CN103421309A - Cold-resistant super-tough reinforced nylon 6 material for automobiles and preparation method thereof - Google Patents
Cold-resistant super-tough reinforced nylon 6 material for automobiles and preparation method thereof Download PDFInfo
- Publication number
- CN103421309A CN103421309A CN2012103199696A CN201210319969A CN103421309A CN 103421309 A CN103421309 A CN 103421309A CN 2012103199696 A CN2012103199696 A CN 2012103199696A CN 201210319969 A CN201210319969 A CN 201210319969A CN 103421309 A CN103421309 A CN 103421309A
- Authority
- CN
- China
- Prior art keywords
- cold
- nylon
- reinforced nylon
- district
- automobile
- 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
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 47
- 230000004048 modification Effects 0.000 claims abstract description 41
- 238000012986 modification Methods 0.000 claims abstract description 41
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000000314 lubricant Substances 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- 238000005453 pelletization Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- -1 irgasfos 168 Chemical compound 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- 229960003742 phenol Drugs 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 244000178289 Verbascum thapsus Species 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract 2
- 239000011347 resin Substances 0.000 abstract 2
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
-
- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polymer modification and provides a cold-resistant super-tough reinforced nylon 6 material for automobiles and a preparation method thereof. The cold-resistant super-tough reinforced nylon 6 material for automobiles is obtained by mixing 20-90 weight parts of a nylon 6 resin, 10-80 weight parts of a modification precursor, 0.1-0.5 weight parts of an anti-oxidant and 0.1-0.5 weight parts of a lubricant, wherein the modification precursor is obtained by mixing a polyolefin resin, a grafting copolymerization monomer and glass fibers. The polyolefin resin and the grafting copolymerization monomer undergo a reaction for full activation and surfaces of the glass fibers have functionalization and hydrophobization effects. The glass fibers and polyolefin form a candlewick structure so that the interfacial compatibility between a flexibilizer and the glass fibers and between the flexibilizer and the nylon 6 resin are good. Therefore, the cold-resistant super-tough reinforced nylon 6 material has improved toughness and rigidity.
Description
Technical field
The present invention relates to the polymer modification technical field, particularly cold-resistance super tough reinforced nylon 6 material and preparation method thereof for a kind of automobile.
Background technology
Nylon 6, the formal name used at school polycaprolactam, be a kind of purposes engineering plastics very widely, fusing point is at 215 ℃ ~ 225 ℃, lower than nylon 66; In addition, due to degree of crystallinity, lower than nylon 66, so its rigidity is lower, water absorbability is larger, and the use temperature scope is at-40 ℃ ~ 150 ℃.Change because common nylon 6 be there will be significantly by the impact of temperature and environment, performance, so its application is greatly limited, therefore, by filling-modified to it, can make its over-all properties obviously be promoted.
Modified nylon-6 material, can be widely used in the industries such as household electrical appliance, power tool and electric connector.Current method of modifying commonly used, be to add polyphenylene oxide (PPO) or acrylonitrile-butadiene-styrene copolymer (ABS) in nylon 6, or add nylon toughener (polypropylene grafted maleic anhydride toughner (PP-g-MAH), ethylene-octene copolymer (POE) grafted maleic anhydride toughner etc.) it is carried out to toughness and the impact property that modification improves material; Add the mineral fillers such as glass fibre, talcum powder, calcium carbonate in nylon 6, improve the strength of materials and rigidity.The patents such as publication number CN101875781A, CN101195707B, CN100532457C disclose modification of several polyamide materials and preparation method thereof, all specifically after the materials such as nylon material, toughner, dispersion agent, lubricant, oxidation inhibitor are stirred, directly through twin screw extruder melt blending extruding pelletization.The shortcomings such as the method for modifying of this " one pot goes out " formula, exist the functional agent synergistic to be difficult to embody, and each component dispersing uniformity is poor.
The patent of publication number CN101121817A discloses a kind of high cold resistance reinforced nylon 6 and preparation method thereof, specifically, first by polycomponent polyolefine and the blend of activator high speed, melt extrudes at a certain temperature granulation, obtains composite elastic body toughner; Then, by composite elastic body and nylon 6 mixing, then melt extrude granulation with glass fibre through twin screw extruder, obtain the finished product.Though this method has been considered the Composite modification advantage of toughner, ignore glass fibre and be combined problem with the interface of nylon 6 and toughner, cause the interface compatibility of whole system not good enough, cause when toughness improves, rigidity is difficult to keep.For this reason, must develop a kind of novel modification technology, both can give full play to the performance of toughner, can at utmost guarantee again the enhancement of glass fibre.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect that prior art exists, cold-resistance super tough reinforced nylon 6 material for a kind of automobile is provided, it is strong that it had both had stronger toughness, has again higher rigidity, and cold tolerance is good.
