CN108504091B - Nylon 66 and semi-aromatic nylon composite material and preparation method thereof - Google Patents
Nylon 66 and semi-aromatic nylon composite material 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—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
Abstract
The invention discloses a nylon 66 and semi-aromatic nylon composite material and a preparation method thereof, wherein the nylon 66 and semi-aromatic nylon composite material comprises the following raw materials in parts by weight: 50-70 parts of semi-aromatic nylon, 0-50 parts of nylon 6630-60 parts of modified glass fiber, 2-4 parts of flame retardant, 1-2 parts of heat stabilizer, 1-2 parts of lubricant and 1680.5-1 part of antioxidant. The nylon 66 and semi-aromatic nylon composite material obtained by the invention has good flame retardant property and mechanical property, low water absorption rate and good heat resistance, can be applied to the fields of automobiles, war industry, electronic and electric appliances and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the field of nylon, in particular to a nylon 66 and semi-aromatic nylon composite material and a preparation method thereof.
Background
Polyamide (abbreviated as PA), commonly known as nylon, is a generic name of thermoplastic resins having a main molecular chain containing a repeating amide group, and has the advantages of excellent mechanical properties, frictional wear properties, self-lubricity, shock absorption and noise reduction, oil resistance, alkali resistance, weak acid resistance, general organic solvents and the like, and good processability, but is inferior in dimensional stability, hygroscopicity, heat deformation resistance under high load and the like.
The semi-aromatic nylon is prepared by melt polycondensation of aliphatic diamine or diacid and diacid or diamine with aromatic rings, and is one of aromatic nylons. The aromatic ring structure is introduced into the main chain of the nylon molecule, so that the heat resistance and the mechanical property of the nylon product are improved, the water absorption is reduced to different degrees, and the performance price ratio is better.
The semi-aromatic nylon has the greatest advantages of excellent heat resistance and lower water absorption compared with nylon 66; meanwhile, compared with wholly aromatic nylon, the nylon has the characteristics of good processing fluidity and easy processing. The polyamide and semi-aromatic nylon are blended to prepare the composite material, so that the defects of easy moisture absorption of PA and poor impact performance of semi-aromatic nylon are overcome, the heat resistance and the dimensional stability of PA are improved, the comprehensive performance of the composite material can be improved, the application range of the composite material is widened, and the composite material has wide application prospects in the fields of electronic appliances, automobiles and the like.
Disclosure of Invention
The invention aims to solve the problem of providing the nylon 66 and semi-aromatic nylon composite material and the preparation method thereof, and the obtained nylon 66 and semi-aromatic nylon composite material has good flame retardant property and mechanical property, low water absorption and good heat resistance.
The invention provides a nylon 66 and semi-aromatic nylon composite material, which comprises the following raw materials: semi-aromatic nylon, nylon 66, modified glass fiber, a flame retardant, a heat stabilizer, a lubricant and an antioxidant 168.
Preferably, the nylon 66 and semi-aromatic nylon composite material comprises the following raw materials in parts by weight: 50-70 parts of semi-aromatic nylon, 0-50 parts of nylon 6630-60 parts of modified glass fiber, 2-4 parts of flame retardant, 1-2 parts of heat stabilizer, 1-2 parts of lubricant and 1680.5-1 part of antioxidant.
The semi-aromatic nylon is selected from one or more of nylon 4T, nylon 5T, nylon 8T, nylon 9T, nylon 10T, nylon 11T and nylon 12T.
The heat stabilizer is one or a mixture of calcium stearate, lanthanum stearate and zirconium stearate.
Preferably, the heat stabilizer is lanthanum stearate.
More preferably, the heat stabilizer is a mixture of lanthanum stearate and zirconium stearate, and the mass ratio of the lanthanum stearate to the zirconium stearate is (8-12): 1.
the lubricant is one of pentaerythritol stearate, glyceryl monostearate and oleamide.
The flame retardant is modified magnesium hydroxide and/or magnesium phytate.
Preferably, the flame retardant is a mixture of modified magnesium hydroxide and magnesium phytate, and the mass ratio of the modified magnesium hydroxide to the magnesium phytate is (2-8): 1.
the modified magnesium hydroxide is prepared by the following method: weighing 10g of magnesium hydroxide and 0.01-0.1g of sodium hexametaphosphate, adding into 240g of water of 200-.
