CN106867249A - One kind enhancing static resistant polyamide composite and preparation method thereof - Google Patents
One kind enhancing static resistant polyamide composite and preparation method thereof Download PDFInfo
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- CN106867249A CN106867249A CN201710102842.1A CN201710102842A CN106867249A CN 106867249 A CN106867249 A CN 106867249A CN 201710102842 A CN201710102842 A CN 201710102842A CN 106867249 A CN106867249 A CN 106867249A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention provides one kind enhancing static resistant polyamide composite and preparation method thereof, the polyamide compoiste material includes：45 85 parts of polyamide, 15 50 parts of glass fibre, and 18 parts of antistatic additive.The preparation method of the enhancing static resistant polyamide composite is：(1) by polyamide and antistatic additive, according to weight portion described in any one of claim 15, it is well mixed, obtains mixture A；(2) by mixture A and glass fibre described in step (1), it is well mixed and by screw machine extruding pelletization in screw machine, obtains final product the polyamide compoiste material.Gained polyamide compoiste material of the invention, while ensure that well even more excellent mechanical performance, imparts the effect of product durable antistatic, has expanded application of the polyamide compoiste material in more areas.
Description
Technical field
The invention belongs to polymeric material field, it is related to a kind of enhancing static resistant polyamide composite and its preparation side
Method.
Background technology
Polyamide refers to the polymer with amide groups repeat unit on macromolecular chain, and it has good combination property,
For example：High intensity and toughness, high-fire resistance, wearability, chemical proofing, also with self lubricity, self-extinguishment, easy processing etc.
Characteristic, is to realize " to mould Dai Gang " one of main polymeric material of theory.
Polyamide modified is the hot topic of current research.Since the 1950's, the modified of polyamide material is turned into more
Carry out more popular topic.By modified, a series of Polyamide Engineering Plastics with more excellent properties can be obtained, answer it
Constantly expanded with field；And for compared to the research and development of new polymers, polyamide modified is a kind of relatively low cost, succinct
And direct method.It is so-called polyamide modified, inorganic or organic matter is exactly added by physics and mechanical means in the polymer
Matter (such as additive), or by the blending of different types of polymer, or chemically realize the copolymerization of polymer, grafting, embedding
Section, crosslinking, or the above method are combined, and decline the manufacturing cost of material to reach, moulding processability or final usability
Can be improved, or polymeric material is only assigned unique function at the aspect such as surface and electricity, magnetic, light, heat, sound, burning
Effect.Polymer modification be exactly the performance of polymer, seek between processing characteristics and production cost three one it is optimal
Equalization point.
Polyamide has been extended to the every field of national product as the application of plastic products, in daily life and life
In product, the theory of " to mould Dai Gang " is increasingly deep into links.However, plastics belong to organic non-metal material, absolutely mostly
The resistivity that number plastics have good insulating properties, the plastics that usual people touch works as plastics more than 1014~1015
When the solid matter contact different from physical state or friction, electric charge can be reallocated in two kinds of surfaces of solids, cause two
After individual solid is separated, each surface of solids is referred to as electrostatic with the positive charge or negative electrical charge more excessive than before contact, this phenomenon.
In people's daily life and production, dust suction, the electric shock caused due to electrostatic, or even cause fire, blast etc. after generation spark
Serious accident is of common occurrence, or even causes great economy and society to lose, so, static electricity prevention and curing has caused people increasingly
Many attention.
Used as a kind of important engineering plastics, polyamide article is widely used in national product with life, but
The surface resistivity of polyamide is general lived 1014~1015 between, as other plastic products, when its with other materials or
After material surface contact or friction, easily substantial amounts of electrostatic charge is accumulated in product surface.Particularly when carrying out fiberglass reinforced to it
Afterwards, product surface is relatively rough, is more beneficial for the generation and aggregation of electrostatic charge, therefore, in order to avoid polyamide article as far as possible
Electrostatic charge is produced when in use, it is necessary to polyamide is carried out antistatic modified, assign its relatively low surface resistivity, be surface
Resistance and volume resistance are reduced as far as possible, eliminate electrostatic hazard.
But, the addition of antistatic additive, the mechanical performance for polyamide compoiste material has a great impact, therefore, examine
Consider specific application field, the research to the combination property of polyamide compoiste material, it appears particularly important.
