CN102311583B - Rigidity-toughness balanced polypropylene - Google Patents
Rigidity-toughness balanced polypropylene Download PDFInfo
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Abstract
The invention discloses rigidity-toughness balanced polypropylene. The rigidity-toughness balanced polypropylene comprises: by weight, 45 to 90% of polypropylene, 5 to 20% of coupling agent-modified low-mesh talcum powder, 5 to 30% of high-mesh talcum powder, 0 to 15% of a flexibilizer, 0 to 2% of one or more antioxygens and 0 to 2% of one or more other additives. A preparation method of the coupling agent-modified low-mesh talcum powder comprises diluting a coupling agent by an appropriate amount of absolute ethanol and mixing the diluted coupling agent and low-mesh talcum powder well to obtain the desired product. Particle sizes of the low-mesh talcum powder are in a range of 400 to 1500 meshes and particle sizes of the high-mesh talcum powder are in a range of 2000 to 10000 meshes. Because of balance between rigidity and toughness, the rigidity-toughness balanced polypropylene can be utilized widely for interior and exterior decorations of middle/high-grade automobiles with a natural color or other colors. The invention also discloses a preparation method of the rigidity-toughness balanced polypropylene. The preparation method does not adopt special equipment.
Description
Technical field
The present invention relates to the modified polypropylene material field, be specifically related to the comparatively polypropylene material and preparation method thereof of balance of a kind of rigidity and toughness.
Background technology
In recent years, along with the continuous development of automotive industry, the low-cost low light-weighted requirement of oil consumption of automobile is more and more higher, impels the ratio cumulative year after year of plastic material in automobile-used material that density is little, preservative property are good.The design of vehicle configuration more and more fashion is attractive in appearance, and this makes the design pursuit of plastic items and car body moulding harmonious and unified, and this just requires the design of automobile plastic component to develop towards direction complex-shaped, that wall is thin, quality is light.Therefore, be used for making the material of automobile plastic component, require to have the matrix material than low-shrinkage again for both having high workability, impact and favorable rigidity, to satisfy the harsh day by day requirement of automobile industry.In numerous plastic materials, modified polypropylene material is because its cheap, easy machine-shaping and good snappiness and more be subjected to the favor of automobile manufacturing company.
Polypropylene, English name: Polypropylene, be called for short: PP is a kind of thermoplastic resin that is made by propylene polymerization.PP is the kind of consumption maximum in automotive plastic, has advantages such as density is little, performance good, easy processing.But being difficult to of polypropylene material obtains the balance between superior stiffness and the toughness, and low temperature brittleness and shrinking percentage be big etc., and shortcoming causes its goods poor impact resistance and yielding, has limited it and has further used on automobile.
Publication number is to disclose a kind of polypropylene composite material with excellent rigid-tough balance in the Chinese patent application of CN 101759911A, becomes by the preparation of raw material of following weight %: polypropylene 55～95%; Wollastonite 3～30%; Other mineral fillers 0～10%; Toughner POE0～20%; Oxidation inhibitor 0.1～2%; Other auxiliary agents 0～5.0%; Can effectively remedy the mineral filler of toughness reinforcing rigidity of sacrificing by interpolation is a kind of in the basic components of toughened polypropylene composite, thereby prepare the polypropylene composite material with excellent rigid-tough balance.But wollastonite is generally grey, be difficult to be used in true qualities or the light goods, and the acicular structure of wollastonite can cause the anisotropy of similar glass fiber reinforced materials that the orientation of wollastonite also can cause the difference of aspects such as goods vertical and horizontal performance, contraction.
Therefore, develop the comparatively polypropylene material of balance (abbreviation: strong and unyielding balance polypropylene material) will have huge market application foreground of the wider rigidity of the new scope of application and toughness.
Summary of the invention
The invention provides a kind of strong and unyielding balance polypropylene, modification processing is extruded in the blend of the raw material by special formulation, make on its basis that keeps high stiffness (as modulus in flexure), promote the toughness (as notched Izod impact strength) of polypropylene material, solved the technical barrier that polypropylene material shock strength and modulus in flexure improve simultaneously, reach strong and unyielding balance, satisfy the application requiring that high-grade automobile is used modified polypropene.
