CN101817978A - High temperature nylon PPA reinforcing material and preparation method thereof - Google Patents
High temperature nylon PPA reinforcing material and preparation method thereof Download PDFInfo
- Publication number
- CN101817978A CN101817978A CN 201010158113 CN201010158113A CN101817978A CN 101817978 A CN101817978 A CN 101817978A CN 201010158113 CN201010158113 CN 201010158113 CN 201010158113 A CN201010158113 A CN 201010158113A CN 101817978 A CN101817978 A CN 101817978A
- Authority
- CN
- China
- Prior art keywords
- temperature
- district
- parts
- ppa
- fire retardant
- 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
- 239000004677 Nylon Substances 0.000 title claims abstract description 29
- 229920001778 nylon Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012779 reinforcing material Substances 0.000 title claims abstract description 16
- 229920006375 polyphtalamide Polymers 0.000 claims abstract description 86
- 239000004954 Polyphthalamide Substances 0.000 claims abstract description 75
- 239000003063 flame retardant Substances 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000003365 glass fiber Substances 0.000 claims abstract description 42
- 239000000314 lubricant Substances 0.000 claims abstract description 31
- 238000011049 filling Methods 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- -1 pentaerythritol ester Chemical class 0.000 claims description 36
- 150000001408 amides Chemical class 0.000 claims description 35
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000001993 wax Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000004952 Polyamide Substances 0.000 abstract description 5
- 229920002647 polyamide Polymers 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 13
- 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 description 13
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 10
- 230000002708 enhancing effect Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 239000004605 External Lubricant Substances 0.000 description 4
- 239000004610 Internal Lubricant Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high temperature nylon PPA reinforcing material and a preparation method thereof. The high temperature nylon PPA reinforcing material comprises the following components in part by weight: 30 to 50 parts of polyphthalamide, 8 to 20 parts of polyamide, 10 to 15 parts of main fire retardant, 3 to 5 parts of assistant fire retardant, 30 to 45 parts of filling reinforcing agent, 0.2 to 0.6 part of antioxidant, 0.2 to 0.8 part of lubricant, and 0.3 to 0.6 part of nucleating agent. The invention overcomes the defects of lower liquidity and difficult processing of the PPA because a polyamide material is introduced; the polyamide material has the characteristics of high liquidity and similar molecular structure, and can be well fused with the PPA material, so that the liquidity is improved, the processing temperature is greatly reduced, and the processing procedure is simplified; and a modified material with excellent performance after being reinforced by a glass fiber is equal to foreign brand materials, and plays a role in laying the foundation for domestic volume production and future quantity demand in the domestic market.
Description
[technical field]
The present invention relates to technical field of polymer materials, relate in particular to a kind of high temperature nylon PPA reinforcing material and preparation method thereof.
[background technology]
Polyphthalamide (being called for short PPA) is a novel fire resistant of being researched and developed and realized volume production by Su Wei company the earliest, the high-performance special engineering plastics.It has advantages such as rigidity is big, thermotolerance is high, the intensity high electrical performance is good.Polyphthalamide is a kind of hemicrystalline thermoplasticity aromatic polyamide, be commonly called as the aromatic series high-temperature nylon, it is a kind of resistant to elevated temperatures material, and fusing point is between 310-325 ℃, heat-drawn wire can be between 260-280 ℃, and its fusing point is higher than PA46 and PPS; Under humid tropical condition, the tensile strength of PPA is higher by 20% than nylon 6, and is higher than nylon 66; The modulus in flexure of PPA material is higher by 20% than nylon, and hardness is bigger, can resist long tensile creep; And the ability of anti-gasoline, grease resistance and the refrigerant of PPA is also strong than PA; A kind of high temperature resistant nylon, this material can anti-200 ℃ continuous high temperatures, and can also keep good dimensional stability .PPA to have superior environmental-protecting performance, can reach the U.S. FDA level.The water-intake rate of PPA is more much lower than general enhancing PA6 or PA66, even soak several years in cold water, its tensile strength also can keep more than 80%
At present domestic modification technology to polyphthalamide also relatively limits to, it is also later to start to walk, also there are a lot of incomplete places, PPA material itself is because its molecular structure, make it that different temperature resistant grades be arranged, for example the PPA material of Su Wei company just is divided into 1 and is, 2 is different grades, and different grades heatproof and flowability are all inequality.But because its high-temperature resistant, so mobile relatively poor, cause comparatively difficulty of processing, must use special processing parameter, machinery equipment can good production.
[summary of the invention]
It is better that the technical problem to be solved in the present invention provides a kind of flowability, is easy to high temperature nylon PPA reinforcing material of processing and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of high temperature nylon PPA reinforcing material is counted by weight, comprises following component:
Polyphthalamide 30～50,
Polymeric amide 8～20,
Main flame retardant 10～15,
Auxilliary fire retardant 3～5,
Fill toughener 30～45,
Oxidation inhibitor 0.2～0.6,
Lubricant 0.2～0.8,
Nucleator 0.3～0.6.
Described main flame retardant is a brominated polystyrene; Auxilliary fire retardant is an antimonous oxide, a kind of or two kinds composite in the sodium antimonate.Described polyphthalamide is the hemicrystalline polyphthalamide, and polymeric amide is PA66, and described filling toughener is a glass fibre.Described oxidation inhibitor is the mixture of hindered phenol type antioxidant four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.Described lubricant is N, one or more in N '-two ethylene hard fatty acids acid amides, stearic amide, paraffin, polyethylene wax or Poly Propylene Wax, the siloxanes.A kind of in the linear saturated carboxylic acid sodium salt of long carbochain, the linear saturated carboxylic acid calcium salt of long carbochain of described nucleator.
