CN104861295A - Preparation method of modified PP (polypropylene) material with improved shock resistance - Google Patents
Preparation method of modified PP (polypropylene) material with improved shock resistance Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention provides a preparation method of a modified PP (polypropylene) material with improved shock resistance. According to the preparation method, the modified PP material is prepared by mixing and modifying raw materials containing following components in one step: 100 parts of PP, 20-40 parts of a main modification agent, 2.5-10 parts of an auxiliary modification agent, 0.5-5 parts of a cross-linking modification agent and 0.5-5 parts of a cross-linking aid, wherein the main modification agent refers to polyolefin elastomers, the auxiliary modification agent refers to high-density polyethylene, the cross-linking modification agent refers to organic peroxides, the cross-linking aid refers to divinyl benzene with the content ranging from 50% to 60%, and the different between the decomposition temperature of the cross-linking modification agent when the half-life period is 1 minute and the melting temperature of the PP is in a range of 1-5 DEG C. With the adoption of the method, the shock resistance of the modified PP can be substantially improved, the composite material can be endowed with excellent shock resistance, rigidity, ageing resistance, cold resistance and gasoline resistance, and meanwhile, other properties are hardly affected.
Description
Technical field
The invention belongs to field of polymer composite material, be specifically related to a kind of preparation method improving the modified polypropylene material of resistance to impact shock.
Background technology
Polypropylene (PP) is the thermoplastic resin be polymerized by propylene monomer, it is one of main raw manufacturing car and light, the forward and backward collision bumper of minicar, because the second-order transition temperature of PP is higher, low temperature impact properties is poor, molding shrinkage is large, limit its application in auto industry field, therefore people often carry out toughness reinforcing with elastomeric material to PP.Utilize polyolefin elastomer (Polyolefin elastomer at present, POE), as ethylene-octene copolymer, ethylene-hexene co-polymers and ethylene-butene copolymer carry out to PP a kind of effective ways that modification is its mechanical property of raising, reason is that POE has very narrow relative molecular mass and short chain distribution, there is snappiness, high strength, high elongation rate and good low-temperature performance, there is again excellent heat-proof aging and uvioresistant performance simultaneously.Such as, in ethylene-octene copolymer elastomerics, polyethylene sections crystallizing field (resin-phase) plays physical crosslinking point, the introducing of a certain amount of octene weakens polyethylene sections crystallization, define the pars amorpha (rubber phase) presenting caoutchouc elasticity, carry out modified when utilizing POE to PP, rubbery state in POE is under external impact force action, a large amount of crazing can be caused, body material PP then produces shear yielding, main by crazing, shear zone absorption energy, thus improve the mechanical property of body material.
Bumper is large, the complex-shaped thin-walled large-sized structural component of a kind of surface-area, and various countries have all formulated relevant technological standard to automotive plastic collision bumper.With regard to collision bumper, raw materials for production must have excellent high/low-temperature impact toughness, rigidity, ageing resistance, thermotolerance, winter hardiness, petrol-resistance, also will have good flame retardant resistance etc.; In the course of processing, necessarily require that raw material has good thermostability, molding shrinkage is little, release property good.Wherein, the PP material of suitable for making bumper must have super high impact strength, minimum under normal temperature will at more than 400J/m, and the highest 50J/m that also can only reach under general PP shock strength normal temperature, have to pass through modification could use (Zhang Shunxi. the development of collision bumper Ultra-high impact PP material. plastics science and technology .1995,108 (4): 10-13).Generally using POE as toughner, physical mechanical blending and modifying is carried out to PP, namely refer to that PP matrix and POE elastomerics, mineral filler are carried out mechanical blending and obtain matrix material, although its shock strength increases, but increase rate is less, shock strength can only reach about 90J/m at most, cannot reach the requirement of bumper.
Chinese patent literature CN102251304A PP is base-material, add the evenly mixture such as high density polyethylene(HDPE) (HDPE), POE, through twin-screw mixer granulation, prepare polypropylene modification masterbatch, then stock high-strength, high-modulus tacryl by Screw Extrusion, this polypropylene fibre brute force is high, unit elongation is low, disconnected rate modulus is high, and weathering resistance is excellent, but not mentioned toughening effect.Chinese patent literature CN102746572A utilizes a kind of television rear shell modified polypropene PP Pipe Compound of preparation such as polyethylene, activated Calcium carbonate, POE, HDPE, oxidation inhibitor, anti UV agent and toner, although its PP material produced partly can meet above-mentioned requirements, modified shock strength only improves more than 30%.