The content of the invention
It is a kind of with durable antistatic effect and the excellent polyamides of mechanical performance it is a primary object of the present invention to provide
Amine composite.
It is another object of the present invention to provide a kind of preparation method of above-mentioned polyamide compoiste material.
To reach above-mentioned purpose, solution of the invention is：
【Polyamide compoiste material】
A kind of polyamide compoiste material, it includes each composition of following weight portion：
Polyamide 45-85 parts,
Glass fibre 15-50 parts,
With antistatic additive 1-8 parts.
Preferably, the polyamide includes polyamide 5X resins, and the polyamide 5X includes：With 1,5- pentanediamines and
Binary acid is the polyamide that monomer polymerization is obtained；Wherein, the binary acid includes dicarboxylic acids；The dicarboxylic acids includes：Fourth
Diacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, DC11, SL-AH, 13
Carbon dicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18, horse
One or more come in sour and Δ 9-1,18 octadecylene binary acid.
Preferably, the polyamide 5X resins include：It is the resin of polyamide 54, the resin of polyamide 55, the resin of polyamide 56, poly-
The resin of acid amides 57, the resin of polyamide 58, the resin of polyamide 59, the resin of polyamide 510, the resin of polyamide 511, the tree of polyamide 512
Fat, the resin of polyamide 512, the resin of polyamide 513, the resin of polyamide 514, the resin of polyamide 515, the resin of polyamide 516, polyamides
One or more in the resin of amine 517 and the resin of polyamide 518.
Preferably, the polyamide is biological based polyamide resin.Preferably, the biological poly amide resin
Polymerized monomer is by obtained by biofermentation method.Preferably, the biogenetic derivation ratio of the biological poly amide resin is
35-100%；
Preferably, the relative viscosity of the polyamide is 2.4-3.2.
Preferably, the glass fibre can be alkali-free glass fibre.The diameter of the glass fibre is preferably 6-15 μm.
Preferably, the antistatic additive includes：Anionic antistatic agent, non-ionic antistatic agent and macromolecular structure
One or more in antistatic additive.Wherein it is preferred to, the anionic antistatic agent includes：ALS
And/or single dodecyloxy potassium phosphate.Preferably, the non-ionic antistatic agent includes：It is fatty acid distribution of coconut oil diacetayl amide, mixed
Close the mixture (Grindsted PGE308) of glycerin monostearate (GMS), polyglycerol ester and molecular distillation monoglyceride, gather
One or more in the phosphate of ethylene glycol 400 and laurel alcohol ether phosphate.Preferably, the macromolecular structure antistatic additive bag
Include：Polyethylene glycol-lithium colloidal sol compound.The antistatic additive is preferably compounding antistatic additive.
Preferably, polyamide compoiste material of the present invention also includes bulking agent.
Preferably, the bulking agent includes：MBS (MBS), methyl-prop
It is e pioic acid methyl ester-ethyl acrylate, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate copolymer, random
Ethylene-methyl acrylate-copolymer-maleic anhydride, Ethylene-butyl acrylate-glycidyl methacrylate copolymer, horse
Maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride grafting ternary
EP rubbers, maleic anhydride grafted ethene-vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer,
Maleic anhydride grafted ethene-BS and MBS terpolymer
In one or more.Preferably, the weight portion of the bulking agent is 1-10 parts.
Polyamide compoiste material of the present invention also includes other processing aids.
Described other processing aids include lubricant, nucleator, antioxidant in one or more.
Wherein, it is preferred that the lubricant includes：N, N'- ethylene bis stearamide (EBS), OPE, poly- second
Alkene-vinyl acetate wax, saponified polyvinyl wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, stearic acid
One kind in calcium, zinc stearate, odium stearate, barium stearate and the macromolecule organic silicon and more than one.Wherein, the saponification gathers
Ethylene waxes preferably partly-hydrolysed Tissuemat E.The preferred silicone powder of the macromolecule organic silicon.
Wherein, it is preferred that the nucleator includes：Brueggemann (BRUGGOLEN) P22, montanic acid calcium, montanic acid sodium,
One kind and one kind in polyacrylic acid ionomer, organo montmorillonite, superfine talcum powder, ultra-fine mica, aluminum oxide and magnesia with
On.
