CN108504091A - Nylon66 fiber and semi-aromatic nylon composite and preparation method thereof - Google Patents
Nylon66 fiber and semi-aromatic nylon composite and preparation method thereof Download PDFInfo
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
The invention discloses a kind of nylon66 fiber and semi-aromatic nylon composite and preparation method thereof, the nylon66 fiber and the raw material that semi-aromatic nylon composite includes following weight parts：50 70 parts of semi-aromatic nylon, 30 50 parts of nylon66 fiber, 30 60 parts of modified glass-fiber, 24 parts of fire retardant, 12 parts of heat stabilizer, 12 parts of lubricant, 0.5 1 parts of irgasfos 168.The nylon66 fiber and semi-aromatic nylon composite that the present invention obtains have good flame retardant property and mechanical property, and water absorption rate is low, and heat resistance is good, can be applied to the fields such as automobile, military project, electronic apparatus, is with a wide range of applications.
Description
Technical field
The present invention relates to nylon fields, and in particular to a kind of nylon66 fiber and semi-aromatic nylon composite and its preparation side
Method.
Background technology
Polyamide (Polyamide, abbreviation PA) is commonly called as nylon, is the heat rolled into a ball containing recurring amide radical on molecular backbone
The general name of plastic resin has excellent mechanical property, friction and wear behavior, self lubricity, shock-absorbing noise reduction, oil resistant, alkali, weak acid
And the advantages that common organic solvents, and there is excellent machinability, but dimensional stability, hygroscopicity, the high lower heat-resistant deforming that bears a heavy burden
Property etc. is poor.
Semi-aromatic nylon is by aliphatic diamine or diacid and diacid or diamines with aromatic rings, through melt polycondensation system
, it is one kind of aromatic nylon.Since nylon molecules main chain introduces aromatic ring structure, thus the heat resistance of nylon product and
Mechanical property is improved, while water absorption rate also has different degrees of reduction, and has preferable cost performance, is between general
High-fire resistance resin between engineering plastic nylon and thermostability engineering plastic PEEK, is mainly used for automobile and electronic and electrical industry
In.
Since semi-aromatic nylon is compared with nylon66 fiber, maximum advantage is excellent heat resistance and lower water absorption rate；
Meanwhile compared with all aromatic nylon, have processing fluidity good, the characteristic being easily worked.By polyamide and semi-aromatic Buddhist nun
Imperial two kinds of resin alloys prepare composite material, have both overcome lacking for PA defects easy to moisture absorption and semi-aromatic nylon impact property difference
It falls into, while improving the heat resistance and dimensional stability of PA, the comprehensive performance of composite material can be promoted, that widens it applies model
It encloses, it is made to be owned by the foreground of being widely applied in fields such as electronic apparatus, automobiles.
Invention content
Problem to be solved by this invention is to provide a kind of nylon66 fiber and semi-aromatic nylon composite and its preparation side
Method, obtained nylon66 fiber have good flame retardant property and mechanical property with semi-aromatic nylon composite, and water absorption rate is low, resistance to
Good in thermal property.
The present invention provides a kind of nylon66 fiber and semi-aromatic nylon composites, including following raw materials：Semi-aromatic Buddhist nun
Dragon, nylon66 fiber, modified glass-fiber, fire retardant, heat stabilizer, lubricant, irgasfos 168.
Preferably, the nylon66 fiber and semi-aromatic nylon composite include the raw material of following weight parts：Semi-aromatic
50-70 parts of nylon, 30-50 parts of nylon66 fiber, 30-60 parts of modified glass-fiber, 2-4 parts of fire retardant, 1-2 parts of heat stabilizer, lubrication
1-2 parts of agent, 0.5-1 parts of irgasfos 168.
The semi-aromatic nylon is selected from nylon 4T, nylon 5T, nylon 8 T, nylon 9 T, nylon 10T, nylon 11 T, Buddhist nun
One or more mixtures in imperial 12T.
The heat stabilizer is one or more mixtures in calcium stearate, Lanthanum Stearate, zirconium stearate.
