CN1215068A - Stuffing mother particle for toughening polyolefine and preparation process and usage thereof - Google Patents
Stuffing mother particle for toughening polyolefine and preparation process and usage thereof Download PDFInfo
- Publication number
- CN1215068A CN1215068A CN 98102448 CN98102448A CN1215068A CN 1215068 A CN1215068 A CN 1215068A CN 98102448 CN98102448 CN 98102448 CN 98102448 A CN98102448 A CN 98102448A CN 1215068 A CN1215068 A CN 1215068A
- Authority
- CN
- China
- Prior art keywords
- stuffing
- mother particle
- polyolefine
- toughening
- filler
- 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
The present invention relates to filling material granules for toughening polyolefine and its preparation method and application, belonging to the field of inorganic particle toughened polyolefine material. Said filling maternal granules are made up by using the inorganic filling material whose particle diameter is 0.5-40 micrometers, surfactant, functionalized thermoplastic elastomer, thermoplastic resin and its mixture and processing adjuvant, and adopting the processes of uniformly mixing all ingredients, extruding by using double screw extruder or mixing by using double roll mixing mill and granulating. Said invented maternal granules contain uniformly-dispersed inorganic filling material, and when they are compounded with polyolefine material, they can be distributed in the polyolefine basal body in the form of "nuclea-shell" structure,so that said invented composite material possesses high rigidity and high toughness.
Description
The present invention relates to a kind of filler parent granule that can strengthen the toughening polyolefine material, specially refer to a kind of cheap, polyolefine filler parent granule of increasing rigidity, high toughening type.
Usually, in the plastic working process, the auxiliary agent, compound such as the stablizer that add, fire retardant, pigment etc. are concentrated in and make filler parent granule on the vector resin, it has lot of advantages, good as the plastics stability, be easy to metered charge and blend operation, purify Working environment etc., so the functionalization research of filler parent granule becomes focus as the filler parent granule that development has enhancing, toughening functions.
Xu Shengxiu is in Chinese invention patent " plastic filler parent granule " (notification number 1021857), reported a kind of plastic filler parent granule of high dispersive type, it is based on pearl filler, chelating titanates etc. are the surface treatment agent of filler, petroleum resin, ethylene-propylene rubber(EPR) etc. form for preparing carriers, the characteristics of this filler parent granule are to have good dispersing property in polymeric matrix, and can be under bigger loading level, improve the rigidity of plastics, as add 20% (wt%) this filler parent granule and be used to make the polypropylene strap, the tensile strength of its goods can by departmental standard>160kg/cm
2Be increased to 329kg/cm
2, unit elongation by departmental standard<25% be reduced to 17%, but therefore plastics do not obtain high tenacity.
Sun Shaoxuan is in Chinese invention patent " all purpose plastics packing parent grain and preparation method thereof " (publication number 1061028A), related to the filler parent granule that a kind of general purpose grade plastics are used, it be by through superfine grinding to the filler zeolite of 1-20 μ and white carbon black, molecular weight is that the carrier polyethylene of 1000-6000 and conditioning agent turps and white oil or oneself penta tetrol methyl esters form through mediating granulation, the characteristics of this filler parent granule are applied widely, can be used among most of thermoplasticss, because this master batch is carrier with the low molecular weight polyethylene, so this master batch can not be very remarkable to the enhancing toughening effect of plastics.
People such as Zhang Yun is bright, multitude Paine are in Chinese invention patent " toughening mother particle for polyolefine plastics and manufacture method thereof " (notification number 1124747) and " Supertough master-pellets for polypropylene plastics and manufacture method thereof " (notification number 1131165), reported with multi-functional coupling agent and help coupling agent to come coupling master batch vector resin and mineral filler to prepare the method for plasticizing mother particle and Supertough master-pellets, this filler parent granule has good toughening effect to polyolefin plastics, and optimum toughening effect can make the notched Izod impact strength of polypropylene material by 7.3KJ/m
2Be increased to 70~80KJ/m
2But this method is because being connected mineral filler and coupling agent the two is a chemical bonding between mineral filler and master batch carrier, the two only is the molecular chain physical entanglement and helping coupling agent and carrier, therefore this filler parent granule and polyolefinic matrix material are difficult to obtain high strength, high rigidity, as when above-mentioned master batch filled polypropylene material obtains optimum tenacity, the tensile strength of polypropylene material is reduced to 17~18MPa by 33.2MPa.
In order to overcome the shortcoming that can not obtain the composite polyolefine material of high rigidity, high tenacity in the above-mentioned prior art simultaneously, the invention provides and adopting mineral filler is main body, the easy dispersion that thermoplastic elastomer, thermoplastic resin, polymer emulsion and composition thereof form for preparing carriers, enhancing, high toughening type filler parent granule, this filler parent granule and polyolefine material carry out compound tense, can obtain cheap, have mineral filler for nuclear carrier be the high rigidity of " nuclear-shell " structured particles of shell, the composite polyolefine material of high tenacity.