Summary of the invention
Goal of the invention
The object of this invention is to provide a kind of preparation method improving the modified polypropylene material of resistance to impact shock, its shock strength is greatly improved.
Summary of the invention
The preparation method of the modified polypropylene material of described raising resistance to impact shock, is obtained through single stage method blending and modifying by the raw material comprising following component:
Wherein, main properties-correcting agent is polyolefin elastomer, and secondary properties-correcting agent is high density polyethylene(HDPE), and cross-linked modifier is organo-peroxide, crosslinking coagent is the Vinylstyrene of content 50%-60%, and the melt temperature difference of decomposition temperature when the described cross-linked modifier transformation period is 1 minute and PP is 1-5 DEG C.
Described single stage method is known polymer blending modification method, specifically refers to and the crosslinking reaction of polymer modification and extruding pelletization is completed on same forcing machine.This requirement adds various auxiliary agent, powdery or aqueous linking agent and crosslinking coagent on same forcing machine in the melting mixing thing of PP constituent, and completes crosslinking reaction and extruding pelletization, and this is higher to the requirement of forcing machine.Solution is: select length-to-diameter ratio (L/D) large (30 ~ 35), and have the forcing machine of degassing function.
Described cross-linked modifier provides living radical in the course of processing, makes PP, POE and HDPE main chain become living radical and crosslinking reaction occurs, and ensures that modified polypropylene material has excellent shock resistance, winter hardiness and ageing-resistant performance.Preferably, described cross-linked modifier is dicumyl peroxide.Described crosslinking coagent avoids PP main chain generation chain-scission degradation to react in the course of processing, thus receives desirable cross-linking effect.Described crosslinking coagent Vinylstyrene is commercially available prod, have neighbour, p-divinyl benzene three kinds of isomer, for time of the present invention without the need to carrying out the separation of isomer; The 50%-60% content Vinylstyrene that the present invention adopts is specification comparatively conventional in commercially available prod, obvious, if adopt other content Vinylstyrenes (as 80%), as long as ensure that the amount of the actual pure Vinylstyrene added is identical, also same technique effect can be obtained.Described content is mass percentage content.
Described main properties-correcting agent POE is at least one in ethylene-octene copolymer, ethylene-hexene co-polymers, ethylene-butene copolymer; Described secondary properties-correcting agent HDPE, is the homopolymer of vinyl monomer by catalytic polymer reaction gained, is commercially available prod, by the blended molding shrinkage reducing PP with PP, ensures that modified polypropylene material has good toughness and petrol-resistance.Preferably, density during described ethylene-octene copolymer 25 DEG C is 0.850-0.913g/cm
3, density during ethylene-hexene co-polymers 25 DEG C is 0.90-0.955g/cm
3, density during ethylene-butene copolymer 25 DEG C is 0.850-0.910g/cm
3.
PP of the present invention can adopt homopolymerization or copolymerization PP according to the performance of MODIFIED PP material or service requirements.When by the present invention for the preparation of bumper with MODIFIED PP material time, preferably adopt homopolymerization PP, more preferably the melting index of described homopolymerization PP is 10-25g/10min, and most preferably the melting index of described homopolymerization PP is 20-25g/10min.According to standard A STM D1238 (2004), (probe temperature and load are respectively 230 DEG C, 2.16kg to described melting index, and the resin extruded Standard Module of melting is of a size of: 2.095 × 8mm) test obtains.