Wherein, it is preferred that the antioxidant includes：N, N- pair-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono)
Hexamethylene diamine, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, three [2.4- di-tert-butyl-phenyls] phosphorous acid
Ester, double (2,4- di-tert-butyl-phenyls) propionic acid] pentaerythritol diphosphites, the 2,2- methylene-bis- (4- ethyl -6- tert-butyl groups
Phenol), inclined fourth support-bis--(the 6- tert-butyl-m-cresols) of 4,4-, (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane of 1,1,3- tri- and
One kind in 1,3,5- trimethyls -2,4,6- three (hydroxybenzyl of 3,5- di-t-butyls -4) benzene and more than one.
Machine pigment or inorganic pigment are may further be enriched with processing aid of the invention according to actual needs.
【The preparation method of polyamide compoiste material】
A kind of preparation method of above-mentioned polyamide compoiste material, comprises the following steps：
(1) by polyamide and antistatic additive, weight portion, is well mixed as described above, obtains mixture A；
(2) by mixture A and glass fibre described in step (1), it is well mixed in screw machine and is extruded by screw machine
Granulation, obtains final product the polyamide compoiste material.
When the polyamide compoiste material also includes bulking agent, the bulking agent is added in step (1).
When the polyamide compoiste material also includes other processing aids, described other processing aids are in step (1)
Add.
Blend step in step (1) is carried out in mixer.The preferred 300-500rpm of rotating speed of the mixer.Institute
State the time preferred 2-5min of mixing.Preferred 20-400 DEG C of the temperature of the mixing.
In step (2), the screw extruder is preferably double screw extruder.
In step (2), the screw extruder preferably point 7th area heating.Wherein, area's temperature of the screw extruder
Preferably 70-90 DEG C, more preferably 75-85 DEG C.And/or, two area's temperature of the screw extruder are preferably 210-230 DEG C,
More preferably 215-225 DEG C.And/or, three area's temperature of the screw extruder are preferably 240-260 DEG C, more preferably 245-
255℃.And/or, four area's temperature of the screw extruder are preferably 260-280 DEG C, more preferably 265-275 DEG C.And/or,
Five area's temperature of the screw extruder are preferably 270-290 DEG C, more preferably 275-285 DEG C.And/or, the Screw Extrusion
The area's temperature of Ji six is preferably 270-290 DEG C, more preferably 275-285 DEG C.And/or, seven area's temperature of the screw extruder
Preferably 265-285 DEG C, more preferably 270-280 DEG C.
In step (2), the die temperature of the double screw extruder is preferably 265-275 DEG C.
In step (2), the mixture A is preferably added from the main spout of screw extruder.
In step (2), the glass fibre is preferably added from the side spout of screw extruder.
In step (2), the screw slenderness ratio of the double screw extruder is preferably 1：(30-50), more preferably 1：(35-
45)。
In step (2), the screw speed of the double screw extruder is 200-500rpm.
After the extruding pelletization, preferably it is dried again.The drying time is preferably 5-7h, more preferably 5.5-
6.5h.Preferred 70-90 DEG C, more preferably 75-85 DEG C of the drying temperature.
Using such scheme, the beneficial effects of the invention are as follows：
(1) in polyamide compoiste material of the present invention, polyamide can select the polyamides that biofermentation technique is obtained
Polyimide resin, is independent of petroleum resources and does not cause severe contamination to environment, and product has environment-friendly and continuable feature.
(2) polyamide compoiste material of the present invention, while ensure that well even more excellent mechanical performance, assigns
The effect of product durable antistatic is given.
(3) polyamide compoiste material of the present invention, is assigning material durable antistatic effect simultaneously, realizes higher
Material balance and the color problem for avoiding conventional antistatic agents from bringing, make composite to be coloured by design in application, improve
The design freedom of product, is conducive to expanding application of the polyamide in more areas.
Specific embodiment
The invention provides a kind of polyamide complex composition and preparation method thereof.
<Polyamide compoiste material>
Polyamide compoiste material includes each composition of following weight portion：45-85 parts of polyamide, 15-50 parts of glass
Glass fiber, 1-8 parts of antistatic additive is obtained.
As the case may be, the polyamide compoiste material can also include that antistatic additive and/or bulking agent and/or processing are helped
Agent.
[polyamide]
Preferably, the polyamide includes that polyamide 5X, the polyamide 5X include：With 1,5- pentanediamines and binary
The polyamide that acid is obtained for monomer polymerization；Wherein, the binary acid includes dicarboxylic acids；The dicarboxylic acids includes：Succinic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, DC11, SL-AH, 13 carbon two
First acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18, maleic acid
With one or more in Δ 9-1,18 octadecylene binary acid.
