylene of said graft modification is the modified polypropene of grafted maleic anhydride.
- 8. preparation methods as claimed in claim 1 or 2 is characterized in that preparation comprises the steps:(1) coupling agent is mixed with water, regulate pH to 2～6 of mixture with water-soluble organic acid;(2) by said ratio, with the aqueous solution thorough mixing of inorganic rigid particle, mixture is dried with above-mentioned coupling agent, obtain a kind of inorganic rigid particle after coupling agent treatment;(3) terpolymer EP rubber and cis-1,4-polybutadiene rubber are dissolved in the solvent, are mixed with rubber solutions, add superoxide and vulcanization accelerator, then with the rigid particles of step (2) and rubber solutions according to the aforementioned proportion thorough mixing, oven dry, removal solvent; Or:Paracril, styrene-butadiene rubber(SBR) and natural rubber are adopted commercially available latex products, with the rubber latex dilute with water, add vulcanizing agent, vulcanization accelerator and activator, mixture is stirred, rigid particles and rubber latex with step (2) mixes then, with the oven dry of gained mixture, remove moisture;(4) will mix according to aforementioned proportion through rigid particles and polypropylene, modified polypropene, the oxidation inhibitor that step (3) is handled, extruding pelletization promptly obtains rigid particles enhancing, flexibilized polypropylene material.
- 9. method as claimed in claim 8 is characterized in that, coupling agent is mixed with water, regulates the pH of mixture with acetum.
- 10. method as claimed in claim 8 is characterized in that, said solvent is a toluene, and said superoxide is a dicumyl peroxide, and said vulcanization accelerator is TMTD; Said vulcanizing agent is a colloid sulphur, and said vulcanization accelerator is TMTD, and said activator is a zinc oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011134143A CN1141335C (en) | 2001-06-12 | 2001-06-12 | Rigid particle reinforced and flexibilized polypropylene material and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011134143A CN1141335C (en) | 2001-06-12 | 2001-06-12 | Rigid particle reinforced and flexibilized polypropylene material and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1323853A true CN1323853A (en) | 2001-11-28 |
| CN1141335C CN1141335C (en) | 2004-03-10 |
Family
ID=4660140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011134143A Expired - Fee Related CN1141335C (en) | 2001-06-12 | 2001-06-12 | Rigid particle reinforced and flexibilized polypropylene material and its prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1141335C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504406A (en) * | 2011-10-12 | 2012-06-20 | 大连工业大学 | Polypropylene reinforced modifying material and preparation method thereof |
| CN102702622A (en) * | 2012-07-02 | 2012-10-03 | 华东理工大学 | Polypropylene/shear thickening fluid high-toughness material and preparation method thereof |
| CN102060951B (en) * | 2009-11-12 | 2012-12-19 | 中国石油化工股份有限公司 | Process for continuously producing co-polypropylene with high ethylene content by using propylene gas-phase polymerization device |
| CN106800672A (en) * | 2016-12-16 | 2017-06-06 | 宁波和塑塑业科技有限公司 | A kind of high abrasion high tenacity chassis |
| CN106864077A (en) * | 2017-03-21 | 2017-06-20 | 金华职业技术学院 | A kind of express delivery list of information security |
| CN109749238A (en) * | 2018-12-27 | 2019-05-14 | 会通新材料股份有限公司 | A kind of polypropylene modified material and preparation method thereof improving impact strength |
| CN110511484A (en) * | 2019-08-26 | 2019-11-29 | 广东圆融新材料有限公司 | Polypropylene material and preparation method thereof |
| CN113817270A (en) * | 2021-11-02 | 2021-12-21 | 常州瑞杰新材料科技有限公司 | Polypropylene composite material and preparation method thereof |
-
2001
- 2001-06-12 CN CNB011134143A patent/CN1141335C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060951B (en) * | 2009-11-12 | 2012-12-19 | 中国石油化工股份有限公司 | Process for continuously producing co-polypropylene with high ethylene content by using propylene gas-phase polymerization device |