A kind of preparation method's of above-mentioned high temperature nylon PPA reinforcing material technical scheme is may further comprise the steps:
A, take by weighing raw material, and described raw material is carried out drying treatment respectively by the described proportioning of claim 1; Wherein, 110 ℃-130 ℃ of polyphthalamide drying treatment temperature, drying treatment time 3-4h, 90 ℃-100 ℃ of polymeric amide drying treatment temperature, drying treatment time 4-5h;
B, polyphthalamide and the polymeric amide that drying is good are added in the high-speed mixer, and add lubricant, nucleator and oxidation inhibitor, carry out the about 2-5min of high-speed mixing;
C, main flame retardant and auxilliary fire retardant put into mix 5-10min in the high-speed mixer, mixed fire retardant joined carry out the about 5-8min of thorough mixing in the material that mixes in the B step, the material that mixes is put into 90-100 ℃ of dry 2-3h in the loft drier;
D, thorough mixing and exsiccant raw material and auxiliary agent are put in the twin screw extruder, added glass fibre and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
Among the described step D, each of twin screw extruder section temperature is set at:
240～260 ℃ of one district's temperature, 290～310 ℃ of two district's temperature, 290～310 ℃ of three district's temperature, 280～310 ℃ of four district's temperature, 250～280 ℃ of five district's temperature, 250～280 ℃ of six district's temperature, 250～280 ℃ of seven district's temperature, 250～280 ℃ of eight district's temperature, head temperature is 280～300 ℃.
Well-mixed raw material residence time in described twin screw extruder is 1～2 minute, and the twin screw extruder internal pressure is 12～18 MPas.。
It is relatively poor to the present invention is directed to the PPA material flowability, processing is the shortcoming of difficulty comparatively, introduce polyamide material, because the good flowability characteristics similar of polymeric amide with molecular structure, can well merge with the PPA material, thereby increase its flowability, processing temperature is reduced greatly, the course of processing is oversimplified.Undertaken obtaining the material modified of excellent property after the enhancement process by the glass fibre of selecting the different trades mark for use, with reciprocity foreign brand name material, for domestic mass production lays the first stone, for domestic market demand from now on lays the first stone.Make this kind of material obtain wide application prospect at home.
[embodiment]
Below the preferred embodiments of the present invention are described in detail.
A kind of modification enhancing high-temperature nylon material that is used for of the embodiment of the invention is counted by weight, comprise following component: polyphthalamide (PPA) 30～45, polymeric amide (PA6, PA66) 8～20, main flame retardant 8～15, auxilliary fire retardant 3～5 is filled enhancing 35～45, oxidation inhibitor 0.4～0.8, lubricant 0.4～0.8, nucleator 0.2～0.4.
The present invention adopts polyphthalamide and polymeric amide, is aided with to fill enhancing, fire retardant, oxidation inhibitor, lubricant, nucleator, makes the modification under molten state of polyphthalamide and polymeric amide.Wherein, polyphthalamide is divided into hemicrystalline and amorphism, and the present invention considers its high-temperature resistant, selects the hemicrystalline material without exception for use, and what select for use is the starting material of Su Wei company.Polyamide material is divided into PA6 and PA66, considers mobile difference, and what the present invention adopted is the PA66 raw material, and what select for use is the PA66 starting material of Luo Diya.
The adding of fire retardant can make material reach the good flame effect, because the PPA material is because its excellent heat resistance and over-all properties, therefore can partly substitute the occupancy volume of LCP (polymeric liquid crystal copolymer Liquid Crystal Polyester) in connector industry, and because the oxygen index of PPA own is than higher, can add the flame retardant effect that less fire retardant just can reach VO, also greatly reduce simultaneously cost, and the adding of fire retardant also has an effect, increase the lubricant effect of PPA material, thereby promote its flowability, better reduced the complexity of processing.The brominated polystyrene (PBS-64HW) that fire retardant of the present invention is produced for big lake company, auxilliary fire retardant are then selected comparatively conventional antimonous oxide for use, and what the present invention selected for use is that domestic Chen Zhou produces antimonous oxide as auxilliary fire retardant.
What the filling enhancing was selected for use is glass fibre commonly used during modification is produced, and the adding of glass fibre can improve the over-all properties of material greatly, and this is a common practise.But the present invention then is at different types of glass fibre reinforced effects difference, select optimum glass fibre to carry out enhancing modified research, thereby the high-temperature nylon that obtains high performance is material modified.That the present invention selects for use is long glass fibres 988A, short glass fiber 534, short glass fiber 560, the long glass fibres T635B of Mount Taishan glass factory production and the section glass fibre 301HP that Chongqing matrix material glass factory produces that megalith glass factory produces.
The adding of oxidation inhibitor is to prevent that material is in the course of processing, because the processing temperature of material own is than higher, be exactly that material frictional heat in the machine screw rod causes machine temperature too high in addition, thereby cause that the decomposition of some auxiliary agents or raw-material hot oxygen decompose and the auxiliary agent of adding, can better urge into modification, make being more prone to of modification processing.Oxidation inhibitor of the present invention is divided into primary antioxidant and secondary oxidation inhibitor and is used by weight 1: 1 ratio, wherein primary antioxidant is hindered phenol type antioxidant four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (code name: 1010), secondary oxidation inhibitor is hindered phenol type antioxidant tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (code name: 168).
The effect of lubricant mainly is to join other auxiliary agents and starting material are better disperseed, and lubricant comprises internal lubricant and external lubricant, or the compounded lubricant of internal lubricant and external lubricant formation.Wherein internal lubricant can be fatty acid amide series lubricant agent or hydro carbons lubricant, and external lubricant can be non-polar lubricant.The fatty acid amide series lubricant agent comprises N, N '-two ethylene hard fatty acids acid amides (TAF), stearic amide; The hydro carbons lubricant comprises paraffin, polyethylene wax or Poly Propylene Wax; Nonpolar lubricant can be one or more in the siloxanes.
The adding of nucleator is in order to urge the into crystallization rate of material, because the PPA material itself is to belong to the hemicrystalline material, if therefore can be good at making material crystalline words in modifying process, both can significantly improve the mechanical property of material, also can improve simultaneously the heat resistance of material greatly, material can be applied in field widely.Nucleator of the present invention is mainly a kind of among long carbochain linear saturated carboxylic acid sodium salt NAV101 and the linear saturated carboxylic acid calcium salt of the long carbochain CAV102.
Illustrate that below by 12 groups of specific embodiments modification provided by the invention strengthens the concrete component of PPA material:
Embodiment 1
Take by weighing 40 parts of polyphthalamides (PPA) by weight, 20 parts of polymeric amide (PA66), 10 parts of main flame retardant PBS-64HW, 4 parts of auxilliary fire retardant Sb2O3,40 parts of long glass fibres 988A, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.3 part of nucleator CAV102.