A kind of strong and unyielding balance polypropylene, made by following raw materials by weight percent:
Described coupling agent modified low mesh number is talcous preparation method comprise: coupling agent is mixed with the low mesh number talcum powder with an amount of dehydrated alcohol dilution back, make coupling agent modified low mesh number talcum powder; Wherein, the weight of coupling agent is 0.5%～1.5% of low mesh number talcum powder weight;
The talcous order number of described low mesh number is 400 orders～1500 orders;
The talcous order number of described high order number is 2000 orders～10000 orders.
In order to reach better invention effect, preferably:
Described polypropylene is selected in the homo-polypropylene of 1g/10min～50g/10min one or more of melt flow rate (MFR) under high-crystallinity polypropylene, block copolymerization polypropylene or the 230 ℃ * 2.16kg test condition for use.
The comonomer of described block copolymerization polypropylene is selected ethene for use.The talcous performance index of described low mesh number are preferably: 750 ℃ of loss on ignition≤10%, and hydrochloric acid insoluble substance 〉=90%, silicone content 〉=50%, % represents weight percent.
The talcous performance index of described high order number are preferably: 750 ℃ of loss on ignition≤3%, and hydrochloric acid insoluble substance 〉=95%, silicone content 〉=60%, % represents weight percent.
Described toughner is selected ethylene-octene copolymer (POE) for use, and density is 0.86g/cm
3～0.88g/cm
3, melt flow rate (MFR) is at 0.5g/10min～10g/10min under the 190 ℃ * 2.16kg test condition.
Described oxidation inhibitor is selected four [β-(3 for use, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2, the 4-di-tert-butyl) ester (antioxidant 168), thio-2 acid stearate (DSTP), the two lauryls (DLTP), 1 of thio-2 acid, 3, in 5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide (antioxidant 3114) one or more.
Described coupling agent is selected a kind of in titanate coupling agent, the silane coupling agent for use.
Described other additive comprises one or more in the additives such as pigment, lubricant, nucleator, compatilizer, photostabilizer.
The polyacrylic preparation method of described strong and unyielding balance may further comprise the steps:
Polypropylene, high order are counted talcum powder, toughner, oxidation inhibitor and other additive to mix, put into twin screw extruder master drawing-in device, coupling agent modified low mesh number talcum powder is put into twin screw extruder side drawing-in device, extrude cooling granulation through melt blending, make strong and unyielding balance polypropylene.
The barrel of described twin screw extruder is ten joint cylindrical shells, and the first segment cylindrical shell connects main drawing-in device, the 5th joint cylindrical shell exhaust, and the 6th joint cylindrical shell connects the side drawing-in device, and the 9th joint cylindrical shell vacuumizes.
Described barrel temperature is set to: 160 ± 5 ℃ in a district, 220 ± 5 ℃ in two districts, 230 ± 5 ℃ in three districts, 230 ± 5 ℃ in four districts, 200 ± 5 ℃ in five districts, 200 ± 5 ℃ in six districts, 230 ± 5 ℃ in seven districts, 230 ± 5 ℃ in eight districts, 200 ± 5 ℃ in nine districts, 220 ± 5 ℃ of heads.
Compared with prior art, the present invention has following advantage:
The present invention adopts coupling agent modified low mesh number talcum powder and high order to count talcum powder (price is higher) coupling, can obviously improve rigidity and the toughness of polypropylene material under the prerequisite that reduces material cost and processing charges.
The present invention enters twin screw extruder by containing the talcous material of high order number from main drawing-in device, shears through the blend of whole twin screw and disperses, and improves the talcous degree of scatter of high order number, improves it to the nucleogenesis of polypropylene matrix; Coupling agent modified low mesh number talcum powder is entered twin screw extruder from the side drawing-in device, can reduce the course of processing to the destruction of its morphological structure, improve the consistency of itself and matrix resin by coupling agent modified processing, improve its strengthening action.Adopt to shear stronger blend screw combinations and higher screw speed, can further improve the degree of scatter of toughner in matrix, reduce material crisp-the needed toughner consumption of tough transformation.
The strong and unyielding comparatively balance of polypropylene material of the present invention, actual measurement over-all properties and the MD206U of Borealis performance are approaching substantially, can be widely used in true qualities and the medium-to-high grade inner and outer decorative parts of automobile of other colors.
