CN107227021A - Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material and preparation method thereof - Google Patents
Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material and preparation method thereof Download PDFInfo
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- CN107227021A CN107227021A CN201710281388.0A CN201710281388A CN107227021A CN 107227021 A CN107227021 A CN 107227021A CN 201710281388 A CN201710281388 A CN 201710281388A CN 107227021 A CN107227021 A CN 107227021A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The present invention relates to a kind of glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material and preparation method thereof, described alloy material is prepared from by the component including following parts by weight content：0~20 part of 40~80 parts of polyamide, 20~60 parts of polyphenylene sulfide, 40~80 parts of short glass fiber, 2~20 parts of fire retardant, 1~10 part of coupling agent and compatilizer；During preparation, first by coupling agent hydrolysis or alcoholysis, polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stir, pre-composition is made, then premixing is transferred in double screw extruder, side adds fire retardant, short glass fiber by weight, side carries out extruding pelletization, and obtained material grain is dried, you can.Compared with prior art, material granulation of the present invention is easily, Bond Strength is high, cost is low, shaping efficiency is high, the problem of efficiently solving PPS high cost and low shaping efficiency.
Description
Technical field
The invention belongs to technical field of composite materials, it is related to a kind of glass fiber reinforcement fatty polyamide/polyphenylene sulfide
Alloy material and preparation method thereof.
Background technology
Polyamide (being commonly called as nylon) is one of engineering plastics that yield is maximum, kind is most, most widely used.With automobile work
The development in the fields such as industry, electric, communications and transportation, machinery, Aero-Space and various dairy industries, this has also significantly promoted poly-
Development in terms of research, production and the application of acid amides, is greatly promoted the variation of polyamide kind and the improvement of performance
With raising.However, because the amide group in polyamide molecule has water imbibition, so the water suction of polyamide material is generally compared
Height, the polyamide after water suction has obvious reduction in terms of mechanical strength, metal adhesion, and this also greatly hinders poly-
The popularization and application of acid amides.
Polyphenylene sulfide English is abbreviated as PPS, is cost performance highest special engineering plastics so far, yield only comes poly-
After acid amides, makrolon, polyester, polyformaldehyde, polyphenylene oxide, auto industry, electric, mechanical, change have been widely used in it
The special industries such as work, pharmacy, military project, Aero-Space.Due in the molecular structure of polyphenylene sulfide, lone pair electrons are contained on sulphur atom
It is right so that it has remarkable adhesion strength with glass, metal etc..But during PPS shapings, mould temperature is very high, cooling effectiveness is low,
To prevent secondary crystallization, sometimes also need to make annealing treatment product, can just come into operation, production efficiency has much room for improvement.
The Chinese invention patent of Application No. 201210506600.6 disclose a kind of Polyphenylene Sulfide/Polyamide alloy material and
Its preparation method, described Polyphenylene Sulfide/Polyamide alloy material is made up of the component comprising following parts by weight：20-30 parts of polyphenyl
Thioether, 40-50 parts of glass fibres, 20-40 parts of nylon, 0.3-0.8 parts of lubricants, 0.2-0.4 parts of antioxidant.The skill of above-mentioned patent
Art scheme is continuous fiber due to the glass of addition, and the requirement to extrusion die is very high, and the quality of production is difficult to ensure that, and is needed
Lubricant is individually added, processing cost is higher.
The Chinese invention patent of Application No. 200710123781.3 discloses a kind of polyphenylene sulfide/polyamide compoiste material
And preparation method thereof, described polyphenylene sulfide/polyamide compoiste material prepared by the raw materials by weight of following proportioning and
Into：Polyphenylene sulfide (PPS) 23-69.3%, polyamide (PA) 10-30%, glass fibre (GF) 20-40%, heat stabilizer 0.2-
2%, silane coupler 0.1-2%, lubricant 0.2-2%, crystallization promoter 0.1-1%.Application No.