Another object of the present invention is to provide the preparation method of a kind of automobile with cold-resistance super tough reinforced nylon 6 material, make toughner and glass fibre interface, toughner and nylon 6 interfaces all obtain consistency preferably, thereby make material of the present invention when toughness strengthens, rigidity also is improved greatly.
The technical solution adopted for the present invention to solve the technical problems is:
Cold-resistance super tough reinforced nylon 6 material for a kind of automobile, by weight, described automobile is mixed by following component with cold-resistance super tough reinforced nylon 6 material: Nylon 6 20-90 part, modification precursor 10-80 part, oxidation inhibitor 0.1-0.5 part, lubricant 0.1-0.5 part; Wherein said modification precursor is mixed by polyolefin resin, graft copolymerization monomer and glass fibre.
Said modification precursor is that polyolefin resin, graft copolymerization monomer, glass fibre three melt blending extruding pelletization form.Polyolefin resin reacts with the graft copolymerization molten monomer and forms toughner, toughner forms the modification precursor with the glass fibre melting again, the modification precursor forms product with other component melts blend such as Nylon 6 again, this kind of differential modification technology, both can allow fully activation after polyolefin resin and copolymerization monomer reaction, can allow again the surface of glass fibre reach functionalization and hydrophobization effect, glass fibre and polyolefine form " candle wick structure ", for follow-up, with blend Nylon 6, carry out the technology place mat.Obtain toughner and glass fibre interface, toughner and nylon 6 interfaces and all obtain consistency preferably, thereby make material of the present invention when toughness strengthens, rigidity also is improved greatly.
As preferably, by weight, described modification precursor is mixed by polyolefin resin 40-90 part, graft copolymerization monomer 0.5-30 part and glass fibre 5-50 part.
As preferably, described polyolefin resin is mixed by the component of following weight part: linear low density polyethylene (LLDPE) 5-60 part, vinyl-vinyl acetate copolymer (EVA) 10-90 part, ethylene-octene copolymer (POE) 5-40 part.
As preferably, described graft copolymerization monomer is one or more the mixture in methyl methacrylate, maleic anhydride, glycidyl methacrylate, dicumyl peroxide.
As preferably, the viscosity of described Nylon 6 is 2.4 ~ 3.6.
As preferably, described oxidation inhibitor is one or more the mixture in antioxidant 1010, irgasfos 168, antioxidant 264, oxidation inhibitor 1045.
As preferably, described lubricant is one or more mixtures in amine hydroxybenzene, stearylamide, ethylene bis stearic amide.
The preparation method of cold-resistance super tough reinforced nylon 6 material for a kind of automobile, described preparation method's step is as follows:
(1) by weight ratio, polyolefin resin, graft copolymerization monomer are fully mixed in high mixer, enter in twin screw extruder, at 140 ℃ ~ 220 ℃ temperature, melt blending is extruded, after normally extruding 0.5 ~ 5 minute, to twin-screw extrusion pusher side spout, add glass fibre, glass fibre with the melt melt blending after extruding pelletization, dry, obtain the modification precursor;
(2) by weight ratio, dried Nylon 6, modification precursor, oxidation inhibitor and lubricant are fully mixed in high mixer, enter in twin screw extruder, at 180 ℃ ~ 248 ℃ temperature, melt extrude granulation, dry, obtain cold-resistance super tough reinforced nylon 6 material for automobile.
As preferably, by weight, described automobile is mixed by following component with cold-resistance super tough reinforced nylon 6 material: Nylon 6 20-90 part, modification precursor 10-80 part, oxidation inhibitor 0.1-0.5 part, lubricant 0.1-0.5 part; Wherein said modification precursor is mixed by polyolefin resin 40-90 part, graft copolymerization monomer 0.5-30 part and glass fibre 5-50 part.
As preferably, described polyolefin resin is mixed by the component of following weight part: linear low density polyethylene 5-60 part, vinyl-vinyl acetate copolymer 10-90 part, ethylene-octene copolymer 5-40 part.
