CN105273402B - A kind of preparation of high rigidity fire-retardant nylon timbering material and application - Google Patents
A kind of preparation of high rigidity fire-retardant nylon timbering material and application Download PDFInfo
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- CN105273402B CN105273402B CN201510833134.6A CN201510833134A CN105273402B CN 105273402 B CN105273402 B CN 105273402B CN 201510833134 A CN201510833134 A CN 201510833134A CN 105273402 B CN105273402 B CN 105273402B
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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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/24—Crystallisation aids
Abstract
The present invention relates to a kind of preparation of high rigidity fire-retardant nylon timbering material and applications.Specifically, the composition contains nylon, coupling agent, chemical capping agents, nucleating agent and packing material the present invention relates to a kind of composition.The invention further relates to a kind of nylon materials, are made of the present composition.
Description
Technical field
The present invention relates to a kind of preparation of high rigidity fire-retardant nylon timbering material and applications.
Background technique
With the continuous development of the industries such as automobile, machinery, electric appliance, new requirement is also constantly proposed to the use of material,
Best quality, lightweight, energy conservation and environmental protection become new trend, and a large amount of metal material is replaced engineering plastics.Nylon conduct
Representative therein accounts for critically important status.
Nylon is a kind of widely used engineering plastics, is formed by diamines, diacid polycondensation, 220-320 DEG C of fusing point, nylon
Resinous molecular structure is as follows:
Compared with Other Engineering plastics, nylon has excellent mechanical performance and preferable hot property, such as high-intensitive, Gao Mo
Amount, high rigidity；Relatively high heat distortion temperature, after glass fiber reinforcement is added, heat distortion temperature can be from 180-270 DEG C
(1.8MPa)；In addition, nylon also shows excellent self-lubricating abrasion-resistant, antifatigue, creep resistant；And good oil resistant and
Solvent borne.
But nylon has free amino N H in the end of each strand2And carboxy CO O-, these active groups
Group makes nylon have very strong polarity, and active group is combined water with water molecules formation with hydrogen bond, shows nylon than other
The stronger water imbibition of high molecular material, dimensional stability is poor when leading to its injection molding, and performance declines under high humidity environment
Obviously.
Nylon comprehensive performance can be greatly improved by material modification technology, improves deficiency, as glass fibre filling becomes one
A very common modified nylon method.Many producers are producing modification of nylon using this method at present, according to different demands point
For different grades, such as high rigidity, uvioresistant, wear-resisting, ultra-toughness.But without based on fiberglass reinforced, water resistant is had both
High temperature resistant function is solved, the low buckling deformation, dimensional stability, good flame resistance that have that commonly enhancing nylon is short of especially also are needed
Feature, while industry is not also found at present plus the mouth of a river of fiber material recycles processing method.
Summary of the invention
First aspect present invention provides a kind of composition, and the composition contains nylon, coupling agent, chemical capping agents, nucleation
Agent and packing material.
In a specific embodiment, the composition also contains anti-hydrolysis agent, fire retardant, fire retarding synergist, lubricant
With any one or more in antioxidant.
In a specific embodiment, by weight, the composition contains:
40~60 parts of nylon,
0.2~0.5 part of coupling agent,
0.5~3 part of chemical capping agents,
0.2~0.5 part of nucleating agent, and
18~35 parts of packing material.
In a specific embodiment, when containing sometimes, anti-hydrolysis agent, fire retardant described in composition, fire retarding synergist, lubrication
The parts by weight of agent and antioxidant are respectively as follows:
0.2~0.5 part of anti-hydrolysis agent,
10~20 parts of fire retardant,
2~5 parts of fire retarding synergist,
0.2~0.5 part of lubricant, and
0.2~0.5 part of antioxidant.
In a specific embodiment, the composition contains:
40~60 parts of nylon,
0.2~0.5 part of coupling agent,
0.5~3 part of chemical capping agents,
0.2~0.5 part of nucleating agent,
18~35 parts of packing material,
0.2~0.5 part of anti-hydrolysis agent,
10~20 parts of fire retardant,
2~5 parts of fire retarding synergist,
0.2~0.5 part of lubricant, and
0.2~0.5 part of antioxidant.
In a specific embodiment, the nylon is nylon 6T/66, nylon 6T/6, nylon 6T/1010, nylon 6T/
1212, nylon 6T/612, nylon 6I/66, nylon 6I/6, nylon 6I/1010, nylon 6I/1212, and/or nylon 6I/612.
In a specific embodiment, the coupling agent is that gamma-aminopropyl-triethoxy-silane (KH550), γ-shrink are sweet
One of oily ether oxygen propyl trimethoxy silicane (KH560).
In a specific embodiment, the nucleating agent is in long-chain carboxylic acid's calcium salt, talcum powder or nano silica
A kind of or any a variety of mixture.
In a specific embodiment, the chemical capping agents are selected from monopentaerythritol, dipentaerythritol, three Ji Wusi
Alcohol, more pentaerythrites and its derivative.
In a specific embodiment, the anti-hydrolysis agent be copper compound class antioxidant and synergist mixture or
Person is polycarbodiimide.
In a specific embodiment, the fire retardant is brominated polystyrene, brominated Polystyrene, decabrominated dipheny second
Alkane, brominated triazine, aluminium hydroxide, magnesium hydroxide, red phosphorus, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, tolyl two
One of phenyl phosphate ester, melamine polyphosphate, melamine cyanurate or any several mixture.
In a specific embodiment, the fire retarding synergist is antimony oxide, antimony pentoxide, zinc borate, oxidation
One of zinc, iron oxide or sodium antimonate or any a variety of mixture.