Adopt following method to prepare matrix material:
A, take by weighing raw material, and described raw material is carried out drying treatment respectively, comprise polyphthalamide (110 ℃ of 3h), polymeric amide (90 ℃ of 4h) are carried out drying treatment respectively;
B, polyphthalamide and the polymeric amide that drying is good are added in the high-speed mixer, and add lubricant, nucleator and oxidation inhibitor, carry out the about 4min of high-speed mixing;
C, main flame retardant and auxilliary fire retardant put into mix about 8min in the high-speed mixer, mix back mixed fire retardant is joined in the material that mixes before and carry out the about 6min of thorough mixing, the material that mixes is put into 100 ℃ of dry 3h in the loft drier;
D, thorough mixing and exsiccant raw material and auxiliary agent are put in the twin screw extruder, added glass fibre and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
Each of twin screw extruder section temperature is set at: 260 ℃ of district's temperature, and 290 ℃ of two district's temperature, 300 ℃ of three district's temperature, 300 ℃ of four district's temperature, 260 ℃ of five district's temperature, 250 ℃ of six district's temperature, 250 ℃ of seven district's temperature, 250 ℃ of eight district's temperature, head temperature is 290 ℃.1 minute residence time in twin screw extruder, pressure is 15 MPas (MPa).
Embodiment 2
Take by weighing 35 parts of polyphthalamides (PPA) by weight, 10 parts of polymeric amide (PA66), 11.5 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,40 parts of long glass fibres 988A, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.3 part of nucleator CAV102.
Adopt following method to prepare matrix material:
A, take by weighing raw material, and described raw material is carried out drying treatment respectively, comprise that polyphthalamide (120 ℃ of 3h), polymeric amide (95 ℃ of 4h) carry out drying treatment respectively;
B, polyphthalamide and the polymeric amide that drying is good are added in the high-speed mixer, and add lubricant, nucleator and oxidation inhibitor, carry out the about 4min of high-speed mixing;
C, main flame retardant and auxilliary fire retardant put into mix about 7min in the high-speed mixer, mix back mixed fire retardant is joined in the material that mixes before and carry out the about 8min of thorough mixing, the material that mixes is put into 100 ℃ of dry 3h in the loft drier;
D, thorough mixing and exsiccant raw material and auxiliary agent are put in the twin screw extruder, added glass fibre and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
Each of twin screw extruder section temperature is set at:
260 ℃ of one district's temperature, 300 ℃ of two district's temperature, 290 ℃ of three district's temperature, 300 ℃ of four district's temperature, 270 ℃ of five district's temperature, 260 ℃ of six district's temperature, 250 ℃ of seven district's temperature, 250 ℃ of eight district's temperature, head temperature is 300 ℃.Preparation method of the present invention, the residence time is 2 minutes in the twin screw extruder, the twin screw extruder internal pressure is 16 MPas.
Embodiment 3
Take by weighing 34 parts of polyphthalamides (PPA) by weight, 9.5 parts of polymeric amide (PA66), 11.5 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,40 parts of long glass fibres T635B, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.3 part of nucleator CAV102.
Adopt following method to prepare matrix material:
A, take by weighing raw material, and described raw material is carried out drying treatment respectively, comprise that polyphthalamide (130 ℃ of 3h), polymeric amide (100 ℃ of 4h) carry out drying treatment respectively;
B, polyphthalamide and the polymeric amide that drying is good are added in the high-speed mixer, and add lubricant, nucleator and oxidation inhibitor, carry out the about 5min of high-speed mixing;
C, main flame retardant and auxilliary fire retardant put into mix about 9min in the high-speed mixer, mix back mixed fire retardant is joined in the material that mixes before and carry out the about 5min of thorough mixing, the material that mixes is put into 90 ℃ of dry 2.5h in the loft drier;
D, thorough mixing and exsiccant raw material and auxiliary agent are put in the twin screw extruder, added glass fibre and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
Each of twin screw extruder section temperature is set at:
240 ℃ of one district's temperature, 290 ℃ of two district's temperature, 290 ℃ of three district's temperature, 280 ℃ of four district's temperature, 260 ℃ of five district's temperature, 250 ℃ of six district's temperature, 260 ℃ of seven district's temperature, 250 ℃ of eight district's temperature, head temperature is 290 ℃.Preparation method of the present invention, the residence time is 2 minutes in the twin screw extruder, the twin screw extruder internal pressure is 15 MPas.
Embodiment 4
Take by weighing 35 parts of polyphthalamides (PPA) by weight, 9.5 parts of polymeric amide (PA66), 11.5 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,40 parts of short glass fiber 301HP, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.3 part of nucleator CAV102.
Adopt following method to prepare matrix material:
A, take by weighing raw material, and described raw material is carried out drying treatment respectively, comprise that polyphthalamide (110 ℃ of 3h), polymeric amide (90 ℃ of 4h) carry out drying treatment respectively;
B, polyphthalamide and the polymeric amide that drying is good are added in the high-speed mixer, and add lubricant, nucleator and oxidation inhibitor, carry out the about 2min of high-speed mixing;
C, main flame retardant and auxilliary fire retardant put into mix about 5min in the high-speed mixer, mix back mixed fire retardant is joined in the material that mixes before and carry out the about 6min of thorough mixing, the material that mixes is put into 100 ℃ of dry 3h in the loft drier;
D, thorough mixing and exsiccant raw material and auxiliary agent are put in the twin screw extruder, added glass fibre and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
Each of twin screw extruder section temperature is set at:
250 ℃ of one district's temperature, 290 ℃ of two district's temperature, 290 ℃ of three district's temperature, 280 ℃ of four district's temperature, 280 ℃ of five district's temperature, 260 ℃ of six district's temperature, 250 ℃ of seven district's temperature, 250 ℃ of eight district's temperature, head temperature is 290 ℃.Preparation method of the present invention, the residence time is 1 minute in the twin screw extruder, the twin screw extruder internal pressure is 14 MPas.
Embodiment 5
Take by weighing 35 parts of polyphthalamides (PPA) by weight, 9.5 parts of polymeric amide (PA66), 11.5 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,534 40 parts of short glass fibers, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.3 part of nucleator CAV102.
The preparation method is with embodiment 1.
Embodiment 6
Take by weighing 35 parts of polyphthalamides (PPA) by weight, 9.5 parts of polymeric amide (PA66), 11.5 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,560 40 parts of short glass fibers, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.2 part of nucleator CAV102.
The preparation method is with embodiment 1.
Embodiment 7
Take by weighing 45 parts of polyphthalamides (PPA) by weight, 8 parts of polymeric amide (PA66), 13 parts of main flame retardant PBS-64HW, 5 parts of auxilliary fire retardant Sb2O3,56030 parts of short glass fibers, antioxidant 1010 and 168 is 0.2 part, and lubricant TAF and siloxanes are 0.6 part, 0.3 part of nucleator CAV102.
The preparation method is with embodiment 1.
Embodiment 8
Take by weighing 50 parts of polyphthalamides (PPA) by weight, 10 parts of polymeric amide (PA66), 11 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,534 30 parts of short glass fibers, antioxidant 1010 and 168 is 0.5 part, and stearic amide and siloxanes are 0.3 part, 0.3 part of nucleator NAV101.
The preparation method is with embodiment 1.
Embodiment 9
Take by weighing 41 parts of polyphthalamides (PPA) by weight, 12 parts of polymeric amide (PA66), 15 parts of main flame retardant PBS-64HW, 3 parts of auxilliary fire retardant Sb2O3,35 parts of long glass fibres T635B, antioxidant 1010 and 168 is 0.6 part, and polyethylene wax and siloxanes are 0.8 part, 0.6 part of nucleator NAV101.
The preparation method is with embodiment 1.
Embodiment 10
Take by weighing 47 parts of polyphthalamides (PPA) by weight, 20 parts of polymeric amide (PA66), 14 parts of main flame retardant PBS-64HW, 4 parts of auxilliary fire retardant Sb2O3,30 parts of long glass fibres 988A, antioxidant 1010 and 168 is 0.4 part, and Poly Propylene Wax and siloxanes are 0.5 part, 0.4 part of nucleator CAV102.
The preparation method is with embodiment 1.
Embodiment 11
Take by weighing 32 parts of polyphthalamides (PPA) by weight, 15 parts of polymeric amide (PA66), 13 parts of main flame retardant PBS-64HW, 4 parts of auxilliary fire retardant Sb2O3,45 parts of short glass fiber 301HP, antioxidant 1010 and 168 is 0.4 part, and stearic amide and siloxanes are 0.7 part, 0.4 part of nucleator CAV102.
The preparation method is with embodiment 1.
Embodiment 12
Take by weighing 33 parts of polyphthalamides (PPA) by weight, 8 parts of polymeric amide (PA66), 14 parts of main flame retardant PBS-64HW, 5 parts of auxilliary fire retardant Sb2O3,53441 parts of short glass fibers, antioxidant 1010 and 168 is 0.3 part, and TAF and siloxanes are 0.3 part, 0.6 part of nucleator NAV101.
The preparation method is with embodiment 1.
Can adopt following detection method, step, condition and standard that the prepared matrix material of above-mentioned 12 groups of embodiment is carried out performance evaluation.
With the matrix material particle of finishing granulation in 100～120 ℃ convection oven dry 4～6 hours,, in the sample making course, keep the mould temperature between 90～120 ℃ again with the injection moulding sample preparation on the 80T injection moulding machine of exsiccant particle.
Tensile strength is tested by the ASTM-D638 standard: specimen types is the I type, batten size (mm): 180 (length) * (12.68 ± 0.2) (neck width) * (3.23 ± 0.2) (thickness), draw speed is 50mm/ minute.
Flexural strength and modulus in flexure are tested by the ASTM-D790 standard: specimen types is specimen size (mm): (128 ± 2) * (12.8 ± 0.2) * (3.21 ± 0.2), rate of bending are 20mm/ minute.
Notched Izod impact strength is tested by the ASTM-D256 standard: specimen types is a V mouth breach type, specimen size (mm): (63 ± 2) * (12.58 ± 0.2) * (4.21 ± 0.2); The breach type is a V mouth class, and the breach residual thickness is 2.44mm.
Heat-drawn wire is tested by the ASTM-D648 standard, and load is 1.82MPa, and span is 100mm, specimen size (mm): (128 ± 2) * (13 ± 0.2) * (6.4 ± 0.2), maximum deformation quantity are 0.25mm.
Flame retardant test is tested by international UL-94 standard, batten size (mm): 1/8 batten: (128 ± 2) * (12.8 ± 0.2) * (3.21 ± 0.2); 1/16 batten: (128 ± 2) * (12.66 ± 0.2) * (1.59 ± 0.2).
Choosing wherein below, composite property test and the result thereof of embodiment 1～6 analyze.For clearly comparing, the matrix material feed composition of enumerating embodiment 1～6 below is as shown in table 1 below.
The matrix material raw material weight umber of table 1 embodiment 1～6 (unit: part)
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment | Embodiment 6 |
| ??PPA | ??40 | ??35 | ??34 | ??35 | ??35 | ??35 |
| ??PA66 | ??20 | ??10 | ??9.5 | ??9.5 | ??9.5 | ??9.5 |
| ??PBS-64HW | ??10 | ??11.5 | ??11.5 | ??11.5 | ??11.5 | ??11.5 |
| ??Sb2O3 | ??4 | ??3.5 | ??3.5 | ??3.5 | ??3.5 | ??3.5 |
| Glass fibre | ??988A | ??988A | ??T635B | ??301HP | ??534 | ??560 |
| Loading level | ??40 | ??40 | ??40 | ??40 | ??40 | ??40 |
| ??1010 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| ??168 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| Internal lubricant | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| External lubricant | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| Nucleator | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
Adopt aforementioned detection method and step that the matrix material of embodiment 1～6 is carried out performance evaluation, and with the typical trade mark of Su Wei company: the AFA-6145 performance comparison, the result is as shown in table 2 below.