The invention has the beneficial effects as follows:
1, the present invention adopts and first polyolefin resin is reacted to toughner and the glass fibre blend granulation in advance formed with the graft copolymerization molten monomer, by differential modification technology advantage, both can allow fully activation after polyolefin resin and copolymerization monomer reaction, can allow again the surface of glass fibre reach functionalization and hydrophobization effect, glass fibre and polyolefine form " candle wick structure ", make toughner and glass fibre interface, toughner and nylon 6 interfaces all obtain consistency preferably, thereby make material of the present invention when toughness strengthens, rigidity also is improved greatly.
2, cold tolerance is good, and the impact property of-40 ℃ of low temperature is better and stable.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is commonly used.Method in following embodiment, if no special instructions, be the ordinary method of this area.In following examples, part of indication is weight part.The viscosity of the Nylon 6 that following examples are used is 2.4 ~ 3.6.
Embodiment 1
(1) polyolefin resin, graft copolymerization monomer are fully mixed and (stir in high mixer 6 ~ 10 minutes in high mixer, mixing speed is 200 ~ 800 rev/mins), send twin screw extruder to melt extrude the raw material mixed, after normally extruding 0.5 ~ 5 minute, add twin-screw extrusion pusher side spout (according to the rotating speed Accurate Estimation in 7 strands of glass fibre (long glass fibres of commercially available routine), 7 strands is just 30 parts of weight parts), glass fibre with the melt melt blending after extruding pelletization, dry, obtain the modification precursor; The expressing technique of twin screw extruder is: 300 rev/mins of ，Ge district Heating temperatures of screw speed are: 190 ℃, 140 150 165 175 175 180 190 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
The component of modification precursor forms: 50 parts of polyolefin resines (wherein LLDPE is 20 parts, 20 parts of EVA, 10 parts of POE), 20 parts of maleic anhydrides, 30 parts, glass fibre.
(2) dried Nylon 6, modification precursor, oxidation inhibitor and lubricant are fully mixed and (stir in high mixer 5 ~ 20 minutes in high mixer, mixing speed is 400 ~ 1000 rev/mins), send twin screw extruder to melt extrude the raw material mixed, granulation, dry, obtain cold-resistance super tough reinforced nylon 6 material for automobile.The expressing technique of twin screw extruder is: 400 rev/mins of ，Ge district Heating temperatures of screw speed are: 235 ℃, 180 190 200 220 235 235 240 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
Automobile forms by the component of cold-resistance super tough reinforced nylon 6 material: 29.5 parts of Nylon 6s, 70 parts of modification precursors, 0.2 part of antioxidant 1010,0.3 part of lubricant oleic acid acid amides.
Embodiment 2
(1) polyolefin resin, graft copolymerization monomer are fully mixed and (stir in high mixer 6 ~ 10 minutes in high mixer, mixing speed is 200 ~ 800 rev/mins), send twin screw extruder to melt extrude the raw material mixed, after normally extruding 0.5 ~ 5 minute, add twin-screw extrusion pusher side spout (according to the rotating speed Accurate Estimation in 10 strands of glass fibre (long glass fibres of commercially available routine), 10 strands is just 50 parts of weight parts), glass fibre with the melt melt blending after extruding pelletization, dry, obtain the modification precursor; The expressing technique of twin screw extruder is: 350 rev/mins of ，Ge district Heating temperatures of screw speed are: 180 ℃, 140 145 160 170 170 175 180 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
The component of modification precursor forms: 40 parts of polyolefin resines (wherein LLDPE is 20 parts, 10 parts of EVA, 10 parts of POE), 10 parts of methyl methacrylate and glycidyl methacrylate compounds (mass ratio 1:1), 50 parts, glass fibre.
(2) dried Nylon 6, modification precursor, oxidation inhibitor and lubricant are fully mixed and (stir in high mixer 5 ~ 20 minutes in high mixer, mixing speed is 400 ~ 1000 rev/mins), send twin screw extruder to melt extrude the raw material mixed, granulation, dry, obtain cold-resistance super tough reinforced nylon 6 material for automobile.The expressing technique of twin screw extruder is: 450 rev/mins of ，Ge district Heating temperatures of screw speed are: 240 ℃, 180 195 205 225 240 245 245 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
Automobile forms by the component of cold-resistance super tough reinforced nylon 6 material: 39.5 parts of Nylon 6s, 60 parts of modification precursors, 0.25 part of irgasfos 168,0.25 part of lubricant ethylene bis stearic amide.