In a specific embodiment, the lubricant is that second two supports one of double stearic amide, dimethicones
Or two kinds.
In a specific embodiment, the antioxidant is selected from: the double -3- (3- tertiary butyl-4-hydroxy -5- methyl of triethylene glycol
Phenyl) acrylonitrile, three (2,4- di-tert-butylphenol) phosphite esters, 2,6- di-t-butyl -4- sylvan (antioxidant 264), N, N'-
Double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), bis- (2,4- DI-tert-butylphenol compounds)
One or more of pentaerythritol diphosphites (antioxidant 626).
In a specific embodiment, the packing material is glass fibre, wollastonite, carbon fiber, calcium carbonate, talcum powder
One or more of.
Second aspect of the present invention provides a kind of nylon material, is prepared from the following components: nylon, coupling agent, chemistry envelope
Appointing in end agent, nucleating agent and packing material and optional anti-hydrolysis agent, fire retardant, fire retarding synergist, lubricant and antioxidant
It anticipates one or more.
In a specific embodiment, the nylon material is by following components by preparing by weight:
40~60 parts of nylon,
0.2~0.5 part of coupling agent,
0.5~3 part of chemical capping agents,
0.2~0.5 part of nucleating agent,
18~35 parts of packing material；With
0.2~0.5 part of optional anti-hydrolysis agent,
10~20 parts of optional fire retardant,
2~5 parts of optional fire retarding synergist,
0.2~0.5 part of optional lubricant, and
0.2~0.5 part of optional antioxidant.
In a specific embodiment, the nylon material is by following components by preparing by weight:
40~60 parts of nylon,
0.2~0.5 part of coupling agent,
0.5~3 part of chemical capping agents,
0.2~0.5 part of nucleating agent,
18~35 parts of packing material,
0.2~0.5 part of anti-hydrolysis agent,
10~20 parts of fire retardant,
2~5 parts of fire retarding synergist,
0.2~0.5 part of lubricant, and
0.2~0.5 part of antioxidant.
In a specific embodiment, the nylon is nylon 6T/66, nylon 6T/6, nylon 6T/1010, nylon 6T/
1212, nylon 6T/612, nylon 6I/66, nylon 6I/6, nylon 6I/1010, nylon 6I/1212, and/or nylon 6I/612.
In a specific embodiment, the coupling agent is that gamma-aminopropyl-triethoxy-silane (KH550), γ-shrink are sweet
One of oily ether oxygen propyl trimethoxy silicane (KH560).
In a specific embodiment, the nucleating agent is in long-chain carboxylic acid's calcium salt, talcum powder or nano silica
A kind of or any a variety of mixture.
In a specific embodiment, the chemical capping agents are selected from monopentaerythritol, dipentaerythritol, three Ji Wusi
Alcohol, more pentaerythrites and its derivative.
In a specific embodiment, the anti-hydrolysis agent be copper compound class antioxidant and synergist mixture or
Person is polycarbodiimide.
In a specific embodiment, the fire retardant is brominated polystyrene, brominated Polystyrene, decabrominated dipheny second
Alkane, brominated triazine, aluminium hydroxide, magnesium hydroxide, red phosphorus, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, tolyl two
One of phenyl phosphate ester, melamine polyphosphate, melamine cyanurate or any several mixture.
In a specific embodiment, the fire retarding synergist is antimony oxide, antimony pentoxide, zinc borate, oxidation
One of zinc, iron oxide or sodium antimonate or any a variety of mixture.
In a specific embodiment, the lubricant is that second two supports one of double stearic amide, dimethicones
Or two kinds.
In a specific embodiment, the antioxidant is selected from: the double -3- (3- tertiary butyl-4-hydroxy -5- methyl of triethylene glycol
Phenyl) acrylonitrile, three (2,4- di-tert-butylphenol) phosphite esters, 2,6- di-t-butyl -4- sylvan (antioxidant 264), N, N'-
Double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), bis- (2,4- DI-tert-butylphenol compounds)
One or more of pentaerythritol diphosphites (antioxidant 626).
In a specific embodiment, the packing material is glass fibre, wollastonite, carbon fiber, calcium carbonate, talcum powder
One or more of.
Third aspect present invention is related to a kind of modified nylon method, and the method includes using to be selected from monopentaerythritol, double
Pentaerythrite, tripentaerythritol, more pentaerythrites and its derivative chemical capping agents handle nylon.
In a specific embodiment, the nylon of every 40~60 parts by weight uses at the chemical capping agents of 0.5~3 parts by weight
Reason.
In a specific embodiment, the modified nylon method, the especially method of the water absorption rate of reduction nylon, packet
It includes, by nylon, coupling agent, chemical capping agents, nucleating agent and packing material and optional anti-hydrolysis agent, fire retardant, fire-retardant synergistic
Any one or more mixing in agent, lubricant and antioxidant squeezes out.
In a specific embodiment, by weight, use is arrived in the method:
40~60 parts of nylon,
0.2~0.5 part of coupling agent,
0.5~3 part of chemical capping agents,
0.2~0.5 part of nucleating agent,
18~35 parts of packing material；With
0.2~0.5 part of optional anti-hydrolysis agent,
10~20 parts of optional fire retardant,
2~5 parts of optional fire retarding synergist,
0.2~0.5 part of optional lubricant, and
0.2~0.5 part of optional antioxidant.
In a specific embodiment, the nylon is nylon 6T/66, nylon 6T/6, nylon 6T/1010, nylon 6T/
1212, nylon 6T/612, nylon 6I/66, nylon 6I/6, nylon 6I/1010, nylon 6I/1212, and/or nylon 6I/612.