The composite property test result of table 2 embodiment 1～6 and comparative group
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | ??Solvay??AFA-614??5 |
| Proportion (g/cm3) | ??1.60 | ??1.64 | ??1.63 | ??1.67 | ??1.67 | ??1.67 | ??1.8 |
| Tensile strength (MPa) | ??140 | ??150 | ??145 | ??195 | ??134 | ??185 | ??193 |
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | ??Solvay??AFA-614??5 |
| Flexural strength (MPa) | ??230 | ??240 | ??233 | ??300 | ??220 | ??280 | ??276 |
| Modulus in flexure (MPa) | ??10000 | ??10500 | ??10600 | ??12500 | ??10000 | ??13000 | ??15500 |
| Socle girder V mouth impacts (J/M) | ??58 | ??63 | ??59 | ??98 | ??65 | ??90 | ??107 |
| UL94 flame retardant test 1/8 and 1/16 | ??HB | ??V1 | ??V1 | ??V0 | ??V0 | ??V0 | ??V0 |
| Thermal distortion HDT 1.82MPa (℃) | ??230 | ??240 | ??240 | ??275 | ??235 | ??270 | ??277 |
As can be seen from Table 2: constant in other conditions, perhaps just under the variation of minor swing, different glass fibre is filled and is strengthened, and the compatible influential effect degree of whole composite system is had nothing in common with each other, and influence is very big.Should, suitable glass fibre strengthens the over-all properties that can significantly improve material, and the consumption of fire retardant also directly has influence on flame retardant rating and over-all properties.Comprehensively comparatively speaking, in line with the similar principle that mixes, because the structure of high-temperature nylon is to belong to amide structure, so the glass fibre of different treatment effect affacts and just embodies different effects in the material, for example embodiment 6 and embodiment 5 are exactly comparison clearly, be both the short glass fiber that megalith glass factory produces, 534 and 560 because treatment effect is different, 534 are suitable for the enhancing of polyester type material, 560 then is the enhancing that is fit to the polymeric amide types of material, so under the constant situation of other conditions, change glass fibre, with regard to the very large over-all properties of difference that occurs, visible glass fibre effect therein.Through evidence, following set of dispense ratio should be best effect: count by weight, 35 parts of polyphthalamides (PPA), 9.5 parts of polymeric amide (PA66), 11.5 parts of main flame retardant PBS-64HW, 3.5 parts of auxilliary fire retardant Sb2O3,40 parts of short glass fiber 301HP, antioxidant 1010 and 168 is 0.3 part, and lubricant TAF and siloxanes are 0.3 part, 0.3 part of nucleator CAV102.Such proportioning, the firstth, selected for use the most suitable glass fibre to carry out enhancing modified, next has selected the fire retardant deal of low ratio for use, can reduce the cost problem in the material modification process so greatly, once more, also obtain about PA66 increase flowability therein embodying, too much adding, both influenced the over-all properties of material, especially thermal characteristics, and material cost is also high, very few adding can not improve overall flow again, therefore such ratio combination should be the optimum combination of selecting for use, has also embodied the subject matter that the present invention will discuss simultaneously, has embodied superiority of the present invention and novelty.
The present invention strengthens by selecting different glass fibre for use, the over-all properties and the thermal characteristics of material have been improved greatly, solve the defective that the high temperature of material in extrusion should not be controlled, preparation technology is simple, cost is low, prepared high-performance, the glass fibre reinforced modified high-temperature nylon of cost degradation also can extensively apply to every field, has more wide prospect, can obtain good economic benefit.For from now on domestic at this material the modification research and development and mass production aspect made basic contribution.Make this material can obtain the approval in market faster, thereby break the situation that offshore company corners the market.
High temperature nylon PPA reinforcing material of the present invention can be widely used in automotive field, field of electronics, as is used to make hood, isolating switch, switch, junctor, plastic conduit, the valve of automobile, impeller etc.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (9)
1. a high temperature nylon PPA reinforcing material is characterized in that, counts by weight, comprises following component:
Polyphthalamide 30～50,
Polymeric amide 8～20,
Main flame retardant 10～15,
Auxilliary fire retardant 3～5,
Fill toughener 30～45,
Oxidation inhibitor 0.2～0.6,
Lubricant 0.2～0.8,
Nucleator 0.3～0.6.
2. high temperature nylon PPA reinforcing material according to claim 1 is characterized in that, described main flame retardant is a brominated polystyrene; Auxilliary fire retardant is an antimonous oxide, a kind of or two kinds composite in the sodium antimonate.
3. high temperature nylon PPA reinforcing material according to claim 1 is characterized in that, described polyphthalamide is the hemicrystalline polyphthalamide, and polymeric amide is PA66, and described filling toughener is a glass fibre.
4. high temperature nylon PPA reinforcing material according to claim 1, it is characterized in that, described oxidation inhibitor is hindered phenol type antioxidant four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] mixture of pentaerythritol ester and hindered phenol type antioxidant tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
5. high temperature nylon PPA reinforcing material according to claim 1 is characterized in that, described lubricant is N, one or more in N '-two ethylene hard fatty acids acid amides, stearic amide, paraffin, polyethylene wax or Poly Propylene Wax, the siloxanes.
6. high temperature nylon PPA reinforcing material according to claim 1 is characterized in that, a kind of in the linear saturated carboxylic acid sodium salt of long carbochain, the linear saturated carboxylic acid calcium salt of long carbochain of described nucleator.
7. the preparation method of the described high temperature nylon PPA reinforcing material of claim 1 is characterized in that, may further comprise the steps:
A, take by weighing raw material, and described raw material is carried out drying treatment respectively by the described proportioning of claim 1; Wherein, 110 ℃-130 ℃ of polyphthalamide drying treatment temperature, drying treatment time 3-4h, 90 ℃-100 ℃ of polymeric amide drying treatment temperature, drying treatment time 4-5h;
B, polyphthalamide and the polymeric amide that drying is good are added in the high-speed mixer, and add lubricant, nucleator and oxidation inhibitor, carry out the about 2-5min of high-speed mixing;
C, main flame retardant and auxilliary fire retardant put into mix 5-10min in the high-speed mixer, mixed fire retardant joined carry out the about 5-8min of thorough mixing in the material that mixes in the B step, the material that mixes is put into 90-100 ℃ of dry 2-3h in the loft drier;
D, thorough mixing and exsiccant raw material and auxiliary agent are put in the twin screw extruder, added glass fibre and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
8. preparation method as claimed in claim 7 is characterized in that, among the described step D, each of twin screw extruder section temperature is set at:
240～260 ℃ of one district's temperature, 290～310 ℃ of two district's temperature, 290～310 ℃ of three district's temperature, 280～310 ℃ of four district's temperature, 250～280 ℃ of five district's temperature, 250～280 ℃ of six district's temperature, 250～280 ℃ of seven district's temperature, 250～280 ℃ of eight district's temperature, head temperature is 280～300 ℃.