Embodiment 3
(1) polyolefin resin, graft copolymerization monomer are fully mixed and (stir in high mixer 6 ~ 10 minutes in high mixer, mixing speed is 200 ~ 800 rev/mins), send twin screw extruder melting (forming toughness reinforcing melt) to extrude the raw material mixed, after normally extruding 0.5 ~ 5 minute, add twin-screw extrusion pusher side spout (according to the rotating speed Accurate Estimation in 9 strands of glass fibre (long glass fibres of commercially available routine), 9 strands is just 40 parts of weight parts), glass fibre with the melt melt blending after extruding pelletization, dry, obtain the modification precursor; The expressing technique of twin screw extruder is: 360 rev/mins of ，Ge district Heating temperatures of screw speed are: 210 ℃, 150 160 180 190 200 220 210 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
The component of modification precursor forms: 40 parts of polyolefin resines (wherein LLDPE is 10 parts, 10 parts of EVA, 20 parts of POE), 20 parts of glycidyl methacrylate, 40 parts, glass fibre.
(2) dried Nylon 6, modification precursor, oxidation inhibitor and lubricant are fully mixed and (stir in high mixer 5 ~ 20 minutes in high mixer, mixing speed is 400 ~ 1000 rev/mins), send twin screw extruder to melt extrude the raw material mixed, granulation, dry, obtain cold-resistance super tough reinforced nylon 6 material for automobile.The expressing technique of twin screw extruder is: 450 rev/mins of ，Ge district Heating temperatures of screw speed are: 240 ℃, 185 195 225 225 245 248 248 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
Automobile forms by the component of cold-resistance super tough reinforced nylon 6 material: 24.5 parts of Nylon 6s, 75 parts of modification precursors, 0.3 part of antioxidant 264 and 1045 1:1 quality compound, lubricant: 0.2 part of the 1:1 quality compound of stearylamide and amine hydroxybenzene.
Comparative Examples 1
The component of comparative sample: 29.5 parts of Nylon 6s, 50 parts of polyolefin resines (wherein LLDPE is 20 parts, 20 parts of EVA, 10 parts of POE), 20 parts of maleic anhydrides, 30 parts, glass fibre, 0.2 part of antioxidant 1010,0.3 part of lubricant oleic acid acid amides.
The preparation method of comparative sample: Nylon 6, polyolefin resin, graft copolymerization monomer, oxidation inhibitor and lubricant are added in high mixer successively fully mix and (stir in high mixer 6 ~ 10 minutes, mixing speed is 200 ~ 800 rev/mins), send twin screw extruder to melt extrude the raw material mixed; After normally extruding 0.5 ~ 5 minute, extruding pelletization after the melt melt blending that adds twin-screw extrusion pusher side spout (according to the rotating speed Accurate Estimation, 7 strands is just 30 parts of weight parts) and front component to form in 7 strands of glass fibre.The expressing technique of twin screw extruder is: 400 rev/mins of ，Ge district Heating temperatures of screw speed are: 235 ℃, 180 190 200 220 235 235 240 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
Comparative Examples 2
The component of comparative sample: 39.5 parts of Nylon 6s, (wherein LLDPE is 20 parts for 40 parts of polyolefin resines, 10 parts of EVA, 10 parts of POE), 10 parts of methyl methacrylate and glycidyl methacrylate compounds (mass ratio 1:1), 50 parts, glass fibre, 0.25 part of irgasfos 168,0.25 part of lubricant ethylene bis stearic amide.
The preparation method of comparative sample: Nylon 6, polyolefin resin, graft copolymerization monomer, oxidation inhibitor and lubricant are added in high mixer successively fully mix and (stir in high mixer 6 ~ 10 minutes, mixing speed is 200 ~ 800 rev/mins), send twin screw extruder to melt extrude the raw material mixed; After normally extruding 0.5 ~ 5 minute, extruding pelletization after the melt melt blending that adds twin-screw extrusion pusher side spout (according to the rotating speed Accurate Estimation, 10 strands is just 50 parts of weight parts) and front component to form in 10 strands of glass fibre.The expressing technique of twin screw extruder is: 450 rev/mins of ，Ge district Heating temperatures of screw speed are: 240 ℃, 180 195 205 225 240 245 245 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
Comparative Examples 3
The component of comparative sample: 24.5 parts of Nylon 6s, (wherein LLDPE is 10 parts for 40 parts of polyolefin resines, 10 parts of EVA, 20 parts of POE), 20 parts of glycidyl methacrylate, 40 parts, glass fibre, 0.3 part of antioxidant 264 and 1045 1:1 quality compound, 0.2 part of the 1:1 quality compound of lubricant stearylamide and amine hydroxybenzene.