Raw material of the present invention can also comprise polypropylene blending modified in conventional various auxiliary agents, preferably, described raw material also comprises toughener 5-10 part, thermo-stabilizer 0.5-5 part, wherein, described toughener is DH-1 toughener (hereinafter referred to as DH-1), described thermo-stabilizer is Zinic stearas, described toughener is commercially available prod, dispersiveness and the mobility of resin can be improved, increase physical strength and the rigidity of material product, also can reduce the molding shrinkage of PP simultaneously, described thermo-stabilizer can suppress or delay polymkeric substance decomposes or crosslinked, ensure the thermostability in the PP course of processing.Raw material of the present invention can also comprise fire retardant 5-10 part, photostabilizer 0.5-5 part, with lubricant 0.5-5 part, described fire retardant can postpone or prevent the burning of polymer plastic, ensure that MODIFIED PP has good flame retardant resistance, described photostabilizer can prevent PP and ethene polymers generation photoaging, ensure that MODIFIED PP has good light stability, described lubricant can reduce the friction between polymer molecule and between polymkeric substance and equipment in the course of processing, increase mobility and the release property of raw material, ensure that MODIFIED PP has excellent releasability from mode.Preferably, described fire retardant is ODPP octyl diphenyl phosphate, and described photostabilizer is O-hydroxyl-diphenyl ketone, and described lubricant is barium stearate.Due to according to the present invention, when adopting described cross-linked modifier, crosslinking coagent, main properties-correcting agent and secondary properties-correcting agent to carry out blending and modifying to improve resistance to impact shock to PP, all the other performances (as the thermostability of rigidity, petrol-resistance, flame retardant resistance, light stability, release property, course of processing Raw and mobility etc.) all can not be subject to significant adverse impact, therefore, when adding above-mentioned various usual auxiliaries, adopt conventional amount used of the prior art.
Concrete preparation process of the present invention is: join in twin screw extruder after raw material blending dispersion is even, by melt extruding granulation, twin screw extrusion process condition is: a district: 220-240 DEG C; 2nd district: 220-240 DEG C; 3rd district: 220-240 DEG C; 4th district: 220-240 DEG C; 5th district: 220-240 DEG C; 6th district: 220-240; Head temperature: 220-240 DEG C; The rotating speed of screw rod is: 300-350 rev/min (r/min), the residence time of material in barrel: 3-5 minute.Preferably, raw material is stirred in homogenizer high speed, joins in twin screw extruder after making raw material blending dispersion evenly, generally need high-speed stirring 10-20 minute, wherein high-speed stirring is that blending means is commonly used in this area, and rotating speed is generally 500-800r/min.The feature of above-mentioned concrete preparation process is to control chemically crosslinked and the extruding pelletization that suitable processing temperature one step completes PP, this is because under the processing temperature of PP, decomposition temperature (171 DEG C) when the cross-linked modifier dicumyl peroxide transformation period is 1 minute is close with the melt temperature (166-170 DEG C) of PP, like this in the cross-linking process of PP, these dicumyl peroxides can decompose completely, be unlikely and delay PP crosslinking time, and then have influence on other performances of the finished product PP/ toughner blend.
The present invention utilizes the properties-correcting agent such as POE and HDPE to carry out blending and modifying to PP, significantly can improve the resistance to impact shock of MODIFIED PP, give the shock resistance of matrix material excellence, rigidity, ageing resistance, winter hardiness and petrol-resistance, meanwhile, all the other performances are influenced hardly.When PP base material adopts aforementioned preferred version, MODIFIED PP can reach the shock strength of bumper requirement, can be widely used in nerf bar, panel board, door inner panel, battery cell case, protect the processing of the part such as solar or lunar halo and mud guard.
Embodiment
Raw material below for using in all comparative examples and embodiment:
Homopolymerization PP, China PetroChemical Corporation, the trade mark: HHP3, melting index 25g/10min;
Ethylene-octene copolymer, DuPont, the trade mark: 8130, density when 25 DEG C is 0.913g/cm
3;
Ethylene-hexene co-polymers, Dow Chemical company, the trade mark: Dowlex 2641G, density when 25 DEG C is 0.9309g/cm
3;
Ethylene-butene copolymer, Mitsui KCC, the trade mark: DF840, density when 25 DEG C is 0.8908g/cm
3;
HDPE, CNPC's Daqing petrochemical company, the trade mark: 5000S;
Dicumyl peroxide, Jining Hui De Chemical Co., Ltd., chemical pure;
Vinylstyrene, the happy together safe Chemicals company limited in Tianjin, Beijing, analytical pure, divinyl benzene content: 55%;
DH-1, the big sincere scientific and technological Power Conservation, Ltd. in Beijing, outward appearance is true qualities transparent solid unrestricted flow particle; Fusing point≤60 DEG C; Tensile strength >=10MPa, elongation at break >=800%;
ODPP octyl diphenyl phosphate, Aladdin reagent, chemical pure;
O-hydroxyl-diphenyl ketone, Aladdin reagent, chemical pure;
Zinic stearas: Hongyuan, Jiangxi chemical industry, chemical pure;
Barium stearate: Hongyuan, Jiangxi chemical industry, chemical pure.