In a specific embodiment, the coupling agent is that gamma-aminopropyl-triethoxy-silane (KH550), γ-shrink are sweet
One of oily ether oxygen propyl trimethoxy silicane (KH560).
In a specific embodiment, the nucleating agent is in long-chain carboxylic acid's calcium salt, talcum powder or nano silica
A kind of or any a variety of mixture.
In a specific embodiment, the anti-hydrolysis agent be copper compound class antioxidant and synergist mixture or
Person is polycarbodiimide.
In a specific embodiment, the fire retardant is brominated polystyrene, brominated Polystyrene, decabrominated dipheny second
Alkane, brominated triazine, aluminium hydroxide, magnesium hydroxide, red phosphorus, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, tolyl two
One of phenyl phosphate ester, melamine polyphosphate, melamine cyanurate or any several mixture.
In a specific embodiment, the fire retarding synergist is antimony oxide, antimony pentoxide, zinc borate, oxidation
One of zinc, iron oxide or sodium antimonate or any a variety of mixture.
In a specific embodiment, the lubricant is that second two supports one of double stearic amide, dimethicones
Or two kinds.
In a specific embodiment, the antioxidant is selected from: the double -3- (3- tertiary butyl-4-hydroxy -5- methyl of triethylene glycol
Phenyl) acrylonitrile, three (2,4- di-tert-butylphenol) phosphite esters, 2,6- di-t-butyl -4- sylvan (antioxidant 264), N,
N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098), bis- (2,4- di-tert-butyls
One or more of phenol) pentaerythritol diphosphites (antioxidant 626).
In a specific embodiment, the packing material is glass fibre, wollastonite, carbon fiber, calcium carbonate, talcum powder
One or more of.
Fourth aspect present invention provides a kind of mounting bracket of socket, the bracket using composition of the present invention or
Nylon material prepares.
Fifth aspect present invention provide selected from monopentaerythritol, dipentaerythritol, tripentaerythritol, more pentaerythrites and its
Application of the chemical capping agents of derivative in modified nylon, or preparation have reduced water absorption rate and optional high intensity,
High tenacity, high rigidity, low warpage, high-low temperature resistant, ageing-resistant, UV radiation aging, fire-retardant, appointing in chemical property stabilization
A kind of application in the nylon material of characteristic.
Specific embodiment
It is an object of the invention to modification of nylon.The present inventor in pentaerythrite and its derivative molecular the study found that have
Multiple activity hydroxies allow activity hydroxy in conjunction with the amino of nylon molecules last-in-chain(LIC) end dissociative, form chemistry sealing end, can make nylon material
The water absorption rate of material declines to a great extent, and obtains revolutionary change, thus completes the present invention.
Therefore, by the present invention in that being modified with pentaerythrite and/or its derivative to existing nylon, had
There are excellent high intensity, high tenacity, high rigidity, low warpage, high-low temperature resistant, ageing-resistant, UV radiation aging, fire-retardant, change
Learn the nylon material of the characteristics such as property stabilization；In addition to this, nylon material of the invention is light-weight, mechanical performance and processing performance
It is excellent, based on fiberglass reinforced, the resistance to temperature function of resistant to hydrolysis is had both, has especially been also equipped with the low warpage that common enhancing nylon is short of
The characteristics of deformation, dimensional stability, good flame resistance, it is instead of metalwork and originally normal to meet specific products switch on wall timbering material
Rule add the unrenewable requirement in the fiber material mouth of a river using PC.Therefore, " modification " as described herein includes but is not limited to intensity, water suction
The characteristics such as rate, toughness, rigidity, warpage, high-low temperature resistant, ageing-resistant, UV radiation aging, fire-retardant, chemical property stabilization
Change, further includes the change of the performances such as mechanical performance, processing performance, resistant to hydrolysis heat resistance.
It should be understood that the degree of "high", " low " used in the present invention etc. is well known in the art.For example, for " high-strength
For degree ", those skilled in the art combine existing material, can judge that the intensity of certain material is high-intensitive or low-intensity.
Pentaerythrite and/or its derivative are used as chemical capping agents to use in the present invention.In other words, chemistry of the invention
End-capping reagent includes monopentaerythritol, dipentaerythritol, tripentaerythritol, more pentaerythrites and its derivative.As an example,
Dipentaerythritol (also known as: the structural formula of 2,2- oxygen dimethylene-bis- (2- methylol -1,3- propylene glycol) is shown below:
Therefore, the present invention provides a kind of composition, and the composition contains nylon and chemical capping agents of the invention.The combination
Object can be used to prepare nylon material, such as be mounted on the bracket etc. of the socket of wall.In addition to chemical capping agents, the composition is also
Coupling agent, nucleating agent and packing material can be contained.Further, anti-hydrolysis agent, fire retardant, fire-retardant association can be also contained in composition
Imitate one of agent, lubricant and antioxidant or any a variety of.
Nylon can be various nylon products well known in the art, including but not limited to nylon 6T/66, nylon 6T/6, Buddhist nun
Imperial 6T/1010, nylon 6T/1212, nylon 6T/612, nylon 6I/66, nylon 6I/6, nylon 6I/1010, nylon 6I/1212,
And/or nylon 6I/612.
In the present composition, in parts by weight, the parts by weight of nylon are usually 40~60 parts.
Be suitable for the invention coupling agent can be it is known in the art for nylon material preparation coupling agent, including but
It is not limited to gamma-aminopropyl-triethoxy-silane (KH550), in γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560)
It is a kind of.
