CN106867249B - A kind of enhancing static resistant polyamide composite material and preparation method - Google Patents
A kind of enhancing static resistant polyamide composite material and preparation method Download PDFInfo
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- CN106867249B CN106867249B CN201710102842.1A CN201710102842A CN106867249B CN 106867249 B CN106867249 B CN 106867249B CN 201710102842 A CN201710102842 A CN 201710102842A CN 106867249 B CN106867249 B CN 106867249B
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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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- 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
Abstract
The present invention provides a kind of enhancing static resistant polyamide composite material and preparation method, which includes: 45-85 parts of polyamide, 15-50 parts of glass fibre and 1-8 parts of antistatic agent.The enhancing static resistant polyamide composite material the preparation method comprises the following steps: (1) by polyamide and antistatic agent, according to any one of the claim 1-5 parts by weight, is uniformly mixed, obtains mixture A；(2) it by mixture A and glass fibre described in step (1), is uniformly mixed in screw machine and by screw machine extruding pelletization to get the polyamide compoiste material.Gained polyamide compoiste material of the invention imparts the effect of product durable antistatic while ensure that good or even superior mechanical performance, has expanded polyamide compoiste material in the application of more areas.
Description
Technical field
The invention belongs to polymeric material field, it is related to a kind of enhancing static resistant polyamide composite material and its preparation side
Method.
Background technique
Polyamide refers to the polymer on macromolecular chain with amide groups repetitive unit, with good comprehensive performance,
Such as: high-intensitive and toughness, high-fire resistance, wearability, chemical resistance also have self-lubrication, self-extinguishment, easy processing etc.
Characteristic is one of the main polymeric material for realizing " mould Dai Gang " theory.
Polyamide modified is the hot topic studied now.Since the 1950s, the modification of polyamide material has been become more
Carry out more popular topic.By modification, a series of Polyamide Engineering Plastics with more excellent properties can be obtained, it is answered
It is constantly expanded with field；And for the research and development of new polymers, it is polyamide modified be a kind of relatively low cost, it is 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 different types of polymer is blended, or chemically realize the copolymerization of polymer, grafting, embedding
Section, crosslinking, or the above method is combined, decline the manufacturing cost of material to reach, moulding processability or final usability
Can be improved, or make polymer material only surface and electricity, magnetic, light, heat, sound, in terms of assign unique function
Effect.Polymer modification is exactly to seek one between the service performance in polymer, processing performance and production cost three most preferably
Equalization point.
Application of the polyamide as plastic products, has been extended to the every field of national product, in daily life and life
In production, the theory of " mould Dai Gang " is increasingly deep into links.However, plastics belong to organic non-metal material, absolutely mostly
Number plastics have good insulating properties, and the resistivity for the plastics that usual people touch works as plastics more than 1014~1015
When the solid matter different with physical state is contacted or rubbed, charge can reallocate in two kinds of surfaces of solids, lead to two
After a solid separation, each surface of solids, which has, is known as electrostatic than excessive positive charge before contacting or negative electrical charge, this phenomenon.
In people's daily life and production, the dust suction as caused by electrostatic, electric shock, or even lead to fire, explosion etc. after generating spark
Serious accident is commonplace, or even great economy and society is caused to lose, so, static electricity prevention and curing has caused people increasingly
More attention.
As a kind of important engineering plastics, polyamide article is widely used in national product and life, but
Between the surface resistivity of polyamide is generally living 1014~1015, as other plastic products, when its with other materials or
After material surface contact or friction, a large amount of electrostatic charge easily is accumulated in product surface.Especially when carrying out fiberglass reinforced to it
Afterwards, product surface is relatively rough, is more advantageous to the generation and aggregation of electrostatic charge, therefore, in order to avoid polyamide article as far as possible
Electrostatic charge is generated when in use, it is necessary to it is antistatic modified to polyamide progress, its lower surface resistivity is assigned, is surface
Resistance and volume resistance reduce as far as possible, eliminate electrostatic hazard.
But the addition of antistatic agent, have a great impact for the mechanical performance of polyamide compoiste material, therefore, examines
Consider specific application field, the research to the comprehensive performance of polyamide compoiste material, it appears particularly important.
Summary of the invention
The main purpose of the present invention is to provide a kind of with durable antistatic effect and the excellent polyamides of mechanical performance
Amine composite material.
It is another object of the present invention to provide a kind of preparation methods of above-mentioned polyamide compoiste material.
In order to achieve the above objectives, solution of the invention is:
[polyamide compoiste material]
A kind of polyamide compoiste material comprising each ingredient of following parts by weight:
45-85 parts of polyamide,
15-50 parts of glass fibre,
With 1-8 parts of antistatic agent.
Preferably, the polyamide includes polyamide 5X resin, the polyamide 5X include: with 1,5- pentanediamine and
Binary acid is the polyamide that monomer polymerization obtains；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, eleven carbon diacids, dodecanedicarboxylic acid, 13
Carbon dicarboxylic acid, tetradecane diacid, pentadecane binary acid, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, horse
Carry out one of sour and Δ 9-1,18 octadecylene binary acid or a variety of.
Preferably, the polyamide 5X resin includes: 54 resin of polyamide, 55 resin of polyamide, 56 resin of polyamide, gathers
57 resin of amide, 58 resin of polyamide, 59 resin of polyamide, 510 resin of polyamide, 511 resin of polyamide, 512 tree of polyamide
Rouge, 512 resin of polyamide, 513 resin of polyamide, 514 resin of polyamide, 515 resin of polyamide, 516 resin of polyamide, polyamides
One of 518 resin of 517 resin of amine and polyamide is a variety of.
Preferably, the polyamide is biological based polyamide resin.Preferably, the biological poly amide resin
Polymerized monomer is by obtained by biofermentation method.Preferably, the biological source 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 agent includes: anionic antistatic agent, non-ionic antistatic agent and macromolecular structure
One of antistatic agent or more than one.Wherein it is preferred to which the anionic antistatic agent includes: Sodium Allyl Sulfonate
And/or single dodecyloxy potassium phosphate.Preferably, the non-ionic antistatic agent includes: fatty acid distribution of coconut oil diacetayl amide, mixes
It closes the mixture (Grindsted PGE308) of glycerin monostearate (GMS), polyglycerol ester and molecular distillation monoglyceride, gather
One of 400 phosphate of ethylene glycol and laurel alcohol ether phosphate are a variety of.Preferably, the macromolecular structure antistatic agent packet
It includes: polyethylene glycol-lithium colloidal sol compound.The antistatic agent preferably compounds antistatic agent.
Preferably, polyamide compoiste material of the present invention further includes expanding material.
Preferably, the expanding material includes: Methyl Methacrylate-Butadiene-Styrene Copolymer (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 are grafted ternary
EP rubbers, maleic anhydride grafted ethene-vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer,
Maleic anhydride grafted ethene-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene terpolymer
One of or more than one.Preferably, the parts by weight of the expanding material are 1-10 parts.
Polyamide compoiste material of the present invention further includes other processing aids.
Other described processing aids include one of lubricant, nucleating agent, antioxidant or more than one.
Wherein, it is preferred that the lubricant includes: N, N'- ethylene bis stearamide (EBS), oxidized polyethylene wax, poly- second
Alkene-vinyl acetate wax, saponified polyvinyl wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, stearic acid
One of calcium, zinc stearate, odium stearate, barium stearate and the macromolecule organic silicon and more than one.Wherein, the saponification is poly-
The preferably partly-hydrolysed polyethylene wax of ethylene waxes.The preferred silicone powder of the macromolecule organic silicon.
Wherein, it is preferred that the nucleating agent include: Brueggemann (BRUGGOLEN) P22, montanic acid calcium, montanic acid sodium,
One of polyacrylic acid ionomer, organo montmorillonite, superfine talcum powder, ultra-fine mica, aluminium oxide and magnesia and it is a kind of with
On.
Wherein, it is preferred that the antioxidant includes: N, and N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono)
Hexamethylene diamine, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphorous acid
Ester, bis- (2,4- di-tert-butyl-phenyl) propionic acid] pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl
Phenol), inclined fourth support-bis--(the 6- tert-butyl-m-cresol) of 4,4-, (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane of 1,1,3- tri- and
One of 1,3,5- trimethyl -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene and more than one.
It may further be enriched with machine pigment or inorganic pigment in processing aid of the invention according to actual needs.
[preparation method of polyamide compoiste material]
A kind of preparation method of above-mentioned polyamide compoiste material, includes the following steps:
(1) by polyamide and antistatic agent, parts by weight, are uniformly mixed, obtain mixture A as described above；
(2) it by mixture A and glass fibre described in step (1), is uniformly mixed in screw machine and is squeezed out by screw machine
It is granulated to get the polyamide compoiste material.
When the polyamide compoiste material further includes expanding material, the expanding material is added in step (1).
When the polyamide compoiste material further includes other processing aids, other described processing aids are in step (1)
It is added.
Mixing step in step (1) is carried out in mixing machine.The preferred 300-500rpm of the revolving speed of the mixing machine.Institute
State the time preferred 2-5min of mixing.Preferred 20-400 DEG C of the mixed temperature.
In step (2), the screw extruder is preferably double screw extruder.
In step (2), the screw extruder preferably divides 7th area to heat.Wherein, a Qu Wendu 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, and more preferably 275-285 DEG C.And/or the Screw Extrusion
Six area's temperature of Ji is preferably 270-290 DEG C, and 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 preferable 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 the above scheme, the beneficial effects of the present invention are:
(1) in polyamide compoiste material of the present invention, the polyamides that biofermentation technique obtains is can be selected in polyamide
Polyimide resin does not depend on petroleum resources and does not cause seriously to pollute to environment, and product has the characteristics that environmental-friendly and sustainable.
(2) polyamide compoiste material of the present invention is assigned while ensure that good or even superior mechanical performance
The effect of product durable antistatic is given.
(3) polyamide compoiste material of the present invention is assigning material durable antistatic effect simultaneously, is realizing higher
Material balance and conventional antistatic agents bring color problem is avoided, colour composite material can by design in application, improve
The design freedom of product is conducive to expand polyamide in the application of more areas.
Specific embodiment
The present invention provides a kind of polyamide complex compositions and preparation method thereof.
<polyamide compoiste material>
Polyamide compoiste material includes each ingredient of following parts by weight: 45-85 parts of polyamide, 15-50 parts of glass
Glass fiber, 1-8 parts of antistatic agent are made.
As the case may be, which can also include that antistatic agent and/or expanding material and/or processing help
Agent.
[polyamide]
Preferably, the polyamide includes polyamide 5X, and the polyamide 5X includes: with 1,5- pentanediamine and binary
Acid is the polyamide that monomer polymerization obtains；Wherein, the binary acid includes dicarboxylic acids；The dicarboxylic acids include: succinic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, eleven carbon diacids, dodecanedicarboxylic acid, 13 carbon two
First acid, tetradecane diacid, pentadecane binary acid, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, maleic acid
With one of Δ 9-1,18 octadecylene binary acid or a variety of.
Preferably, the polyamide 5X resin includes: 54 resin of polyamide, 55 resin of polyamide, 56 resin of polyamide, gathers
57 resin of amide, 58 resin of polyamide, 59 resin of polyamide, 510 resin of polyamide, 511 resin of polyamide, 512 tree of polyamide
Rouge, 512 resin of polyamide, 513 resin of polyamide, 514 resin of polyamide, 515 resin of polyamide, 516 resin of polyamide, polyamides
One of 518 resin of 517 resin of amine and polyamide is a variety of.
The relative viscosity of the polyamide is 2.4-3.2.
The polymerized monomer of the polyamide can be prepared by biological raw material by bioanalysis, raw material biological source
Ratio is 35-100%.
[glass fibre]
Glass fibre can be alkali-free glass fibre, and fibre diameter is preferably 6-15 μm.
[antistatic agent]
Antistatic agent is selected in anionic antistatic agent, non-ionic antistatic agent or macromolecular structure antistatic agent
It is one or more kinds of, wherein
Anionic antistatic agent can be one of Sodium Allyl Sulfonate, 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), polyethylene glycol 400 phosphate, laruyl alcohol
One of ether phosphate；
Macromolecular structure antistatic agent can be polyethylene glycol-lithium colloidal sol compound.
[expanding material]
The expanding material that the raw materials for production of polyamide compoiste material of the invention can also be 1-10 parts comprising parts by weight.
Methyl Methacrylate-Butadiene-Styrene Copolymer, methyl methacrylate-acrylic acid may be selected in expanding material
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 are grafted ethylene propylene diene rubber, Malaysia
Anhydride grafted ethylene-vinyl acetate, maleic anhydride grafting hydrogenated butadiene-styrene block copolymer, maleic anhydride grafting
One of ethylene-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene terpolymer are a kind of
More than.
[processing aid]
The processing aid that the raw materials for production of polyamide compoiste material of the invention can also be 1-5 parts comprising parts by weight.
The processing aid can select as needed one of lubricant, nucleating agent, antioxidant or more than one, wherein
The lubricant can be selected from N, N'- ethylene bis stearamide, oxidized polyethylene wax, ethylene vinyl acetate wax, soap
Change polyethylene wax, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate, zinc stearate, tristearin
One of sour sodium, barium stearate, the macromolecule organic silicon and more than one.
Saponified polyvinyl wax described in the preferred embodiment of the present invention is partly-hydrolysed polyethylene wax, and the macromolecule is organic
The preferred silicone powder of silicon.
The nucleating agent can be selected from P22, montanic acid calcium, montanic acid sodium, polyacrylic acid ionomer, organo montmorillonite, surpass
One of fine and smooth mountain flour, ultra-fine mica, aluminium oxide, magnesia and more than one.The antioxidant includes N, and N- is bis--(3- (3,
5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, the positive octadecanol of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Ester, three [2.4- di-tert-butyl-phenyl] phosphite esters, bis- (2,4- di-tert-butyl-phenyl) propionic acid] pentaerythritol diphosphites,
The inclined fourth support of 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenol), 4,4--bis--(6- tert-butyl-m-cresol), (the 2- first of 1,1,3- tri-
Base -4- hydroxyl -5- tert-butyl-phenyl) butane, in 1,3,5- trimethyl -2,4,6- three (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene
One kind and more than one.
It may further be enriched with machine pigment or inorganic pigment in processing aid of the invention according to actual needs.
<preparation method of polyamide compoiste material>
A kind of preparation method of above-mentioned polyamide compoiste material, includes the following steps:
(1) by polyamide and antistatic agent, parts by weight, are uniformly mixed, obtain mixture A as described above；
(2) it by mixture A and glass fibre described in step (1), is uniformly mixed in screw machine and is squeezed by screw machine
It is granulated out to get the polyamide compoiste material.
When the polyamide compoiste material further includes expanding material, the expanding material is added in step (1).
When the polyamide compoiste material further includes other processing aids, other described processing aids are in step (1)
It is added.
Mixing step in step (1) is carried out in mixing machine.The preferred 300-500rpm of the revolving speed of the mixing machine.Institute
State the time preferred 2-5min of mixing.Preferred 20-40 DEG C of the mixed temperature.
In step (2), the screw extruder is preferably double screw extruder.
In step (2), the screw extruder preferably divides 7th area to heat.Wherein, a Qu Wendu 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, and more preferably 275-285 DEG C.And/or the Screw Extrusion
Six area's temperature of Ji is preferably 270-290 DEG C, and 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 preferable 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.
[test method]
Polyamide compoiste material made from above-mentioned preparation method is molded into test bars, injection molding temperature at 80 DEG C after dry 6h
Degree is 260~275 DEG C.
The dependence test of product is referring to such as the following table 1.
Table 1
Embodiment 1:
Polyamide compoiste material, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 150g
Expanding material (MBS): 100g
Processing aid combination (wherein includes EBS, calcium stearate, silicone powder, montanic acid calcium, talcum powder, antioxidant 1098
Deng): 50g；
Sample preparation and testing procedure:
(1) it by biological poly amide PA56, antistatic agent, expanding material, processing aid, is weighed by formula, then in high speed
It is mixed in mixing machine；Mixing temperature is 25 DEG C, and high-speed mixer revolving speed is 400rpm, and incorporation time 3min must be mixed
Object A；
(2) mixture A is placed in the main spout of double screw extruder, and alkali-free glass fibre is placed in twin-screw extrusion
In the side spout of machine；Extruding pelletization；The draw ratio of double screw extruder is 1:40, and each area's temperature of extruder is (from feeding to mould
Mouthful) setting is 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 amide of preparation is sliced in 80 DEG C of dry 8h, is then molded, injection molding machine temperature
Setting is followed successively by 250 DEG C, 275 DEG C, 275 DEG C, 280 DEG C from feeding container to nozzle, and nozzle temperature is 275 DEG C.
Batten test:
The test bars of injection molding are placed into 28h at 23 DEG C, are tested by iso standard.Test result is referring to table 2.
Embodiment 2:
Polyamide compoiste material, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 150g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 150g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 100g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 50g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 75g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 75g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 50g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 100g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 100g
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 50g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 75g
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 75g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (Sodium Allyl Sulfonate): 50
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 100g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 100g
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 50g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 75g
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 75g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 2950g
Alkali-free glass fibre: 1750g
Antistatic agent (fatty acid distribution of coconut oil diacetayl amide): 50g
Antistatic agent (polyethylene glycol-lithium colloidal sol compound): 100g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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, each ingredient including following weight:
Biological poly amide (PA56, relative sulfuric acid viscosity 2.72): 3100g
Alkali-free glass fibre: 1750g
Expanding material (MBS): 100g
Processing aid combination (wherein includes 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 compares
By the test result of table 2 it follows that antistatic agent, especially specific compounding antistatic agent can be obvious
Reduce the surface resistivity of glass fibre reinforced composion.Also, Sodium Allyl Sulfonate, fatty acid distribution of coconut oil diacetayl amide and poly-
Two kinds of compounding two-by-two in ethylene glycol-lithium colloidal sol compound, can be substantially reduced the surface of glass fibre reinforced composion
Resistivity.For single antistatic agent, ionic anti-static agent is slightly better than the using effect of non-ionic antistatic agent.Two kinds
Antistatic agent is used in compounding, dosage under the same conditions, using effect antistatic agent effect more same than single use is good.
Antistatic agent not only has the effect of reducing composite material surface resistivity, but also can also play in process
The effect of lubricant, in terms of mechanical experimental results, after adding antistatic agent, the intensity and modulus of composite material is not obvious
Variation, illustrates that being properly added antistatic agent does not influence the mechanical property of composite material.
This hair can be understood and used the above description of the embodiments is intended to facilitate 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 embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments,
Those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in this hairs
Within bright protection scope.
Claims (23)
1. a kind of polyamide compoiste material comprising each ingredient of following parts by weight:
45 parts of polyamide,
15-50 parts of glass fibre,
And antistatic agent, the weight ratio of the antistatic agent and polyamide are 1:19.67；
The antistatic agent is Sodium Allyl Sulfonate and polyethylene glycol-lithium colloidal sol compound compounding antistatic agent, wherein described
Sodium Allyl Sulfonate and polyethylene glycol-lithium colloidal sol compound mass ratio are any proportion in 1:1,1:2 and 2:1；
The polyamide includes polyamide 5X resin, and it is single that the polyamide 5X, which includes: with 1,5- pentanediamine and binary acid,
The polyamide that body polymerize；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, eleven carbon diacids, dodecanedicarboxylic acid, tridecanyldicarboxylic acid,
Tetradecane diacid, pentadecane binary acid, 16-dicarboxylic acid, seventeen carbon diacids, octadecane diacid, maleic acid and Δ 9-
One of 1,18 octadecylene binary acid are a variety of.
2. polyamide compoiste material as described in claim 1, it is characterised in that:
The polyamide 5X resin include: 54 resin of polyamide, 55 resin of polyamide, 56 resin of polyamide, 57 resin of polyamide,
58 resin of polyamide, 59 resin of polyamide, 510 resin of polyamide, 511 resin of polyamide, 512 resin of polyamide, polyamide 513
Resin, 514 resin of polyamide, 515 resin of polyamide, in 518 resin of 516 resin of polyamide, 517 resin of polyamide and polyamide
It is one or more.
3. polyamide compoiste material as claimed in claim 2, it is characterised in that:
The polyamide is biological based polyamide resin.
4. polyamide compoiste material as claimed in claim 3, it is characterised in that:
The polymerized monomer of the biological poly amide resin is by obtained by biofermentation method.
5. polyamide compoiste material as described in claim 1, it is characterised in that:
The glass fibre is alkali-free glass fibre.
6. polyamide compoiste material as described in claim 1, it is characterised in that:
The antistatic agent is compounding antistatic agent.
7. polyamide compoiste material as described in claim 1, it is characterised in that: the polyamide compoiste material further includes increase-volume
Agent.
8. polyamide compoiste material as claimed in claim 7, it is characterised in that:
The expanding material includes: Methyl Methacrylate-Butadiene-Styrene Copolymer, methyl methacrylate-acrylic acid second
Ester, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate copolymer, random ethylene-methyl acrylate-horse
Come acid anhydride copolymer, Ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene,
Maleic anhydride inoculated polypropylene, maleic anhydride stem grafting polyolefin elastomer, maleic anhydride are grafted ethylene propylene diene rubber, maleic anhydride
Grafted ethene-vinyl acetate, maleic anhydride are grafted hydrogenated butadiene-styrene block copolymer, maleic anhydride grafted ethene-
One of butadiene-styrene copolymer or more than one.
9. polyamide compoiste material as described in claim 1, it is characterised in that:
The polyamide compoiste material further includes other processing aids；Other described processing aids include lubricant, nucleating agent, resist
One of oxygen agent or more than one.
10. polyamide compoiste material as claimed in claim 9, it is characterised in that:
The lubricant includes: N, and N'- ethylene bis stearamide, oxidized polyethylene wax, ethylene vinyl acetate wax, saponification are poly-
Ethylene waxes, oleamide, erucyl amide, pentaerythritol stearate, montanate, calcium stearate, zinc stearate, stearic acid
One of sodium, barium stearate and the macromolecule organic silicon or more than one.
11. polyamide compoiste material as claimed in claim 10, it is characterised in that:
The saponified polyvinyl wax is partly-hydrolysed polyethylene wax；The macromolecule organic silicon is silicone powder.
12. polyamide compoiste material as claimed in claim 9, it is characterised in that:
The nucleating agent includes: Brueggemann P22, montanic acid calcium, montanic acid sodium, polyacrylic acid ionomer, organo montmorillonite, surpasses
One of fine and smooth mountain flour, ultra-fine mica, aluminium oxide and magnesia or more than one.
13. polyamide compoiste material as claimed in claim 9, it is characterised in that:
The antioxidant includes: N, and N- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2,4- di-tert-butyl-phenyl] phosphite esters, bis- (tertiary fourths of 2,4- bis-
Base phenyl) propionic acid] pentaerythritol diphosphites, 2,2- methylene-bis- (4- ethyl -6- tert-butyl phenol), the inclined fourth support-of 4,4-
Double-(6- tert-butyl-m-cresol), (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane of 1,1,3- tri- and trimethyl -2 1,3,5-,
One of 4,6- tri- (- 4 hydroxybenzyl of 3,5- di-t-butyl) benzene or more than one.
14. polyamide compoiste material as claimed in claim 9, it is characterised in that:
Organic pigment or inorganic pigment are also added in the processing aid.
15. a kind of preparation method of polyamide compoiste material, ingredient such as claim included by the polyamide compoiste material
Described in any one of 1-14, the preparation method includes the following steps:
(1) polyamide and antistatic agent are uniformly mixed, obtain mixture A；
(2) it by mixture A and glass fibre described in step (1), is uniformly mixed in screw extruder and passes through Screw Extrusion
Machine extruding pelletization is to get the polyamide compoiste material；
When the polyamide compoiste material further includes expanding material, the expanding material is added in step (1)；
When the polyamide compoiste material further includes other processing aids, other described processing aids are added in step (1).