Embodiment
The used talcous performance index of low mesh number of following each embodiment and Comparative Examples are: 750 ℃ of loss on ignition≤10%, and hydrochloric acid insoluble substance 〉=90%, silicone content 〉=50%, % represents weight percent;
The used talcous performance index of high order number are: 750 ℃ of loss on ignition≤3%, and hydrochloric acid insoluble substance 〉=95%, silicone content 〉=60%, % represents weight percent.
Embodiment 1
Low mesh number talcum powder surface treatment: 1kg silane coupling agent KH550 (γ-An Bingjisanyiyangjiguiwan) dilutes with the dehydrated alcohol of 1 bottle of 500mL, with 100kg order number be that 400 purpose low mesh number talcum powder mix in mixing machine, make coupling agent modified low mesh number talcum powder.The coupling agent modified low mesh number talcum powder of 8Kg is put into twin screw extruder side feed hopper.
By weight proportion in the table 1 take by weighing 79.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), 12Kg order number is that the high order of 3000 purposes is counted talcum powder, 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, make mixing of materials even, put into twin screw extruder master feed hopper.
The barrel of twin screw extruder is ten joint cylindrical shells, and the first segment cylindrical shell connects main drawing-in device, the 5th joint cylindrical shell exhaust, and the 6th joint cylindrical shell connects the side drawing-in device, and the 9th joint cylindrical shell vacuumizes.
Barrel temperature is set to: 160 ℃ in a district, 220 ℃ in two districts, 230 ℃ in three districts, 230 ℃ in four districts, 200 ℃ in five districts, 200 ℃ in six districts, 230 ℃ in seven districts, 230 ℃ in eight districts, 200 ℃ in nine districts, 220 ℃ of heads.
Material adds twin screw extruder from main feed hopper and side feed hopper respectively, extrudes cooling granulation through melt blending, makes strong and unyielding balance polypropylene.
At air dry oven, 90 ℃ of dryings 1 hour prepare test bars by injection moulding machine then with the strong and unyielding balance polypropylene granules that makes.
Density measurement is pressed GB/T 1033.1-2008 standard and is carried out; The tensile strength test is pressed the GB/T1040.2-2006 standard and is carried out, and draw speed is 50mm/min; The bending property test is pressed the GB/T9341-2008 standard and is carried out, and specimen size is 80mm * 10mm * 4mm, and speed is 2mm/min, and span is 64mm; The simply supported beam notched Izod impact strength is pressed GB/T 1043.1-2008 standard and is carried out, and specimen size is 80mm * 10mm * 4mm, notch depth 2mm, pendulum energy 4J.
Embodiment 2
Low mesh number talcum powder surface treatment: 1kg silane coupling agent KH550 (γ-An Bingjisanyiyangjiguiwan) dilutes with the dehydrated alcohol of 1 bottle of 500mL, with 100kg order number be that 1250 purpose low mesh number talcum powder mix in mixing machine, make coupling agent modified low mesh number talcum powder.The coupling agent modified low mesh number talcum powder of 8Kg is put into twin screw extruder side feed hopper.
By weight proportion in the table 1 take by weighing 25Kg block copolymerization PP K8303 (Yanshan Petrochemical), 54.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), 12Kg order number is that the high order of 5000 purposes is counted talcum powder, 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, mix, put into twin screw extruder master feed hopper.
Other operation makes strong and unyielding balance polypropylene with embodiment 1.
Testing method is with embodiment 1.
Embodiment 3
Low mesh number talcum powder surface treatment: 1kg silane coupling agent KH550 (γ-An Bingjisanyiyangjiguiwan) dilutes with the dehydrated alcohol of 1 bottle of 500mL, with 100kg order number be that 1250 purpose low mesh number talcum powder mix in mixing machine, make coupling agent modified low mesh number talcum powder.The coupling agent modified low mesh number talcum powder of 8Kg is put into twin screw extruder side feed hopper.
Taking by weighing 12.5Kg block copolymerization PP K8303 (Yanshan Petrochemical), 50.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), 12.5Kg block copolymerization PP K7726 (Yanshan Petrochemical), 12Kg order number by weight proportion in the table 1 is that the high order of 5000 purposes is counted talcum powder, (density is 0.86g/cm to 4Kg toughner POE
3, melt flow rate (MFR) is at 0.5g/10min under the 190 ℃ * 2.16kg test condition), 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, make mixing of materials even, put into twin screw extruder master feed hopper.