Preferably, the polyamide 5X resins include：It is the resin of polyamide 54, the resin of polyamide 55, the resin of polyamide 56, poly-
The resin of acid amides 57, the resin of polyamide 58, the resin of polyamide 59, the resin of polyamide 510, the resin of polyamide 511, the tree of polyamide 512
Fat, the resin of polyamide 512, the resin of polyamide 513, the resin of polyamide 514, the resin of polyamide 515, the resin of polyamide 516, polyamides
One or more in the resin of amine 517 and the resin of polyamide 518.
The relative viscosity of the polyamide is 2.4-3.2.
The polymerized monomer of the polyamide can be prepared from by biological raw material by bioanalysis, its raw material biogenetic derivation
Ratio is 35-100%.
[glass fibre]
Glass fibre can be alkali-free glass fibre, and fibre diameter is preferably 6-15 μm.
[antistatic additive]
Antistatic additive is from anionic antistatic agent, non-ionic antistatic agent or macromolecular structure antistatic additive
One or more, wherein,
Anionic antistatic agent can be the one kind in ALS, single dodecyloxy potassium phosphate；
Non-ionic antistatic agent can for fatty acid distribution of coconut oil diacetayl amide, mixing glycerin monostearate (GMS),
GrindstedPGE308 (mixture of polyglycerol ester and molecular distillation monoglyceride), PEG400 phosphate, laruyl alcohol
One kind in ether phosphate；
Macromolecular structure antistatic additive can be polyethylene glycol-lithium colloidal sol compound.
[bulking agent]
The raw materials for production of polyamide compoiste material of the invention can also include the bulking agent that weight portion is for 1-10 parts.
Bulking agent may be selected MBS, methyl methacrylate-acrylic acid
Ethyl ester, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate copolymer, random ethylene-methyl acrylate-
Copolymer-maleic anhydride, Ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride are grafted poly- second
Alkene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride grafting ethylene propylene diene rubber, Malaysia
Anhydride grafted ethylene-vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer, maleic anhydride grafting
One kind or one kind in ethylene-butadiene-styrene copolymer, MBS terpolymer
More than.
[processing aid]
The raw materials for production of polyamide compoiste material of the invention can also include the processing aid that weight portion is for 1-5 parts.
The processing aid can as needed select one or more in lubricant, nucleator, antioxidant, wherein,
The lubricant may be selected from N, N'- ethylene bis stearamides, OPE, ethylene vinyl acetate wax, soap
Change Tissuemat E, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate, zinc stearate, tristearin
One kind in sour sodium, barium stearate, the macromolecule organic silicon and more than one.
Saponified polyvinyl wax described in the preferred embodiments of the present invention is partly-hydrolysed Tissuemat E, and the macromolecule is organic
The preferred silicone powder of silicon.
The nucleator can be selected from P22, montanic acid calcium, montanic acid sodium, polyacrylic acid ionomer, organo montmorillonite, super
One kind in fine and smooth stone flour, ultra-fine mica, aluminum oxide, magnesia and more than one.The antioxidant includes N, N- is double-(3- (3,
5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, β-(3,5- di-tert-butyl-hydroxy phenyls) positive octadecanol of propionic acid
Ester, three [2.4- di-tert-butyl-phenyls] phosphite esters, double (2,4- di-tert-butyl-phenyls) propionic acid] pentaerythritol diphosphites,
Inclined fourth support-bis--(the 6- tert-butyl-m-cresols) of 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenols), 4,4-, (the 2- first of 1,1,3- tri-
Base -4- hydroxyl -5- tert-butyl-phenyls) butane, in 1,3,5- trimethyls -2,4,6- three (hydroxybenzyl of 3,5- di-t-butyls -4) benzene
One kind and more than one.
Machine pigment or inorganic pigment are may further be enriched with processing aid of the invention according to actual needs.
<The preparation method of polyamide compoiste material>
A kind of preparation method of above-mentioned polyamide compoiste material, comprises the following steps：
(1) by polyamide and antistatic additive, weight portion, is well mixed as described above, obtains mixture A；
(2) by mixture A and glass fibre described in step (1), it is well mixed in screw machine and is squeezed by screw machine
Go out granulation, obtain final product the polyamide compoiste material.