Comparative example 1
Modified polypropylene material, the weight quota of its each component is:
Comparative example 2
Modified polypropylene material, the weight quota of its each component is:
Embodiment 1
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 2
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 3
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 4
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 5
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 6
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 7
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 8
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 9
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 10
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 11
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 12
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 13
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 14
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
Embodiment 15
The modified polypropylene material of described raising resistance to impact shock, the weight quota of its each component is:
The preparation method of the modified polypropylene material of the raising resistance to impact shock in above-mentioned comparative example 1-2, embodiment 1-15 is: take required material by proportioning, stirs 10-20 minute in homogenizer high speed; The material mixed is joined in twin screw extruder, by melt extruding granulation; The residence time of material in barrel is 3-5 minute.
Twin screw extrusion process condition is: a district: 220-240 DEG C; 2nd district: 220-240 DEG C; 3rd district: 220-240 DEG C; 4th district: 220-240 DEG C; 5th district: 220-240 DEG C; 6th district: 220-240 DEG C; Head temperature: 220-240 DEG C; The rotating speed of screw rod is: 300-350r/min.
Two pile bar forcing machine: Nanjing Ju Li chemical machinery company limited, model: SHJ-20, screw diameter D:21.7mm, length-to-diameter ratio L/D:35;
Homogenizer: Shanghai Zhen Xuan Electromechanical Technology Co., Ltd, model: SDF550
Performance test:
Tensile strength is tested by ASTM D638 (2003) standard; Flexural strength is tested by ASTM D790 (2010) standard; Notched Izod impact strength is tested by ASTM D256 (1997); Result is as shown in table 1,2.
Table 1 cross-linked modifier dicumyl peroxide content is to PP performance table
Table 2 POE content, Vinylstyrene, HDPE content and POE kind are to PP performance table
From table 1,2, unmodified its notched Izod impact strength of toughness reinforcing PP only has 45J/m, when adding POE and HDPE as plasticized modifier, its notched Izod impact strength increases substantially, can reach 223J/m, this illustrates the resistance to impact shock can being improved PP by blended POE and HDPE of physical mechanical well.But this intensity level can't meet nerf bar uses standard, after blended to PP chemically crosslinked by single stage method, even if the content of linking agent seldom (0.5 part), notched Izod impact strength can reach 2.5 times (520J/m) of common mechanical physical blending, and use the increase of content along with linking agent, the bending strength of MODIFIED PP material, composite bending modulus and notched Izod impact strength strengthen all to some extent, simultaneously along with the increase of POE content, Vinylstyrene, HDPE content, PP notched Izod impact strength increases; When changing the kind of POE, as embodiment 6,12,13, the notched Izod impact strength of MODIFIED PP material all can meet bumper and use standard, when wherein POE is ethylene-octene copolymer, PP notched Izod impact strength is maximum, and this illustrates that ethylene-octene copolymer is best to toughening effect.The experimental result of above embodiment fully meets the use standard (under normal temperature minimum will at 400J/m) of bumper, and this illustrates that the present invention is the effective means of preparation high impact strength modified polypropylene material, and method is simple, is easy to realize.
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various the field of the invention completely, for those skilled in the art, amendment can be made easily, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific detail.
Claims (10)
1. improve a preparation method for the modified polypropylene material of resistance to impact shock, it is characterized in that, obtained through single stage method blending and modifying by the raw material comprising following component:
Wherein, main properties-correcting agent is polyolefin elastomer, and secondary properties-correcting agent is high density polyethylene(HDPE), and cross-linked modifier is organo-peroxide, crosslinking coagent is the Vinylstyrene of content 50%-60%, and the melt temperature difference of decomposition temperature when the described cross-linked modifier transformation period is 1 minute and PP is 1-5 DEG C.
2. the preparation method improving the modified polypropylene material of resistance to impact shock as claimed in claim 1, it is characterized in that, described cross-linked modifier is dicumyl peroxide.
