CN107345068A - A kind of low water suction fire-retardant Nylon 66 composition and preparation method thereof - Google Patents
A kind of low water suction fire-retardant Nylon 66 composition and preparation method thereof Download PDFInfo
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- CN107345068A CN107345068A CN201710476333.5A CN201710476333A CN107345068A CN 107345068 A CN107345068 A CN 107345068A CN 201710476333 A CN201710476333 A CN 201710476333A CN 107345068 A CN107345068 A CN 107345068A
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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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- 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
- C08L2201/14—Gas barrier composition
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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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Abstract
The invention discloses a kind of low water suction fire-retardant Nylon 66 composition and preparation method thereof.A kind of low water suction fire-retardant Nylon 66 composition, by mass percentage including consisting of：Nylon66 fiber, polyketone, low water absorbing agent, fire retardant, fire retarding synergist, antioxidant, glass fibre.Also disclose a kind of preparation method of low water suction fire-retardant Nylon 66 composition.Low water suction fire-retardant Nylon 66 composition produced by the present invention has extremely low water absorption rate, water absorption rate≤0.1%, has high barrier to steam, remains dimensionally-stable for a long time, the characteristic of good anti-flammability and high-rigidity high-ductility.Low water suction fire-retardant Nylon 66 composition belongs to the long-term fire-retardant Nylon 66 composition for keeping dry state, and its excellent combination property can extend the application field of fire-retardant Nylon 66.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of low water suction fire-retardant Nylon 66 composition and its preparation side
Method.
Background technology
Nylon66 fiber is one of synthesis exploitation earliest, relatively inexpensive kind in polyamide, has light, mechanical strength
The characteristics of high and easy processing and forming, while there is wear-resisting, oil resistant, self lubricity and the excellent combination property such as corrosion-resistant,
Good application is obtained in many industries.Hydrone is easier through nylon66 fiber molecule and formed with nylon66 fiber molecule
Hydrogen bond, mechanical strength, the stability of size is caused to reduce.By adding reinforcing material, fire retardant, functional aid, alloying
The methods of, nylon66 fiber is fabricated to low water suction fire proofing, expands the application of nylon, is very important research topic.
A kind of formula of nylon66 fiber modified plastics and preparation method thereof (CN104962076A), discloses a kind of nylon66 fiber and changes
The formula of property plastics, by weight percentage including following components：Nylon 66 resin 52-77%, nylon 6 resin 9-18%, toughness reinforcing
Agent 1.2-1.8%, coupling agent 0.5-1.2%, fire retardant 5-17%, antioxidant 0.5-1.2% and filler 5-10%.
A kind of high temperature resistant low water absorption polyamide 66 composite material and preparation method thereof (CN101302337A), discloses one kind
High temperature resistant low water absorption polyamide 66 composite material, it is made up of following raw material：Polyamide 66 resin 25-50 parts by weight, heat stable resin
24-38 parts by weight, glass fibre 25-35 parts by weight, alumina silicate 0.5-1 parts by weight, fire retardant 0-20 parts by weight.
A kind of red phosphorus flame-retardant reinforced plastic PA66 and POK alloy materials and preparation method thereof (CN106336658A), the patent material
Material formula include nylon resin, polyketone resin, red phosphor masterbatch, synergist, antioxidant, lubricant, glass fibre, such material with
Percentage by weight calculates, and main component is as follows：PA66 5%-50%, POK 15%-25%, red phosphor masterbatch 10%-25%, glass
Glass fiber 20%-35%, synergist 5%-10%, antioxidant 0.2%-0.5% and lubricant 0.1%-0.5%.
A kind of thermoplas tic resin composite and preparation method thereof (CN105907095A), the thermoplas tic resin composite
Including following components by mass percentage：Polyphenylene sulfide, 20~50%；Nylon66 fiber, 3~40%；The alkali-free glass that is chopped is fine
Dimension, 25%~55%；Nano imvite, 1~6%；Bulking agent, 1~5%；Toughener, 2.5~6%；Coupling agent, 0.25~
0.55%；Antioxidant, 0.05~0.4%；Heat stabilizer, 0~0.4%.