When the polyamide compoiste material also includes bulking agent, the bulking agent is added in step (1).
When the polyamide compoiste material also includes other processing aids, described other processing aids are in step (1)
Add.
Blend step in step (1) is carried out in mixer.The preferred 300-500rpm of rotating speed of the mixer.Institute
State the time preferred 2-5min of mixing.Preferred 20-40 DEG C of the temperature of the mixing.
In step (2), the screw extruder is preferably double screw extruder.
In step (2), the screw extruder preferably point 7th area heating.Wherein, area's temperature of the screw extruder
Preferably 70-90 DEG C, more preferably 75-85 DEG C.And/or, two area's temperature of the screw extruder are preferably 210-230 DEG C,
More preferably 215-225 DEG C.And/or, three area's temperature of the screw extruder are preferably 240-260 DEG C, more preferably 245-
255℃.And/or, four area's temperature of the screw extruder are preferably 260-280 DEG C, more preferably 265-275 DEG C.And/or,
Five area's temperature of the screw extruder are preferably 270-290 DEG C, more preferably 275-285 DEG C.And/or, the Screw Extrusion
The area's temperature of Ji six is preferably 270-290 DEG C, more preferably 275-285 DEG C.And/or, seven area's temperature of the screw extruder
Preferably 265-285 DEG C, more preferably 270-280 DEG C.
In step (2), the die temperature of the double screw extruder is preferably 265-275 DEG C.
In step (2), the mixture A is preferably added from the main spout of screw extruder.
In step (2), the glass fibre is preferably added from the side spout of screw extruder.
In step (2), the screw slenderness ratio of the double screw extruder is preferably 1：(30-50), more preferably 1：(35-
45)。
In step (2), the screw speed of the double screw extruder is 200-500rpm.
After the extruding pelletization, preferably it is dried again.The drying time is preferably 5-7h, more preferably 5.5-
6.5h.Preferred 70-90 DEG C, more preferably 75-85 DEG C of the drying temperature.
Above-mentioned parameters can be in any combination and suitable for each embodiment.
[method of testing]
Polyamide compoiste material obtained in above-mentioned preparation method is molded into test bars, injection temperature after drying 6h at 80 DEG C
Spend is 260~275 DEG C.
The dependence test of product is referring to such as table 1 below.
Table 1
Embodiment 1：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：150g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g；
Sample preparation and testing procedure：
(1) by biological poly acid amides PA56, antistatic additive, bulking agent, processing aid, weighed by formula, then at a high speed
Mixed in mixer；Mixing temperature is 25 DEG C, and homogenizer rotating speed is 400rpm, and incorporation time is 3min, must be mixed
Thing A；
(2) mixture A is positioned in the main spout of double screw extruder, and alkali-free glass fibre is positioned over twin-screw extrusion
In the side spout of machine；Extruding pelletization；The draw ratio of double screw extruder is 1:40, each area's temperature of extruder is (from feeding to mould
Mouthful) set and be followed successively by 80 DEG C, 220 DEG C, 250 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 275 DEG C, die temperature is 270 DEG C, and screw rod turns
Fast 300rpm；
(3) the antistatic biological poly acid amides section that will be prepared dries 8h at 80 DEG C, is then molded, injection machine temperature
Set and 250 DEG C, 275 DEG C, 275 DEG C, 280 DEG C are followed successively by from feeding container to nozzle, nozzle temperature is 275 DEG C.
Batten is tested：
The test bars of injection are placed into 28h at 23 DEG C, is tested by iso standard.Test result is referring to table 2.
Embodiment 2：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：150g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 3：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：150g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 4：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：100g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：50g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 5：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：75g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：75g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 6：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：50g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：100g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 7：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：100g
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：50g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 8：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：75g
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：75g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 9：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (ALS)：50
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：100g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 10：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：100g
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：50g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 11：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：75g
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：75g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Embodiment 12：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：2950g
Alkali-free glass fibre：1750g
Antistatic additive (fatty acid distribution of coconut oil diacetayl amide)：50g
Antistatic additive (polyethylene glycol-lithium colloidal sol compound)：100g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Comparative example：
Polyamide compoiste material, including following weight each composition：
(2.72) PA56, relative sulfuric acid viscosity is to biological poly acid amides：3100g
Alkali-free glass fibre：1750g
Bulking agent (MBS)：100g
Processing aid is combined (wherein comprising EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng)：50g
Sample preparation and testing procedure are referring to embodiment 1.Dependence test result is referring to table 2.