Relative to the parts by weight of nylon, the dosage of coupling agent is usually 0.2~0.5 parts by weight.
Being suitable for the invention nucleating agent can be the various nucleating agents of the preparation known in the art for nylon material,
Including but not limited to one of long-chain carboxylic acid's calcium salt, talcum powder or nano silica or any a variety of mixture.It can make
With long-chain carboxylic acid's calcium salt, talcum powder or nano silica known in the art.For example, long-chain carboxylic acid's calcium salt can be
CAV102；Talcum powder can be the talcum powder of 6000~12000 mesh.
Relative to the parts by weight of nylon, the dosage of nucleating agent is usually 0.2~0.5 parts by weight.
Be suitable for the invention chemical capping agents include but is not limited to monopentaerythritol, dipentaerythritol, tripentaerythritol,
More pentaerythrites and its derivative.Relative to the parts by weight of nylon, dosage is usually 0.5~3 parts by weight.
Being suitable for the invention packing material can be the various fillings of the preparation known in the art for nylon material
One or more of material, including but not limited to glass fibre, wollastonite, carbon fiber, calcium carbonate, talcum powder.These fillings
Material can be all commercially available from commercially available approach.For example, in a specific embodiment, using the model from megalith group
The glass fibre of ER14-2000-988A.
Relative to the parts by weight of nylon, the dosage of packing material is usually 18~35 parts by weight, preferably 20~30 parts by weight.
Being suitable for the invention anti-hydrolysis agent can be the various anti-of the preparation that can be used for nylon material well known in the art
Hydrolytic reagent, the including but not limited to antioxidant of copper compound class and the mixture of synergist are polycarbodiimide.
When in use, parts by weight relative to nylon, the dosage of anti-hydrolysis agent is usually 0.2~0.5 parts by weight.
Being suitable for the invention fire retardant can be the various fire retardants that can be used for nylon material preparation well known in the art,
Including but not limited to brominated polystyrene, brominated Polystyrene, decabromodiphenylethane, brominated triazine, aluminium hydroxide, hydroxide
Magnesium, red phosphorus, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, melamine polyphosphate,
One of melamine cyanurate or any several mixture.
When in use, parts by weight relative to nylon, the dosage of fire retardant is usually 10~20 parts by weight.
Being suitable for the invention fire retarding synergist can be the various resistances that can be used for nylon material preparation well known in the art
Fire synergist, including but not limited to one in antimony oxide, antimony pentoxide, zinc borate, zinc oxide, iron oxide or sodium antimonate
Kind or any a variety of mixture.
When in use, parts by weight relative to nylon, the dosage of fire retarding synergist is usually 2~5 parts by weight.
Being suitable for the invention lubricant can be the various lubricants for nylon material preparation well known in the art, packet
It includes but is not limited to second two and support one or both of double stearic amide, dimethicones.
When in use, parts by weight relative to nylon, the dosage of lubricant is usually 0.2~0.5 parts by weight.
Being suitable for the invention antioxidant can be the various antioxidant for nylon material preparation well known in the art, packet
It includes but is not limited to double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) acrylonitrile of triethylene glycol, three (2,4- di-tert-butylphenols) Asia
Phosphate, 2,6- di-t-butyl -4- sylvan (antioxidant 264), N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl)
Propiono) hexamethylene diamine (antioxidant 1098), in bis- (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites (antioxidant 626)
One or more.
When in use, parts by weight relative to nylon, the dosage of antioxidant is usually 0.2~0.5 parts by weight.
In composition of the invention, each ingredient can independent packaging, can also be hybrid packed by its nature.When hybrid packed,
Mixed component would not react between each other.
Another aspect of the present invention provides a kind of nylon material, which is made of composition of the invention.Specifically, this
The nylon material of invention is prepared from the following components: nylon, coupling agent, chemical capping agents, nucleating agent and packing material, and is appointed
Any one or more in the anti-hydrolysis agent of choosing, fire retardant, fire retarding synergist, lubricant and antioxidant.
Third aspect present invention is related to a kind of modified nylon method, and the method includes using to be selected from monopentaerythritol, double
Pentaerythrite, tripentaerythritol, more pentaerythrites and its derivative chemical capping agents handle nylon.
It is modified include water absorption rate, intensity, toughness, rigidity, warpage, high-low temperature resistant, ageing-resistant, UV radiation aging,
The change of any characteristic during fire-retardant and chemical property is stable, the especially reduction of water absorption rate.
In general, the nylon of every 40~60 parts by weight is handled using the chemical capping agents of 0.5~3 parts by weight.
Preferably, the modified nylon method, the especially method of the water absorption rate of reduction nylon, including combine the present invention
It is squeezed out after each component mixing of object.Specifically, the method includes by nylon, coupling agent, chemical capping agents, nucleating agent and filling out
Fill any one or more mixing in material and optional anti-hydrolysis agent, fire retardant, fire retarding synergist, lubricant and antioxidant
It squeezes out.
In a specific embodiment, by weight, use is arrived in the method:
40~60 parts of nylon,
0.2~0.5 part of coupling agent,
0.5~3 part of chemical capping agents,
0.2~0.5 part of nucleating agent,
18~35 parts of packing material；With
0.2~0.5 part of optional anti-hydrolysis agent,
10~20 parts of optional fire retardant,
2~5 parts of optional fire retarding synergist,
0.2~0.5 part of optional lubricant, and
0.2~0.5 part of optional antioxidant.
In general, first in 80~90 DEG C of dry feedstocks, drying time is unlimited, can be such as 1 in the case where needing dry
~8 hours, such as 4~8 hours.In general, the dry nylon of the above method can be used.