The preparation method of comparative sample: Nylon 6, polyolefin resin, graft copolymerization monomer, oxidation inhibitor and lubricant are added in high mixer successively fully mix and (stir in high mixer 6 ~ 10 minutes, mixing speed is 200 ~ 800 rev/mins), send twin screw extruder to melt extrude the raw material mixed; After normally extruding 0.5 ~ 5 minute, extruding pelletization after the melt melt blending that adds twin-screw extrusion pusher side spout (according to the rotating speed Accurate Estimation, 9 strands is just 40 parts of weight parts) and front component to form in 9 strands of glass fibre.The expressing technique of twin screw extruder is: 450 rev/mins of ，Ge district Heating temperatures of screw speed are: 240 ℃, 185 195 225 225 245 248 248 ℃, 8th district, ℃, 7th district, ℃, 6th district, ℃, 5th district, ℃, 4th district, ℃, 3rd district, ℃, 2nd district, a district.
Mechanics Performance Testing:
The product prepared is placed in 110 ℃ of baking ovens under condition and dries 4 ~ 6 hours, and then injection moulding prepares batten, and embodiment 1,2,3 is identical with corresponding Comparative Examples 1,2,3 Shooting Techniques respectively.
The test of tensile property, bending property, impact property, undertaken by national standard fully.Draw speed is 20mm/min, rate of bending 5mm/min, and shock strength is undertaken by socle girder breach method, and the low temperature impact test condition is that-40 ℃, the 24h status adjustment, regulate rear taking-up and test immediately.
Various test performances are as shown in table 1.
From finding out with table 1, with the material that same composition is prepared with the usual way under condition, to compare, the prepared material property of the present invention has the lifting of certain amplitude, is specially:
1) to the bending property index of reflection strength of materials rigidity, 10% raising is approximately arranged;
2) to the normal temperature impact property index of reflection toughness of material, 10 ~ 20% raising is approximately arranged;
3) to the low temperature impact strength of reaction material cold tolerance, the increase rate maximum surpasses 70%.
Hence one can see that, adopts the prepared novel material of method of the present invention, on rigidity and toughness, all is greatly improved, and particularly cold tolerance has larger breakthrough.
The proportioning of following each feed composition of the present invention:
Automobile with cold-resistance super tough reinforced nylon 6 material prescription is: Nylon 6 20-90 part, modification precursor 10-80 part, oxidation inhibitor 0.1-0.5 part, lubricant 0.1-0.5 part.The modification precursor is mixed by polyolefin resin 40-90 part, graft copolymerization monomer 0.5-30 part and glass fibre 5-50 part.Polyolefin resin was comprised of the mixing of linear low density polyethylene 5-60 part, vinyl-vinyl acetate copolymer 10-90 part and ethylene-octene copolymer 5-40 part.
During the invention process, the amount of each feed composition all can rationally change in above-mentioned scope, adopts the method for embodiment 1-3 to obtain product as resulting as embodiment 1-3.The performance of the performance of products obtained therefrom and the resulting product of embodiment 1-3 is similar, and therefore therefore not to repeat here.
Above-described embodiment is a kind of preferably scheme of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (10)
1. cold-resistance super tough reinforced nylon 6 material for an automobile, it is characterized in that: by weight, described automobile is mixed by following component with cold-resistance super tough reinforced nylon 6 material: Nylon 6 20-90 part, modification precursor 10-80 part, oxidation inhibitor 0.1-0.5 part, lubricant 0.1-0.5 part; Wherein said modification precursor is mixed by polyolefin resin, graft copolymerization monomer and glass fibre.
2. cold-resistance super tough reinforced nylon 6 material for a kind of automobile according to claim 1, it is characterized in that: by weight, described modification precursor is mixed by polyolefin resin 40-90 part, graft copolymerization monomer 0.5-30 part and glass fibre 5-50 part.
3. cold-resistance super tough reinforced nylon 6 material for a kind of automobile according to claim 1, it is characterized in that: described polyolefin resin is mixed by the component of following weight part: linear low density polyethylene 5-60 part, vinyl-vinyl acetate copolymer 10-90 part, ethylene-octene copolymer 5-40 part.
4. according to claim 1 or cold-resistance super tough reinforced nylon 6 materials for 2 or 3 described a kind of automobiles, it is characterized in that: described graft copolymerization monomer is one or more the mixture in methyl methacrylate, maleic anhydride, glycidyl methacrylate, dicumyl peroxide.
5. according to claim 1 or 2 or 3 described a kind of automobile cold-resistance super tough reinforced nylon 6 materials, it is characterized in that: the viscosity of described Nylon 6 is 2.4 ~ 3.6.