9. preparation method as claimed in claim 7 is characterized in that, among the described step D, described well-mixed raw material residence time in described twin screw extruder is 1～2 minute, and the twin screw extruder internal pressure is 12～18 MPas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101581136A CN101817978B (en) | 2010-04-21 | 2010-04-21 | High temperature nylon PPA reinforcing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101581136A CN101817978B (en) | 2010-04-21 | 2010-04-21 | High temperature nylon PPA reinforcing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101817978A true CN101817978A (en) | 2010-09-01 |
| CN101817978B CN101817978B (en) | 2012-08-08 |
Family
ID=42653261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101581136A Active CN101817978B (en) | 2010-04-21 | 2010-04-21 | High temperature nylon PPA reinforcing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101817978B (en) |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948619A (en) * | 2010-09-29 | 2011-01-19 | 深圳市科聚新材料有限公司 | poly(nonamethyleneterephthalamide) material and preparation method thereof |
| CN102311641A (en) * | 2010-10-15 | 2012-01-11 | 深圳市科聚新材料有限公司 | High glowing filament flame-retardant PA (polyamide)/PPO (polyphenyleneoxide) alloy and preparation method thereof |
| CN102321366A (en) * | 2010-12-02 | 2012-01-18 | 北京首塑新材料科技有限公司 | Preparation and application of high-wear-resistance modified nylon composition |
| CN102337022A (en) * | 2011-05-31 | 2012-02-01 | 深圳市科聚新材料有限公司 | Nylon material special for breakers and preparation method thereof |
| CN102382454A (en) * | 2011-10-19 | 2012-03-21 | 深圳市科聚新材料有限公司 | High-strength antistatic heat-conductive PPA (Polyphthalamide) material and preparation method of same |
| CN102408707A (en) * | 2011-06-24 | 2012-04-11 | 深圳市科聚新材料有限公司 | Glass fiber reinforced poly (hexamethylene terephthalamide) material and preparation method thereof |
| CN102408709A (en) * | 2011-09-30 | 2012-04-11 | 中山市纳普工程塑料有限公司 | Polyphthalamide long fiber coated reinforcing material |
| CN102534832A (en) * | 2011-09-26 | 2012-07-04 | 上海贵达科技有限公司 | Preparation method for high-temperature-resistant and corrosion-resistant sheath-core type composite fiber |
| WO2012103747A1 (en) * | 2011-01-31 | 2012-08-09 | 上海金发科技发展有限公司 | Highly fatigue-resistant glass fiber reinforced nylon material and preparation method therefor |
| CN102634189A (en) * | 2011-02-15 | 2012-08-15 | 汉达精密电子(昆山)有限公司 | PPA (polyphthalamide) reinforced material and preparation method thereof |
| CN103087517A (en) * | 2013-02-20 | 2013-05-08 | 上海俊尔新材料有限公司 | Glass-reinforced nylon 6 material and preparation method thereof |
| CN103351635A (en) * | 2013-06-21 | 2013-10-16 | 苏州新区特氟龙塑料制品厂 | High-temperature resistant plastic |
| CN103834167A (en) * | 2014-03-25 | 2014-06-04 | 东莞市德颖光电有限公司 | PPA (Polyphthal-Amide) modified material with high heat resistance and high dimensional stability and preparation method thereof |
| CN103834166A (en) * | 2014-03-25 | 2014-06-04 | 东莞市德颖光电有限公司 | Mineral reinforced high-performance PPA (Polyphthal Amide) material and preparation method thereof |
| CN104262954A (en) * | 2014-09-03 | 2015-01-07 | 东莞市川旭塑料科技有限公司 | High-performance polyamide plastic PA8T and preparation method thereof |
| CN104292825A (en) * | 2014-07-08 | 2015-01-21 | 东莞市众一新材料科技有限有限公司 | Flame-retardant reinforced high temperature nylon composite material and its preparation method |
| CN104479352A (en) * | 2014-12-18 | 2015-04-01 | 安徽科聚新材料有限公司 | Polyphthalamide (PPA) composite material with high temperature resistance and abrasion resistance and preparation method of PPA composite material |
| CN104629355A (en) * | 2013-11-08 | 2015-05-20 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic nylon/liquid crystal polymer composite material with enhanced flame retardant property and preparation method thereof |
| CN105038219A (en) * | 2015-09-01 | 2015-11-11 | 东莞市华盈新材料有限公司 | Heat-conducting high-temperature nylon composite material and preparation method thereof |
| CN107139379A (en) * | 2017-06-05 | 2017-09-08 | 岳西县同兴尼龙橡胶制品有限公司 | A kind of air-conditioning mask injection moulding process |
| CN107645999A (en) * | 2015-05-26 | 2018-01-30 | 克诺尔商用车制动系统有限公司 | The housing member of the housing of the pressure medium guide device of vehicle |
| CN108779306A (en) * | 2017-07-10 | 2018-11-09 | 东莞市森特塑胶制品有限公司 | A kind of plastic film layer and the plastic foil using the plastic film layer |
| CN109320956A (en) * | 2018-10-22 | 2019-02-12 | 滁州吉胜新材料科技有限公司 | A kind of tension temperature-resistant nylon and preparation method thereof |
| CN109401296A (en) * | 2018-09-13 | 2019-03-01 | 丹阳市三能电器配件有限公司 | Air-conditioning supplementary heating element bracket PPA composite material and preparation method |
| CN109504074A (en) * | 2018-10-22 | 2019-03-22 | 滁州吉胜新材料科技有限公司 | Fire-retardant enhancing high-temperature nylon of one kind and preparation method thereof |
| CN109880350A (en) * | 2019-02-01 | 2019-06-14 | 宁波峻源复合材料科技有限公司 | Based on charging pile production good flame retardation effect plastic grain and preparation method thereof |
| CN110204893A (en) * | 2019-06-11 | 2019-09-06 | 宁德市华昊新材料有限公司 | A kind of enhancing nylon composite materials and preparation method thereof |
| EP3690978A1 (en) * | 2019-02-01 | 2020-08-05 | SABIC Global Technologies B.V. | Injection moldable, flame retardant long glass fiber based materials for electric vehicle battery casing |
| CN113652084A (en) * | 2021-08-16 | 2021-11-16 | 创合新材料科技江苏有限公司 | Corrosion-resistant plastic PA and preparation method thereof |
| CN114262513A (en) * | 2021-08-27 | 2022-04-01 | 广东博事达新材料有限公司 | Glass fiber reinforced nylon 6 composite material |