It is based on mineral filler that the technology of a kind of stuffing mother particle for toughening polyolefine of the present invention constitutes, coupling agent, organic monomer are the surface treatment agent of mineral filler, thermoplastic elastomer, thermoplastic resin, polymer emulsion and composition thereof are carrier, and low-molecular(weight)polymer, low branch seed oil, fatty acid ester, lipid acid and salt thereof are processing aid.Filler parent granule comprises following component and content (weight percentage):
Mineral filler 47.5-84.5
Surface treatment agent 0.5-2.5
Carrier 10-30
Processing aid 5-18
Oxidation inhibitor 0-2
Above-mentioned mineral filler is talcum powder, kaolin, lime carbonate, wollastonite, mica, silicon-dioxide, aluminum oxide, aluminium hydroxide, titanium dioxide, agalmatolite, wilkinite, and its particle dia is at 0.5 μ m-40 μ m, and particle dia is 1.5 μ m-5 μ m preferably.Above-mentioned surface treatment agent is silane coupling agent such as γ-An Jibingjisanyiyangjiguiwan, γ-propyl methacrylate base Trimethoxy silane, γ-Racemic glycidol oxygen propyl trimethoxy silicane, titanate coupling agent such as sec.-propyl three different stearoyl titanic acid ester, positively charged ion, negatively charged ion, nonionic surface active agent, vinyl monomer and esters of gallic acid monomer (containing initiator) are as the mixture of vinylbenzene and maleic anhydride (containing initiator DTBP).Above-mentioned carrier is a natural rubber, cis-1,4-polybutadiene rubber, isoprene-isobutylene rubber; styrene-butadiene rubber(SBR); paracril; chloroprene rubber; polyisoprene rubber; EPDM; EVA; SBS; ethene-alpha-olefin copolymer; polyester; urethane; polyolefine such as hydroxy-terminated polybutadienes; polypropylene; high density polyethylene(HDPE); new LDPE (film grade) and maleic anhydride thereof; bismaleimides; acrylate; the ethylene-propylene-diene copolymer of vinyl monomer grafting or copolymerized grafting modification thermoplastic elastomer and thermoplastic resin such as bismaleimides graft modification; the ethylene-propylene-diene copolymer of trimethoxy propane triacrylate modification; the ethylene-propylene rubber(EPR) of modified by maleic acid anhydride graft, its melt flow rate (MFR) are 0.5g/10min-50g/10min.Above-mentioned processing aid is petroleum resin, Poly Propylene Wax, polyethylene wax, solid paraffin, whiteruss, naphthenic oil, laurate, oleic acid ester, oleic acid, stearate, stearic acid and salt thereof such as calcium stearate.Above-mentioned oxidation inhibitor is homemade phenolic antioxidant, amine antioxidants.
The preparation method of a kind of stuffing mother particle for toughening polyolefine of the present invention follows these steps to order carry out: (1) is percentage ratio by weight, above-mentioned surface treatment agent 0.5-2.5 is added thinner to be handled the surface of mineral filler 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 that handles well, carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly, the kneading time is 5-30 minute, mediating temperature is 10 ℃-100 ℃, and extrude kneaded material and granulation forms so that 140 ℃-200 ℃ processing temperature is compound in twin screw extruder (3).
Another preparation method of a kind of stuffing mother particle for toughening polyolefine of the present invention follows these steps to order carry out: (1) is percentage ratio by weight, above-mentioned surface treatment agent 0.5-2.5 is added thinner to be handled the surface of mineral filler 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 that handles well, carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly, the kneading time is 5-30 minute, mediating temperature is 10 ℃-100 ℃, (3) with kneaded material in mixing roll, temperature with 120 ℃-150 ℃ is mixing, in flakes, pelletizing forms.
The purposes of a kind of stuffing mother particle for toughening polyolefine of the present invention is the preparation composite polyolefine material.Above-mentioned polyolefine is homo-polypropylene, Co-polypropylene, high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, ethylene copolymer.
The purpose that inorganic filler surface is handled is to introduce reactive group or unsaturated link(age) on its surface, when above-mentioned mineral filler and have can with the carrier or the modified support of the functional group of filling surface reactive group generation chemical reaction, or have can with the carrier of filling surface unsaturated link(age) generation copolymerization or modified support mediate, in the extrusion, cause by heat or initiator, the two surperficial reactive group of mineral filler and carrier partly contacts concurrent biochemical reaction, the two is linked up with certain linking intensity and is present in the filler parent granule of preparation.Filler parent granule and polyolefine compound tense when preparation, filler and master batch carrier can be that the nuclear carrier is that " hard core-soft core " structured particles form of shell is dispersed in the polyolefin substrate with the mineral filler in the filler parent granule, replace simple rubber elastomer toughening polyolefine material.