A kind of low water absorption polyamide composite and its product (CN103073877A), a kind of low water absorption of the disclosure of the invention
Daiamid composition and its product, the main component of low water absorption polyamide composite include：(a) polyamide, the polyamide
Inherent viscosity be 2.0dL/g~3.2dL/g；(b) fire retardant, the fire retardant include phosphorus flame retardant and nitrogenated flame retardant；
(c) fire retarding synergist；(d) glass fibre；(e) optional crosslinking agent；(f) optional other materials.
High-insulation fiber-adding antiflaming blow-molding nylon composite and preparation method thereof (CN101921476A), the disclosure of the invention
A kind of high-insulation fiber-adding antiflaming blow-molding nylon composite and preparation method thereof, by the component of following parts by weight：PA66 50
~70 parts；EOVA10~20 part；MXD65~10 part；1~5 part of compatilizer；15~20 parts of glass；20~25 parts of fire retardant；Plasticising
5~10 parts of agent；0.1~0.3 part of heat stabilizer；0.1~1 part of antioxidant, 1~5 part of nano imvite.
Above patent disclosure contains the Flameproof polyamide of low water absorbable, has good anti-flammability, mechanically performance
And low water absorption.But these patented products still have water imbibition, still there is hidden danger in mechanical strength, the stability of size, and
Some patented products employ the not extensive low absorbent material in expensive, source, such as long carbon chain nylon, aromatic series Buddhist nun
The materials such as dragon, semi-aromatic nylon, polyphenylene sulfide, cause the problems such as with high costs, source is limited.Above patented product is a bit low
The nylon66 fiber of water suction, color limitation, or there is the defects of low molecule separates out.These defects of the fire-retardant Nylon 66 of low water suction,
It result in the limitation of its application, the precise electronic part such as made using flame-retardant PPO, water pump electrical appliance kit.
The content of the invention
It is an object of the invention to provide a kind of low water suction fire-retardant Nylon 66 composition and preparation method thereof, of the invention is low
Water suction refers to water absorption rate≤0.1% of nylon 66 composition.
The technical solution used in the present invention is：
A kind of low water suction fire-retardant Nylon 66 composition, by mass percentage including consisting of：
Low water absorbing agent is to contain anhydride group, carboxylic acid group, the ethylene waxes of epoxy radicals, propylene wax, butylene wax, octene in molecule
At least one of wax, silicone.
Fire retardant is brominated Polystyrene, polyacrylic acid pentabromo- benzyl ester, TDE, deca-BDE, dialkyl group
At least one of phosphinates, melamine polyphosphate, melamine cyanurate.
Fire retarding synergist is antimony oxide, antimony pentoxide, sodium antimonate, magnesium hydroxide, aluminium hydroxide, alumina silicate, boron
At least one of sour zinc, zinc oxide, ammonium octamolybdate, hydrotalcite.
Antioxidant is at least one of Hinered phenols, phosphorous acid esters, hindered amines, inorganic phosphate kind antioxidant.
Glass fibre be surface through silane coupler modified alkali-free glass fibre, its diameter range is 7 μm~17 μm.
A kind of preparation method of above-mentioned low water suction fire-retardant Nylon 66 composition, comprises the following steps：
1) each component in addition to glass fibre is weighed in proportion, be stirred, premix is made；
2) premix is added in the main feed mouth of double screw extruder, adds glass fibre from side charging aperture, extrusion, make
Grain, obtain low water suction fire-retardant Nylon 66 composition.
Double screw extruder is ratcheting type equidirectional parallel double-screw extruder, draw ratio >=32:1；Double screw extruder is each
It is 245 DEG C~305 DEG C that area, which sets temperature range,.
