CN101817978B - 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
- CN101817978B CN101817978B CN2010101581136A CN201010158113A CN101817978B CN 101817978 B CN101817978 B CN 101817978B CN 2010101581136 A CN2010101581136 A CN 2010101581136A CN 201010158113 A CN201010158113 A CN 201010158113A CN 101817978 B CN101817978 B CN 101817978B
- 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.)
- Active
Links
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 in cold water, soak several years, 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, and also has a lot of incomplete places, and PPA material itself is because its molecular structure; Make it that different temperature resistant grades 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 and equipment can good production.
[summary of the invention]
It is better that the technical problem that the present invention will solve 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 scheme that the present invention adopts 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.
Said main flame retardant is a brominated polystyrene; Auxilliary fire retardant is an Antimony Trioxide: 99.5Min, 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 spun glass.Said 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.Said 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 said nucleator.
A kind of preparing 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 said 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 mixed at high speed;
C, main flame retardant and auxilliary fire retardant put into mix 5-10min in the high-speed mixer; Join mixed fire retardant and 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 spun glass and strengthen the filling extruding pelletization, make high-performance high-temperature nylon strongthener.
Among the said 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 said 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, introduces polyamide material, because the good flowability of polymeric amide and the characteristics of similar molecular; Can well merge with the PPA material; Thereby increase its flowability, processing temperature is reduced greatly, the course of processing is oversimplified.Carry out obtaining the material modified of excellent property after the enhancement process through the spun glass of selecting the different trades mark for use, with reciprocity foreign brand name material, for domestic mass production lays the first stone, for home market demand from now on lays the first stone.Make this kind of material obtain wide application prospect at home.
[embodiment]
Describe in detail in the face of the preferred embodiments of the present invention down.
A kind of modification enhancing high temperature nylon material that is used for of the embodiment of the invention is counted by weight, comprises 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 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 owing to the oxygen index of PPA own than higher; Can add the flame retardant effect that less fire retardant just can reach VO; Simultaneously also greatly reduce cost, and the adding of fire retardant also has an effect, the lubricant effect of increase PPA material; Thereby promote its flowability, better reduced the complexity of processing.The brominated polystyrene (PBS-64HW) that the fire retardant that the present invention adopted is produced for big lake company, auxilliary fire retardant are then selected comparatively conventional Antimony Trioxide: 99.5Min for use, and what the present invention selected for use is that domestic Chen Zhou produces Antimony Trioxide: 99.5Min as auxilliary fire retardant.
What the filling enhancing was selected for use is spun glass commonly used during modification is produced, and the adding of spun glass can improve the over-all properties of material greatly, and this is a common practise.But the present invention then is different to different types of spun glass reinforced effects, select optimum spun glass 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 spun glass 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.The oxidation inhibitor that the present invention adopted 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.The nucleator that the present invention adopted is mainly a kind of among the linear saturated carboxylic acid sodium salt of long carbochain NAV101 and the linear saturated carboxylic acid calcium salt of the long carbochain CAV102.
Explain that through 12 groups of specific embodiments modification provided by the invention strengthens the concrete component of PPA material below:
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 said 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 mixed at high speed;
C, main flame retardant and auxilliary fire retardant put into mix about 8min in the high-speed mixer; Mix back joining mixed fire retardant 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 spun glass 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 said 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 mixed at high speed;
C, main flame retardant and auxilliary fire retardant put into mix about 7min in the high-speed mixer; Mix back joining mixed fire retardant 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 spun glass 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 ℃.Preparing 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 said 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 mixed at high speed;
C, main flame retardant and auxilliary fire retardant put into mix about 9min in the high-speed mixer; Mix back joining mixed fire retardant 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 spun glass 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 ℃.Preparing 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 said 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 mixed at high speed;
C, main flame retardant and auxilliary fire retardant put into mix about 5min in the high-speed mixer; Mix back joining mixed fire retardant 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 spun glass 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 ℃.Preparing 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 are 0.3 part; 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 above-mentioned 12 groups of embodiment prepared composite materials are carried out performance evaluation.