3. the preparation method improving the modified polypropylene material of resistance to impact shock as claimed in claim 1, it is characterized in that, described polypropylene is homo-polypropylene.
4. the preparation method improving the modified polypropylene material of resistance to impact shock as claimed in claim 3, it is characterized in that, the melting index of described homo-polypropylene is 10-25g/10min.
5. the preparation method of the modified polypropylene material of the raising resistance to impact shock according to any one of claim 1-4, is characterized in that, described raw material also comprises toughener 5-10 part, thermo-stabilizer 0.5-5 part, wherein, described toughener is DH-1 toughener, and described thermo-stabilizer is Zinic stearas.
6. the preparation method improving the modified polypropylene material of resistance to impact shock as claimed in claim 5, it is characterized in that, described raw material also comprises fire retardant 5-10 part, photostabilizer 0.5-5 part and lubricant 0.5-5 part, described fire retardant is ODPP octyl diphenyl phosphate, described photostabilizer is O-hydroxyl-diphenyl ketone, and described lubricant is barium stearate.
7. the preparation method of the modified polypropylene material of the raising resistance to impact shock according to any one of claim 1-6, it is characterized in that, described polyolefin elastomer is at least one in ethylene-octene copolymer, ethylene-hexene co-polymers, ethylene-butene copolymer.
8. the preparation method improving the modified polypropylene material of resistance to impact shock as claimed in claim 7, it is characterized in that, density during described ethylene-octene copolymer 25 DEG C is 0.850-0.913g/cm
3, density during ethylene-hexene co-polymers 25 DEG C is 0.90-0.955g/cm
3, density during ethylene-butene copolymer 25 DEG C is 0.850-0.910g/cm
3.
9. the preparation method of the modified polypropylene material of the raising resistance to impact shock according to any one of claim 1-8, it is characterized in that, join in twin screw extruder after raw material blending dispersion is even, by melt extruding granulation, twin screw extrusion process condition is: a district: 220-240 DEG C; 2nd district: 220-240 DEG C; 3rd district: 220-240 DEG C; 4th district: 220-240 DEG C; 5th district: 220-240 DEG C; 6th district: 220-240; Head temperature: 220-240 DEG C; The rotating speed of screw rod is: 300-350 rev/min, the residence time of material in barrel: 3-5 minute.
10. the preparation method improving the modified polypropylene material of resistance to impact shock as claimed in claim 6, is characterized in that, is stirred by raw material in homogenizer high speed, joins in twin screw extruder after making raw material blending dispersion evenly.
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| CN105156851A (en) * | 2015-09-29 | 2015-12-16 | 宁波狮球线缆有限公司 | Tablet PC bracket |
| CN109776938A (en) * | 2019-02-12 | 2019-05-21 | 优矿塑新材料科技(芜湖)有限公司 | A kind of calcium carbonate master batch |
| CN110791015A (en) * | 2019-10-25 | 2020-02-14 | 天津金发新材料有限公司 | Special material for micro-foaming polypropylene for vehicles and preparation method and application thereof |
| CN113930015A (en) * | 2021-10-28 | 2022-01-14 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
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| CN101111557A (en) * | 2004-12-30 | 2008-01-23 | 玛尔提贝斯股份有限公司 | Polyolefin composition intended for producing a cover for housing a motor vehicle safety airbag |
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| CN105156851A (en) * | 2015-09-29 | 2015-12-16 | 宁波狮球线缆有限公司 | Tablet PC bracket |
| CN109776938A (en) * | 2019-02-12 | 2019-05-21 | 优矿塑新材料科技(芜湖)有限公司 | A kind of calcium carbonate master batch |
| CN110791015A (en) * | 2019-10-25 | 2020-02-14 | 天津金发新材料有限公司 | Special material for micro-foaming polypropylene for vehicles and preparation method and application thereof |
| CN110791015B (en) * | 2019-10-25 | 2022-06-14 | 天津金发新材料有限公司 | Special material for micro-foaming polypropylene for vehicles and preparation method and application thereof |
| CN113930015A (en) * | 2021-10-28 | 2022-01-14 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
| CN113930015B (en) * | 2021-10-28 | 2023-12-15 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
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| CN104861295B (en) | 2017-11-10 |
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