Then, each material is mixed by weight ratio.It can routinely technological means be mixed.For example, each material is mixed
It is mixed 4-6 minutes in agitator after conjunction, revolving speed is at 500-1200 revs/min.
Then it is melting extrusion in the double screw extruder of 1:36~48 by the feedstock transportation mixed to draw ratio, makes
Grain.The processing technology of extruding pelletization is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, four area 290-310
DEG C, 295-310 DEG C of 5th area, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed.In general, producing
In the process, packing material is added from extruder middle section.
The present invention also provides a kind of nylon bracket, and the nylon bracket uses composition of the present invention or nylon material
It prepares.
The present invention also provides be selected from monopentaerythritol, dipentaerythritol, tripentaerythritol, more pentaerythrites and its derivative
Application of the chemical capping agents in modified nylon, or preparation have reduced water absorption rate and optional high intensity, high tenacity,
High rigidity, low warpage, high-low temperature resistant, ageing-resistant, UV radiation aging, fire-retardant, in chemical property stabilization any spy
Application in the nylon material of property.
Material prepared by the present invention has excellent high intensity, low water absorption, high tenacity, high rigidity, low warpage, resistance to height
Warm, ageing-resistant, UV radiation aging, fire-retardant, chemical property such as stablize at the characteristics, and material weight is light, mechanical performance and plus
Work function admirable, alternative part metals material or high-intensitive high-cost special material, can be widely applied to building electricity
The fields such as device, Industry Control switch, aerospace, rail traffic, automobile, petrochemical industry.
The present invention meets specific products switch on wall timbering material instead of metalwork and original most of client uses plus fibre
The unrenewable requirement in the material mouth of a river is met environmental requirements while improving Business Economic Benefit.In addition, using the production of the technology
Product have the outstanding features such as exquisite, ultra-thin, beautiful, are all now to use the realization of metal steel frame construction ultra-thin in the industry, its maximum lacks
Falling into is exactly that can not reset influence product function after upper wall installation deforms, which had not only been able to satisfy the rigidity of plastic material but also had been able to satisfy
The toughness that structure needs, solves a great problem in industry.
Another aspect of the present invention, which also provides one kind, has cross-link nylon characteristic, and production operation is simple, product cost low cross-linking
Spend controllable composite material.Specifically, micro- cross-linking flame-retardant fire retardation wear-resistance nylon composite material is by following components according to parts by weight system
It is standby to form:
50~60 parts of nylon (such as nylon66 fiber),
10~20 parts of anti-wear agent,
1~2 part of crosslinking agent,
1~2 part of toughener,
15~20 parts of fire retardant,
0.2~0.5 part of lubricant,
0.2~0.5 part of antioxidant, and
0~30 part of filler.
Anti-wear agent can be PTFE micro mist；Crosslinking agent can be monopentaerythritol；Toughener can be POE graft；Resistance
Combustion agent can be BPS+ antimony oxide；Lubricant can be EBS；Antioxidant can be 626+1098；Filler can be glass
Glass fiber.
The preparation method of the low-density flame-proof abrasion-resistant nylon composite materials comprises the steps of:
1) dried flame-retardant nylon 66 raw material, anti-wear agent, crosslinking agent, processing aid and packing material are added to high mixer
In, for high-speed stirred to being uniformly mixed, PA66 raw material drying temperature is 80~90 DEG C, drying time 4~8 hours；
2) mixture mixed is delivered to the extruder that draw ratio is 1:36~48 to be granulated, extruder temperature 250
~290 DEG C, 300~500rpm of rotary speed.
The beneficial effects of the present invention are:
Cross-link nylon is in foreign applications comparative maturity, and famous is German PTS Inc., and cross-link nylon price is high, and about 100
Member/kilogram, product will pass through radiation treatment after having injected.Thus restrict the popularization of the material.Some domestic manufacturer's thermosetting properties
Material phenolic resin substitution, and thermosetting material processing high rejection rate, material cannot recycle.The present invention passes through addition asphalt mixtures modified by epoxy resin
Rouge, POE grafted maleic anhydride, the auxiliary agents such as ptfe micropowder, improve nylon66 fiber anti-flammability, wearability and high-low temperature resistant and
Chemical-resistance, down to 0.05~0.15, fire-retardant rank reaches micro- cross-linking flame-retardant fire retardation wear-resistance nylon composite material coefficient of friction of preparation
To UL94V-0,1.2~1.4g/cm of density3Left and right can be applied to Industry Control, build and build electric appliance, aerospace, track friendship
Fire-retardant, wear-resisting, the high-low temperature resistant component in the fields such as logical, automobile, new energy, such as connector, handle, sealing ring and sealing strip, biography
Lever, sliding block etc.；And equipment and material that the fields such as chemical industry, petroleum, mine are fire-retardant, wear-resisting, low temperature resistant, resistant to chemical etching,
Such as pipeline sealing jointing ring, equipment bearing set, universal driving shaft, sealing ring and sealing strip, driving block.Present invention process is succinct, raw
Produce high-efficient, pollution-free waste.Raw material keeps product uniformity more preferable by extruding pelletization after high mixed premix, fire-retardant, wear-resisting etc. each
Aspect mechanical property reaches most preferably, can meet harsher application requirement.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple case of the invention, does not represent or limit the scope of the present invention,
Protection scope of the present invention is subject to claims.