Preferably, the heat stabilizer is Lanthanum Stearate.
It is highly preferred that the heat stabilizer is the mixture of Lanthanum Stearate and zirconium stearate, the Lanthanum Stearate and tristearin
The mass ratio of sour zirconium is (8-12)：1.
The lubricant is one kind in pentaerythritol stearate, glycerin monostearate, oleamide.
The fire retardant is modified magnesium hydroxide and/or phytic acid magnesium.
Preferably, the fire retardant is the mixture of modified magnesium hydroxide and phytic acid magnesium, the modified magnesium hydroxide and plant
The mass ratio of sour magnesium is (2-8)：1.
The modified magnesium hydroxide is prepared by following methods：Weigh 10g magnesium hydroxides and 0.01-0.1 hexa metaphosphoric acids
Sodium is added in 200-240g water, is stirred 60-90 minutes with 300-500 revs/min at 20-30 DEG C, lauric acid 0.5-1g is added,
It is stirred 60-90 minutes, is centrifuged 15-30 minutes with 3000-5000 revs/min, obtained solid with 100-300 revs/min at 80-90 DEG C
It is dried to constant weight at 100-110 DEG C, obtains modified magnesium hydroxide.
The preparation method of the modified glass-fiber includes the following steps：
(1) it pre-processes：Glass fibre is kept the temperature 20-40 minutes at 400-500 DEG C, is washed with water only, in 80-90 DEG C of drying
To constant weight, pretreated glass fiber is obtained；
(2) it is acidified：By pretreated glass fiber impregnation 80-90 minutes in the hydrochloric acid solution of 3mol/L, then use water
Washing to washing lotion is neutrality, is dried to constant weight at 80-90 DEG C, and acidification glass fibre is obtained；
(3) first modified：The toluene of 200-240mL is added in 500mL flasks, adds Isosorbide-5-Nitrae-paraphenylene diisocyanate
2-5g is stirred 20-40 minutes with 300-500 revs/min at 20-30 DEG C, adds acidification glass fibre 6-10g and tin dilaurate two
Butyl tin 0.1-1g is stirred 4-6 hours at 30-50 DEG C with 100-300 revs/min, and with 300 mesh filter-cloth filterings, obtained solid is used
Toluene washs three times, is dried to constant weight at 65-85 DEG C, obtains first modified glass-fiber；
(4) twice-modified：By 1-3g silica and 180-120mL1,4- dioxane mixing, with 300-500 revs/min
It is stirred 20-40 minutes at 20-30 DEG C, first modified glass fibre peacekeeping triethylamine 0.1-1g is added, 18-22 is reacted at 30-50 DEG C
Hour, with 300 mesh filter-cloth filterings, obtained solid is washed three times with Isosorbide-5-Nitrae-dioxane, is dried to constant weight, is obtained at 80-90 DEG C
To modified glass-fiber.
The present invention also provides the preparation methods of a kind of nylon66 fiber and semi-aromatic nylon composite, including following step
Suddenly：
(1) semi-aromatic nylon, nylon66 fiber are separately dried at 80-90 DEG C 6-10 hours respectively, modified glass-fiber exists
60-80 DEG C 4-6 hours dry, then claims semi-aromatic nylon by weight, nylon66 fiber, fire retardant, heat stabilizer, lubricant, resists
Oxygen agent 168, is put into blender, is stirred 3-8 minutes with 300-500 revs/min, obtains mixture；
(2) mixture is put into the main spout in double screw extruder, then modified glass-fiber is introduced into Screw Extrusion
The long fibre charge door of machine, extruded, traction are granulated, and obtain nylon66 fiber and semi-aromatic nylon composite.
Nylon66 fiber of the present invention and semi-aromatic nylon composite and preparation method thereof, obtained composite material have good
Flame retardant property and mechanical property, water absorption rate is low, and heat resistance is good, can be applied to the fields such as automobile, military project, electronic apparatus, tool
Have wide practical use.