Stuffing mother particle for toughening polyolefine of the present invention has mineral filler and can be dispersed in the filler parent granule carrier, and is evenly distributed on the characteristics in the polyolefin substrate with mineral filler-master batch carrier " hard core-soft core " structure formation.When the filler parent granule addition is 30-40wt%, can make the modulus of composite polyolefine material improve 0.5-1 doubly, notched Izod impact strength improves 1-4 doubly, and easy to process, and cost is low.
Embodiment 1
To handle through γ-propyl methacrylate base Trimethoxy silane 11.5g, granularity is the talcum powder 774.5g of 5 μ m, the ethylene-propylene-diene copolymer 91.2g of bismaleimides graft modification, its melt flow rate is 2.5g/10min, polypropylene 60.8g, its melt flow rate is 30g/10min, Poly Propylene Wax 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, after in homogenizer, mediating 20min under the room temperature, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 150-160-190-200-190 ℃ from the import to the outlet, and the water-cooled pelletizing forms.
With this talcum powder filler parent granule with the ethylene-propylene copolymer acrylic resin mixes 3-5min in 10: 90 ratio (weight percentage) in super mixer after, compound in twin screw extruder, the extruder barrel temperature is followed successively by 195-205-205-220-195 ℃ from the import to the outlet, its composite materials property test result sees Table 1.Embodiment 2:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 20: 80.Embodiment 3:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 30: 70.Embodiment 4:
With the talcum powder filler parent granule of embodiment 1 preparation and ethylene-propylene copolymer polypropylene ratio (weight percentage), with method and the condition composite moulding identical with embodiment 1 in 40: 60.
After table 1 talcum powder filler parent granule and copolymerization acrylic resin are compound, the mechanical property of its material
Embodiment 5 (comparative example):
Mixture | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
Notched izod shock strength (J/m) tensile strength (MPa) elongation at break (%) flexural strength (MPa) modulus in flexure (GPa) | ???218.0 ???28.5 ???1044.8 ???27.4 ???0.7 | ????267.0 ????27.8 ????1020.0 ????26.1 ????0.8 | ?308.0 ?26.1 ?979.2 ?25.0 ?0.8 | ?525.0 ?24.7 ?997.8 ?23.2 ?0.9 |
With talcum powder and ethylene-propylene copolymer acrylic resin in 10: 90 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.Embodiment 6 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 20: 80 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.Embodiment 7 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 30: 70 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.Embodiment 8 (comparative example):
With talcum powder and ethylene-propylene copolymer acrylic resin in 40: 60 ratio (weight percentage) after mixing, with the processing conditions compound and injection moulding identical with embodiment 1.
The mechanical property of table 2 talcum powder and copolymerization polypropylene composite material
Embodiment 9:
Mixture | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
Notched izod shock strength (J/m) tensile strength (MPa) elongation at break (%) flexural strength (MPa) modulus in flexure (GPa) | ?181.0 ?29.8 ?1021.2 ?34.1 ?1.0 | ????178.0 ????30.5 ????1122.4 ????37.9 ????1.1 | ?160.5 ?30.2 ?659.8 ?38.5 ?1.2 | ?129.0 ?29.8 ?389.2 ?40.2 ?1.2 |
To handle through sec.-propyl three different stearoyl titanic acid ester 11.5g, granularity is the talcum powder 704.5g of 5 μ m, titanium dioxide 70g, ethene-alpha-olefin copolymer 91.2g, its melt flow rate is 0.5g/10min, polypropylene 60.8g, its melt flow rate is 50g/10min, naphthenic oil 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, in homogenizer, mediate 30min with 40 ℃-50 ℃ kneading temperature after, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 160-180-190-200-170 ℃ from the import to the outlet, the water-cooled pelletizing forms.