201210142806.5 Chinese invention patent disclose a kind of fire-retardant fiber glass reinforced polyamide/polyphenylene sulfide alloy material and
Preparation method, the alloy material is mainly made up of the component comprising following parts by weight：25~40 parts of polyamide, polyphenylene sulfide 9~
32 parts, 30~50 parts of glass fibre, 0.5~0.7 part of antioxidant, 0.7~1.2 part of lubricant, 1~1.5 part of other auxiliary agents；This
The outer halogen-free flame retardants that may further include not greater than 18 parts by weight.Individually addition is required in the recipe ingredient of above-mentioned two patented technology
Nylon nucleator, processing cost is higher, and when polyamide is improved, the fire resistance of material is difficult to ensure that.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind can be effectively improved Buddhist nun
Dragon after absorbing water with metal adhesion energy, preparation technology is simple, and financial cost is low, and shaping efficiency is high, it is easy to industrialized production
Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material.
Another object of the present invention is just to provide the system of above-mentioned glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material
Preparation Method.
The purpose of the present invention can be achieved through the following technical solutions：
Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material, the alloy material is by including following parts by weight content
Component is prepared from：40~80 parts of polyamide, 20~60 parts of polyphenylene sulfide, 40~80 parts of short glass fiber, fire retardant 2~20
0~20 part of part, 1~10 part of coupling agent and compatilizer.
Described polyamide includes one kind in PA6, PA9T, PA10T, PA66, PA510 or PA610.
Described polyphenylene sulfide is linear thermoplastic's polyphenylene sulfide that relative molecular weight is 30000-45000.
Described short glass fiber draw ratio is 50~200.
Described fire retardant includes aluminum diethylphosphinate, brominated Polystyrene, polydibromstyrol, brominated oxygen tree
One or more in fat, melamine cyanurate or antimony oxide.
Described coupling agent includes 3- glycidylpropyls trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl
Trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane, 3- glycidylpropyls triethoxysilane,
One or more in 3- glycidylpropyls methyldiethoxysilane or gamma-aminopropyl-triethoxy-silane.
Described compatilizer includes epoxy acrylate, ethylene-methyl acrylate-methylmethacrylate copolymer, bromine
Change the one or more in epoxy resin or epoxy resin.
The preparation method of glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material, this method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
40~80 parts of polyamide, 20~60 parts of polyphenylene sulfide, 40~80 parts of short glass fiber, 2~20 parts of fire retardant,
0~20 part of 1~10 part of coupling agent and compatilizer；
Step (2)：First by coupling agent hydrolysis or alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
In step (2), described coupling agent hydrolysis or alcoholysis are that coupling agent is made into concentration is the molten of 10~50% (wt)
Liquid, the water in hydrolysis can not contain fluorine ion.Alcoholysis or water, the alcohol of alcohol in the mixed solvent, preferably cheaply, be easy to get, nontoxic second
Alcohol or isopropanol.In actual mechanical process, in addition to gamma-aminopropyl-triethoxy-silane does not need acetic acid on the rocks, other epoxies
Class can add a little to promote hydrolysis or alcoholysis, and the pH value of final solution is controlled 4.0~5.5.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180~220 DEG C, 2nd area：220~260 DEG C, three
Area：260~280 DEG C, 4th area：280~300 DEG C, 5th area：280~320 DEG C, 6th area：280~320 DEG C, 7th area：280~300
DEG C, die head temperature：260~300 DEG C.
Judge the compatibility between two kinds of polymer, relatively common method is to use solubility parameters and Huggins-Flory
Interaction parameter.
Scott has derived critical Huggins-Flory interaction parameters when two kinds of polymer is separated：
M1、M2：The molecular weight of component 1,2.
The molecular weight of polymer is generally very big so that this critical value meeting very little, it is seen that really thermodynamically dissolve each other
Polymer is seldom, so judging that the compatibility between two kinds of polymer is more common with solubility parameters.
Hildebrand gives the expression formula of the enthalpy of mixing in two kinds of polymer mixed process：
N1、N2：The molal quantity of component 1,2；
V1、V2：The molal volume of component 1,2；
ΔE1、ΔE2：The cohesive energy of component 1,2；
ΔE1/V1、ΔE2/V2：The cohesion energy density of component 1,2.
Referred to as solubility parameters, is represented with symbol δ.
For the polymer that can be consulted without data, Lentinus Edodes, group molar attraction constant, group can be used
The methods such as contribution, computer simulation, dilute solution viscosity, reverse-phase chromatography are obtained.
For the ease of being compared to each other, it is unified using molecule inner injection energy density can additive property estimate the molten of unknown polymer
Spend parameter：
ρ：Density；
F：Group molar attraction constant；
M：Molecular weight
Table 1
Note：Data in table 1 are drawn according to estimation equation, from the numerical value drawn in different method of testings or having
Enter.
The free energy change of two kinds of polymer mixing is turned to：
ΔGM=Δ HM-TΔSM······················[4]
The Gibbs free of mixing is smaller to be more conducive to the mixing of two kinds of polymer.As Δ GMWhen ＜ 0, it is meant that two
It is a kind of spontaneous process that the segment of kind polymer, which dissolves each other,.From formula [2], Δ HM>=0, and it is desirable that Δ G in formula [4]M
Decline, it is evident that, it is necessary to | δ1-δ2| it is the smaller the better.Understand, be followed successively by with PPS compatibilities from good to difference sequence with reference to table 1：PA6、
PA9T、PA66、PA10T、PA510、PA610。
In PA6, PA9T, PA66, PA10T, PA510, PA610 this six kinds of Nylon-type polymers, price is big from high to low
Cause be：PA9T、PA10T、PA510、PA610、PA66、PA6.
Research shows that epoxide group can both react with-the SH in PPS, can be sent out again with the amido in polyamide
Raw reaction, generates PPS-g-PA grafts so that the interface of alloy is substantially improved.
The present invention using brominated epoxy resin when making fire retardant, and it can play a part of compatilizer simultaneously；Using
When melamine cyanurate makees fire retardant, it can play a part of lubricant simultaneously.
PPS crystallizes obvious quickening in the presence of nylon melt, this with PPS and the component of nylon two in melt interracial contact,
Surface mutual induction nucleation and crystallization is relevant.PPS and nylon all be polar polymer, and its solubility parameters it is extremely close (PA6,
PA9T, PA66, PA10T, PA510, PA610 etc.), PPS there may be preferable compatibility, PPS in melt state with nylon
Sulphur atom and nylon amide groups between there is certain polar interaction (repelling or sucking action), and the hydrogen bond of nylon is made
Tend to Regularization with the motion for being beneficial to PPS segments, so as to promote PPS nucleation and accelerate crystalline growth, improve PPS's
Shaping efficiency.
Compared with prior art, the present invention substantially improves nylon after absorbing water, the decline with metal adhesion strength, solves
The problem of PPS high cost and low shaping efficiency.Material prepared by present invention granulation easily, Bond Strength it is high,
Cost is low, shaping efficiency is high, combination property is balanced.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：60 parts of PPS, 40 parts of PA66,60 parts of glass fibre, 4 parts of epoxy resin, 6 parts of BPS, 3 parts of antimony oxide,
1 part of gamma-aminopropyl-triethoxy-silane, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,0.5 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
60 parts of PPS, 40 parts of PA66,60 parts of glass fibre, 4 parts of epoxy resin, 6 parts of BPS, 3 parts of antimony oxide, γ-
1 part of aminopropyl triethoxysilane, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,0.5 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：240 DEG C, 3rd area：260 DEG C,
4th area：280 DEG C, 5th area：300 DEG C, 6th area：310 DEG C, 7th area：300 DEG C, die head temperature：280℃.
Embodiment 2：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：60 parts of PPS, 40 parts of PA6,40 parts of glass fibre, 2 parts of epoxy resin, 8 parts of BPS, 4 parts of antimony oxide, γ-
1 part of aminopropyl triethoxysilane, 0.4 part of antioxidant 1010,0.2 part of irgasfos 168,0.8 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
60 parts of PPS, 40 parts of PA6,40 parts of glass fibre, 2 parts of epoxy resin, 8 parts of BPS, 4 parts of antimony oxide, γ-
1 part of aminopropyl triethoxysilane, 0.4 part of antioxidant 1010,0.2 part of irgasfos 168,0.8 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：220 DEG C, 3rd area：260 DEG C,
4th area：280 DEG C, 5th area：290 DEG C, 6th area：300 DEG C, 7th area：290 DEG C, die head temperature：280℃.
Embodiment 3：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：60 parts of PPS, 40 parts of PA9T, 60 parts of glass fibre, 2 parts of epoxy resin, 4 parts of BPS, 2 parts of antimony oxide,
1 part of gamma-aminopropyl-triethoxy-silane, 1 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
60 parts of PPS, 40 parts of PA9T, 60 parts of glass fibre, 2 parts of epoxy resin, 4 parts of BPS, 2 parts of antimony oxide, γ-
1 part of aminopropyl triethoxysilane, 1 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：260 DEG C, 3rd area：280 DEG C,
4th area：300 DEG C, 5th area：320 DEG C, 6th area：320 DEG C, 7th area：300 DEG C, die head temperature：300℃.
Embodiment 4：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：50 parts of PPS, 50 parts of PA9T, 50 parts of glass fibre, 2 parts of epoxy resin, 6 parts of BPS, 3 parts of antimony oxide,
1 part of gamma-aminopropyl-triethoxy-silane, 1 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
50 parts of PPS, 50 parts of PA9T, 50 parts of glass fibre, 2 parts of epoxy resin, 6 parts of BPS, 3 parts of antimony oxide, γ-
1 part of aminopropyl triethoxysilane, 1 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：260 DEG C, 3rd area：280 DEG C,
4th area：300 DEG C, 5th area：320 DEG C, 6th area：320 DEG C, 7th area：300 DEG C, die head temperature：300℃.
Embodiment 5：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：40 parts of PPS, 60 parts of PA6,60 parts of glass fibre, 10 parts of brominated epoxy resin, 5 parts of antimony oxide, γ-ammonia
1.5 parts of propyl-triethoxysilicane, 0.4 part of antioxidant 1076,0.2 part of irgasfos 168,1 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
40 parts of PPS, 60 parts of PA6,60 parts of glass fibre, 10 parts of brominated epoxy resin, 5 parts of antimony oxide, γ-ammonia
1.5 parts of propyl-triethoxysilicane, 0.4 part of antioxidant 1076,0.2 part of irgasfos 168,1 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：220 DEG C, 3rd area：260 DEG C,
4th area：280 DEG C, 5th area：290 DEG C, 6th area：300 DEG C, 7th area：290 DEG C, die head temperature：280℃.
Embodiment 6：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：30 parts of PPS, 70 parts of PA66,70 parts of glass fibre, 10 parts of brominated epoxy resin, 5 parts of antimony oxide, γ-ammonia
1.5 parts of propyl-triethoxysilicane, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,1 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
30 parts of PPS, 70 parts of PA66,70 parts of glass fibre, 10 parts of brominated epoxy resin, 5 parts of antimony oxide, γ-ammonia
1.5 parts of propyl-triethoxysilicane, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,1 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：220 DEG C, 3rd area：260 DEG C,
4th area：280 DEG C, 5th area：290 DEG C, 6th area：300 DEG C, 7th area：290 DEG C, die head temperature：280℃.
Embodiment 7：
The present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material is by including the component of following parts by weight content
It is prepared from：20 parts of PPS, 80 parts of PA66,80 parts of glass fibre, 2 parts of epoxy resin, 15 parts of BPS, 5 parts of antimony oxide,
2 parts of gamma-aminopropyl-triethoxy-silane, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,1 part of zinc stearate.
Preparation method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
20 parts of PPS, 80 parts of PA66,80 parts of glass fibre, 2 parts of epoxy resin, 15 parts of BPS, 5 parts of antimony oxide,
2 parts of gamma-aminopropyl-triethoxy-silane, 0.2 part of antioxidant 1010,0.1 part of irgasfos 168,1 part of zinc stearate；
Step (2)：First by coupling agent alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：220 DEG C, 3rd area：260 DEG C,
4th area：280 DEG C, 5th area：290 DEG C, 6th area：300 DEG C, 7th area：290 DEG C, die head temperature：280℃.
The quantitative measurement result of alloy material made from embodiment 1-7 is as shown in table 1.
Table 1
Note：Control group 1 is PA46 (GF40) FR17, DSM46HF5040；
Control group 2 is PA6T (GF45) FR17, golden hair Vicnyl R445.
Embodiment 8：
Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material, the alloy material is by including following parts by weight content
Component is prepared from：40 parts of polyamide, 20 parts of polyphenylene sulfide, 40 parts of short glass fiber, 20 parts of fire retardant, 1 part of coupling agent and
20 parts of compatilizer.
Wherein, polyamide is PA10T；Polyphenylene sulfide is linear thermoplastic's polyphenylene sulfide that relative molecular weight is 30000.It is short
It is 50 to cut glass fibre draw ratio.Fire retardant is in mass ratio by brominated Polystyrene, polydibromstyrol and antimony oxide
1:2:1 mixes.Coupling agent is by 3- glycidylpropyls trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl three
Methoxy silane is 1 in mass ratio with 3- glycidylpropyls triethoxysilane:1:2 mix.Compatilizer is brominated
Oxygen tree fat.
The preparation method of the present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material specifically includes following step
Suddenly：
Step (1)：Got the raw materials ready by the component of following parts by weight：
40 parts of polyamide, 20 parts of polyphenylene sulfide, 40 parts of short glass fiber, 20 parts of fire retardant, 1 part of coupling agent and compatible
20 parts of agent；
Step (2)：First by coupling agent hydrolysis or alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
In step (2), described coupling agent hydrolysis or alcoholysis are that coupling agent is made into the solution that concentration is 10% (wt), water
Water in solution can not contain fluorine ion.Alcoholysis or water, the alcohol of alcohol in the mixed solvent, preferably cheaply, be easy to get, nontoxic ethanol or different
Propyl alcohol.In actual mechanical process, in addition to gamma-aminopropyl-triethoxy-silane does not need acetic acid on the rocks, other epoxies can be with
Plus it is a little to promote hydrolysis or alcoholysis, the pH value of final solution is controlled 4.0.
The process conditions of extruding pelletization are in step (4)：One area's temperature：180 DEG C, 2nd area：220 DEG C, 3rd area：260 DEG C,
4th area：270 DEG C, 5th area：280 DEG C, 6th area：290 DEG C, 7th area：300 DEG C, die head temperature：260℃.
Embodiment 9：
Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material, the alloy material is by including following parts by weight content
Component is prepared from：80 parts of polyamide, 60 parts of polyphenylene sulfide, 80 parts of short glass fiber, 2 parts of fire retardant, 10 parts of coupling agent and
0.5 part of compatilizer.
Wherein, polyamide is PA610；Polyphenylene sulfide is linear thermoplastic's polyphenylene sulfide that relative molecular weight is 45000.It is short
It is 200 to cut glass fibre draw ratio.Fire retardant is 1 in mass ratio by aluminum diethylphosphinate and melamine cyanurate:1 mixes
Conjunction is formed.Coupling agent is gamma-aminopropyl-triethoxy-silane.Compatilizer is epoxy acrylate.
The preparation method of the present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material specifically includes following step
Suddenly：
Step (1)：Got the raw materials ready by the component of following parts by weight：
80 parts of polyamide, 60 parts of polyphenylene sulfide, 80 parts of short glass fiber, 2 parts of fire retardant, 10 parts of coupling agent and compatible
0.5 part of agent；
Step (2)：First by coupling agent hydrolysis or alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
In step (2), described coupling agent hydrolysis or alcoholysis are that coupling agent is made into the solution that concentration is 50% (wt), water
Water in solution can not contain fluorine ion.Alcoholysis or water, the alcohol of alcohol in the mixed solvent, preferably cheaply, be easy to get, nontoxic ethanol or different
Propyl alcohol.In actual mechanical process, in addition to gamma-aminopropyl-triethoxy-silane does not need acetic acid on the rocks, other epoxies can be with
Plus it is a little to promote hydrolysis or alcoholysis, the pH value of final solution is controlled 5.5.
The process conditions of extruding pelletization are in step (4)：One area's temperature：220 DEG C, 2nd area：260 DEG C, 3rd area：280 DEG C,
4th area：280 DEG C, 5th area：320 DEG C, 6th area：300 DEG C, 7th area：280 DEG C, die head temperature：300℃.
Embodiment 10：
Glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material, the alloy material is by including following parts by weight content
Component is prepared from：5 parts of polyamide 6,32 parts of polyphenylene sulfide, 54 parts of short glass fiber, 6 parts of fire retardant, 7 parts of coupling agent and
13 parts of compatilizer.
Wherein, polyamide is PA510；Polyphenylene sulfide is linear thermoplastic's polyphenylene sulfide that relative molecular weight is 40000.It is short
It is 100 to cut glass fibre draw ratio.Fire retardant is polydibromstyrol.Coupling agent is 3- glycidylpropyl triethoxysilicanes
Alkane.Compatilizer is ethylene-methyl acrylate-methylmethacrylate copolymer.