Specific implementation mode
With reference to specific embodiment, the present invention is further explained.It should be appreciated, however, that these embodiments are only used for
It is bright the present invention and be not meant to limit the scope of the invention.The test method of actual conditions is not specified in the following example, usually
According to normal condition, or according to the normal condition proposed by manufacturer.
Nylon66 fiber, Dupont production, trade mark 70G33L.
Nylon 10T, JinFa Science Co., Ltd's production, trade mark PA10T.
Glass fibre, the alkali-free glass fibre of Lingshou County De Heng mineral products processings factory production, 11-13 μm of fibre diameter are long
Spend 3-4mm.
Irgasfos 168, the model IRGAFOS168 produced using BASF.
Zirconium stearate, using the AquaProofWB31B of FedChem companies.
Lanthanum Stearate, Shanghai deer China intelligent technology limited provide.
Calcium stearate, Zhengzhou De Yuan chemical products Co., Ltd provide.
Phytic acid magnesium, Dangyang City Xu Sheng chemical industry Co., Ltd provide.
Pentaerythritol stearate, the production of the Guangzhou bio tech ltd HuangRidge, model PETS-4.
Magnesium hydroxide, the production of Hefei Zhong Ke flame-retarding new materials Co., Ltd, number FR-2810,15 μm of average grain diameter.
Calgon, Sinopharm Chemical Reagent Co., Ltd.'s production, product identification：20039628
Lauric acid, the production of this biochemical technology Co., Ltd of Tianjin Skien, product identification：D-97385.
Toluene, the production of Tianjin Fu Yu Fine Chemical Co., Ltd.
Isosorbide-5-Nitrae-paraphenylene diisocyanate, Sigma-Aldrich productions.
Dibutyl tin laurate, Sinopharm Chemical Reagent Co., Ltd.'s production, product identification：80044627.
Silica, the production of Shanghai Aladdin biochemical technology limited liability company, product grade：S104591, average grain diameter
7-40nm。
Isosorbide-5-Nitrae-dioxane, Sinopharm Chemical Reagent Co., Ltd.'s production, product identification：10008918.
Triethylamine, Sinopharm Chemical Reagent Co., Ltd.'s production, product identification product identification：80134328.
By obtained nylon66 fiber and semi-aromatic nylon composite using injection molding machine (Ningbo sea day T80) according to gauge
The very little standard batten for being molded into test and using, 275-305 DEG C of processing temperature, 105-115 DEG C of mould temperature.
Limit oxygen index is tested：According to GB2406-1993, method is lighted using top, measures the limit oxygen index of batten, sample
Product length 100mm, wide 10mm, thick 4mm.
Heat distortion temperature is tested with reference to ASTM D648, and water absorption rate is tested with reference to ASTM D570.
Mechanics Performance Testing：Tensile strength is tested according to ASTM D638, and Izod notch impact strengths are according to ASTM
D256 is tested.
Embodiment 1
The raw material (parts by weight) of nylon66 fiber and semi-aromatic nylon composite：60 parts of semi-aromatic nylon, nylon66 fiber 40
Part, 45 parts of modified glass-fiber, 3 parts of fire retardant, 1.5 parts of heat stabilizer, 1.5 parts of lubricant, 0.8 part of irgasfos 168.
The semi-aromatic nylon is nylon 10T.
The heat stabilizer is calcium stearate.
The lubricant is pentaerythritol stearate.
The fire retardant is modified magnesium hydroxide.
The modified magnesium hydroxide is prepared by following methods：10g magnesium hydroxides and 0.05 calgon are weighed, is added
Enter into 220g water, stirred 75 minutes with 400 revs/min at 25 DEG C, lauric acid 0.8g is added, at 85 DEG C with 200 revs/min of stirrings 75
Minute, it is centrifuged 25 minutes with 4000 revs/min, obtained solid is dried at 105 DEG C to constant weight, and modified magnesium hydroxide is obtained.
The preparation method of the modified glass-fiber includes the following steps：Glass fibre is kept the temperature 30 minutes at 450 DEG C, then
It is eluted with water, is dried to constant weight at 85 DEG C, obtain modified glass-fiber.