16. preparation method as claimed in claim 15, it is characterised in that: in step (1), the mixing step is in mixing machine
It carries out；The revolving speed of the mixing machine is 300-500rpm；The mixed time is 2-5min；The mixed temperature is 20-
40℃。
17. preparation method as claimed in claim 15, it is characterised in that: in step (2), the screw extruder is twin-screw
Extruder.
18. preparation method as claimed in claim 17, it is characterised in that:
In step (2), the heating of 7th area of the screw extruder point；Wherein, area's temperature of the screw extruder is 70-90
℃；And/or two area's temperature of the screw extruder are 210-230 DEG C；And/or three area's temperature of the screw extruder are
240-260℃；And/or four area's temperature of the screw extruder are 260-280 DEG C；And/or the five of the screw extruder
Area's temperature is 270-290 DEG C；And/or six area's temperature of the screw extruder are 270-290 DEG C；And/or the screw rod squeezes
Seven area's temperature of Ji is 265-285 DEG C out；And/or
In step (2), the die temperature of the double screw extruder is 265-275 DEG C；And/or
In step (2), the screw speed of the double screw extruder is 200-500rpm.
19. preparation method as claimed in claim 18, it is characterised in that:
One area's temperature of the screw extruder is 75-85 DEG C；And/or two area's temperature of the screw extruder are 215-225
℃；And/or three area's temperature of the screw extruder are 245-255 DEG C；And/or four area's temperature of the screw extruder are
265-275℃；And/or five area's temperature of the screw extruder are 275-285 DEG C；And/or the six of the screw extruder
Area's temperature is 275-285 DEG C；And/or seven area's temperature of the screw extruder are 270-280 DEG C.
20. preparation method as claimed in claim 17, it is characterised in that: in step (2), the screw rod of the double screw extruder
Draw ratio is 1:(30-50).
21. preparation method as claimed in claim 20, it is characterised in that:
The screw slenderness ratio of the double screw extruder is 1:(35-45).
22. preparation method as claimed in claim 15, it is characterised in that:
After the extruding pelletization, then it is dried；
The drying time is 5-7h；
The drying temperature is 70-90 DEG C.
23. preparation method as claimed in claim 22, it is characterised in that:
The drying time is 5.5-6.5h；The drying temperature is 75-85 DEG C.
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| CN109957239B (en) * | 2017-12-14 | 2021-10-15 | 凯赛(乌苏)生物材料有限公司 | Thermoplastic reinforced bio-based PA56/PA66 alloy and preparation method thereof |
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| CN111592755B (en) * | 2019-02-21 | 2022-07-19 | 上海凯赛生物技术股份有限公司 | Enhanced bio-based polyamide 56 composition and preparation method thereof |
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| CN111117220A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide composition with permanent static dissipation function and application thereof |
| CN111117231A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Halogen-free polyamide 56 composition capable of resisting long-term aging of hot air and application thereof |
| CN111117229A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Odor-improved polyamide composition with permanent static dissipation function and application thereof |
| 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 |
| CN112011112A (en) * | 2020-09-10 | 2020-12-01 | 安徽源洲包装材料有限公司 | Easy-adhesion and easy-tearing plastic film and preparation method thereof |
| CN114790330B (en) * | 2021-01-25 | 2023-12-08 | 上海凯赛生物技术股份有限公司 | Flame-retardant polyamide glass fiber composition and preparation method thereof |
| CN115260753B (en) * | 2021-04-30 | 2024-02-09 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
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Effective date of registration: 20210519 Address after: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 5 No. 1690 Patentee after: CATHAY R&D CENTER Co.,Ltd. Patentee after: CIBT USA Patentee after: Kaisai (Taiyuan) biomaterials Co.,Ltd. Address before: 201203 Building 5, 1690 Cailun Road, Zhangjiang hi tech park, Shanghai Patentee before: CATHAY R&D CENTER Co.,Ltd. Patentee before: CIBT USA |