Specific embodiment and result are as follows:
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1
The formula of the nylon material of the present embodiment is as follows:
Specific preparation process is as follows:
(1) 80~90 DEG C of dry feedstock PA6T and PA6, drying time 4-8 hour；
(2) by dried nylon resin, coupling agent, chemical capping agents, nucleating agent, anti-hydrolysis agent, fire retardant, fire-retardant association
It is mixed 4-6 minutes in agitator after effect agent, lubricant and antioxidant mixing, revolving speed is at 500-1200 revs/min；
(3) melting extrusion in the double screw extruder for being 36~48 by the feedstock transportation mixed to draw ratio, is granulated,
Its processing technology is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, five area 295-
310 DEG C, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed；
(4) glass fibre is added from extruder middle section in process of production；
(5) injection molding machine is added in the resin material prepared, adjustment injection temperature is 255 DEG C of first segment, second segment 240
DEG C, 230 DEG C of third section, injection molded plaques test, as a result as shown in table 1 below.
Table 1: the high rigidity fire-retardant nylon timbering material performance table that embodiment 1 is prepared
| Project name | Unit | Standard | Detection data |
| Tensile strength intensity | MPa | ASTM D-412 | 130 |
| Elongation rate of tensile failure | % | ASTM D-412 | 3.5 |
| Bending modulus | Mpa | ASTM D-790 | 6500 |
| Density | g/cm3 | ASTM D-792 | 1.4 |
| Water absorption rate | % | 23℃,24h | 0.002 |
| Anti-flammability | - | UL941.6mm | V-0 |
| GWFI | ℃ | GB/T5169.111.6mm | 875 |
| Cantilever block interface impact strength | KJ/M2 | ASTM D25623℃ | 12 |
| Cantilever beam impact strength | KJ/M2 | ASTM D25623℃ | It is unbroken |
Embodiment 2
The formula of the nylon material of the present embodiment is as follows:
Specific preparation process is as follows:
(1) 80~90 DEG C of dry feedstock PA6T and PA66, drying time 4-8 hour；
(2) by dried nylon resin, coupling agent, chemical capping agents, nucleating agent, anti-hydrolysis agent, fire retardant, fire-retardant association
It is mixed 4-6 minutes in agitator after effect agent, lubricant and antioxidant mixing, revolving speed is at 500-1200 revs/min；
(3) melting extrusion in the double screw extruder for being 36~48 by the feedstock transportation mixed to draw ratio, is granulated,
Processing technology is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, five area 295-310
DEG C, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed；
(4) glass fibre is added from extruder middle section in process of production；
(5) injection molding machine is added in the resin material prepared, adjustment injection temperature is 265 DEG C of first segment, second segment 260
DEG C, 240 DEG C of third section, injection molded plaques test, as a result as shown in table 2 below.
Table 2: the high rigidity fire-retardant nylon timbering material performance table that embodiment 2 is prepared
| Project name | Unit | Standard | Detection data |
| Tensile strength intensity | MPa | ASTM D-412 | 150 |
| Elongation rate of tensile failure | % | ASTM D-412 | 3.5 |
| Bending modulus | Mpa | ASTM D-790 | 8500 |
| Density | g/cm3 | ASTM D-792 | 1.5 |
| Water absorption rate | % | 23℃,24h | 0.002 |
| Anti-flammability | - | UL941.6mm | V-0 |
| GWFI | ℃ | GB/T5169.111.6mm | 875 |
| Cantilever block interface impact strength | KJ/M2 | ASTM D25623℃ | 13 |
| Cantilever beam impact strength | KJ/M2 | ASTM D25623℃ | It is unbroken |
Embodiment 3
The timbering material of standard testing embodiment 1,2 and commercial product (Du Pont Zytel shown according to the form below 3 and 4
FR50NC010, LG LUPOY GN2301F PC+GF30) density, water absorption rate, heat distortion temperature, the impact of cantilever block interface it is strong
Degree.As a result as shown in Tables 3 and 4.
Table 3
The results show that nylon material of the present invention can be than existing advanced material while guaranteeing to reach anti-flammability and high rigidity
The toughness of material is more preferable, and notch shock is higher, low water absorption and low-density.
Table 4
The results show that nylon material of the present invention, in heat distortion temperature, notch shock, water absorption rate is higher than LG PC+30GF and expects,
And the mouth of a river can recycle, and reduce use cost, and the PC for being equally used for bracket adds the fiber material mouth of a river that cannot recycle completely.
Embodiment 4
The formula of the nylon material of the present embodiment is as follows:
Specific preparation process is as follows:
(1) 80~90 DEG C of dry feedstock PA6T and PA6, drying time 4-8 hour；
(2) 4- is mixed in agitator after mixing dried nylon resin, coupling agent, chemical capping agents and nucleating agent
6 minutes, revolving speed was at 500-1200 revs/min；
(3) melting extrusion in the double screw extruder for being 36~48 by the feedstock transportation mixed to draw ratio, is granulated,
Processing technology is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, five area 295-310
DEG C, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed；
(4) glass fibre is added from extruder middle section in process of production；
(5) injection molding machine is added in the resin material prepared, adjustment injection temperature is 255 DEG C of first segment, second segment 240
DEG C, 230 DEG C of third section, injection molded plaques test, as a result as shown in table 5 below.
Embodiment 5
The formula of the nylon material of the present embodiment is as follows:
Specific preparation process is as follows:
(1) 80~90 DEG C of dry feedstock PA6T and PA6, drying time 4-8 hour；
(2) 4- is mixed in agitator after mixing dried nylon resin, coupling agent, chemical capping agents and nucleating agent
6 minutes, revolving speed was at 500-1200 revs/min；
(3) melting extrusion in the double screw extruder for being 36~48 by the feedstock transportation mixed to draw ratio, is granulated,
Processing technology is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, five area 295-310
DEG C, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed；
(4) glass fibre is added from extruder middle section in process of production；
(5) injection molding machine is added in the resin material prepared, adjustment injection temperature is 255 DEG C of first segment, second segment 240
DEG C, 230 DEG C of third section, injection molded plaques test, as a result as shown in table 5 below.