Other operation makes strong and unyielding balance polypropylene with embodiment 1.
Testing method is with embodiment 1.
Embodiment 4
Low mesh number talcum powder surface treatment: 1kg silane coupling agent KH550 (γ-An Bingjisanyiyangjiguiwan) dilutes with the dehydrated alcohol of 1 bottle of 500mL, with 100kg order number be that 1250 purpose low mesh number talcum powder mix in mixing machine, make coupling agent modified low mesh number talcum powder.The coupling agent modified low mesh number talcum powder of 8Kg is put into twin screw extruder side feed hopper.
By weight proportion in the table 1 take by weighing 50.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), 25Kg block copolymerization PP K7726 (Yanshan Petrochemical), 12Kg order number is that the high order of 5000 purposes is counted talcum powder, (density is 0.88g/cm to 4Kg toughner POE
3, melt flow rate (MFR) is at 10g/10min under the 190 ℃ * 2.16kg test condition), 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, make mixing of materials even, put into twin screw extruder master feed hopper.
Barrel temperature is set to: 165 ℃ in a district, 215 ℃ in two districts, 225 ℃ in three districts, 225 ℃ in four districts, 195 ℃ in five districts, 195 ℃ in six districts, 225 ℃ in seven districts, 225 ℃ in eight districts, 195 ℃ in nine districts, 215 ℃ of heads.
Other operation makes strong and unyielding balance polypropylene with embodiment 1.
Testing method is with embodiment 1.
Embodiment 5
Low mesh number talcum powder surface treatment: 1kg silane coupling agent KH550 (γ-An Bingjisanyiyangjiguiwan) dilutes with the dehydrated alcohol of 1 bottle of 500mL, with 100kg order number be that 400 purpose low mesh number talcum powder mix in mixing machine, make coupling agent modified low mesh number talcum powder.The coupling agent modified low mesh number talcum powder of 8Kg is put into twin screw extruder side feed hopper.
By weight proportion in the table 1 take by weighing 59.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), the high crystallization PP of 15Kg BX3800 (Korea S SK), 12Kg order number is that the high order of 3000 purposes is counted talcum powder, (density is 0.87g/cm to 5Kg toughner POE
3, melt flow rate (MFR) is at 5g/10min under the 190 ℃ * 2.16kg test condition), 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, make mixing of materials even, put into twin screw extruder master feed hopper.
Barrel temperature is set to: 155 ℃ in a district, 225 ℃ in two districts, 235 ℃ in three districts, 235 ℃ in four districts, 205 ℃ in five districts, 205 ℃ in six districts, 235 ℃ in seven districts, 235 ℃ in eight districts, 205 ℃ in nine districts, 225 ℃ of heads.
Other operation makes strong and unyielding balance polypropylene with embodiment 1.
Testing method is with embodiment 1.
Embodiment 6
Low mesh number talcum powder surface treatment: 1kg silane coupling agent KH550 (γ-An Bingjisanyiyangjiguiwan) dilutes with the dehydrated alcohol of 1 bottle of 500mL, with 100kg order number be that 1250 purpose low mesh number talcum powder mix in mixing machine, make coupling agent modified low mesh number talcum powder, the coupling agent modified low mesh number talcum powder of 8Kg is put into twin screw extruder side feed hopper.
By weight proportion in the table 1 take by weighing 69.6Kg homopolymerization PP F401 (raise sub-petrochemical industry, melt flow rate (MFR) is at 25g/10min under the 230 ℃ * 2.16kg test condition), 12Kg order number is that the high order of 2000 purposes is counted talcum powder, (density is 0.86g/cm to 10Kg toughner POE
3, melt flow rate (MFR) is at 2g/10min under the 190 ℃ * 2.16kg test condition), 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, make mixing of materials even, put into twin screw extruder master feeding barrel.
Other operation makes strong and unyielding balance polypropylene with embodiment 1.
Testing method is with embodiment 1.