The beneficial effects of the invention are as follows：
Low water suction fire-retardant Nylon 66 composition produced by the present invention has extremely low water absorption rate, water absorption rate≤0.1%, to water
Vapour has high barrier, remains dimensionally-stable for a long time, the characteristic of good anti-flammability and high-rigidity high-ductility.Low water suction fire-retardant Nylon 66
Composition belongs to the long-term fire-retardant Nylon 66 composition for keeping dry state, and its excellent combination property can extend fire-retardant Nylon 66
Application field.
Specifically：
In a kind of low water suction fire-retardant Nylon 66 composition of the present invention, while polyketone and low water absorbing agent are added, played association
Same-action：
1st, the addition of polyketone reduces the water absorption rate of nylon66 fiber.Polyketone molecule has good barrier to steam；Polyketone
Molecule and the winding of nylon66 fiber molecule, reduce the formation of nylon66 fiber intermolecular hydrogen bonding, reduce the power of nylon66 fiber water suction.
2nd, the low water absorbing agent being had more than needed during hot worked is enriched in shallow-layer and the top layer of product, is formed on the top layer of product
The low absorbing membrane of one layer of fine and close macromolecule, and it is low water suction agent molecule in reactive functional group and nylon66 fiber amide groups it is anti-
It should combine, low absorbing membrane is anchored to the surface of product, prevention steam that can be permanently effective penetrates, while prevents in product
The precipitation of small molecule and product is changed colour.
Embodiment
A kind of low water suction fire-retardant Nylon 66 composition, by mass percentage including consisting of：
Preferably, a kind of low water suction fire-retardant Nylon 66 composition, by mass percentage including consisting of：
Preferably, the relative viscosity of nylon66 fiber is 2.2~3.3；Have it is further preferred that nylon66 fiber is refreshing horse industry share
PA66EPR24 (relative viscosity 2.45 ± 0.05), PA66EPR27 (relative viscosity 2.67 ± 0.05), the PA66EPR32 of limit company
One of which in (relative viscosity 3.2 ± 0.1).
Above-mentioned polyketone is to utilize environment-friendly type polyketone made of carbon monoxide, ethylenediamine and propylene etc.；Preferably, polyketone is
South Korea Hyosung POK M340A.
Preferably, low water absorbing agent is to contain anhydride group, carboxylic acid group, the ethylene waxes of epoxy radicals, propylene wax, butylene in molecule
At least one of wax, octene wax, silicone；It is further preferred that low water absorbing agent is ethylene maleic acid anhydride copolymer, polyester graft
At least one of modified silicone；Still further preferably, low water absorbing agent creates Degussa H-Si6441P, Honeywell AC- to win
At least one of 573A.
Preferably, fire retardant be brominated Polystyrene, polyacrylic acid pentabromo- benzyl ester, TDE, deca-BDE,
At least one of dialkylphosphinic salts, melamine polyphosphate, melamine cyanurate；It is further preferred that resistance
Combustion agent is fraternal chemical industry brominated Polystyrene GREATBAY XZ-6700, defends eastern chemical industry TDE RDT-3, and Israel is dead
At least one of extra large bromine FR1025, Clariant OP1314.
Preferably, fire retarding synergist is antimony oxide, antimony pentoxide, sodium antimonate, magnesium hydroxide, aluminium hydroxide, silicon
At least one of sour aluminium, Firebrake ZB, zinc oxide, ammonium octamolybdate, hydrotalcite；It is further preferred that fire retarding synergist is three oxygen
Change at least one of two antimony, magnesium hydroxide, aluminium hydroxide, Firebrake ZB, ammonium octamolybdate, hydrotalcite；Still further preferably, hinder
Combustion synergist is at least one of safe star antimony oxide HT-105, safe star Firebrake ZB HT-207.
Preferably, antioxidant be Hinered phenols, phosphorous acid esters, hindered amines, in inorganic phosphate kind antioxidant extremely
Few one kind；It is further preferred that antioxidant is at least one of irgasfos 168,626,1010,1098, H10；Further
Preferably, antioxidant for Rianlon Corporation THANOX series 1010,168,1098,626, cloth
At least one of Lv Geman H10.