A kind of preparation method of nylon66 fiber and semi-aromatic nylon composite, includes the following steps：(1) by semi-aromatic
Nylon, nylon66 fiber are separately dried 8 hours respectively at 85 DEG C, and modified glass-fiber is 5 hours dry at 70 DEG C, then claims half by weight
Aromatic nylon, nylon66 fiber, fire retardant, heat stabilizer, lubricant, irgasfos 168, are put into blender, are stirred with 400 revs/min
It mixes 6 minutes, obtains mixture；
(2) mixture is put into the main spout in double screw extruder, then modified glass-fiber is introduced into Screw Extrusion
The long fibre charge door of machine, extruded, traction are granulated, and obtain nylon66 fiber and semi-aromatic nylon composite, wherein double spiral shells
The temperature of bar extruder is：One 260 DEG C of area, two 270 DEG C of areas, three 280 DEG C of areas, four 285 DEG C of areas, five 290 DEG C of areas, six 290 DEG C of areas,
Seven 295 DEG C of areas, eight 295 DEG C of areas, nine 295 DEG C of areas, ten 295 DEG C of areas, 290 DEG C of head temperature, screw speed 200r/min.
Embodiment 2
It is substantially the same manner as Example 1, it differs only in, the preparation method of the modified glass-fiber includes the following steps：
(1) it pre-processes：Glass fibre is kept the temperature 30 minutes at 450 DEG C, is washed with water only, dries to constant weight, obtains at 85 DEG C
To pretreated glass fiber；
(2) it is acidified：By pretreated glass fiber in the hydrochloric acid solution of 3mol/L impregnation 85 minutes, the glass fibers
The solid-to-liquid ratio of peacekeeping hydrochloric acid solution is 1g：5mL is washed with water and washs to washing lotion to be neutral, dries to constant weight, be acidified at 85 DEG C
Glass fibre；
(3) first modified：The toluene of 220mL is added in 500mL flasks, adds Isosorbide-5-Nitrae-paraphenylene diisocyanate 4g,
It is stirred 30 minutes at 25 DEG C with 400 revs/min, acidification glass fibre 8g and dibutyl tin laurate 0.5g is added, at 40 DEG C
It is stirred 5 hours with 200 revs/min, with 300 mesh filter-cloth filterings, obtained solid is washed three times with toluene, is dried to perseverance at 75 DEG C
Weight, obtains first modified glass-fiber；
(4) twice-modified：By 2g silica and 200mL1, the mixing of 4- dioxane is stirred with 400 revs/min at 25 DEG C
30 minutes, first modified glass fibre peacekeeping triethylamine 0.5g is added, reacts 20 hours at 40 DEG C, with 300 mesh filter-cloth filterings, obtains
Solid washed three times with Isosorbide-5-Nitrae-dioxane, at 85 DEG C dry to constant weight, obtain modified glass-fiber.
Embodiment 3
It is substantially the same manner as Example 2, it differs only in, the heat stabilizer is Lanthanum Stearate.
Embodiment 4
It is substantially the same manner as Example 2, it differs only in, the heat stabilizer is zirconium stearate.
Embodiment 5
It is substantially the same manner as Example 2, it differs only in, the heat stabilizer is the mixing of Lanthanum Stearate and zirconium stearate
The mass ratio of object, the Lanthanum Stearate and zirconium stearate is 10：1.
Embodiment 6
The raw material (parts by weight) of nylon66 fiber and semi-aromatic nylon composite：60 parts of semi-aromatic nylon, nylon66 fiber 40
Part, 45 parts of modified glass-fiber, 3 parts of fire retardant, 1.5 parts of heat stabilizer, 1.5 parts of lubricant, 0.8 part of irgasfos 168.
The semi-aromatic nylon is nylon 10T.
The heat stabilizer is the mixture of Lanthanum Stearate and zirconium stearate, the quality of the Lanthanum Stearate and zirconium stearate
Than being 10：1.