| CN102504406A (en) * | 2011-10-12 | 2012-06-20 | 大连工业大学 | Polypropylene reinforced modifying material and preparation method thereof |
| CN102504406B (en) * | 2011-10-12 | 2013-05-01 | 大连工业大学 | Polypropylene reinforced modifying material and preparation method thereof |
| CN102702622A (en) * | 2012-07-02 | 2012-10-03 | 华东理工大学 | Polypropylene/shear thickening fluid high-toughness material and preparation method thereof |
| CN106800672A (en) * | 2016-12-16 | 2017-06-06 | 宁波和塑塑业科技有限公司 | A kind of high abrasion high tenacity chassis |
| CN106800672B (en) * | 2016-12-16 | 2019-09-06 | 宁波安川大道机电科技有限公司 | A kind of high abrasion high tenacity chassis |
| CN106864077A (en) * | 2017-03-21 | 2017-06-20 | 金华职业技术学院 | A kind of express delivery list of information security |
| CN109749238A (en) * | 2018-12-27 | 2019-05-14 | 会通新材料股份有限公司 | A kind of polypropylene modified material and preparation method thereof improving impact strength |
| CN110511484A (en) * | 2019-08-26 | 2019-11-29 | 广东圆融新材料有限公司 | Polypropylene material and preparation method thereof |
| CN110511484B (en) * | 2019-08-26 | 2022-03-22 | 广东圆融新材料有限公司 | Polypropylene material and preparation method thereof |
| CN113817270A (en) * | 2021-11-02 | 2021-12-21 | 常州瑞杰新材料科技有限公司 | Polypropylene composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1141335C (en) | 2004-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1100087C (en) | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof | |
| CN1155652C (en) | Toughened plastics and its preparing process | |
| CN1950446A (en) | Functionalized propylene polymer compositions and composites containing same | |
| CN1760265A (en) | A kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite | |
| CN1210345C (en) | Polyvinyl chloride reinforcing and tougheness improving modifier and preparation and application thereof | |
| CN1141335C (en) | Rigid particle reinforced and flexibilized polypropylene material and its prepn. method | |
| CN1865335A (en) | High concentration plastic nano flame-proof agglomerate production method | |
| CN1147529C (en) | Formula and production process of filling modified reinformed PE/PP/PS composite material | |
| CN1827682A (en) | Process for preparing predispersed masterbatch of polyolefin and nano calcium carbonate | |
| CN1247682C (en) | Dynamic polypropylene sulfide composite material and its preparation method | |
| CN1191300C (en) | Tertiary polypropylene/elastomer/inorganic filler composite material and preparing method thereof | |
| CN1648158A (en) | Wood-plastic composite material and its preparing method | |
| CN1537131A (en) | Composite materials made from treated cellulose and plastic | |
| CN1300236C (en) | Mineral/ whisker reinforced polypropylene composition | |
| CN1194998C (en) | Nano-class rubber-laminated inorganic substance composition and its preparing process | |
| CN101067014A (en) | Process of grafting maleic anhydride with vinyl methacrylate | |
| CN1250638C (en) | Nylon particle toughness increased polypropylene composite material and preparing method | |
| CN110734630A (en) | high-toughness PET material for plastic uptake box | |
| CN1137933C (en) | High-rigidity high-toughness plastics and its preparing process | |
| CN1180012C (en) | Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method | |
| CN1164663C (en) | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process | |
| CN1052987C (en) | Method for preparing modified styrene butadiene rubber powder used as toughness-increased agent for poly vinyl chloride | |
| CN1257939C (en) | Polyamide composition and its preparing method | |
| CN1114657C (en) | Composite polypropylene material filled by nm-class organized montmorillonite and inorganic spherical rigid particles and its preparing process | |
| CN1280347C (en) | Polyolefin composite material filled with modified gangue powder and method for preparing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |