CN108727810A - Long glass fiber reinforced daiamid composition and preparation method thereof - Google Patents
Long glass fiber reinforced daiamid composition and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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Abstract
The invention discloses a kind of long glass fiber reinforced daiamid compositions, it adds metal salt compound and roving glass fiber size in traditional roving glass fiber modified polyamide, anion is hydroxide ion in metal salt compound, carbanion, hydrogen sulfate ion, at least one of saturated fat acid ion and unsaturated fat acid ion, and roving glass fiber size is the modified ultra-branching polyester containing special construction, metal salt compound can solve to use halide ion in common metal salt compound, the metal salt compound fusing point that nitrate anion and sulfate radical are brought is high, to make it unsuitable for that the problems in matrix is added or can not be dispersed in melt process；And special roving glass fiber size can effectively improve product surface glossiness and reduce floating fibre, simultaneously and metal salt compound collective effect, composition mechanics and processing performance are can obviously improve, makes it that can obtain the obtainable appearance of ability and mechanical property under the conditions of high temperature process under relatively low processing temperature.
Description
Technical field
The present invention relates to a kind of daiamid composition and preparation method thereof more particularly to a kind of long glass fiber reinforced polyamide groups
Object and preparation method thereof is closed, polymer modification and preparation method thereof technical field is belonged to.
Background technology
Polyamide is because with excellent mechanical performance, heat resistance, resistance to chemical corrosion, self-lubricating property, well adding
Many advantages, such as work performance and the row such as be widely used in automobile, household electrical appliances, electronic apparatus, electric tool, Medical Devices, building
In industry, while in order to obtain the characteristics such as mechanical performance more outstanding, heat resistance, antifatigue, creep resistant, it will usually which selection will
It carries out enhancing filling with other reinforcing fillers such as glass fibre, while can also reduce material cost.Due to processing method and
The difference of products characteristics, which is distinguished roving glass fiber and short glass fiber enhancing nylon material, wherein long
Fiber glass reinforced polyamide material has the outstanding features such as higher intensity, modulus, impact strength, endurance, creep resistance.But by
Belong to semi-crystalline material in traditional polyamide material such as nylon 6, nylon66 fiber, have higher crystallization onset temperature and compared with
Fast crystalline rate, for fiberglass reinforced product, resin is with crystallinity and it is with higher crystallinity, knot
Brilliant temperature and faster crystalline rate can influence the movement of molecular resin segment, be unfavorable for leaching of the resin to fiberglass surfacing
Profit, the problem is particularly severe for long glass fiber reinforced polyamide product, and glass non-wetting can lead to floating fine such appearance
The negative effects such as defect and mechanical performance decaying.
In order to solve the above technical problems, have in the prior art propose long glass fiber reinforced nylon composite materials using metal salt or
With amide group ligand complex effect occurs for metal complex, to improve the tensile property of glass fiber enhanced nylon composite material,
The disadvantage that integral material elongation at break is relatively low caused by enhancing nylon using roving glass fiber can be solved, but this is existing
The shortcomings that technology, is：The coordination high degree formed with polyamide using metal salt or metal complex limits polyamide
The mode of action of the movement of segment, this similar crosslinked action has obvious effect to improving tensile strength, bending strength and modulus,
But it will necessarily bring the insufficient defect of toughness while improving material stiffness and intensity, therefore can cause to be broken extension rate
Decline with sag, can't occur the case where effectively promoting elongation at break in practical operation.Additionally due to such existing
There is the metal salt used in technology that there is higher fusing point, as lithium chloride fusing point is higher than 600 DEG C, it is meant that it can not be in long glass
It is melted in the process of fine reinforced polyamide composite material, causes metal salt that can not be evenly dispersed into tiny particle,
These can not scattered larger particles metal salt be present in resin and form stress concentration point, the performance of material can be made to occur
Greatly decaying, especially above-described elongation at break, amount of deflection etc. represent the performance and shock resistance of toughness of material.
Invention content
In order to solve the above technical problems, the present invention provides a kind of long glass fiber reinforced daiamid composition and its preparation sides
Method, the long glass fiber reinforced daiamid composition for preparing gained by the preparation method have good physical property and excellent product
Appearance.