The preparation method of the modified glass fiber comprises the following steps:
(1) pretreatment: keeping the temperature of the glass fiber at 400-500 ℃ for 20-40 minutes, cleaning with water, and drying at 80-90 ℃ to constant weight to obtain pretreated glass fiber;
(2) acidifying, namely soaking the pretreated glass fiber in a hydrochloric acid solution of 3 mol/L for 80-90 minutes, washing with water until the washing liquid is neutral, and drying at 80-90 ℃ to constant weight to obtain acidified glass fiber;
(3) the first modification is that 200-240m L of toluene is added into a 500m L flask, 2-5g of 1, 4-p-phenylene diisocyanate is added, the mixture is stirred for 20-40 minutes at 20-30 ℃ at 500 rpm of 300-;
(4) and (2) secondary modification, namely mixing 1-3g of silicon dioxide and 180-120m L1-1, 4-dioxane, stirring at 20-30 ℃ for 20-40 minutes at 500 revolutions per minute of 300-dioxane, adding 0.1-1g of primary modified glass fiber and triethylamine, reacting at 30-50 ℃ for 18-22 hours, filtering by 300-mesh filter cloth, washing the obtained solid by 1, 4-dioxane for three times, and drying at 80-90 ℃ to constant weight to obtain the modified glass fiber.
The invention also provides a preparation method of the nylon 66 and semi-aromatic nylon composite material, which comprises the following steps:
(1) respectively drying the semi-aromatic nylon and the nylon 66 at 80-90 ℃ for 6-10 hours, respectively drying the modified glass fiber at 60-80 ℃ for 4-6 hours, weighing the semi-aromatic nylon, the nylon 66, the flame retardant, the heat stabilizer, the lubricant and the antioxidant 168 according to parts by weight, putting the materials into a stirrer, and stirring the materials at 300-500 r/min for 3-8 minutes to obtain a mixture;
(2) and (3) putting the mixture into a main feeding port in a double-screw extruder, introducing the modified glass fiber into a long fiber feeding port of the screw extruder, and performing extrusion, traction and granulation to obtain the nylon 66 and semi-aromatic nylon composite material.
The composite material prepared from the nylon 66 and the semi-aromatic nylon and the preparation method thereof have the advantages of good flame retardant property and mechanical property, low water absorption rate and good heat resistance, can be applied to the fields of automobiles, war industry, electronic and electric appliances and the like, and has wide application prospect.
Detailed Description
The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Nylon 66, manufactured by DuPont, USA, under the designation 70G 33L.
Nylon 10T, available from Jinfa technologies, Inc., under the designation PA 10T.
The glass fiber is alkali-free glass fiber produced by a processing plant of constant mineral products in Lingshou county, the fiber diameter is 11-13 mu m, and the length is 3-4 mm.
Antioxidant 168, model IRGAFOS168 available from BASF.
Zirconium stearate was obtained as AquaProofWB31B from FedChem.
Lanthanum stearate, available from Shanghai Luhua Intelligent science and technology Co.
Calcium stearate, available from Zhengzhou Deyuan chemical products Co., Ltd.
Magnesium phytate, available from Asahi Sunghua chemical company Limited in Dangyang.
Pentaerythritol stearate, model PETS-4, manufactured by Guangzhou Brilliant Biotech, Inc.
Magnesium hydroxide, made by flame retardant new material Co, Ltd, No. FR-2810, and has an average particle size of 15 μm.
Sodium hexametaphosphate, produced by chemical reagents of national drug group limited, and having a product number of: 20039628
Lauric acid, produced by Tianjin Xiansi Biotechnology Limited, product number: d-97385.
Toluene, Fuyu Fine chemical Co., Ltd, Tianjin.
1, 4-p-phenylene diisocyanate, manufactured by Sigma-Aldrich.
Dibutyltin dilaurate, produced by national drug group chemical reagents limited, product number: 80044627.
silica, manufactured by Shanghai Aladdin Biotechnology, Inc., product designation: s104591, average grain diameter 7-40 nm.
1, 4-dioxane, produced by national drug group chemical reagents limited, product number: 10008918.
triethylamine, chemical reagent of national drug group, product number: 80134328.
the obtained nylon 66 and semi-aromatic nylon composite material is subjected to injection molding by an injection molding machine (Ningbo Haitian T80) according to a standard size to form a standard sample strip used for testing, wherein the processing temperature is 275-305 ℃, and the mold temperature is 105-115 ℃.
Limiting oxygen index test: the limiting oxygen index of the specimens was determined according to GB2406-1993 using the tip ignition method, the specimens having a length of 100mm, a width of 10mm and a thickness of 4 mm.
Heat distortion temperature was tested according to ASTM D648 and water absorption was tested according to ASTM D570.
And (3) testing mechanical properties: tensile strength was measured according to ASTM D638 and notched Izod impact strength was measured according to ASTM D256.
Example 1
Raw materials (parts by weight) of the nylon 66 and semi-aromatic nylon composite material are as follows: 60 parts of semi-aromatic nylon, 6640 parts of nylon, 45 parts of modified glass fiber, 3 parts of flame retardant, 1.5 parts of heat stabilizer, 1.5 parts of lubricant and 1680.8 parts of antioxidant.
The semi-aromatic nylon is nylon 10T.
The heat stabilizer is calcium stearate.
The lubricant is pentaerythritol stearate.
The flame retardant is modified magnesium hydroxide.