| CN115746543A (en) * | 2022-11-18 | 2023-03-07 | 广东道生科技股份有限公司 | Nylon material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773500A (en) * | 1996-05-14 | 1998-06-30 | Amoco Corporation | Flame retardant high temperature polyphthalamides having improved thermal stability |
| CN1255933A (en) * | 1998-02-04 | 2000-06-07 | Bp阿莫科公司 | Fire resistant anti-drip polyamide compsns. |
| CN101302337A (en) * | 2008-07-03 | 2008-11-12 | 杭州临安宏凯工程塑料有限公司 | High temperature resistant low water absorption polyamide 66 composite material and preparation thereof |
-
2010
- 2010-04-21 CN CN2010101581136A patent/CN101817978B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773500A (en) * | 1996-05-14 | 1998-06-30 | Amoco Corporation | Flame retardant high temperature polyphthalamides having improved thermal stability |
| CN1255933A (en) * | 1998-02-04 | 2000-06-07 | Bp阿莫科公司 | Fire resistant anti-drip polyamide compsns. |
| CN101302337A (en) * | 2008-07-03 | 2008-11-12 | 杭州临安宏凯工程塑料有限公司 | High temperature resistant low water absorption polyamide 66 composite material and preparation thereof |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948619A (en) * | 2010-09-29 | 2011-01-19 | 深圳市科聚新材料有限公司 | poly(nonamethyleneterephthalamide) material and preparation method thereof |
| CN102311641A (en) * | 2010-10-15 | 2012-01-11 | 深圳市科聚新材料有限公司 | High glowing filament flame-retardant PA (polyamide)/PPO (polyphenyleneoxide) alloy and preparation method thereof |
| CN102321366A (en) * | 2010-12-02 | 2012-01-18 | 北京首塑新材料科技有限公司 | Preparation and application of high-wear-resistance modified nylon composition |
| WO2012103747A1 (en) * | 2011-01-31 | 2012-08-09 | 上海金发科技发展有限公司 | Highly fatigue-resistant glass fiber reinforced nylon material and preparation method therefor |
| CN102634189A (en) * | 2011-02-15 | 2012-08-15 | 汉达精密电子(昆山)有限公司 | PPA (polyphthalamide) reinforced material and preparation method thereof |
| CN102337022A (en) * | 2011-05-31 | 2012-02-01 | 深圳市科聚新材料有限公司 | Nylon material special for breakers and preparation method thereof |
| CN102408707A (en) * | 2011-06-24 | 2012-04-11 | 深圳市科聚新材料有限公司 | Glass fiber reinforced poly (hexamethylene terephthalamide) material and preparation method thereof |
| CN102534832A (en) * | 2011-09-26 | 2012-07-04 | 上海贵达科技有限公司 | Preparation method for high-temperature-resistant and corrosion-resistant sheath-core type composite fiber |
| CN102408709A (en) * | 2011-09-30 | 2012-04-11 | 中山市纳普工程塑料有限公司 | Polyphthalamide long fiber coated reinforcing material |
| CN102382454A (en) * | 2011-10-19 | 2012-03-21 | 深圳市科聚新材料有限公司 | High-strength antistatic heat-conductive PPA (Polyphthalamide) material and preparation method of same |
| CN102382454B (en) * | 2011-10-19 | 2013-10-16 | 深圳市科聚新材料有限公司 | High-strength antistatic heat-conductive PPA (Polyphthalamide) material and preparation method of same |
| CN103087517A (en) * | 2013-02-20 | 2013-05-08 | 上海俊尔新材料有限公司 | Glass-reinforced nylon 6 material and preparation method thereof |
| CN103351635A (en) * | 2013-06-21 | 2013-10-16 | 苏州新区特氟龙塑料制品厂 | High-temperature resistant plastic |
| CN104629355A (en) * | 2013-11-08 | 2015-05-20 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic nylon/liquid crystal polymer composite material with enhanced flame retardant property and preparation method thereof |
| CN103834167A (en) * | 2014-03-25 | 2014-06-04 | 东莞市德颖光电有限公司 | PPA (Polyphthal-Amide) modified material with high heat resistance and high dimensional stability and preparation method thereof |
| CN103834166A (en) * | 2014-03-25 | 2014-06-04 | 东莞市德颖光电有限公司 | Mineral reinforced high-performance PPA (Polyphthal Amide) material and preparation method thereof |
| CN103834166B (en) * | 2014-03-25 | 2016-03-02 | 东莞市德颖光电有限公司 | A kind of mineral strengthen high-performance PPA material and preparation method thereof |
| CN104292825A (en) * | 2014-07-08 | 2015-01-21 | 东莞市众一新材料科技有限有限公司 | Flame-retardant reinforced high temperature nylon composite material and its preparation method |
| CN104262954A (en) * | 2014-09-03 | 2015-01-07 | 东莞市川旭塑料科技有限公司 | High-performance polyamide plastic PA8T and preparation method thereof |
| CN104479352A (en) * | 2014-12-18 | 2015-04-01 | 安徽科聚新材料有限公司 | Polyphthalamide (PPA) composite material with high temperature resistance and abrasion resistance and preparation method of PPA composite material |
| US10730494B2 (en) | 2015-05-26 | 2020-08-04 | Knorr-Bremse Systeme Fuer Nutzfahrzeuge Gmbh | Housing component of a housing of a vehicle device conducting pressure medium |
| CN107645999A (en) * | 2015-05-26 | 2018-01-30 | 克诺尔商用车制动系统有限公司 | The housing member of the housing of the pressure medium guide device of vehicle |
| CN107645999B (en) * | 2015-05-26 | 2021-02-19 | 克诺尔商用车制动系统有限公司 | Housing component of a housing of a pressure medium guiding device of a vehicle |
| CN105038219A (en) * | 2015-09-01 | 2015-11-11 | 东莞市华盈新材料有限公司 | Heat-conducting high-temperature nylon composite material and preparation method thereof |
| CN107139379A (en) * | 2017-06-05 | 2017-09-08 | 岳西县同兴尼龙橡胶制品有限公司 | A kind of air-conditioning mask injection moulding process |
| CN108779306A (en) * | 2017-07-10 | 2018-11-09 | 东莞市森特塑胶制品有限公司 | A kind of plastic film layer and the plastic foil using the plastic film layer |
| CN109401296A (en) * | 2018-09-13 | 2019-03-01 | 丹阳市三能电器配件有限公司 | Air-conditioning supplementary heating element bracket PPA composite material and preparation method |
| CN109504074A (en) * | 2018-10-22 | 2019-03-22 | 滁州吉胜新材料科技有限公司 | Fire-retardant enhancing high-temperature nylon of one kind and preparation method thereof |