With above-mentioned filler parent granule and ethylene-propylene copolymer acrylic resin ratio in 40: 60 (weight percentage), obtain filling the Co-polypropylene matrix material with the working method identical with embodiment 1, its mechanical property sees Table 3.Embodiment 10:
To handle through the 11.5g γ-An Jibingjisanyiyangjiguiwan, granularity is the talcum powder 774.5g of 5 μ m, the ethylene-propylene-diene copolymer 152g of trimethoxy propane triacrylate modification, its melt flow rate is 5g/10min, Poly Propylene Wax 53.5g, calcium stearate 10g, N-cyclohexyl-N '-diphenyl-para-phenylene diamine 10g, under the working method and processing conditions identical, be prepared into filler parent granule and be combined into filled composite materials in the ratio of 40: 60 (weight percentage) with the copolymerization acrylic resin with embodiment 1.Embodiment 11 (comparative example):
Ethylene-propylene copolymer acrylic resin, the trade mark are PP1330, and chemical industry two factories of Beijing Yanshan Petro-Chemical Industry Corporation produce, pellet, and processing conditions and embodiment 9 are together.Embodiment 12 (comparative example):
When Co-polypropylene and ethylene-propylene-diene elastomer are pressed the master batch filled polyolefin matrix material of embodiment 9 preparations, wherein the Co-polypropylene matrix is with after the two identical ratio (weight percentage) of ethylene-propylene-diene elastomer as the master batch carrier mixes, composite molding, condition of molding and embodiment 9 are together.
Table 3 embodiment 9, embodiment 10 and embodiment 8, embodiment 11, embodiment 12 results' comparison
Embodiment 13:
Mixture | Embodiment 9 | Embodiment 10 | Embodiment 8 | Embodiment 11 | Embodiment 12 |
Notched izod impact strength (J/m) hot strength (MPa) elongation at break (%) bending strength (MPa) bending modulus (GPa) | ?343.8 ?22.0 ?511.4 ?34.7 ?1.5 | ?429.5 ?24.7 ?752.8 ?25.3 ?1.0 | ?129.0 ?29.8 ?389.2 ?40.2 ?1.2 | ?239.0 ?27.8 ?592.0 ?30.7 ?0.8 | ?615.0 ?21.9 ?530.2 ?24.9 ?0.7 |
To adsorb initiator DTBP0.1g, styrene monomer 8.0g, maleic anhydride 1.6g, granularity is the lime carbonate 750.8g of 1.5 μ m, and propylene-alpha-olefin copolymers 158.0g, its melt flow rate are 0.5g/10min, hydroxy-terminated polybutadienes 39.6g, laurate 7.9g, polyethylene wax 42.1g is at room temperature after homogenizer is mediated 10min, mixing on double roll mill, in flakes, pelletizing forms, and melting temperature is 120-150 ℃.
With above-mentioned filler parent granule and acrylic resin prescription by 40: 60 (weight percentage), the filling polypropylene composite material that obtains with the working method identical with embodiment 1.Embodiment 14 (comparative example):
With lime carbonate and the polypropylene matrix proportioning by 40: 60 (weight percentage), the mechanical property of the filling polypropylene composite material that obtains with working method identical with embodiment 13 and processing conditions also sees Table 4.Embodiment 15 (comparative example):
Homo-polypropylene, the trade mark are PP2401, and chemical industry two factories of Beijing Yanshan Petro-Chemical Industry Corporation produce, pellet, and the processing conditions processing identical with embodiment 13 also is injection molded into national testing standard sample.Table 4 embodiment 13 and embodiment 14, result's contrast of embodiment 15
Embodiment 16:
Mixture | Notched izod shock strength (J/m) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) |
Embodiment 13 embodiment 14 embodiment 15 | ????166.3 ????47.5 ????22.5 | ????29.2 ????35.0 ????37.3 | ????156.0 ????212.6 ????381.7 | ????48.5 ????52.1 ????50.3 | ????2.0 ????1.7 ????1.4 |
2.5 μ m kaolin 679.5g with 7.5g γ-Racemic glycidol oxygen propyl trimethoxy silicane processing, 2.5 μ m aluminium hydroxide 75.5g, high density polyethylene(HDPE) 47.3g, its melt flow rate is 5g/10min, new LDPE (film grade) 47.3g, its melt flow rate is 50g/min, the ethylene-propylene rubber(EPR) 94.6g of maleic anhydride graft, its melt flow rate is 3g/min, whiteruss 37.8g, calcium stearate 8g, four [β-(and 3,5-di-tert-butyl-4-hydroxy phenyl propionic acid] pentaerythritol ester 4g, the two ten diester 6g of thio-2 acid mediate 20min with room temperature in homogenizer after, extrude through twin screw extruder, the extruder barrel temperature is followed successively by 140-160-180-200-190 ℃ from the import to the outlet, and the water-cooled pelletizing forms.
Above-mentioned filler parent granule and high-density polyethylene resin are pressed the prescription of 20: 80 (weight percentage), after simple the mixing, in injector, directly be injection molded into national testing standard sample, injection temperature is 200 ℃, injection pressure is 13.5MPa, and its composite materials property test result sees Table 5.Embodiment 17:
High-density polyethylene resin, the trade mark are HDPE DMD7006, and plastic molding and processing plant of Qilu Petrochemical company produces, pellet, and processing conditions and embodiment 16 are together.Embodiment 18:
Will with the kaolin of embodiment 16 identical proportionings and aluminium hydroxide mixed fillers and high-density polyethylene resin prescription by 20: 80 (weight percentage), with the filling high-density polyethylene matrix material that working method identical with embodiment 16 and processing conditions obtain, its Mechanics Performance Testing result also can see Table 5.