The preparation method of the present embodiment glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material specifically includes following step
Suddenly：
Step (1)：Got the raw materials ready by the component of following parts by weight：
5 parts of polyamide 6,32 parts of polyphenylene sulfide, 54 parts of short glass fiber, 6 parts of fire retardant, 7 parts of coupling agent and compatilizer
13 parts；
Step (2)：First by coupling agent hydrolysis or alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, is made pre-
Mixed thing；
Step (4)：Premixing is transferred in double screw extruder, it is fine that side adds fire retardant, staple glass by weight
Dimension, side carries out extruding pelletization, and then obtained material grain is dried, i.e., obtained described glass-fiber-reinforced polyamide/poly-
Diphenyl sulfide alloy material.
In step (2), described coupling agent hydrolysis or alcoholysis are that coupling agent is made into the solution that concentration is 35% (wt), water
Water in solution can not contain fluorine ion.Alcoholysis or water, the alcohol of alcohol in the mixed solvent, preferably cheaply, be easy to get, nontoxic ethanol or different
Propyl alcohol.In actual mechanical process, in addition to gamma-aminopropyl-triethoxy-silane does not need acetic acid on the rocks, other epoxies can be with
Plus it is a little to promote hydrolysis or alcoholysis, the pH value of final solution is controlled 5.0.
The process conditions of extruding pelletization are in step (4)：One area's temperature：200 DEG C, 2nd area：230 DEG C, 3rd area：265 DEG C,
4th area：300 DEG C, 5th area：300 DEG C, 6th area：285 DEG C, 7th area：280 DEG C, die head temperature：275℃.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (9)
1. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material, it is characterised in that the alloy material is by including following weight
The component of part content is prepared from：40~80 parts of polyamide, 20~60 parts of polyphenylene sulfide, 40~80 parts of short glass fiber, resistance
Fire 0~20 part of 2~20 parts of agent, 1~10 part of coupling agent and compatilizer.
2. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 1, it is characterised in that described
Polyamide include PA6, PA9T, PA10T, PA66, PA510 or PA610 in one kind.
3. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 1, it is characterised in that described
Polyphenylene sulfide be linear thermoplastic's polyphenylene sulfide that relative molecular weight is 30000-45000.
4. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 1, it is characterised in that described
Short glass fiber draw ratio be 50~200.
5. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 1, it is characterised in that described
Fire retardant include aluminum diethylphosphinate, brominated Polystyrene, polydibromstyrol, brominated epoxy resin, melamine cyanogen
One or more in lithate or antimony oxide.
6. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 1, it is characterised in that described
Coupling agent include 3- glycidylpropyls trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane,
2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane, 3- glycidylpropyls triethoxysilane, 3- glycidols third
One or more in ylmethyl diethoxy silane or gamma-aminopropyl-triethoxy-silane.
7. glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 1, it is characterised in that described
Compatilizer include epoxy acrylate, ethylene-methyl acrylate-methylmethacrylate copolymer, brominated epoxy resin or
One or more in epoxy resin.
8. the preparation side of glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material as described in any one of claim 1 to 7
Method, it is characterised in that this method specifically includes following steps：
Step (1)：Got the raw materials ready by the component of following parts by weight：
40~80 parts of polyamide, 20~60 parts of polyphenylene sulfide, 40~80 parts of short glass fiber, 2~20 parts of fire retardant, coupling agent
1~10 part and 0~20 part of compatilizer；
Step (2)：First by coupling agent hydrolysis or alcoholysis；
Step (3)：Polyamide, polyphenylene sulfide, coupling agent and compatilizer are mixed by weight, stirred, pre-composition is made；
Step (4)：Premixing is transferred in double screw extruder, side adds fire retardant, short glass fiber, side by weight
Extruding pelletization is carried out, then obtained material grain is dried, that is, described glass-fiber-reinforced polyamide/polyphenylene sulfide is made
Alloy material.
9. the preparation method of glass-fiber-reinforced polyamide/polyphenylene sulfide alloy material according to claim 8, its feature
It is, the process conditions of extruding pelletization are in step (4)：One area's temperature：180~220 DEG C, 2nd area：220~260 DEG C, 3rd area：
260~280 DEG C, 4th area：280~300 DEG C, 5th area：280~320 DEG C, 6th area：280~320 DEG C, 7th area：280~300 DEG C, mould
Head temperature：260~300 DEG C.
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