| CN109320956A (en) * | 2018-10-22 | 2019-02-12 | 滁州吉胜新材料科技有限公司 | A kind of tension temperature-resistant nylon and preparation method thereof |
| CN109880350A (en) * | 2019-02-01 | 2019-06-14 | 宁波峻源复合材料科技有限公司 | Based on charging pile production good flame retardation effect plastic grain and preparation method thereof |
| EP3690978A1 (en) * | 2019-02-01 | 2020-08-05 | SABIC Global Technologies B.V. | Injection moldable, flame retardant long glass fiber based materials for electric vehicle battery casing |
| CN110204893A (en) * | 2019-06-11 | 2019-09-06 | 宁德市华昊新材料有限公司 | A kind of enhancing nylon composite materials and preparation method thereof |
| CN113652084A (en) * | 2021-08-16 | 2021-11-16 | 创合新材料科技江苏有限公司 | Corrosion-resistant plastic PA and preparation method thereof |
| CN114262513A (en) * | 2021-08-27 | 2022-04-01 | 广东博事达新材料有限公司 | Glass fiber reinforced nylon 6 composite material |
| CN115746543A (en) * | 2022-11-18 | 2023-03-07 | 广东道生科技股份有限公司 | Nylon material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101817978B (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817978B (en) | High temperature nylon PPA reinforcing material and preparation method thereof | |
| CN101875783B (en) | Reinforced polytetramethyleneadiamide material and preparation method thereof | |
| CN102015889B (en) | Manufacturing method for polylactic acid resin compositions | |
| CN104583329B (en) | Thermoplastic resin composition and synthetic resin | |
| CN102504529B (en) | Halogen-free flame-retardant long glass fiber reinforced nylon 6 material and preparation method thereof | |
| CN101759953B (en) | Polyacrylonitrile-butadiene-styrene/polyvinyl chloride (ABS/PVC) polymeric material and preparation method thereof | |
| JP5376656B2 (en) | Method for producing polyamide resin | |
| CN102329477A (en) | Modification-enhanced polyether ether ketone material and preparation method thereof | |
| CN101508840A (en) | Green environment friendly flame-proof PA6/PP alloy and method for producing the same | |
| CN101717568A (en) | Polycarbonate/nylon 6 alloy material and preparation method thereof | |
| CN102585478A (en) | Toughened polyphenyl ether and nylon alloy and preparation method for toughened polyphenyl ether and nylon alloy | |
| CN101280105A (en) | Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material | |
| CN102093705A (en) | High fatigue resistance glass fiber reinforced nylon material and preparation method thereof | |
| CN102408707A (en) | Glass fiber reinforced poly (hexamethylene terephthalamide) material and preparation method thereof | |
| CN102241860A (en) | Reinforced polypropylene material and preparation method thereof | |
| CN101134847A (en) | Polyphenylene sulfide/polyamide composite material and method for making same | |
| CN101948619A (en) | poly(nonamethyleneterephthalamide) material and preparation method thereof | |
| CN101787199B (en) | PPO/PBT composite material used for industrial large-sized workpiece and preparation method thereof | |
| CN102241857A (en) | Polypropylene flame-retardant masterbatch material and preparation method thereof | |
| CN102382432A (en) | High-impact polyethylene terephthalate (PET) composite material and preparation method thereof | |
| CN104861595A (en) | Halogen-free flame-retardant PBT (polybutylene terephthalate) material and preparation method thereof | |
| CN105419253A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN108530887B (en) | High-heat-resistance and high-strength semi-aromatic polyamide/polyester alloy material and preparation method and application thereof | |
| CN101787182A (en) | Method for preparing polybutylene terephthalate composite and mineral filler thereof | |
| CN104479352A (en) | Polyphthalamide (PPA) composite material with high temperature resistance and abrasion resistance and preparation method of PPA composite material |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: XU DONG Free format text: FORMER OWNER: SHENZHEN KEJU NEW MATERIAL CO., LTD. Effective date: 20141016 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 518000 SHENZHEN, GUANGDONG PROVINCE TO: 518101 SHENZHEN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20141016 Address after: 518101, Guangdong, Shenzhen province Baoan District Xin'an street, No. 74, No. 13, Plaza building, Plaza Patentee after: Xu Dong Address before: 518000 Guangdong, Baoan District, Fuyong Town, Fu Qiao Industrial Zone, the three phase of the two phase A19 building Patentee before: Shenzhen Keju New Material Co., Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: High temperature nylon PPA reinforcing material and preparation method thereof Effective date of registration: 20150817 Granted publication date: 20120808 Pledgee: China Everbright Bank Shenzhen branch Pledgor: Xu Dong Registration number: 2015990000680 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20161202 Granted publication date: 20120808 Pledgee: China Everbright Bank Shenzhen branch Pledgor: Xu Dong Registration number: 2015990000680 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: High temperature nylon PPA reinforcing material and preparation method thereof Effective date of registration: 20170106 Granted publication date: 20120808 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Anhui science and Technology Co., Ltd.|Shenzhen branch poly new materials Co., Ltd.|Xu Dong Registration number: 2016990001133 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180904 Granted publication date: 20120808 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Polymer Science (Anhui) New Material Co., Ltd.|Shenzhen Keju New Material Co., Ltd.|Xu Dong Registration number: 2016990001133 |