Table 5 embodiment 16 and embodiment 17, embodiment 18 results' contrast
Mixture | Notched izod shock strength (J/m) | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (GPa) |
Embodiment 16 comparative examples 17 comparative examples 18 | ????56.0 ????34.1 ????37.6 | ????22.7 ????25.9 ????26.3 | ?????72.0 ????150.0 ????136.0 | ????39.8 ????33.8 ????37.6 | ????1.5 ????0.8 ????1.3 |
Claims (10)
1 one kinds of stuffing mother particle for toughening polyolefine is characterized in that described filler parent granule comprises following component and content (weight percentage)
Mineral filler 47.5-84.5
Surface treatment agent 0.5-2.5
Carrier 10-30
Processing aid 5-18
Oxidation inhibitor 0-2
2 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described mineral filler is talcum powder, kaolin, lime carbonate, titanium dioxide or aluminium hydroxide.
3 a kind of stuffing mother particle for toughening polyolefine according to claim 2, the particle dia that it is characterized in that described mineral filler are 1.5 μ m-5 μ m.
4 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described inorganic filler surface treatment agent is the mixture of γ-propyl methacrylate base Trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-Racemic glycidol oxygen propyl trimethoxy silicane, sec.-propyl three different stearoyl titanic acid ester or vinylbenzene and maleic anhydride.
5 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described carrier is the ethylene-propylene-diene copolymer of bismaleimides graft modification, the ethylene-propylene-diene copolymer of trimethoxy propane triacrylate graft modification, ethylene-propylene rubber(EPR), ethene-alpha-olefin copolymer, polypropylene, new LDPE (film grade), high density polyethylene(HDPE) or the hydroxy-terminated polybutadienes of maleic anhydride graft.
6 a kind of stuffing mother particle for toughening polyolefine according to claim 5, the melt flow rate that it is characterized in that described carrier is 0.5g/10min-50g/10min.
7 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described processing aid is Poly Propylene Wax, polyethylene wax, laurate, calcium stearate, whiteruss or naphthenic oil.
The preparation method of 8 a kind of stuffing mother particle for toughening polyolefine according to claim 1, it is characterized in that following these steps to order carries out: (1) is percentage ratio by weight, surface with surface treatment agent 0.5-2.5 treatment inorganic filling material 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 and the carrier 10-30 that handle well, processing aid 5-18, oxidation inhibitor 0-2 mediates in super mixer evenly, the kneading time is 20-30 minute, mediating temperature is 25 ℃-50 ℃, (3) above-mentioned kneaded material is extruded through twin screw extruder is compound under 140 ℃-200 ℃, granulation is made.
The preparation method of 9 a kind of stuffing mother particle for toughening polyolefine according to claim 1, it is characterized in that following these steps to order carries out: (1) is percentage ratio by weight, surface with surface treatment agent 0.5-2.5 treatment inorganic filling material 47.5-84.5 in super mixer, (2) with the mineral filler 48.0-87.0 that handles well and carrier 10-30, processing aid 5-18, oxidation inhibitor 0-2, in super mixer, mediate evenly, (3) with above-mentioned kneaded material in 120 ℃ of-150 ℃ of mixing rolls, through mixing, in flakes, pelletizing forms.