Comparative Examples 1
Except 20Kg coupling agent KH550 modification low mesh number 400 order talcum powder are put into twin screw extruder side feed hopper, take by weighing 79.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium by weight proportion in the table 1, pour mixing machine into, make mixing of materials even, put into outside the twin screw extruder master feed hopper, all the other operations make polypropylene material with embodiment 1.
Testing method is with embodiment 1.
Comparative Examples 2
Except not using coupling agent modified low mesh number talcum powder, by weight proportion in the table 1 take by weighing 79.6Kg block copolymerization PP M700R (Shanghai petrochemical industry), 20Kg order number is that the high order of 3000 purposes is counted talcum powder, 0.1Kg antioxidant 1010,0.1Kg oxidation inhibitor 168 and 0.2Kg lubricant stearic acid calcium, pour mixing machine into, make mixing of materials even, put into outside the twin screw extruder master feed hopper, all the other operations make polypropylene material with embodiment 1.
Testing method is with embodiment 1.
Each embodiment, Comparative Examples composition of raw materials see Table 1:
Table 1
Each Comparative Examples of table 2, embodiment The performance test results
The ratio of the deformation that modulus in flexure is stress in bending to be produced with bending, the reflection material is resisted diastrophic ability in elastic limit.
The simply supported beam notched Izod impact strength is the energy that absorbs in the impact fracture process of sample and the ratio of original cross-sectional area, the ability of reflection material opposing crack propagation and anti-brittle failure.
Contrast Comparative Examples 1, Comparative Examples 2 and embodiment 1: Comparative Examples 1 only adopts the side feeding to advance coupling agent modified low mesh number talcum powder, does not use high order to count talcum powder, and the rigidity of polypropylene material is relative with toughness relatively poor; Embodiment 1 adopts the side feeding to advance the talcum powder of coupling agent modified low mesh number, the performance that main feeding advances the polypropylene material that makes after the talcum powder of a small amount of high order number and Comparative Examples 2 be complete, and to count the performance of the polypropylene material that talcum powder makes from the mode of main feeding charging with high order approaching substantially, as seen adopt the talcum powder coupling of talcum powder and the high order number of coupling agent modified low mesh number, can under the prerequisite that reduces material cost and processing charges, obviously improve rigidity and the toughness of polypropylene material.
Comparative example 2, embodiment 3 and embodiment 4, block copolymerization PP K8303 and toughner POE that eutectic refers to have better synergy, and the toughness of material is better when existing simultaneously, but the molten finger of K8303 is lower, and consumption is crossed the processing fluidity that conference influences material.High molten block copolymerization PP K7726 and the POE blend that refers to also can obtain the comparatively polypropylene of balance of rigidity and toughness.
Embodiment 5, add high crystallization PP and POE in block copolymerization PP, can obtain the comparatively polypropylene of balance of rigidity and toughness.
Embodiment 6, add POE in homopolymerization PP, can obtain the comparatively polypropylene of balance of rigidity and toughness.
Claims (8)
1. strong and unyielding balance polypropylene, made by following raw materials by weight percent:
Described coupling agent modified low mesh number is talcous preparation method comprise: coupling agent is mixed with the low mesh number talcum powder with an amount of dehydrated alcohol dilution back, make coupling agent modified low mesh number talcum powder; Wherein, the weight of coupling agent is 0.5%～1.5% of low mesh number talcum powder weight;
The talcous order number of described low mesh number is 400 orders～1500 orders;
The talcous order number of described high order number is 2000 orders～10000 orders;
Described other additive comprises one or more in pigment, lubricant, nucleator, compatilizer, the photostabilizer;
The polyacrylic preparation method of described strong and unyielding balance may further comprise the steps:
Polypropylene, high order are counted talcum powder, toughner, oxidation inhibitor and other additive to mix, put into twin screw extruder master drawing-in device, coupling agent modified low mesh number talcum powder is put into twin screw extruder side drawing-in device, extrude cooling granulation through melt blending, make strong and unyielding balance polypropylene.
2. strong and unyielding balance polypropylene according to claim 1, it is characterized in that described polypropylene is melt flow rate (MFR) one or more in the homo-polypropylene of 1g/10min～50g/10min under high-crystallinity polypropylene, block copolymerization polypropylene or the 230 ℃ * 2.16kg test condition.