6. according to claim 1 or cold-resistance super tough reinforced nylon 6 materials for 2 or 3 described a kind of automobiles, it is characterized in that: described oxidation inhibitor is one or more the mixture in antioxidant 1010, irgasfos 168, antioxidant 264, oxidation inhibitor 1045.
7. according to claim 1 or 2 or 3 described a kind of automobile cold-resistance super tough reinforced nylon 6 materials, it is characterized in that: described lubricant is one or more mixtures in amine hydroxybenzene, stearylamide, ethylene bis stearic amide.
8. the preparation method of cold-resistance super tough reinforced nylon 6 material for an automobile, it is characterized in that: described preparation method's step is as follows:
(1) by weight ratio, polyolefin resin, graft copolymerization monomer are fully mixed in high mixer, enter in twin screw extruder, at 140 ℃ ~ 220 ℃ temperature, melt blending is extruded, after normally extruding 0.5 ~ 5 minute, to twin-screw extrusion pusher side spout, add glass fibre, glass fibre with the melt melt blending after extruding pelletization, dry, obtain the modification precursor;
(2) by weight ratio, dried Nylon 6, modification precursor, oxidation inhibitor and lubricant are fully mixed in high mixer, enter in twin screw extruder, at 180 ℃ ~ 248 ℃ temperature, melt extrude granulation, dry, obtain cold-resistance super tough reinforced nylon 6 material for automobile.
9. preparation method according to claim 8, it is characterized in that: by weight, described automobile is mixed by following component with cold-resistance super tough reinforced nylon 6 material: Nylon 6 20-90 part, modification precursor 10-80 part, oxidation inhibitor 0.1-0.5 part, lubricant 0.1-0.5 part; Wherein said modification precursor is mixed by polyolefin resin 40-90 part, graft copolymerization monomer 0.5-30 part and glass fibre 5-50 part.
10. preparation method according to claim 8 or claim 9, it is characterized in that: described polyolefin resin is mixed by the component of following weight part: linear low density polyethylene 5-60 part, vinyl-vinyl acetate copolymer 10-90 part, ethylene-octene copolymer 5-40 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210319969.6A CN103421309B (en) | 2012-09-03 | 2012-09-03 | A kind of automobile cold-resistance super tough reinforced nylon 6 material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210319969.6A CN103421309B (en) | 2012-09-03 | 2012-09-03 | A kind of automobile cold-resistance super tough reinforced nylon 6 material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103421309A true CN103421309A (en) | 2013-12-04 |
| CN103421309B CN103421309B (en) | 2015-08-05 |
Family
ID=49646714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210319969.6A Active CN103421309B (en) | 2012-09-03 | 2012-09-03 | A kind of automobile cold-resistance super tough reinforced nylon 6 material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103421309B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177825A (en) * | 2014-08-27 | 2014-12-03 | 东莞市卡尔文塑胶科技有限公司 | A kind of polyamide toughening agent, preparation method and use thereof |
| CN105001630A (en) * | 2015-06-10 | 2015-10-28 | 苏州宏恒化工有限公司 | Polyethylene/nylon composite material and preparing method thereof |
| CN106283310A (en) * | 2016-08-30 | 2017-01-04 | 安徽翰文运动用品股份有限公司 | It is exclusively used in the nylon wire of racket |
| CN107195285A (en) * | 2017-05-24 | 2017-09-22 | 连云港纶洋单丝科技有限公司 | A kind of musical instrument string |
| CN107254166A (en) * | 2017-07-28 | 2017-10-17 | 张乃斌 | A kind of maleic anhydride is grafted the POE high tenacity nylon material of high dispersive |
| CN107936553A (en) * | 2017-11-14 | 2018-04-20 | 东莞科姆新材料有限公司 | Effective multilayer inner tube layer polymer composite of vehicle fuel and preparation method thereof |
| CN107955370A (en) * | 2017-11-14 | 2018-04-24 | 东莞科姆新材料有限公司 | Vehicle fuel multilayer outer tube layer polymer composite and preparation method thereof |
| CN107955366A (en) * | 2017-11-14 | 2018-04-24 | 东莞科姆新材料有限公司 | Effective multilayer inner tube layer polymer composite of vehicle fuel and preparation method thereof |