The purposes of 10 a kind of stuffing mother particle for toughening polyolefine according to claim 1 is characterized in that described filler parent granule is used to prepare composite polyolefine material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN98102448A CN1100087C (en) | 1998-06-18 | 1998-06-18 | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN98102448A CN1100087C (en) | 1998-06-18 | 1998-06-18 | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1215068A true CN1215068A (en) | 1999-04-28 |
CN1100087C CN1100087C (en) | 2003-01-29 |
Family
ID=5217350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN98102448A Expired - Fee Related CN1100087C (en) | 1998-06-18 | 1998-06-18 | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1100087C (en) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1109062C (en) * | 2000-05-10 | 2003-05-21 | 山西漳源农业环保开发有限公司 | Degradable composite mother particles of plastics based on inorganic materials |
CN1312217C (en) * | 2004-02-02 | 2007-04-25 | 山西新阳新材料有限公司 | Preparation method of ABS (acrilonitrile-butadiene-phenyl ethylene copolymer) functional filling mother particle |
CN100448918C (en) * | 2004-01-30 | 2009-01-07 | 三洋化成工业株式会社 | Resin dispersion and resin particle |
CN1875063B (en) * | 2003-10-29 | 2011-01-05 | 旭化成化学株式会社 | Rubber composition for footwear |
CN102070918A (en) * | 2009-11-19 | 2011-05-25 | 台州市黄岩明江塑胶有限公司 | Preparation method of calcium carbonate masterbatch |
CN1934186B (en) * | 2004-02-13 | 2011-07-06 | 赢创德固赛有限责任公司 | Highly filled polyolefin compounds |
CN102167856A (en) * | 2010-02-26 | 2011-08-31 | 张万鹏 | Ethylene propylene rubber grafted maleic anhydride modified polyethylene toughening master batch and preparation method thereof |
CN102558915A (en) * | 2010-12-30 | 2012-07-11 | 上海宝利纳材料科技有限公司 | Modified talcum powder and preparation method and application thereof |
CN102585368A (en) * | 2012-02-17 | 2012-07-18 | 南京炫胜塑料科技股份有限公司 | High-speed spinning non-woven fabric master batch |
CN102827454A (en) * | 2012-08-28 | 2012-12-19 | 安徽双荣电器电缆有限公司 | Polyethylene insulated power cable for coal mines and preparation method thereof |
CN102964679A (en) * | 2012-10-31 | 2013-03-13 | 安徽省易达电子有限公司 | Capacitor film containing modified talc and preparation method thereof |
CN103074009A (en) * | 2013-01-24 | 2013-05-01 | 上海普力通新材料科技有限公司 | Adhesion promoter for bonding elastomers and metals and adhesive composition |
CN103214734A (en) * | 2013-03-26 | 2013-07-24 | 安徽双荣电器电缆有限公司 | Multifunctional polypropylene masterbatch and preparation method thereof |
CN103756040A (en) * | 2014-01-08 | 2014-04-30 | 青岛科技大学 | Application of alkadiene polymer in rubber masterbatch, masterbatch and preparation method |
CN104479227A (en) * | 2012-04-16 | 2015-04-01 | 上海韬鸿化工科技有限公司 | Polypropylene plastic filled with coupling agent modified talcum powder |
CN104744812A (en) * | 2013-12-31 | 2015-07-01 | 南京金杉汽车工程塑料有限责任公司 | Ultralow-temperature high-toughness modified polypropylene and preparation method thereof |
CN105536642A (en) * | 2015-12-14 | 2016-05-04 | 上海金发科技发展有限公司 | Preparation method of mineral powder master batch |
CN105646993A (en) * | 2014-11-17 | 2016-06-08 | 天津华今集团有限公司 | Reinforced and toughened master batch specially used for reclaimed polypropylene woven bags and preparing method thereof |
CN106566164A (en) * | 2016-10-14 | 2017-04-19 | 江西广源新材料有限公司 | Toughening filler master batch and preparation method thereof |
CN108059756A (en) * | 2017-12-29 | 2018-05-22 | 张玉红 | A kind of polyethylene filling master batch |
CN108467548A (en) * | 2018-05-03 | 2018-08-31 | 万华化学集团股份有限公司 | A kind of modified polypropene and preparation method thereof |
CN109771359A (en) * | 2018-12-30 | 2019-05-21 | 武汉华丽环保科技有限公司 | A kind of bio-based plastics microballon and preparation method thereof |
CN111534066A (en) * | 2020-05-13 | 2020-08-14 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
CN111592691A (en) * | 2020-05-25 | 2020-08-28 | 贵州利东环保科技有限公司 | Phosphogypsum filled plastic modified particle and preparation method thereof |
CN112876760A (en) * | 2021-01-15 | 2021-06-01 | 宿迁联盛科技股份有限公司 | Light stabilizer controlled release type polymer composite material with light aging property prolonging function |
CN112876842A (en) * | 2021-01-15 | 2021-06-01 | 宿迁联盛科技股份有限公司 | Preparation method of anti-aging polymer composite material with enhanced core-shell structure |
CN114316415A (en) * | 2021-11-23 | 2022-04-12 | 金发科技股份有限公司 | Master batch for improving coating adhesive force, polypropylene material and application thereof |