Table 5
Note: 70G33L is the material that Dupont PA66 adds 30% glass material.
Comparative example 1
The formula of the nylon material of this comparative example is as follows:
Specific preparation process is as follows:
(1) 80~90 DEG C of dry feedstock PA6T and PA6, drying time 4-8 hour；
(2) it is mixed 4-6 minutes in agitator after mixing dried nylon resin, coupling agent and nucleating agent, revolving speed
At 500-1200 revs/min；
(3) melting extrusion in the double screw extruder for being 36~48 by the feedstock transportation mixed to draw ratio, is granulated,
Processing technology is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, five area 295-310
DEG C, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed；
(4) glass fibre is added from extruder middle section in process of production；
(5) injection molding machine is added in the resin material prepared, adjustment injection temperature is 255 DEG C of first segment, second segment 240
DEG C, 230 DEG C of third section, injection molded plaques test, as a result as shown in table 6 below.
Comparative example 2
The formula of the nylon material of the present embodiment is as follows:
Specific preparation process is as follows:
(1) 80~90 DEG C of dry feedstock PA6T and PA6, drying time 4-8 hour；
(2) it is mixed 4-6 minutes in agitator after mixing dried nylon resin, coupling agent and nucleating agent, revolving speed
At 500-1200 revs/min；
(3) melting extrusion in the double screw extruder for being 36~48 by the feedstock transportation mixed to draw ratio, is granulated,
Processing technology is 280-300 DEG C of an area, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, five area 295-310
DEG C, 285-300 DEG C of 6th area, 270-285 DEG C of 7th area；300~500rpm of rotary speed；
(4) glass fibre is added from extruder middle section in process of production；
(5) injection molding machine is added in the resin material prepared, adjustment injection temperature is 255 DEG C of first segment, second segment 240
DEG C, 230 DEG C of third section, injection molded plaques test, as a result as shown in table 6 below.
Table 6
Embodiment 6
By 5kg nylon66 fiber and 1kg ptfe micropowder, 100g epoxy resin, 100g POE grafted maleic anhydride,
1500g brominated polystyrene, 300g antimony oxide, 10g second two support double stearic amide, 10g antioxidant 264,5g antioxidant
1098 are added in high mixer, adjust revolving speed 1200rpm, 3min is to being mixed thoroughly for stirring.
The mixture mixed is delivered to the extruder that draw ratio is 1:40 to be granulated, control extruder temperature is first segment
250 DEG C, 265 DEG C of second segment, 265 DEG C of third section, the 4th section 265 DEG C, the 5th section 265 DEG C, the 6th section 265 DEG C, the 7th section 265
DEG C, the 8th section 265 DEG C, head temperature is 290 DEG C, rotary speed 450rpm, and drying temperature is 90 DEG C.
Injection molding machine is added in the resin material prepared, adjustment injection temperature is 275 DEG C of first segment, 260 DEG C of second segment, the
Three sections 260 DEG C, injection molded plaques test, as a result as shown in table 7 below.
Table 7: the low-density flame-proof abrasion-resistant nylon composite materials performance table that embodiment 6 prepares
| Project name | Unit | Standard | Detection data |
| Tensile strength intensity | MPa | ASTM D-412 | 80 |
| Elongation rate of tensile failure | % | ASTM D-412 | 30 |
| Bending modulus | Mpa | ASTM D-790 | 3000 |
| Density | g/cm3 | ASTM D-792 | 1.23 |
| Coefficient of friction | - | - | 0.08 |
| Anti-flammability | - | UL941.6mm | V-0 |
| GWFI | ℃ | GB/T5169.113.2mm | 875 |
| Cantilever beam impact strength | KJ/M2 | ASTM D25623℃ | It is unbroken |
| Cantilever beam impact strength | KJ/M2 | ASTM D256-40℃,24h | It is unbroken |
Embodiment 7
By 5kg nylon66 fiber and 1kg ptfe micropowder, 100g epoxy resin, 100g POE grafted maleic anhydride,
1500g brominated polystyrene, 300g antimony oxide, 1500g glass fibre, 10g second two support double stearic amides, 5g dimethyl
Silicone oil, 7.5g antioxidant 626,5g antioxidant 1098 are added in high mixer, adjust revolving speed 1200rpm, 3min is to complete for stirring
It is uniformly mixed.
The mixture mixed is delivered to the extruder that draw ratio is 1:40 to be granulated, control extruder temperature is first segment
250 DEG C, 265 DEG C of second segment, 265 DEG C of third section, the 4th section 265 DEG C, the 5th section 265 DEG C, the 6th section 265 DEG C, the 7th section 265
DEG C, the 8th section 265 DEG C, head temperature is 290 DEG C, rotary speed 450rpm, and drying temperature is 90 DEG C.
Injection molding machine is added in the resin material prepared, adjustment injection temperature is 275 DEG C of first segment, 260 DEG C of second segment, the
Three sections 260 DEG C, injection molded plaques test, as a result as shown in table 8 below.