Preferably, glass fibre be surface through silane coupler modified alkali-free glass fibre, its diameter range is 7 μm~
17μm；It is further preferred that glass fibre is at least one of ER13-988A-2000, ECS 301HP.
A kind of preparation method of above-mentioned low water suction fire-retardant Nylon 66 composition, comprises the following steps：
1) each component in addition to glass fibre is weighed in proportion, be stirred, premix is made；
2) premix is added in the main feed mouth of double screw extruder, adds glass fibre from side charging aperture, extrusion, make
Grain, obtain low water suction fire-retardant Nylon 66 composition.
Preferably, double screw extruder is ratcheting type equidirectional parallel double-screw extruder, draw ratio >=32:1；Twin-screw squeezes
It is 245 DEG C~305 DEG C that Chu Jige areas, which set temperature range,；It is further preferred that the draw ratio of double screw extruder for (36~
40)：1.
Present disclosure is described in further detail below by way of specific embodiment.
Embodiment 1：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 36 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition.
Embodiment 2：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 36 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition.
Embodiment 3：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 40 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition.
Embodiment 4：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 40 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition
Comparative example 1：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 36 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition.
Comparative example 2：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 36 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition.
Comparative example 3：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 40 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition
Comparative example 4：
Using following raw material：
Component in addition to glass fibre is put into homogenizer by weight percentage, at normal temperatures, 60 revs/min
2-5 minutes are stirred under conditions of clock, premix is made；It is 40 from draw ratio：1 ratcheting type corotating twin-screw extrusion
Machine, it is 245-305 DEG C that each area, which sets temperature range, and premix is fed in extruder by double screw extruder main feed mouth,
Simultaneously by side charging aperture feeding extruder of the glass fibre through double screw extruder, by tie rod, water cooling, dehumidifying, pelletizing, make
Obtain low water suction fire-retardant Nylon 66 composition
By nylon 66 composition produced above, using ISO battens mould, test bars are molded by injection machine.This
Each performance indications are tested by iso standard in invention, specific as follows：
1st, tensile strength presses ISO 527-2 standard testings.
2nd, bending strength and bending modulus press the standard testings of ISO 178.
3rd, Izod notched impact strength presses the standard testings of ISO 180.
4th, absorptivity presses ISO62:2008 standard testings.
5th, flame retardant test uses UL94 standard testings.
Conventionally test data are as shown in table 1；ISO test bars are dried 24 hours in 50 DEG C of baking ovens, in 23 ± 2 DEG C of water
It is middle immersion 24 hours after test result it is as shown in table 2；ISO test bars are dried 24 hours in 50 DEG C of baking ovens, at 23 ± 2 DEG C
Test result is as shown in table 3 after being soaked 96 hours in water.
The nylon 66 composition material property effect of the embodiment of table 1 and comparative example
The ISO test bars of table 2 are dried 24 hours in 50 DEG C of baking ovens, are tested after being soaked 24 hours in 23 ± 2 DEG C of water
As a result
The ISO test bars of table 3 are dried 24 hours in 50 DEG C of baking ovens, are tested after being soaked 96 hours in 23 ± 2 DEG C of water
As a result
To above test data analysis conclusion：
1st, 1~embodiment of embodiment 4, by water absorption rate test, water absorption rate≤0.1%, mechanical property does not change substantially；
2nd, 1~comparative example of comparative example 4, by water absorption rate test, water absorption rate produces apparently higher than 1~embodiment of embodiment 4
The mechanical strength of product declines to a great extent.
Claims (9)
- A kind of 1. low water suction fire-retardant Nylon 66 composition, it is characterised in that：Include consisting of by mass percentage：Nylon66 fiber 20%-50%；Polyketone 5%-30%；Low water absorbing agent 0.5%-6%；Fire retardant 5%-30%；Fire retarding synergist 0.5%-10%；Antioxidant 0.1%-2.5%；Glass fibre 10%-40%.
- 2. the low fire-retardant Nylon 66 composition that absorbs water of one kind according to claim 1, it is characterised in that：Nylon66 fiber glues relatively Spend for 2.2~3.3.