Table 2：Antistatic glass-fiber-reinforced polyamide Performance comparision
Can be drawn by the test result of table 2：Antistatic additive, particularly specific compounding antistatic additive, can be obvious
Reduce the surface resistivity of glass fibre reinforced composion.Also, ALS, fatty acid distribution of coconut oil diacetayl amide and poly-
Two kinds in ethylene glycol-lithium colloidal sol compound of compounding two-by-two, can substantially reduce the surface of glass fibre reinforced composion
Resistivity.For single antistatic additive, ionic anti-static agent is slightly better than the using effect of non-ionic antistatic agent.Two kinds
Antistatic additive compounding use, under the conditions of consumption identical, using effect is better using same antistatic additive effect than single.
Antistatic additive not only has reduces the effect of composite material surface resistivity, and can also play in process
The effect of lubricant, from terms of mechanical experimental results, after addition antistatic additive, the intensity and modulus of composite are without obvious
Change, illustrates that be properly added antistatic additive does not influence on the mechanical property of composite.
The above-mentioned description to embodiment is to be understood that and use this hair for ease of those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment,
Those skilled in the art's announcement of the invention, does not depart from improvement that scope made and modification all should be in this hair
Within bright protection domain.
Claims (10)
1. a kind of polyamide compoiste material, it includes each composition of following weight portion：
Polyamide 45-85 parts,
Glass fibre 15-50 parts,
With antistatic additive 1-8 parts.
2. polyamide compoiste material as claimed in claim 1, it is characterised in that：
The polyamide includes polyamide 5X resins, and the polyamide 5X includes：With 1,5- pentanediamines and binary acid as single
The polyamide that body polymerization is obtained；Wherein, the binary acid includes dicarboxylic acids；The dicarboxylic acids includes：Succinic acid, penta 2
Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, DC11, SL-AH, tridecanyldicarboxylic acid,
DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18, maleic acid and Δ 9-
One or more in 1,18 octadecylene binary acid.
Preferably, the polyamide 5X resins include：The resin of polyamide 54, the resin of polyamide 55, the resin of polyamide 56, polyamide
It is 57 resins, the resin of polyamide 58, the resin of polyamide 59, the resin of polyamide 510, the resin of polyamide 511, the resin of polyamide 512, poly-
The resin of acid amides 512, the resin of polyamide 513, the resin of polyamide 514, the resin of polyamide 515, the resin of polyamide 516, polyamide 517
One or more in resin and the resin of polyamide 518.
Preferably, the polyamide is biological based polyamide resin；
Preferably, the polymerized monomer of the biological poly amide resin is by obtained by biofermentation method；
Preferably, the biogenetic derivation ratio of the biological poly amide resin is 35-100%；
Preferably, the relative viscosity of the polyamide is 2.4-3.2.
3. polyamide compoiste material as claimed in claim 1, it is characterised in that：
The glass fibre is alkali-free glass fibre；
And/or, the antistatic additive includes：Anionic antistatic agent, non-ionic antistatic agent and macromolecular structure resist quiet
One or more in electric agent；Wherein it is preferred to, the anionic antistatic agent includes：ALS and/or
Single dodecyloxy potassium phosphate.Preferably, the non-ionic antistatic agent includes：Fatty acid distribution of coconut oil diacetayl amide, mixing are single
One kind or many in tristerin, Grindsted PGE308, PEG400 phosphate and laurel alcohol ether phosphate
Kind.Preferably, the macromolecular structure antistatic additive includes polyethylene glycol-lithium colloidal sol compound.The antistatic additive is preferably
Compounding antistatic additive.
4. the polyamide compoiste material as described in claim any one of 1-3, it is characterised in that：The polyamide compoiste material is also wrapped
Include bulking agent.
Preferably, the bulking agent includes：MBS (MBS), methacrylic acid
Methyl esters-ethyl acrylate, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate copolymer, random ethylene-
Methyl acrylate-copolymer-maleic anhydride, Ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic acid
Acid anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride grafting EPDM
Rubber, maleic anhydride grafted ethene-vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer, Malaysia
In anhydride grafted ethylene-BS and MBS terpolymer
One or more；
Preferably, the weight portion of the bulking agent is 1-10 parts.