The technical scheme is that：
The present invention provides a kind of long glass fiber reinforced daiamid composition, the composition include kymene 0-70 parts by weight,
Metal salt compound 0.05-5.0 parts by weight, roving glass fiber 10-60 parts by weight and dosage are roving glass fiber dosage 0.08-5.0wt.%'s
Roving glass fiber size.
The wherein described polyamide is formed by diamine and binary acid Step Condensation, or is formed by lactams ring-opening polymerisation, or
It is formed by amino acid Step Condensation, or is copolymerized by the component in diamine, binary acid, lactams, amino acid, can be
PA46、PA66、PA6、PA11、PA12、PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、
At least one of PA10T, PA6I, PAMXD6, PA6I, PA66/6, PA6/66, PA6T/6I and PA6T/66, can be according to final
The purposes of product selected；Preferably in PA66, PA6, PA610, PA612, PA1010, PA11, PA12 and PA66/6
It is at least one；More preferably at least one of PA6, PA66, PA6/66, PA66/6 and PA610.Above-mentioned polyamide is ability
The type of domain conventional polyamide is selected in practical operation according to the performance requirement of specific product, but is worked as and the application institute
State the other components in technical solution, especially metal salt compound and roving glass fiber size carry out with the use of when, it is preferably molten
The polyamide that polyamide of the point less than 270 DEG C or glass transition temperature are 60-140 DEG C is less than 270 DEG C with fusing point
Polyamide mixture.Definition of the above-mentioned fusing point less than " fusing point " in 270 DEG C of polyamide be：According to
ISO11357-3 is cooled to room temperature after carrying out heating elimination thermal history using differential scanning calorimetry (DSC) with 10 DEG C/min
It is heated up again with 10 DEG C/min afterwards, the temperature obtained at the maximum endothermic peak in second of temperature-rise period is fusing point.Above-mentioned glass
It is poly- for other of the polyamide different from aforementioned fusing point less than 270 DEG C to change the polyamide that transition temperature is 60-140 DEG C
Amide can be the crystalline polyamide resin or microcrystalline polyamide resin or amorphous polyamides resin with fusing point；Above-mentioned " glass
The definition of glass transition temperature " is：Use differential scanning calorimeter DSC with the heating rate of 10 DEG C/min according to ISO11357-2
Test the transition temperature of gained.It selects glass transition temperature to be less than 60 DEG C of polyamide, the resistance to of final material will be influenced
Hot property；And the polyamide for selecting glass transition temperature to be higher than 140 DEG C, it will be unfavorable for obtaining the length with excellent appearance
Fiber glass reinforced polyamide material.
Metal cation in the wherein described metal salt compound is the first major element, the second major element, the first pair
At least one of the cation of metallic element in race's element and the second subgroup element, preferably lithium ion, sodium ion, potassium from
At least one of son, calcium ion, zinc ion and copper ion, more preferably at least one of lithium ion and zinc ion；And it should
Anion in metal salt compound be hydroxide ion, carbanion, hydrogen sulfate ion, saturated fat acid ion and
At least one of unsaturated fat acid ion, preferably in saturated fat acid ion and unsaturated fat acid ion
At least one, more preferably at least one of acetate ion and stearate radical ion.With the length provided in the prior art
Glass fiber enhanced nylon composite material is compared, and metal salt compound used in this application can mitigate or even avoid metal salinization
Close influence of the object because of type and its bad mechanical performance brought to long glass fiber reinforced polyamide material of dispersion.Metal in the application
The selection of anion in compound, can solve the used anion of common metal salt compound (such as halogen, nitrate anion from
Son, sulfate ion) the metal salt compound fusing point that is formed is high, and it is unsuitable for metal salt compound and is added in melt process
Or it cannot achieve evenly dispersed problem.Fully effect can occur with polyamide using herein described metal salt compound,
To reduce its additive amount, the promotion to long glass fiber reinforced daiamid composition mechanical performance is obtained with less additive amount, is changed
Material cost is reduced while kind product appearance, this can find out from the specific embodiment of the application.
The wherein described roving glass fiber is the long glass fibres of 5-50 μm of diameter, the preferred long glass fibres of 7-20 μm of diameter, directly
Diameter is smaller to mean that the draw ratio of final fiber in the composite is bigger, has compared with the composite material of same fiber content
More resins and fiber contacts area and stronger active force, it may have higher mechanical performance, it is also possible to causing more
Add difficult production and subsequent processing.The preferred glass fiber bundle of existence form of roving glass fiber described herein, the glass fiber bundle
Also referred to as rove, it is preferred to include 500-8000 root glass monofilaments per beam glass fiber bundle, more preferably per beam glass fiber bundle packet
The glass monofilament of root containing 1000-4000, and the linear density of foregoing glass fibers beam is 1000-3000tex, i.e., every 1000 meters of glass
Glass fibre bundle has the weight of 1000-3000g.
The wherein described roving glass fiber size is in high-branched polyethylene wax, modified low molecular weight polypropylene, mineral oil
At least one and modified ultra-branching polyester mixture or only modified ultra-branching polyester, wherein being used in conjunction with traditional glass infiltration
The technical solution of agent and modified ultra-branching polyester is to be able to play while the purpose of regulation composition mobility.It is wherein described
High-branched polyethylene wax, modified low molecular weight polypropylene and mineral oil be more conventional in this field to be used for resin base
The size of roving glass fiber in body, the technical solution being well known to those skilled in the art, therefore repeated no more in the application.Wherein
The modified ultra-branching polyester carries out obtained by terminal groups modification superbrnaching end-hydroxy polyester by the organic matter containing acidic functionality, and
The ratio between the amount of substance of organic matter and superbrnaching end-hydroxy polyester containing acidic functionality is that n is (containing the organic of acidic functionality
Object):N (superbrnaching end-hydroxy polyester)=n (acidic functionality):N (the hydroxyl values of single superbrnaching end-hydroxy polyester × (30-
40) %).The wherein described organic matter containing acidic functionality is at least one in saturated fat acid anhydrides and unsaturated fat acid anhydrides
Kind, it can also be the copolymer of above-mentioned saturated fat acid anhydrides and unsaturated fat acid anhydrides, can also be above-mentioned saturated fat acid anhydrides
The constant various derivatives with the anhydride group of unsaturated fat acid anhydrides, which is preferably maleic acid
At least one of acid anhydride, lauric anhydride and succinic anhydride.The wherein described superbrnaching end-hydroxy polyester is by ABx(x >=2) type monomer
It self condenses and is polymerized or by Ax+By(x > 1 and y > 1) type polyfunctional monomer is copolymerized, and the superbrnaching end-hydroxy polyester
Weight average molecular weight be 2000-5500, preferable weight-average molecular weight 3500-5000；The hydroxyl value of the superbrnaching end-hydroxy polyester
For 40-50/mol, preferably hydroxyl value is 40-45/mol；And the degree of branching of the superbrnaching end-hydroxy polyester is 0.4-0.5,
The branched degrees of data is measured by capillary chromatography assessor.Above-mentioned ABxType monomer can be aliphatic monomer 2,2- dihydroxy first
Base propionic acid, aromatic monomer 3,5- dihydroxy-benzoic acids or mixed type monomer 5- (2- hydroxyl-oxethyls) M-phthalic acid, also may be used
To be to meet ABxSelf condense the other monomers of polymerization；The Ax+ByType polyfunctional monomer is preferably A2+B3Type monomer, wherein A2
Monomer is aliphatic dicarboxylic acid or aliphatic diol, works as A2B when monomer is aliphatic diacid3Monomer is aliphatic triol accordingly,
Work as A2B when monomer is aliphatic diol3Monomer is aliphatic tricarboxylic acids accordingly；Above-mentioned aliphatic dicarboxylic acid is hexanedioic acid, third
At least one of diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid, can also be on
State the various derivatives that two carboxyl-reactives are constant in aliphatic dicarboxylic acid；The aliphatic diol be as ethylene glycol, propylene glycol,
At least one of butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol and decanediol can also be above-mentioned fat
The constant various derivatives of two hydroxyl activities in fat race glycol；The aliphatic tricarboxylic acids can be tricarballylic acid and tricarboxylic
At least one of base benzene can also be the various derivatives that three carboxyl-reactives are constant in above-mentioned aliphatic tricarboxylic acids；It is described
Aliphatic triol can be glycerine, butantriol, penta triol, hexanetriol, tri hydroxy methyl butane, trimethylolpropane and three hydroxyl first
At least one of base ethane can also be the various derivatives that three hydroxyl activities are constant in above-mentioned aliphatic triol, may be used also
To be with penta tetrol and bis- (trihydroxy methyl) propane that cannot participate in reaction hydroxyl.In addition, above-mentioned using containing acidic functionality
Organic matter to superbrnaching end-hydroxy polyester carry out terminal groups modification method be hydroxy functional group conventional in the art and acidity
Reaction between functional group, common method are to be added to superbrnaching end-hydroxy polyester by certain molar ratio with above-mentioned acid anhydrides
Equipped with condenser pipe, mechanical agitator four-hole bottle in, protected using nitrogen, and a small amount of polymerization inhibitor is added, certain anti-
Heat while stirring reaction at a temperature of answering, during the reaction by acid number titration method come following response degree, when acid value drops to
The half of initial acid value and when no longer changing, stops reaction, going out product washing with solvent deposition dries；In above-mentioned reaction
The routine operation means and reagent that involved operational means and used reagent are well known to the skilled person, such as
Precipitation, washing, drying of product etc., such as polymerization inhibitor type and dosage selection, no longer repeat in the application, and involved
And acid value measuring method be measured according to national standard GB/T12008.5-1989.
The use of above-mentioned roving glass fiber size is to improve the binding force between roving glass fiber and polyamide, dosage
Depending on additive amount of the roving glass fiber in daiamid composition, as component shared by glass is higher, roving glass fiber size adds
Dosage is higher, and dosage usually accounts for the 0.8wt.%-5.0wt.% of roving glass fiber gross weight.The addition of glass fiber treating compound can very big journey
Degree improve roving glass fiber and polyamide binding force, so that roving glass fiber is preferably disperseed in process of production, and reduce the later stage at
Defect caused by long glass disperses bad in resin occurs for type process, as loss of mechanical properties, appearance occur obviously
The floating fine or distinguishable undispersed glass beam of naked eyes.It is disclosed in resin system using conventional glass although having in the prior art
Fiber treating compound (such as high-branched polyethylene wax, modified low molecular weight polypropylene, mineral oil) improves roving glass fiber in resin
The effect of dispersion, infiltration, but when its use is in system described herein do not have obvious effects on.And use the application institute
State the mixture of modified ultra-branching polyester or itself and conventional glass fiber treating compound, it can be clearly seen that it is not only to improving glass dispersion
It is obviously helped with being impregnated with, resulting composition has excellent appearance, such as improves surface gloss and the reduction of product
Floating fine degree, while being obviously improved tensile strength and elongation at break；But also make composition that there is excellent processing performance,
Compared with the composition for being not added with herein described roving glass fiber size, the application can relatively low processing temperature similarly hereinafter
Sample can get improved appearance and physical property, conversely, because the reduction of processing temperature, tradition is not added with the roving glass fiber size
Composition occur the serious floating fine and a degree of reduction of tensile strength, elongation at break in terms of appearance, it is above-mentioned
It can find out from the application specific embodiment.
Long glass fiber reinforced daiamid composition described herein further includes various auxiliary agents, usually polyamide compoiste material
In common various auxiliary agents, such as lubricant, compatilizer, nucleating agent, crystallization promoter, crystallization inhibitor, fire retardant, flow modifier
Agent, chain extender, releasing agent, colorant, pigment, dyestuff, antistatic agent, conductive filler, light stabilizer, stabilizer, antioxidant,
Filler, Nano filling etc..Preferred emollient and compatilizer in the application, the wherein dosage of lubricant are 0.05-5.0 weight
Part, the dosage of compatilizer is 5-10 parts by weight.Above-mentioned lubricant is preferably glycerin monostearate, glyceryl tristearate, second
Support the double oleamides of the double lauramide of bis-stearamides, ethylene, ethylene, low molecular weight ionomer, ethylene-acrylic acid copolymer,
At least one of ethylene-vinyl acetate copolymer.Above-mentioned compatilizer is polar monomer graft polymer, the polar monomer graft
The polymer of polymer is polyethylene, polypropylene, ethylene-octene copolymer, styrene-butadiene copolymer, polyethylene-polyphenyl
Ethylene-polypropylene copolymer, ethylene-propylene-diene copolymer, vinyl-acrylate copolymer and ethylene-acrylate-
At least one of glycidyl methacrylate copolymer；The polar monomer of the polar monomer graft polymer is unsaturation
At least one of fatty acid anhydride, acrylic acid and acrylate.
Disclosed herein as well is a kind of preparation method of above-mentioned long glass fiber reinforced daiamid composition, which includes
Following step：
(1) each component in long glass fiber reinforced daiamid composition accurately is weighed, then will removes other groups outside roving glass fiber
Lease making processing temperature is after 280-330 DEG C of melt compounding equipment is mixed and is plasticized, and it is 280-330 DEG C to be transported to temperature
High-temperature fusant rolls in impregnation mold, and wherein melt compounding equipment is screw extruder, preferably double screw extruder；
(2) roving glass fiber is entered into length in the mold of 2-4m, fully calendering is soaked with the speed drawing of 100-150m/min
After stain, cooling, pelletizing is carried out, the long glass fiber reinforced daiamid composition is obtained.
The method have the benefit that：The long glass fiber reinforced daiamid composition is modified polyamides in traditional roving glass fiber
Metal salt compound and roving glass fiber size are added in amine composition simultaneously, the wherein anion in metal salt compound is hydrogen
In oxygen radical ion, carbanion, hydrogen sulfate ion, saturated fat acid ion and unsaturated fat acid ion at least
One kind, and roving glass fiber size is the size containing special construction modified ultra-branching polyester, which can solve
It is certainly molten using metal salt compound caused by halide ion, nitrate ion and sulfate ion in common metal salt compound
Point is high, to make it unsuitable for that the problems in matrix is added or can not be dispersed in melt process；And this is special
Roving glass fiber size be capable of the binding force improved between roving glass fiber and polyamide of high degree, keep it better in the process
Dispersion can effectively improve the surface gloss of product and reduce floating fine phenomenon, at the same with metal salt compound collective effect,
It can be obviously improved the mechanical property of daiamid composition, while the use of the modified ultra-branching polyester can also improve the polyamide
The processing performance of composition, making it that can obtain under relatively low processing temperature can obtain under the conditions of high temperature process
Appearance and mechanical property.
Specific implementation mode
In order to better understand the technical means of the present invention, it and can be implemented in accordance with the contents of the specification, below
In conjunction with specific embodiments, the specific implementation mode of the present invention is described in further detail, following embodiment is for illustrating this hair
It is bright, but it is not limited to the scope of the present invention.
Each raw material used in following specific embodiments and comparative example are as described in the following table 1：
Raw material used in 1 specific embodiment of table and comparative example
PA6, PA66 and PA610 are the polyamide that fusing point is less than 270 DEG C in polyamide used in table 1；
Roving glass fiber size used in table 1, wherein modified ultra-branching polyester are preparation method made of self-control
For：By superbrnaching end-hydroxy polyester (Boltorn U3000, the Shanghai bio tech ltd Xi Bao) and maleic anhydride according to rubbing
You are than being 1:9 are added in the four-hole bottle equipped with condenser pipe and mechanical agitator, are protected using nitrogen, and are added on a small quantity
Polymerization inhibitor is stirred to react on 90 DEG C of following heating sides, during the reaction by acid number titration method come following response degree.Work as acid
When value is down to the half of initial acid value and no longer changes, stops reaction, product is settled out with acetone and ether, through repeatedly washing
It is dried after washing filtering, obtains the modified ultra-branching polyester in upper table；It is above-mentioned to use maleic anhydride to terminal hydroxy group hyperbranched poly
The method that ester carries out terminal groups modification is the popular response in this field between hydroxy functional group and anhydride functional group, wherein involved
Operational means and the routine operation means that are well known to the skilled person of used reagent and reagent, such as product
Precipitation, washing, dry etc., such as polymerization inhibitor type and dosage selection, therefore no longer repeated in the application.And above-mentioned
The assay method of involved acid value is measured according to national standard GB/T12008.5-1989 in preparation process.
Roving glass fiber size used in table 1, wherein traditional glass fiber treating compound is highly -branched commonly used in the prior art
At least one of polyethylene wax, modified low molecular weight polypropylene, mineral oil are spent, this is skill well-known to those skilled in the art
Art scheme repeats no more in the application.
Maleic anhydride inoculated polypropylene used in table 1 is commonly used for improving the phase of roving glass fiber and resin surface binding force
Hold agent, to embody the features of the present invention, the application is compared as one of contrast factor.
It is needed simultaneously for convenience of comparison each component to polyamide compoiste material final performance and processing performance to meet processing
Influence, the lubricant, heat stabilizer and antioxidant of identical type and dosage are added in following specific embodiments and comparative example,
Wherein lubricant selects pentaerythritol stearate (PETS), dosage to account for the 0.3wt.% of raw material gross mass；Heat stabilizer selects
It is 1 with mass ratio:The mixture of 6 CuI and KI, dosage account for the 0.2wt.% of raw material gross mass；Antioxidant selects bis- (2,6-
Di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate, dosage accounts for the 0.3wt.% of raw material gross mass.
According to amounts of components described in table 2 to table 4, polyamide compositions are prepared with following processing scheme I or processing scheme II
Object, in component described in table 2 to table 4, polyamide, roving glass fiber and metal salt compound are measured according to parts by weight, roving glass fiber leaching
Profit agent is measured according to the weight percent of roving glass fiber total weight.
Processing scheme I：Each component accurately is weighed, then will remove the processed temperature of other components outside roving glass fiber is 280-
After 330 DEG C of melt compounding equipment is mixed and is plasticized, it is transported to the high-temperature fusant that temperature is 280-330 DEG C and rolls dipping former
In tool, wherein melt compounding equipment is screw extruder, preferably double screw extruder；Then by roving glass fiber with 100-150m/
The speed drawing of min enters in the mold that length is 2-4m, fully after calendering dipping, carries out cooling, pelletizing, obtains polyamide group
Close object.
Processing scheme II：Each component accurately is weighed, is then by the processed temperature of other components removed outside roving glass fiber
After 260-310 DEG C of melt compounding equipment is mixed and is plasticized, it is transported to the high-temperature fusant calendering leaching that temperature is 280-330 DEG C
In stain mold, wherein melt compounding equipment is screw extruder, preferably double screw extruder；Then by roving glass fiber with 100-
The speed drawing of 150m/min enters in the mold that length is 2-4m, fully after calendering dipping, carries out cooling, pelletizing, is gathered
Amide compositions.
The daiamid composition of gained is subjected to Mechanics Performance Testing and carries out ocular estimate, wherein Mechanics Performance Testing packet
Include the tensile strength (ISO527/2-93) to daiamid composition, elongation at break (ISO527/2-93) and notch impact strength
(ISO180-93) test, ocular estimate include the evaluation to the glossiness of daiamid composition and floating fine situation, glossiness and
Floating fibre situation is divided according to grade, be divided into it is excellent, in, poor three grades.Test acquired results in table 2 to table 4 referring to respectively having
Body embodiment corresponds in the performance column at below column.
Table 2 specific embodiment 1-3 and comparative example 1-4
From Table 2, it can be seen that when containing roving glass fiber size described herein in composition, the application is used
When the metal salt compound containing representative examples of saturated aliphatic acid ion or unsaturated aliphatic acid ion, and in the prior art
(specific embodiment 1,2 and comparative example 2) is compared using the metal salt compound containing halide ion, mechanical property and appearance are equal
It is apparent more excellent, such as tensile strength, elongation at break and notch impact strength, also floating fine situation and glossiness, especially with
When metal salt compound containing acetate ion, gained PA6 daiamid composition comprehensive performances are optimal.
In addition, making it can also be seen that when using herein described metal salt compound of the same race in composition from table 2
With the daiamid composition (specific embodiment 2 and 3) of the roving glass fiber size containing herein described modified ultra-branching polyester, and
It is compared without using roving glass fiber size (comparative example 3), and using only traditional roving glass fiber size (comparative example 4), uses this Shen
The component of modified ultra-branching polyester that please be described as roving glass fiber size, can obtain mechanical property and appearance preferably PA6
Daiamid composition.
And both without using herein described metal salt compound, also without using herein described modified ultra-branching polyester
As the group timesharing (comparative example 1) of roving glass fiber size, the mechanical property and appearance of gained PA6 daiamid compositions are most
Difference.
Table 3 specific embodiment 4-6 and comparative example 4-8
It can be seen that when use is with diverse polyamide used in table 3, and use from above-mentioned table 3
Metal salt compound dosage, the dosage difference of roving glass fiber size when, equally have table 3 in specific embodiment and comparative example
The characteristic shown.That is, in composition contain roving glass fiber size described herein when, using it is herein described containing
When the metal salt compound of representative examples of saturated aliphatic acid ion or unsaturated aliphatic acid ion, and in the prior art using containing
The metal salt compound of halide ion compares (specific embodiment 4,5,6 and comparative example 7), mechanical property and appearance obviously compared with
It is excellent, such as tensile strength, elongation at break and notch impact strength, also floating fine situation and glossiness, especially with containing vinegar
When the metal salt compound of acid ion, gained PA66 daiamid composition comprehensive performances are optimal.
In addition, making it can also be seen that when using herein described metal salt compound of the same race in composition from table 3
With the daiamid composition (specific embodiment 4,6) of the roving glass fiber size containing herein described modified ultra-branching polyester, and
It is compared without using roving glass fiber size (comparative example 6), and using only traditional roving glass fiber size (comparative example 8), uses this Shen
The component of modified ultra-branching polyester that please be described as roving glass fiber size, can obtain mechanical property and appearance preferably PA66
Daiamid composition.
And both without using herein described metal salt compound, also without using herein described modified ultra-branching polyester
As the group timesharing (comparative example 4 and 5) of roving glass fiber size, the mechanical property and appearance of gained PA66 daiamid compositions are equal
It is worst.
Table 4 specific embodiment 7-8 and comparative example 9-11
As can be seen from Table 4, using metal salt compound described herein, use herein described
The daiamid composition of modified ultra-branching polyester has excellent processing performance, and is not added with herein described modified ultra-branching
The daiamid composition of polyester is compared, and can be obtained under relatively low processing temperature equally in higher processing temperature
Just obtainable mechanical property and appearance under degree, referring specifically to specific embodiment 7,8 and comparative example 9,10.Conversely, because processing
The reduction of temperature, be not added with herein described modified ultra-branching polyester daiamid composition occur in terms of appearance it is serious
Floating fine and tensile strength and elongation at break reduction.In addition, it can also be seen that herein described equally using from table 4
In the case of metal salt compound, even if without using herein described modified ultra-branching polyester as glass fiber treating compound, and only adopt
Enhance the binding force between glass and resin matrix with maleic anhydride inoculated polypropylene common in currently available technology, most
The mechanical property and appearance of whole daiamid composition connect with the mechanical property and appearance of comparative example 9 and 10 daiamid compositions
Closely, referring specifically to comparative example 11.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of long glass fiber reinforced daiamid composition, it is characterised in that：Including kymene 0-70 parts by weight, metal salt chemical combination
The roving glass fiber that object 0.05-5.0 parts by weight, roving glass fiber 10-60 parts by weight and dosage are roving glass fiber dosage 0.08-5.0wt.% infiltrates
Agent；
Metal cation in the metal salt compound be the first major element, the second major element, the first subgroup element and
At least one of the cation of metallic element in second subgroup element, and the anion in the metal salt compound is hydrogen-oxygen
At least one in radical ion, carbanion, hydrogen sulfate ion, saturated fat acid ion and unsaturated fat acid ion
Kind；
The roving glass fiber size is at least one of high-branched polyethylene wax, modified low molecular weight polypropylene, mineral oil
With the mixture of modified ultra-branching polyester or only modified ultra-branching polyester, wherein the modified ultra-branching polyester is by containing acid official
The organic matter that can be rolled into a ball carries out obtained by terminal groups modification superbrnaching end-hydroxy polyester, and the organic matter containing acidic functionality and terminal hydroxy group
The ratio between amount of substance of hyper-branched polyester is n (organic matter containing acidic functionality):N (superbrnaching end-hydroxy polyester)=n (acid
Property functional group):N (hydroxyl value of single superbrnaching end-hydroxy polyester × (30-40) %)；Wherein described the having containing acidic functionality
Machine object is at least one of saturated fat acid anhydrides and unsaturated fat acid anhydrides；The wherein described superbrnaching end-hydroxy polyester is served as reasons
ABx(x >=2) type monomer, which self condenses, to be polymerized or by Ax+By(x > 1 and y > 1) type polyfunctional monomer is copolymerized, and should
The weight average molecular weight of superbrnaching end-hydroxy polyester is 2000-5500, and hydroxyl value is 40-50/mol, and the degree of branching is 0.4-
0.5。
2. long glass fiber reinforced daiamid composition according to claim 1, it is characterised in that：In the metal salt compound
Metal cation be at least one of lithium ion, sodium ion, potassium ion, calcium ion, zinc ion and copper ion, and metal salt
Anion in compound is at least one of saturated fat acid ion and unsaturated fat acid ion.
3. long glass fiber reinforced daiamid composition according to claim 2, it is characterised in that：In the metal salt compound
Metal cation be at least one of lithium ion and zinc ion, and the anion in metal salt compound be acetate ion
At least one of with stearate radical ion.
4. long glass fiber reinforced daiamid composition according to claim 1, it is characterised in that：The ABxType monomer is 2,2-
Dihydromethyl propionic acid, 3,5- dihydroxy-benzoic acids or 5- (2- hydroxyl-oxethyls) M-phthalic acid；The Ax+ByType polyfunctionality
Monomer is A2+B3Type monomer, wherein A2Monomer is aliphatic dicarboxylic acid or aliphatic diol, works as A2B when monomer is aliphatic diacid3
Monomer is accordingly aliphatic triol, works as A2B when monomer is aliphatic diol3Monomer is aliphatic tricarboxylic acids accordingly.
5. long glass fiber reinforced daiamid composition according to claim 4, it is characterised in that：The aliphatic dicarboxylic acid is
At least one of hexanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decanedioic acid；
The aliphatic diol is such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol and the last of the ten Heavenly stems
At least one of glycol；The aliphatic tricarboxylic acids are at least one of tricarballylic acid and three carboxyl benzene；The fat
Race's triol is in glycerine, butantriol, penta triol, hexanetriol, tri hydroxy methyl butane, trimethylolpropane and trimethylolethane
At least one.
6. long glass fiber reinforced daiamid composition according to claim 1, it is characterised in that：The polyamide is that fusing point is low
The polyamide and fusing point for being 60-140 DEG C in 270 DEG C of polyamides or glass transition temperature are poly- less than 270 DEG C
The mixture of amide resin；The roving glass fiber is the long glass fibres of 5-50 μm of diameter.
7. long glass fiber reinforced daiamid composition according to claim 1, it is characterised in that：The long glass fiber reinforced polyamides
Amine composition further includes lubricant 0.05-5.0 parts by weight and compatilizer 5-10 parts by weight.
8. long glass fiber reinforced daiamid composition according to claim 7, it is characterised in that：The lubricant is single stearic
The double lauramides of acid glyceride, glyceryl tristearate, ethylene bis stearamide, ethylene, ethylene double oleamide, low molecular weights
At least one of ionomer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer.
9. long glass fiber reinforced daiamid composition according to claim 7, it is characterised in that：The compatilizer is polarity list
The polymer of body graft polymers, the polar monomer graft polymer is polyethylene, polypropylene, ethylene-octene copolymer, benzene second
Alkene-butadiene copolymer, polyethylene-polystyrene-polypropylene copolymer, ethylene-propylene-diene copolymer, ethylene-propylene
At least one of acid ester copolymer and ethylene-acrylate-glycidyl methacrylate copolymer, the polar monomer connect
The polar monomer of branch polymer is at least one of unsaturated fat acid anhydrides, acrylic acid and acrylate.
10. the preparation method of long glass fiber reinforced daiamid composition described in any claim in a kind of claim 1 to 9,
It is characterized in that：Include the following steps：
(1) each component in long glass fiber reinforced daiamid composition accurately is weighed, then will removes the other components outside roving glass fiber and passes through
Processing temperature is to be transported to the high temperature that temperature is 280-330 DEG C after 280-330 DEG C of melt compounding equipment is mixed and is plasticized
Melt rolls in impregnation mold, and wherein melt compounding equipment is screw extruder；
(2) roving glass fiber is entered into length in the mold of 2-4m with the speed drawing of 100-150m/min, fully after calendering dipping,
Cooling, pelletizing is carried out, the long glass fiber reinforced daiamid composition is obtained.
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