| CN107964238A (en) * | 2017-11-14 | 2018-04-27 | 东莞科姆新材料有限公司 | Vehicle fuel multilayer outer tube layer polymer composite and preparation method thereof |
| CN107974081A (en) * | 2017-11-14 | 2018-05-01 | 东莞科姆新材料有限公司 | Vehicle fuel multilayer pipe adhesive linkage polymer composite and preparation method thereof |
| CN108739689A (en) * | 2018-05-07 | 2018-11-06 | 巢湖市俊业渔具有限公司 | A kind of wear-resisting fishing net of copolymer reinforced nylon |
| CN110922750A (en) * | 2019-11-29 | 2020-03-27 | 惠州市良化新材料有限公司 | Cold-resistant reinforced nylon 66 composition for baby carriage and preparation method thereof |
| CN111849154A (en) * | 2020-07-23 | 2020-10-30 | 江苏恒峰线缆有限公司 | Preparation method of novel nylon |
| CN112592584A (en) * | 2020-12-11 | 2021-04-02 | 山东非金属材料研究所 | Low-temperature-resistant low-water-absorption modified nylon material and preparation method thereof |
| CN112812551A (en) * | 2021-01-07 | 2021-05-18 | 江苏必得科技股份有限公司 | Preparation method of high-strength glass fiber composite material applied to rail transit |
| CN112831177A (en) * | 2021-01-11 | 2021-05-25 | 中国第一汽车股份有限公司 | Nylon for automobile water-assisted forming pipeline and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657952A (en) * | 1985-02-22 | 1987-04-14 | Ems Inventa Ag | Thermoplastic glass fiber-reinforced polyamide molding material |
| CN1696199A (en) * | 2005-06-06 | 2005-11-16 | 白山市喜丰塑料股份有限公司汽车工程塑料厂 | Technique for manufacturing secondary air inlet pipe in autombile engine and products |
| CN101121817A (en) * | 2006-08-09 | 2008-02-13 | 上海金发科技发展有限公司 | High cold resistance reinforced nylon 6 and preparation method thereof |
-
2012
- 2012-09-03 CN CN201210319969.6A patent/CN103421309B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657952A (en) * | 1985-02-22 | 1987-04-14 | Ems Inventa Ag | Thermoplastic glass fiber-reinforced polyamide molding material |
| CN1696199A (en) * | 2005-06-06 | 2005-11-16 | 白山市喜丰塑料股份有限公司汽车工程塑料厂 | Technique for manufacturing secondary air inlet pipe in autombile engine and products |
| CN101121817A (en) * | 2006-08-09 | 2008-02-13 | 上海金发科技发展有限公司 | High cold resistance reinforced nylon 6 and preparation method thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177825A (en) * | 2014-08-27 | 2014-12-03 | 东莞市卡尔文塑胶科技有限公司 | A kind of polyamide toughening agent, preparation method and use thereof |
| CN105001630A (en) * | 2015-06-10 | 2015-10-28 | 苏州宏恒化工有限公司 | Polyethylene/nylon composite material and preparing method thereof |
| CN106283310A (en) * | 2016-08-30 | 2017-01-04 | 安徽翰文运动用品股份有限公司 | It is exclusively used in the nylon wire of racket |
| CN107195285B (en) * | 2017-05-24 | 2020-08-11 | 连云港纶洋单丝科技有限公司 | Musical instrument string |
| CN107195285A (en) * | 2017-05-24 | 2017-09-22 | 连云港纶洋单丝科技有限公司 | A kind of musical instrument string |
| CN107254166A (en) * | 2017-07-28 | 2017-10-17 | 张乃斌 | A kind of maleic anhydride is grafted the POE high tenacity nylon material of high dispersive |
| CN107955370A (en) * | 2017-11-14 | 2018-04-24 | 东莞科姆新材料有限公司 | Vehicle fuel multilayer outer tube layer polymer composite and preparation method thereof |
| CN107955366A (en) * | 2017-11-14 | 2018-04-24 | 东莞科姆新材料有限公司 | Effective multilayer inner tube layer polymer composite of vehicle fuel and preparation method thereof |
| CN107964238A (en) * | 2017-11-14 | 2018-04-27 | 东莞科姆新材料有限公司 | Vehicle fuel multilayer outer tube layer polymer composite and preparation method thereof |
| CN107974081A (en) * | 2017-11-14 | 2018-05-01 | 东莞科姆新材料有限公司 | Vehicle fuel multilayer pipe adhesive linkage polymer composite and preparation method thereof |
| CN107936553A (en) * | 2017-11-14 | 2018-04-20 | 东莞科姆新材料有限公司 | Effective multilayer inner tube layer polymer composite of vehicle fuel and preparation method thereof |
| CN108739689A (en) * | 2018-05-07 | 2018-11-06 | 巢湖市俊业渔具有限公司 | A kind of wear-resisting fishing net of copolymer reinforced nylon |
| CN110922750A (en) * | 2019-11-29 | 2020-03-27 | 惠州市良化新材料有限公司 | Cold-resistant reinforced nylon 66 composition for baby carriage and preparation method thereof |
| CN111849154A (en) * | 2020-07-23 | 2020-10-30 | 江苏恒峰线缆有限公司 | Preparation method of novel nylon |
| CN112592584A (en) * | 2020-12-11 | 2021-04-02 | 山东非金属材料研究所 | Low-temperature-resistant low-water-absorption modified nylon material and preparation method thereof |