With the matrix material particle of accomplishing 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 |
| Spun glass | 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 |
| 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 |
From table 2, can find out: constant in other conditions, perhaps just under the variation of minor swing, different spun glass 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 spun glass 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 spun glass of different treatment effect affacts and just embodies different effects in the material, for example embodiment 6 is exactly comparison clearly with embodiment 5, is both the short glass fiber that megalith glass factory produces; 534 and 560 because treatment effect is different, and 534 are suitable for the enhancing of polyester type material, and 560 then is enhancing suitable and polyamide-based type material; So under the constant situation of other conditions; Change spun glass, the very large over-all properties of difference that just occurs, visible spun glass effect therein.Through evidence, following set of dispense ratio should be best effect: count 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.Such proportioning, the firstth, selected for use the most suitable spun glass 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 embodying about PA66 increase flowability therein; Too much adding had both influenced the over-all properties of material, especially thermal property; And material cost is also high, and very few adding can not improve overall flow property again, and therefore such ratio combination should be the optimum combination of selecting for use; Simultaneously also embodied the present invention the subject matter that will discuss, embodied meliority of the present invention and novelty.
The present invention strengthens through selecting different spun glass for use; Improved the over-all properties and the thermal property of material greatly, solved 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.Aspect domestic modification research and development and mass production at this material from now on, 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, concerning those of ordinary skills, can improve or conversion, and all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
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 8～10,
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, said main flame retardant is a brominated polystyrene; Auxilliary fire retardant is an Antimony Trioxide: 99.5Min, 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 spun glass.
4. high temperature nylon PPA reinforcing material according to claim 1; It is characterized in that; Said oxidation inhibitor is the mixture of hindered phenol type antioxidant four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 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, said 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 said 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 said 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 mixed at high speed 2-5min;
C, main flame retardant and auxilliary fire retardant put into mix 5-10min in the high-speed mixer; Join mixed fire retardant and carry out thorough mixing 5-8min 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 spun glass 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 said 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 said step D, said well-mixed raw material residence time in said 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 CN101817978A (en) | 2010-09-01 |
| CN101817978B true 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) |
Families Citing this family (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 |
| CN102093705A (en) * | 2011-01-31 | 2011-06-15 | 上海金发科技发展有限公司 | High fatigue resistance glass fiber reinforced nylon material and preparation method thereof |
| 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 strengthened 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 |
| CN102408709B (en) * | 2011-09-30 | 2014-08-20 | 中山市纳普工程塑料有限公司 | Polyphthalamide (PPA) long-fiber-coated reinforced material |
| 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 |
| 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 |
| CN103834167B (en) * | 2014-03-25 | 2016-02-24 | 东莞市德颖光电有限公司 | The PPA of high heat resistance, high-dimensional stability is material modified 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 |
| DE102015108210A1 (en) * | 2015-05-26 | 2016-12-01 | Knorr-Bremse Systeme für Nutzfahrzeuge GmbH | Housing component of a housing of a pressure medium leading 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 |
| WO2019010609A1 (en) * | 2017-07-10 | 2019-01-17 | 东莞市森特塑胶制品有限公司 | Plastic film layer and plastic film having same |
| 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 |
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101817978A (en) | 2010-09-01 |
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 | |
| CN101311223B (en) | High impact resistance fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN100590146C (en) | Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material | |
| CN102015889B (en) | Manufacturing method for polylactic acid resin compositions | |
| CN102504529B (en) | Halogen-free flame-retardant long glass fiber reinforced nylon 6 material and preparation method thereof | |
| JP5376656B2 (en) | Method for producing polyamide resin | |
| CN102329477A (en) | Modification-enhanced polyether ether ketone material and preparation method thereof | |
| CN102093705A (en) | High fatigue resistance glass fiber reinforced nylon material and preparation method thereof | |
| CN102408707A (en) | Glass fiber strengthened poly-hexamethylene terephthalamide material and preparation method thereof | |
| CN101948619A (en) | poly(nonamethyleneterephthalamide) material and preparation method thereof | |
| CN101918482A (en) | Polyamide resin compositions | |
| CN102241860A (en) | Reinforced polypropylene material and preparation method thereof | |
| CN102241857A (en) | Polypropylene flame-retardant masterbatch material and preparation method thereof | |
| CN101787199B (en) | PPO/PBT composite material used for industrial large-sized workpiece and preparation method thereof | |
| CN102382432A (en) | High-impact polyethylene terephthalate (PET) composite material and preparation method thereof | |
| CN105419253A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN103102660A (en) | Fibrilia/polylactic acid biodegradable composite material and preparation method thereof | |
| CN103740025A (en) | Glass fiber reinforced inflaming retarding AES (Acrylonitrile-Ethylene propylene diene monomer-Styrene) composite material 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 | |
| CN102241885B (en) | Composite material of polyphthalamide (PPA) and polyphenylene sulfide (PPS) and preparation method thereof | |
| CN103627164A (en) | Aramid fiber-reinforced high-temperature-resistant nylon composite material and preparation method thereof | |
| CN110669332B (en) | Flame-retardant polyamide 6/polyphenyl ether composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| 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 |