Table 8: the low-density flame-proof abrasion-resistant nylon composite materials performance table that embodiment 7 obtains
| Project name | Unit | Standard | Detection data |
| Tensile strength intensity | MPa | ASTM D-412 | 110 |
| Elongation rate of tensile failure | % | ASTM D-412 | 4.5 |
| Bending modulus | Mpa | ASTM D-790 | 6000 |
| Density | g/cm3 | ASTM D-792 | 1.40 |
| Coefficient of friction | - | - | 0.10 |
| Anti-flammability | - | UL941.6mm | V-0 |
| GWFI | ℃ | GB/T5169.113.2mm | 875 |
| Cantilever beam impact strength | KJ/M2 | ASTM D25623℃ | 40 |
| Cantilever beam impact strength | KJ/M2 | ASTM D256-40℃,24h | 15 |
Claims (4)
1. it is a kind of reduce nylon water absorption rate method, which is characterized in that the method includes by the nylon of 40~60 parts by weight,
The coupling agent of 0.2~0.5 parts by weight, the chemical capping agents of 0.5~3 parts by weight, the nucleating agent of 0.2~0.5 parts by weight, 18~35
The resistance of the packing material of parts by weight, the anti-hydrolysis agent of 0.2~0.5 parts by weight, the fire retardant of 10~20 parts by weight, 2~5 parts by weight
The antioxidant for firing synergist, the lubricant of 0.2~0.5 parts by weight and 0.2~0.5 parts by weight mixes the step of squeezing out, wherein institute
It states chemical capping agents and is selected from monopentaerythritol, more pentaerythrites or derivatives thereof.
2. the method as described in claim 1, which is characterized in that more pentaerythrites are dipentaerythritol or three Ji Wusi
Alcohol.
3. such as method of any of claims 1-2, which is characterized in that the method has following one or more special
Sign:
The nylon is nylon 6T/66, nylon 6T/6, nylon 6T/1010, nylon 6T/1212, nylon 6T/612, nylon 6I/
66, nylon 6I/6, nylon 6I/1010, nylon 6I/1212, and/or nylon 6I/612；
The coupling agent is gamma-aminopropyl-triethoxy-silane, one in γ-glycidyl ether oxygen propyl trimethoxy silicane
Kind；
The nucleating agent is one of long-chain carboxylic acid's calcium salt, talcum powder or nano silica or any a variety of mixture；
The anti-hydrolysis agent is the antioxidant of copper compound class and the mixture of synergist or is polycarbodiimide；
The fire retardant is brominated polystyrene, brominated Polystyrene, decabromodiphenylethane, brominated triazine, aluminium hydroxide, hydrogen-oxygen
Change magnesium, red phosphorus, ammonium polyphosphate, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, melamine polyphosphoric acid
One of salt, melamine cyanurate or any several mixture；
The fire retarding synergist is one in antimony oxide, antimony pentoxide, zinc borate, zinc oxide, iron oxide or sodium antimonate
Kind or any a variety of mixture；
It is that second two supports one or both of double stearic amide, dimethicones in the lubricant；
The antioxidant is selected from: triethylene glycol double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) acrylonitrile, three (2,4- bis- uncles
Butylphenol) phosphite ester, 2,6- di-t-butyl -4- sylvan, N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) third
Acyl group) hexamethylene diamine, one or more of bis- (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites；With
The packing material is one or more of glass fibre, wollastonite, carbon fiber, calcium carbonate, talcum powder.
4. such as method of any of claims 1-2, which is characterized in that the extrusion includes: the raw material that will be mixed
It is delivered to melting extrusion in the double screw extruder that draw ratio is 1:36~48, is granulated；The processing technology of extruding pelletization is an area
280-300 DEG C, 280-300 DEG C of 2nd area, 290-305 DEG C of 3rd area, 290-310 DEG C of 4th area, 295-310 DEG C of 5th area, six area 285-300
DEG C, 270-285 DEG C of 7th area；300~500rpm of rotary speed.
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| CN106633836A (en) * | 2016-11-30 | 2017-05-10 | 宁波仁慈新材料科技有限公司 | High-intensity deformation-resistant PA/PC alloy fixing frame material |
| CN112409785B (en) * | 2019-08-21 | 2022-11-04 | 青岛瑞益信新材料科技有限公司 | Halogen-free flame-retardant nylon material and preparation method thereof |
| CN111117223A (en) * | 2019-12-18 | 2020-05-08 | 南京聚隆科技股份有限公司 | Nylon material for automobile bearing and preparation method thereof |
| CN111961341B (en) * | 2020-08-25 | 2022-10-21 | 宁波公牛电器有限公司 | Composite material, preparation method thereof, fixing frame and wall switch |
| CN112521749A (en) * | 2020-12-19 | 2021-03-19 | 杭州本松新材料技术股份有限公司 | Semi-aromatic nylon composition and preparation method thereof |
| CN114539484B (en) * | 2022-02-11 | 2024-03-19 | 浙江脉通智造科技(集团)有限公司 | Crosslinked nylon medical device, preparation method thereof, nylon composition and application |
| CN115340763A (en) * | 2022-08-16 | 2022-11-15 | 湖北合聚新材料有限公司 | Hydrolysis-resistant glass fiber reinforced PA66 material and preparation method thereof |
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| CN103834161B (en) * | 2012-11-26 | 2017-08-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of high temperature resistant semi-aromatic nylon composite and preparation method thereof |
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| CN102120879A (en) * | 2011-02-19 | 2011-07-13 | 本松工程塑料（杭州）有限公司 | High-temperature resistant and high-CTI (Comparative Tracing Index) flame-retardant polyamide composite material and preparation method thereof |
| CN103890097A (en) * | 2011-08-31 | 2014-06-25 | 英威达技术有限公司 | Compositions of polyhydric alcohols and polyamides |
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