The lubricant is pentaerythritol stearate.
The fire retardant is phytic acid magnesium.
The preparation method of the modified glass-fiber includes the following steps：
(1) it pre-processes：Glass fibre is kept the temperature 30 minutes at 450 DEG C, is washed with water only, dries to constant weight, obtains at 85 DEG C
To pretreated glass fiber；
(2) it is acidified：By pretreated glass fiber in the hydrochloric acid solution of 3mol/L impregnation 85 minutes, the glass fibers
The solid-to-liquid ratio of peacekeeping hydrochloric acid solution is 1g：5mL is washed with water and washs to washing lotion to be neutral, dries to constant weight, be acidified at 85 DEG C
Glass fibre；
(3) first modified：The toluene of 220mL is added in 500mL flasks, adds Isosorbide-5-Nitrae-paraphenylene diisocyanate 4g,
It is stirred 30 minutes at 25 DEG C with 400 revs/min, acidification glass fibre 8g and dibutyl tin laurate 0.5g is added, at 40 DEG C
It is stirred 5 hours with 200 revs/min, with 300 mesh filter-cloth filterings, obtained solid is washed three times with toluene, is dried to perseverance at 75 DEG C
Weight, obtains first modified glass-fiber；(4) twice-modified：By 2g silica and 200mL1,4- dioxane mixing, with 400
It rev/min is stirred 30 minutes at 25 DEG C, first modified glass fibre peacekeeping triethylamine 0.5g is added, is reacted 20 hours at 40 DEG C, with 300
Mesh filter-cloth filtering, obtained solid are washed three times with Isosorbide-5-Nitrae-dioxane, are dried to constant weight at 85 DEG C, are obtained modified glass fibre
Dimension.
A kind of preparation method of nylon66 fiber and semi-aromatic nylon composite, includes the following steps：
(1) semi-aromatic nylon, nylon66 fiber are separately dried 8 hours respectively at 85 DEG C, modified glass-fiber is done at 70 DEG C
Dry 5 hours, then claim semi-aromatic nylon, nylon66 fiber, fire retardant, heat stabilizer, lubricant, irgasfos 168 by weight, it is put into
In blender, is stirred 6 minutes with 400 revs/min, obtain mixture；
(2) mixture is put into the main spout in double screw extruder, modified glass-fiber is introduced into screw extruder
Long fibre charge door, it is extruded, traction, be granulated, obtain nylon66 fiber and semi-aromatic nylon composite, wherein twin-screw
The temperature of extruder is：One 260 DEG C of area, two 270 DEG C of areas, three 280 DEG C of areas, four 285 DEG C of areas, five 290 DEG C of areas, six 290 DEG C of areas, seven
295 DEG C of area, eight 295 DEG C of areas, nine 295 DEG C of areas, ten 295 DEG C of areas, 290 DEG C of head temperature, screw speed 200r/min.
The limit oxygen index test result of obtained nylon66 fiber and semi-aromatic nylon composite：24.9%；Mechanical property
It can test result：Tensile strength 242MPa, Izod notch impact strength 15.7KJ/m2, water absorption rate 0.11%, heat distortion temperature
285℃。
Embodiment 7
The raw material (parts by weight) of nylon66 fiber and semi-aromatic nylon composite：60 parts of semi-aromatic nylon, nylon66 fiber 40
Part, 45 parts of modified glass-fiber, 3 parts of fire retardant, 1.5 parts of heat stabilizer, 1.5 parts of lubricant, 0.8 part of irgasfos 168.
The semi-aromatic nylon is nylon 10T.
The heat stabilizer is the mixture of Lanthanum Stearate and zirconium stearate, the quality of the Lanthanum Stearate and zirconium stearate
Than being 10：1.
The lubricant is pentaerythritol stearate.
The fire retardant is the mixture of modified magnesium hydroxide and phytic acid magnesium, the matter of the modified magnesium hydroxide and phytic acid magnesium
Amount is than being 5：1.
The modified magnesium hydroxide is prepared by following methods：10g magnesium hydroxides and 0.05 calgon are weighed, is added
Enter into 220g water, stirred 75 minutes with 400 revs/min at 25 DEG C, lauric acid 0.8g is added, at 85 DEG C with 200 revs/min of stirrings 75
Minute, it is centrifuged 25 minutes with 4000 revs/min, obtained solid is dried at 105 DEG C to constant weight, and modified magnesium hydroxide is obtained.
The preparation method of the modified glass-fiber includes the following steps：
(1) it pre-processes：Glass fibre is kept the temperature 30 minutes at 450 DEG C, is washed with water only, dries to constant weight, obtains at 85 DEG C
To pretreated glass fiber；
(2) it is acidified：By pretreated glass fiber in the hydrochloric acid solution of 3mol/L impregnation 85 minutes, the glass fibers
The solid-to-liquid ratio of peacekeeping hydrochloric acid solution is 1g：5mL is washed with water and washs to washing lotion to be neutral, dries to constant weight, be acidified at 85 DEG C
Glass fibre；
(3) first modified：The toluene of 220mL is added in 500mL flasks, adds Isosorbide-5-Nitrae-paraphenylene diisocyanate 4g,
It is stirred 30 minutes at 25 DEG C with 400 revs/min, acidification glass fibre 8g and dibutyl tin laurate 0.5g is added, at 40 DEG C
It is stirred 5 hours with 200 revs/min, with 300 mesh filter-cloth filterings, obtained solid is washed three times with toluene, is dried to perseverance at 75 DEG C
Weight, obtains first modified glass-fiber；(4) twice-modified：By 2g silica and 200mL1,4- dioxane mixing, with 400
It rev/min is stirred 30 minutes at 25 DEG C, first modified glass fibre peacekeeping triethylamine 0.5g is added, is reacted 20 hours at 40 DEG C, with 300
Mesh filter-cloth filtering, obtained solid are washed three times with Isosorbide-5-Nitrae-dioxane, are dried to constant weight at 85 DEG C, are obtained modified glass fibre
Dimension.
A kind of preparation method of nylon66 fiber and semi-aromatic nylon composite, includes the following steps：
(1) semi-aromatic nylon, nylon66 fiber are separately dried 8 hours respectively at 85 DEG C, modified glass-fiber is done at 70 DEG C
Dry 5 hours, then claim semi-aromatic nylon, nylon66 fiber, fire retardant, heat stabilizer, lubricant, irgasfos 168 by weight, it is put into
In blender, is stirred 6 minutes with 400 revs/min, obtain mixture；
(2) mixture is put into the main spout in double screw extruder, modified glass-fiber is introduced into screw extruder
Long fibre charge door, it is extruded, traction, be granulated, obtain nylon66 fiber and semi-aromatic nylon composite, wherein twin-screw
The temperature of extruder is：One 260 DEG C of area, two 270 DEG C of areas, three 280 DEG C of areas, four 285 DEG C of areas, five 290 DEG C of areas, six 290 DEG C of areas, seven
295 DEG C of area, eight 295 DEG C of areas, nine 295 DEG C of areas, ten 295 DEG C of areas, 290 DEG C of head temperature, screw speed 200r/min.
The limit oxygen index test result of obtained nylon66 fiber and semi-aromatic nylon composite：28.8%；Mechanical property
It can test result：Tensile strength 277MPa, Izod notch impact strength 18.5KJ/m2, water absorption rate 0.08%, heat distortion temperature
323℃。
Test case 1
The limit oxygen index of the obtained nylon66 fibers of embodiment 1-5 and semi-aromatic nylon composite is tested, is had
Body the results are shown in Table 1.
1 limit oxygen index test result table of table
| Limit oxygen index, % | |
| Embodiment 1 | 21.6 |
| Embodiment 2 | 22.7 |
| Embodiment 3 | 23.6 |
| Embodiment 4 | 23.1 |
| Embodiment 5 | 25.8 |
Test case 2
The mechanical property of the obtained nylon66 fibers of embodiment 1-5 and semi-aromatic nylon composite is measured.Specifically
It the results are shown in Table 2.
2 nylon66 fiber of table and semi-aromatic nylon composite mechanical experimental results table
Test case 3
The water absorption rate and heat distortion temperature of the obtained nylon66 fibers of embodiment 1-5 and semi-aromatic nylon composite are carried out
It measures.Concrete outcome is shown in Table 3.
3 nylon66 fiber of table and semi-aromatic nylon composite mechanical experimental results table
It is the anti-flammability of nylon66 fiber and semi-aromatic nylon composite that embodiment 2 obtains, mechanical property, water imbibition, resistance to
Hot to be better than embodiment 1, this is because fiberglass surfacing is smooth, active group is few, glass fibre and resin in composite material
The interface cohesion of matrix is weak, to affect the performance of composite material.By being modified for the first time, fiberglass surfacing coat to be formed it is different
Cyanic acid ester layer improves the reactivity of fiberglass surfacing.After twice-modified, surface coats the glass fibers of polyisocyanate ester layer
Dimension will carry out graft reaction with silica, obtain silica modified glass fibre.The silicone hydroxyl of silica surface easily with
Physics chemical action occurs for high molecular material, and then plays the role of activeness and quietness, improves heat resistance, improves mechanical performance.
Different heat stabilizers is respectively adopted in embodiment 2-4, it is found that embodiment 3 uses Lanthanum Stearate, obtained nylon66 fiber
It is preferable with the comprehensive performance of semi-aromatic nylon composite.
Claims (10)
1. a kind of nylon66 fiber and semi-aromatic nylon composite, which is characterized in that the raw material including following weight parts：Semiaromatic
Nylon 50-70 parts of race, 30-50 parts of nylon66 fiber, 30-60 parts of modified glass-fiber, 2-4 parts of fire retardant, 1-2 parts of heat stabilizer, profit
1-2 parts of lubrication prescription, 0.5-1 parts of irgasfos 168.
2. nylon66 fiber as described in claim 1 and semi-aromatic nylon composite, which is characterized in that the semi-aromatic Buddhist nun
One or more mixing of the dragon in nylon 4T, nylon 5T, nylon 8 T, nylon 9 T, nylon 10T, nylon 11 T, nylon 12T
Object.
3. nylon66 fiber as described in claim 1 and semi-aromatic nylon composite, which is characterized in that the heat stabilizer is hard
One or more mixtures in resin acid calcium, Lanthanum Stearate, zirconium stearate.
4. nylon66 fiber as described in claim 1 and semi-aromatic nylon composite, which is characterized in that the heat stabilizer is hard
Resin acid lanthanum.
5. nylon66 fiber as claimed in claim 3 and semi-aromatic nylon composite, which is characterized in that the heat stabilizer is hard
The mass ratio of the mixture of resin acid lanthanum and zirconium stearate, the Lanthanum Stearate and zirconium stearate is (8-12)：1.
6. nylon66 fiber as described in claim 1 and semi-aromatic nylon composite, which is characterized in that the lubricant is season penta
One kind in tetrol stearate, glycerin monostearate, oleamide.
7. nylon66 fiber as described in claim 1 and semi-aromatic nylon composite, which is characterized in that the fire retardant is to be modified
Magnesium hydroxide and/or phytic acid magnesium.
8. nylon66 fiber as claimed in claim 7 and semi-aromatic nylon composite, which is characterized in that the modified magnesium hydroxide
It is prepared by following methods：10g magnesium hydroxides and 0.01-0.1 calgons are weighed, is added in 200-240g water,
20-30 DEG C is stirred 60-90 minutes, and lauric acid 0.5-1g is added, is stirred 60-90 minutes at 80-90 DEG C, with 3000-5000 revs/min
Centrifugation 15-30 minutes, obtained solid are dried at 100-110 DEG C to constant weight, and modified magnesium hydroxide is obtained.
9. nylon66 fiber as described in claim 1 and semi-aromatic nylon composite, which is characterized in that the modified glass-fiber
Preparation method include the following steps：
(1) it pre-processes：Glass fibre is kept the temperature 20-40 minutes at 400-500 DEG C, is washed with water only, is dried to perseverance at 80-90 DEG C
Weight, obtains pretreated glass fiber；
(2) it is acidified：By pretreated glass fiber impregnation 80-90 minutes in the hydrochloric acid solution of 3mol/L, it is washed with water and washs
It is neutrality to washing lotion, is dried to constant weight at 80-90 DEG C, obtains acidification glass fibre；
(3) first modified：The toluene of 200-240mL is added in flask, adds Isosorbide-5-Nitrae-paraphenylene diisocyanate 2-5g,
20-30 DEG C is stirred 20-40 minutes, acidification glass fibre 6-10g and dibutyl tin laurate 0.1-1g is added, in 30-50
DEG C stirring 4-6 hour, with 300 mesh filter-cloth filterings, obtained solid is washed three times with toluene, at 65-85 DEG C drying to constant weight, obtain
To first modified glass-fiber；
(4) twice-modified：By 1-3g silica and 180-120mL1,20-40 is stirred in the mixing of 4- dioxane at 20-30 DEG C
Minute, first modified glass fibre peacekeeping triethylamine 0.1-1g is added, is reacted 18-22 hours at 30-50 DEG C, with 300 mesh filter cloth mistakes
Filter, obtained solid are washed three times with Isosorbide-5-Nitrae-dioxane, are dried to constant weight at 80-90 DEG C, are obtained modified glass-fiber.
10. the preparation method of any one of claim the 1-9 nylon66 fiber and semi-aromatic nylon composite, including it is following
Step：
(1) semi-aromatic nylon, nylon66 fiber are separately dried at 80-90 DEG C 6-10 hours respectively, modified glass-fiber is in 60-80
DEG C dry 4-6 hour, then title semi-aromatic nylon, nylon66 fiber, fire retardant, heat stabilizer, lubricant, antioxidant by weight
168, it is put into blender, is stirred 3-8 minutes with 300-500 revs/min, obtain mixture；
(2) mixture is put into the main spout in double screw extruder, then modified glass-fiber is introduced into screw extruder
Long fibre charge door, extruded, traction are granulated, and obtain nylon66 fiber and semi-aromatic nylon composite.
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| CN110016227A (en) * | 2019-05-05 | 2019-07-16 | 合肥工业大学 | A kind of nylon composite materials and preparation method thereof containing secondary surface modifying stuffing |
| CN110229516A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | A kind of preparation method of the intrinsic fire-retardant Nylon 66 composite material of low smoke, zero halogen |
| CN111718576A (en) * | 2019-03-19 | 2020-09-29 | 上海术博新材料技术有限公司 | High-strength friction-resistant nylon composite material and preparation method thereof |
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| CN106700535A (en) * | 2017-02-13 | 2017-05-24 | 上海跃贝塑化科技有限公司 | Glass fiber-reinforced polyamide 66 and semi-aromatic nylon composite material for vehicular structural member and preparation method |
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| US20110240930A1 (en) * | 2006-12-28 | 2011-10-06 | Ems-Chemie Ag | Polyamide molding materials reinforced with glass fibers and injection molded parts thereof |
| CN102321361A (en) * | 2011-08-04 | 2012-01-18 | 金发科技股份有限公司 | Low-warpage halogen-free flame retardant reinforced polyamide composite material |
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| CN111718576A (en) * | 2019-03-19 | 2020-09-29 | 上海术博新材料技术有限公司 | High-strength friction-resistant nylon composite material and preparation method thereof |
| CN110016227A (en) * | 2019-05-05 | 2019-07-16 | 合肥工业大学 | A kind of nylon composite materials and preparation method thereof containing secondary surface modifying stuffing |
| CN110016227B (en) * | 2019-05-05 | 2021-06-04 | 合肥工业大学 | Nylon composite material containing secondary surface modified filler and preparation method thereof |
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