- 3. the low fire-retardant Nylon 66 composition that absorbs water of one kind according to claim 1, it is characterised in that：Low water absorbing agent is molecule In contain at least one of anhydride group, carboxylic acid group, the ethylene waxes of epoxy radicals, propylene wax, butylene wax, octene wax, silicone.
- 4. the low fire-retardant Nylon 66 composition that absorbs water of one kind according to claim 1, it is characterised in that：Fire retardant is that bromination is gathered Styrene, polyacrylic acid pentabromo- benzyl ester, TDE, deca-BDE, dialkylphosphinic salts, melamine polyphosphoric acid At least one of salt, melamine cyanurate.
- 5. the low fire-retardant Nylon 66 composition that absorbs water of one kind according to claim 1, it is characterised in that：Fire retarding synergist is three Aoxidize two antimony, antimony pentoxide, sodium antimonate, magnesium hydroxide, aluminium hydroxide, alumina silicate, Firebrake ZB, zinc oxide, ammonium octamolybdate, water At least one of talcum.
- 6. the low fire-retardant Nylon 66 composition that absorbs water of one kind according to claim 1, it is characterised in that：Antioxidant is hindered phenol At least one of class, phosphorous acid esters, hindered amines, inorganic phosphate kind antioxidant.
- 7. the low fire-retardant Nylon 66 composition that absorbs water of one kind according to claim 1, it is characterised in that：Glass fibre is surface Through silane coupler modified alkali-free glass fibre, its diameter range is 7 μm~17 μm.
- 8. a kind of preparation method of low water suction fire-retardant Nylon 66 composition described in any one of claim 1~7, its feature exist In：Comprise the following steps：1) each component in addition to glass fibre is weighed in proportion, be stirred, premix is made；2) premix is added in the main feed mouth of double screw extruder, adds glass fibre from side charging aperture, extrude, be granulated, obtain To low water suction fire-retardant Nylon 66 composition.
- A kind of 9. preparation method of low water suction fire-retardant Nylon 66 composition according to claim 8, it is characterised in that：Double spiral shells Bar extruder is ratcheting type equidirectional parallel double-screw extruder, draw ratio >=32:1；Each area of double screw extruder sets temperature model Enclose for 245 DEG C~305 DEG C.
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| CN107974076A (en) * | 2017-11-21 | 2018-05-01 | 横店集团得邦工程塑料有限公司 | One kind enhancing flame-proof PA 6/POK alloy materials and preparation method thereof |
| CN108436388A (en) * | 2018-03-29 | 2018-08-24 | 昆山铭仁快速成型技术有限公司 | Add the automatic forming technique of fine PA |
| CN109666291A (en) * | 2018-12-07 | 2019-04-23 | 厦门德丰行塑胶工业有限公司 | A kind of low water suction nylon 6 composite material of high rigidity |
| CN112592585A (en) * | 2020-12-11 | 2021-04-02 | 山东非金属材料研究所 | Low-temperature-resistant low-water-absorption low-expansion modified nylon material and preparation method thereof |
| CN112592584A (en) * | 2020-12-11 | 2021-04-02 | 山东非金属材料研究所 | Low-temperature-resistant low-water-absorption modified nylon material and preparation method thereof |
| US11572455B2 (en) | 2017-10-12 | 2023-02-07 | Si Group, Inc. | Antidegradant blend |
| WO2023030937A1 (en) * | 2021-08-30 | 2023-03-09 | Basf Se | Polyamide composition and article |
| US11879050B2 (en) | 2018-05-03 | 2024-01-23 | Si Group, Inc. | Antidegradant blend |
| CN117511197A (en) * | 2024-01-05 | 2024-02-06 | 山东祥龙新材料股份有限公司 | Hydrolysis-resistant extrusion-moldable polyamide material and preparation method and application thereof |
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| CN106221204A (en) * | 2016-08-26 | 2016-12-14 | 青岛海尔新材料研发有限公司 | Fiber glass reinforced polyamide compositions and its preparation method and application |
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