5. the polyamide compoiste material as described in claim any one of 1-3, it is characterised in that：
The polyamide compoiste material also includes other processing aids；Described other processing aids include lubricant, nucleator, resist
One or more in oxygen agent.
Wherein, it is preferred that the lubricant includes：N, N'- ethylene bis stearamide, OPE, polyethylene-acetic acid second
Alkene wax, saponified polyvinyl wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate, stearic acid
One kind in zinc, odium stearate, barium stearate and the macromolecule organic silicon and more than one；Wherein, the saponified polyvinyl wax is excellent
Select partly-hydrolysed Tissuemat E；The preferred silicone powder of the macromolecule organic silicon；
Wherein, it is preferred that the nucleator includes：Brueggemann P22, montanic acid calcium, montanic acid sodium, polyacrylic acid ionomer,
One kind in organo montmorillonite, superfine talcum powder, ultra-fine mica, aluminum oxide and magnesia and more than one；
Wherein, it is preferred that the antioxidant includes：N, N- be double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) oneself two
Amine, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, three [2.4- di-tert-butyl-phenyls] phosphite esters,
Double (2,4- di-tert-butyl-phenyls) propionic acid] pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenols),
Inclined fourth support-bis--(the 6- tert-butyl-m-cresols) of 4,4-, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane and 1,3,
One kind in 5- trimethyls -2,4,6- three (hydroxybenzyl of 3,5- di-t-butyls -4) benzene and more than one.
Machine pigment or inorganic pigment are may further be enriched with processing aid of the invention according to actual needs.
6. a kind of preparation method of polyamide compoiste material, comprises the following steps：
(1) by polyamide and antistatic additive, according to weight portion described in claim any one of 1-5, it is well mixed, is mixed
Compound A；
(2) by mixture A and glass fibre described in step (1), it is well mixed in screw machine and is extruded by screw machine and made
Grain, obtains final product the polyamide compoiste material.
When the polyamide compoiste material also includes bulking agent, the bulking agent is added in step (1).
When the polyamide compoiste material also includes other processing aids, described other processing aids are added in step (1).
7. preparation method as claimed in claim 6, it is characterised in that：In step (1), the blend step enters in mixer
OK；The preferred 300-500rpm of rotating speed of the mixer；The time preferred 2-5min of the mixing；The temperature of the mixing is preferred
20-40℃。
8. preparation method as claimed in claim 6, it is characterised in that：In step (2), the screw extruder is preferably double spiral shells
Bar extruder；
In step (2), the screw extruder preferably point 7th area heating；Wherein, area's temperature of the screw extruder is preferred
It is 70-90 DEG C, more preferably 75-85 DEG C；And/or, two area's temperature of the screw extruder are preferably 210-230 DEG C, more excellent
Elect 215-225 DEG C as；And/or, three area's temperature of the screw extruder are preferably 240-260 DEG C, more preferably 245-255
℃；And/or, four area's temperature of the screw extruder are preferably 260-280 DEG C, more preferably 265-275 DEG C；And/or, it is described
Five area's temperature of screw extruder are preferably 270-290 DEG C, more preferably 275-285 DEG C；And/or, the screw extruder
Six area's temperature are preferably 270-290 DEG C, more preferably 275-285 DEG C；And/or, seven area's temperature of the screw extruder are preferred
It is 265-285 DEG C, more preferably 270-280 DEG C；And/or,
In step (2), the die temperature of the double screw extruder is preferably 265-275 DEG C；And/or,
In step (2), the screw speed of the double screw extruder is 200-500rpm.
9. preparation method as claimed in claim 6, it is characterised in that：In step (2), the screw rod of the double screw extruder is long
Footpath ratio preferably 1：(30-50), more preferably 1：(35-45).
10. the preparation method as described in claim any one of 6-9, it is characterised in that：
After the extruding pelletization, then it is dried；
The drying time is preferably 5-7h, more preferably 5.5-6.5h；
Preferred 70-90 DEG C, more preferably 75-85 DEG C of the drying temperature.
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| CN111117237A (en) * | 2020-01-14 | 2020-05-08 | 深圳海源恒业高新材料科技研发有限公司 | Polyamide composite material and preparation method thereof |
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| CN114854193B (en) * | 2022-03-28 | 2023-06-06 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
| CN116574372A (en) * | 2023-05-15 | 2023-08-11 | 金发科技股份有限公司 | Polyamide composition and preparation method and application thereof |
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