CN115449216A (en) * | 2022-08-30 | 2022-12-09 | 浙江工业大学 | Preparation method of high-strength high-toughness PA66/GF |
CN115558209A (en) * | 2022-11-01 | 2023-01-03 | 河南华瑞兴业防水科技有限公司 | Toughening master batch for waterproof coiled material and preparation method thereof |
CN115895166A (en) * | 2022-03-14 | 2023-04-04 | 江苏永顺新材料科技有限公司 | Novel composite polymer material for refrigerator shell and preparation method and application thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106243496A (en) * | 2016-08-03 | 2016-12-21 | 安庆市悦发管业有限公司 | A kind of plum tube toughening type masterbatch and preparation method |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07103261B2 (en) * | 1990-03-08 | 1995-11-08 | 燐化学工業株式会社 | Flame-retardant masterbatch |
JPH07113031A (en) * | 1993-10-15 | 1995-05-02 | Lion Corp | Antistatic master pellet |
CN1036787C (en) * | 1995-08-10 | 1997-12-24 | 南京化工大学 | Toughening mother particle for polyolefine plastics and producing process thereof |
CN1038421C (en) * | 1995-11-17 | 1998-05-20 | 南京化工大学 | Supertough master-pellets for polypropylene plastics and making method thereof |
JP3259956B2 (en) * | 1998-05-01 | 2002-02-25 | コクヨ株式会社 | Reinforcement structure of double floor border panel and construction method |
-
1998
- 1998-06-18 CN CN98102448A patent/CN1100087C/en not_active Expired - Fee Related
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1109062C (en) * | 2000-05-10 | 2003-05-21 | 山西漳源农业环保开发有限公司 | Degradable composite mother particles of plastics based on inorganic materials |
CN1875063B (en) * | 2003-10-29 | 2011-01-05 | 旭化成化学株式会社 | Rubber composition for footwear |
CN100448918C (en) * | 2004-01-30 | 2009-01-07 | 三洋化成工业株式会社 | Resin dispersion and resin particle |
CN1312217C (en) * | 2004-02-02 | 2007-04-25 | 山西新阳新材料有限公司 | Preparation method of ABS (acrilonitrile-butadiene-phenyl ethylene copolymer) functional filling mother particle |
CN1934186B (en) * | 2004-02-13 | 2011-07-06 | 赢创德固赛有限责任公司 | Highly filled polyolefin compounds |
CN102070918A (en) * | 2009-11-19 | 2011-05-25 | 台州市黄岩明江塑胶有限公司 | Preparation method of calcium carbonate masterbatch |
CN102167856A (en) * | 2010-02-26 | 2011-08-31 | 张万鹏 | Ethylene propylene rubber grafted maleic anhydride modified polyethylene toughening master batch and preparation method thereof |
CN102558915A (en) * | 2010-12-30 | 2012-07-11 | 上海宝利纳材料科技有限公司 | Modified talcum powder and preparation method and application thereof |
CN102585368A (en) * | 2012-02-17 | 2012-07-18 | 南京炫胜塑料科技股份有限公司 | High-speed spinning non-woven fabric master batch |
CN102585368B (en) * | 2012-02-17 | 2014-06-11 | 南京炫胜塑料科技股份有限公司 | High-speed spinning non-woven fabric master batch |
CN104479227A (en) * | 2012-04-16 | 2015-04-01 | 上海韬鸿化工科技有限公司 | Polypropylene plastic filled with coupling agent modified talcum powder |
CN102827454A (en) * | 2012-08-28 | 2012-12-19 | 安徽双荣电器电缆有限公司 | Polyethylene insulated power cable for coal mines and preparation method thereof |
CN102964679A (en) * | 2012-10-31 | 2013-03-13 | 安徽省易达电子有限公司 | Capacitor film containing modified talc and preparation method thereof |
CN102964679B (en) * | 2012-10-31 | 2015-06-17 | 安徽省易达电子有限公司 | Capacitor film containing modified talc and preparation method thereof |
CN103074009A (en) * | 2013-01-24 | 2013-05-01 | 上海普力通新材料科技有限公司 | Adhesion promoter for bonding elastomers and metals and adhesive composition |
CN103074009B (en) * | 2013-01-24 | 2015-01-07 | 上海普力通新材料科技有限公司 | Adhesion promoter for bonding elastomers and metals and adhesive composition |
CN103214734A (en) * | 2013-03-26 | 2013-07-24 | 安徽双荣电器电缆有限公司 | Multifunctional polypropylene masterbatch and preparation method thereof |
CN104744812A (en) * | 2013-12-31 | 2015-07-01 | 南京金杉汽车工程塑料有限责任公司 | Ultralow-temperature high-toughness modified polypropylene and preparation method thereof |
CN103756040B (en) * | 2014-01-08 | 2016-02-17 | 青岛科技大学 | The application of diene polymer in Rubber master batch, masterbatch particles and preparation method |
CN103756040A (en) * | 2014-01-08 | 2014-04-30 | 青岛科技大学 | Application of alkadiene polymer in rubber masterbatch, masterbatch and preparation method |
CN105646993A (en) * | 2014-11-17 | 2016-06-08 | 天津华今集团有限公司 | Reinforced and toughened master batch specially used for reclaimed polypropylene woven bags and preparing method thereof |
CN105536642A (en) * | 2015-12-14 | 2016-05-04 | 上海金发科技发展有限公司 | Preparation method of mineral powder master batch |
CN106566164A (en) * | 2016-10-14 | 2017-04-19 | 江西广源新材料有限公司 | Toughening filler master batch and preparation method thereof |
CN108059756A (en) * | 2017-12-29 | 2018-05-22 | 张玉红 | A kind of polyethylene filling master batch |