3. strong and unyielding balance polypropylene according to claim 2 is characterized in that, the comonomer of described block copolymerization polypropylene is ethene.
4. strong and unyielding balance polypropylene according to claim 1 is characterized in that, the talcous performance index of described low mesh number are: 750 ℃ of loss on ignition≤10%, and hydrochloric acid insoluble substance 〉=90%, silicone content 〉=50%, % represents weight percent.
5. strong and unyielding balance polypropylene according to claim 1 is characterized in that, the talcous performance index of described high order number are: 750 ℃ of loss on ignition≤3%, and hydrochloric acid insoluble substance 〉=95%, silicone content 〉=60%, % represents weight percent.
6. strong and unyielding balance polypropylene according to claim 1 is characterized in that, described toughner is ethylene-octene copolymer, and density is 0.86g/cm
3～0.88g/cm
3, melt flow rate (MFR) is at 0.5g/10min～10g/10min under the 190 ℃ * 2.16kg test condition;
Perhaps, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl) ester, the two lauryls, 1 of thio-2 acid, in 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide one or more;
Perhaps, described coupling agent is a kind of in titanate coupling agent, the silane coupling agent.
7. strong and unyielding balance polypropylene according to claim 1 is characterized in that, the barrel of described twin screw extruder is ten joint cylindrical shells, the first segment cylindrical shell connects main drawing-in device, the 5th joint cylindrical shell exhaust, the 6th joint cylindrical shell connects the side drawing-in device, and the 9th joint cylindrical shell vacuumizes.
8. strong and unyielding balance polypropylene according to claim 7, it is characterized in that described barrel temperature is set to: 160 ± 5 ℃ in a district, 220 ± 5 ℃ in two districts, 230 ± 5 ℃ in three districts, 230 ± 5 ℃ in four districts, 200 ± 5 ℃ in five districts, 200 ± 5 ℃ in six districts, 230 ± 5 ℃ in seven districts, 230 ± 5 ℃ in eight districts, 200 ± 5 ℃ in nine districts, 220 ± 5 ℃ of heads.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102604214A (en) * | 2012-02-29 | 2012-07-25 | 杨谢 | Formula and preparation method of high-crystallization PP (polypropylene) |
| CN106810759A (en) * | 2015-11-30 | 2017-06-09 | 合肥杰事杰新材料股份有限公司 | A kind of scratch-resistant filled polypropylene material and preparation method thereof |
| CN110539971A (en) * | 2019-07-09 | 2019-12-06 | 中山市金群瑞科技有限公司 | Adopt packing carton of individual layer degradable carbon calcium board preparation |
| CN111286122A (en) * | 2019-11-29 | 2020-06-16 | 东风汽车有限公司 | Polypropylene modified material |
| CN111454515A (en) * | 2020-04-20 | 2020-07-28 | 盘锦海兴科技股份有限公司 | Rigidity-enhancing and toughening antistatic polypropylene master batch and preparation method thereof |
| CN114605738B (en) * | 2022-03-15 | 2023-12-15 | 上海金发科技发展有限公司 | Polypropylene composite material easy to bond and preparation method and application thereof |
| CN114806014A (en) * | 2022-05-10 | 2022-07-29 | 宁波金富亮塑料科技有限公司 | Polypropylene ecological plastic convenient for biodegradation and preparation method thereof |
| CN114806017A (en) * | 2022-05-20 | 2022-07-29 | 宁波金富亮塑料科技有限公司 | Biodegradable plastic capable of being regenerated and used and preparation method thereof |
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| CN1282757A (en) * | 1999-07-29 | 2001-02-07 | 上海杰事杰新材料股份有限公司 | Modified polypropylene |
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| CN101759911A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Polypropylene composite material with excellent rigid-tough balance and preparation method thereof |
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| CN1282757A (en) * | 1999-07-29 | 2001-02-07 | 上海杰事杰新材料股份有限公司 | Modified polypropylene |
| CN1631959A (en) * | 2004-11-30 | 2005-06-29 | 上海普利特复合材料有限公司 | Talc powder filled polypropylene with high rigidity, high heat resistance and high scratch resistance and method for preparing same |
| CN101759911A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Polypropylene composite material with excellent rigid-tough balance and preparation method thereof |
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