| CN112812551A (en) * | 2021-01-07 | 2021-05-18 | 江苏必得科技股份有限公司 | Preparation method of high-strength glass fiber composite material applied to rail transit |
| CN112812551B (en) * | 2021-01-07 | 2022-04-22 | 江苏必得科技股份有限公司 | Preparation method of high-strength glass fiber composite material applied to rail transit |
| CN112831177A (en) * | 2021-01-11 | 2021-05-25 | 中国第一汽车股份有限公司 | Nylon for automobile water-assisted forming pipeline and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103421309B (en) | 2015-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103421309B (en) | A kind of automobile cold-resistance super tough reinforced nylon 6 material and preparation method thereof | |
| CN102993556B (en) | Polypropylene composite, its preparation method and application thereof | |
| CN101311223B (en) | High impact resistance fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN101311222B (en) | High impact resistance fiberglass reinforced engineering plastics and preparation method | |
| CN102391432B (en) | High-fluidity ethylene-alpha-octene graft copolymer and preparation method thereof | |
| CN102417561B (en) | Ultrahigh-mobility propenyl elastomer grafting copolymer and preparation method thereof | |
| CN101311221A (en) | Fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN102532874B (en) | Thermo-oxidative ageing-resistant nylon/acrylonitrile-butadiene-styrene resin mixed material | |
| CN103073783A (en) | Polypropylene-high molecular weight high density polyethylene-filling material blend and preparation method thereof | |
| CN104403258A (en) | Antiflaming reinforcing ABS composite material and preparation method thereof | |
| CN103849044A (en) | Anti-aging masterbatch used for polyethylene and preparation method of anti-aging masterbatch | |
| CN103540013A (en) | Nylon 6/polypropylene plastic alloy and preparation method thereof | |
| CN106928544A (en) | A kind of cold-resistant high-impact long glass fiber-reinforced polypropylene proprietary material and preparation method thereof | |
| CN104629324A (en) | High-strength toughened functionalized PC/ABS alloy material | |
| CN106750347A (en) | A kind of nylon toughener and its preparation method and application | |
| CN103160052A (en) | High-gloss ABS/PMMA alloy material, and preparation method and application thereof | |
| CN109504081B (en) | Good-touch easy-encapsulation polyamide composite material and preparation method thereof | |
| CN110746700A (en) | Antibacterial reinforced color master batch for polypropylene and preparation method thereof | |
| CN108285629B (en) | PC/ABS/PA6 composition and preparation method thereof | |
| CN103665570B (en) | A kind of ultralow-temperature flexibility polypropene composition and preparation method thereof | |
| CN103571123A (en) | Antishock polypropylene composition used for automobile bumper and preparation method of the composition | |
| CN108948510A (en) | A kind of basic zirconium phosphate/PP composite material and preparation method thereof | |
| CN105802018B (en) | A kind of damage resistant fiber glass reinforced polypropylene composition and preparation method thereof | |
| CN110684348B (en) | Polyamide material with metal texture and preparation method thereof | |
| CN106928624A (en) | A kind of nucleocapsid nylon toughener and preparation method and application based on extruder technique |
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 | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160104 Address after: Beilun District of Zhejiang city in Ningbo Province, 315830 West Road No. 479 Patentee after: NINGBO NENGZHIGUANG NEW MATERIALS TECHNOLOGY CO., LTD. Address before: Seven road 315800 Zhejiang province Chunxiao town of Beilun District in Ningbo City No. 79 Patentee before: Ningbo Nengju Engineering Plastic Co., Ltd. |
|
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 315830 Zhejiang Province, Ningbo city Beilun District Chunxiao Road No. 669 to Patentee after: Ningbo nengzhiguang new materials Polytron Technologies Inc Address before: Beilun District of Zhejiang city in Ningbo Province, 315830 West Road No. 479 Patentee before: NINGBO NENGZHIGUANG NEW MATERIALS TECHNOLOGY CO., LTD. |