CN108467548A (en) * | 2018-05-03 | 2018-08-31 | 万华化学集团股份有限公司 | A kind of modified polypropene and preparation method thereof |
CN109771359A (en) * | 2018-12-30 | 2019-05-21 | 武汉华丽环保科技有限公司 | A kind of bio-based plastics microballon and preparation method thereof |
CN111534066B (en) * | 2020-05-13 | 2022-07-05 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
CN111534066A (en) * | 2020-05-13 | 2020-08-14 | 江西广源新材料有限公司 | Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material |
CN111592691A (en) * | 2020-05-25 | 2020-08-28 | 贵州利东环保科技有限公司 | Phosphogypsum filled plastic modified particle and preparation method thereof |
CN112876760A (en) * | 2021-01-15 | 2021-06-01 | 宿迁联盛科技股份有限公司 | Light stabilizer controlled release type polymer composite material with light aging property prolonging function |
CN112876842A (en) * | 2021-01-15 | 2021-06-01 | 宿迁联盛科技股份有限公司 | Preparation method of anti-aging polymer composite material with enhanced core-shell structure |
CN114316415A (en) * | 2021-11-23 | 2022-04-12 | 金发科技股份有限公司 | Master batch for improving coating adhesive force, polypropylene material and application thereof |
CN114316415B (en) * | 2021-11-23 | 2023-09-12 | 金发科技股份有限公司 | Masterbatch for improving coating adhesion, polypropylene material and application thereof |
CN115895166A (en) * | 2022-03-14 | 2023-04-04 | 江苏永顺新材料科技有限公司 | Novel composite polymer material for refrigerator shell and preparation method and application thereof |
CN115449216A (en) * | 2022-08-30 | 2022-12-09 | 浙江工业大学 | Preparation method of high-strength high-toughness PA66/GF |
CN115449216B (en) * | 2022-08-30 | 2023-09-05 | 浙江工业大学 | Preparation method of high-strength high-toughness PA66/GF |
CN115558209A (en) * | 2022-11-01 | 2023-01-03 | 河南华瑞兴业防水科技有限公司 | Toughening master batch for waterproof coiled material and preparation method thereof |
CN115558209B (en) * | 2022-11-01 | 2023-11-24 | 河南华瑞兴业防水科技有限公司 | Toughening master batch for waterproof coiled material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1100087C (en) | 2003-01-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1215068A (en) | Stuffing mother particle for toughening polyolefine and preparation process and usage thereof | |
CN1184265C (en) | Fully cured thermoplastic elastomer, process for its manufacture and applications | |
CN1322774A (en) | Material specially for communication optical cable protecting casing and its prepn | |
CN111592707B (en) | Plastic product filled and modified by artificial granite waste residue and processing method thereof | |
CN1737042A (en) | Polyolefin composition and its preparation method and uses | |
CN1737039A (en) | Polyolefin composition and its preparation method and uses | |
CN1737043A (en) | Polyolefin composition and its preparation method and uses | |
WO1998050463A1 (en) | Thermoplastic elastomer compositions | |
CN1191300C (en) | Tertiary polypropylene/elastomer/inorganic filler composite material and preparing method thereof | |
JPS6317297B2 (en) | ||
CN1063199C (en) | High-toughness polypropylene composite | |
CN1154691C (en) | Thermoplastic full-sulfurized polyolefin elastomer and its preparing process | |
CN1765984A (en) | Thermoplastic elastomer material and its preparation method | |
CN102295802A (en) | High-toughness and high-strength polypropylene composition, and preparation method thereof | |
CN1511872A (en) | Nylon particle toughness increased polypropylene composite material and preparing method | |
CN1164663C (en) | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process | |
CN1283715C (en) | Triple composite of polystyrene/elastomer/nano calcium carbonate and preparation process thereof | |
CN1353136A (en) | High-rigidity high-toughness plastics and its preparing process | |
CN1180012C (en) | Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method | |
CN1154692C (en) | Toughened polypropylene and its preparing process | |
CN1114657C (en) | Composite polypropylene material filled by nm-class organized montmorillonite and inorganic spherical rigid particles and its preparing process | |
CN1188469C (en) | Toughening polyamide combination and prepn method | |
CN101684189B (en) | Sprayable and toughened polypropylene composition and preparation method thereof | |
CN1229437C (en) | Polybutanediol terephthalate composition and its preparation method | |
CN113845733B (en) | Polypropylene blend material filled with waste rubber powder and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
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 |