The modified magnesium hydroxide is prepared by the following method: 10g of magnesium hydroxide and 0.05 g of sodium hexametaphosphate are weighed, added into 220g of water, stirred for 75 minutes at the temperature of 25 ℃ at 400 rpm, 0.8g of lauric acid is added, stirred for 75 minutes at the temperature of 85 ℃ at 200 rpm, centrifuged for 25 minutes at 4000 rpm, and the obtained solid is dried to constant weight at the temperature of 105 ℃ to obtain the modified magnesium hydroxide.
The preparation method of the modified glass fiber comprises the following steps: and (3) keeping the temperature of the glass fiber at 450 ℃ for 30 minutes, washing the glass fiber with water, and drying the glass fiber at 85 ℃ to constant weight to obtain the modified glass fiber.
A preparation method of a nylon 66 and semi-aromatic nylon composite material comprises the following steps: (1) respectively drying the semi-aromatic nylon and the nylon 66 at 85 ℃ for 8 hours, respectively drying the modified glass fiber at 70 ℃ for 5 hours, weighing the semi-aromatic nylon, the nylon 66, the flame retardant, the heat stabilizer, the lubricant and the antioxidant 168 according to parts by weight, putting the materials into a stirrer, and stirring the materials at 400 revolutions per minute for 6 minutes to obtain a mixture;
(2) putting the mixture into a main feeding port in a double-screw extruder, introducing the modified glass fiber into a long fiber feeding port of the double-screw extruder, and performing extrusion, traction and granulation to obtain the nylon 66 and semi-aromatic nylon composite material, wherein the temperature of the double-screw extruder is as follows: 260 ℃ in the first zone, 270 ℃ in the second zone, 280 ℃ in the third zone, 285 ℃ in the fourth zone, 290 ℃ in the fifth zone, 290 ℃ in the sixth zone, 295 ℃ in the seventh zone, 295 ℃ in the eighth zone, 295 ℃ in the ninth zone, 295 ℃ in the tenth zone, 290 ℃ in the head temperature and 200r/min in the screw rotation speed.
Example 2
Essentially the same as example 1 except that the modified glass fiber was prepared by a process comprising the steps of:
(1) pretreatment: keeping the temperature of the glass fiber at 450 ℃ for 30 minutes, cleaning the glass fiber with water, and drying the glass fiber at 85 ℃ to constant weight to obtain pretreated glass fiber;
(2) acidifying, namely soaking the pretreated glass fiber in a hydrochloric acid solution of 3 mol/L for 85 minutes, wherein the solid-to-liquid ratio of the glass fiber to the hydrochloric acid solution is 1 g: 5m L, washing with water until the washing liquid is neutral, and drying at 85 ℃ to constant weight to obtain acidified glass fiber;
(3) a first modification, namely adding 220m L of toluene into a 500m L flask, adding 4g of 1, 4-p-phenylene diisocyanate, stirring at 25 ℃ for 30 minutes at 400 r/min, adding 8g of acidified glass fiber and 0.5g of dibutyltin dilaurate, stirring at 40 ℃ for 5 hours at 200r/min, filtering by a 300-mesh filter cloth, washing the obtained solid with toluene for three times, and drying at 75 ℃ to constant weight to obtain a first modified glass fiber;
(4) and (2) mixing 2g of silicon dioxide and 200m of L1, 4-dioxane, stirring at the temperature of 25 ℃ for 30 minutes at the speed of 400 rpm, adding 0.5g of primary modified glass fiber and triethylamine, reacting at the temperature of 40 ℃ for 20 hours, filtering by a 300-mesh filter cloth, washing the obtained solid by the 1, 4-dioxane for three times, and drying at the temperature of 85 ℃ to constant weight to obtain the modified glass fiber.
Example 3
Essentially the same as example 2 except that the thermal stabilizer was lanthanum stearate.
Example 4
Essentially the same as example 2 except that the thermal stabilizer was zirconium stearate.
Example 5
Substantially the same as example 2, except that the heat stabilizer is a mixture of lanthanum stearate and zirconium stearate, and the mass ratio of the lanthanum stearate to the zirconium stearate is 10: 1.
example 6
Raw materials (parts by weight) of the nylon 66 and semi-aromatic nylon composite material are as follows: 60 parts of semi-aromatic nylon, 6640 parts of nylon, 45 parts of modified glass fiber, 3 parts of flame retardant, 1.5 parts of heat stabilizer, 1.5 parts of lubricant and 1680.8 parts of antioxidant.
The semi-aromatic nylon is nylon 10T.
The heat stabilizer is a mixture of lanthanum stearate and zirconium stearate, and the mass ratio of the lanthanum stearate to the zirconium stearate is 10: 1.
the lubricant is pentaerythritol stearate.
The flame retardant is magnesium phytate.
The preparation method of the modified glass fiber comprises the following steps:
(1) pretreatment: keeping the temperature of the glass fiber at 450 ℃ for 30 minutes, cleaning the glass fiber with water, and drying the glass fiber at 85 ℃ to constant weight to obtain pretreated glass fiber;
(2) acidifying, namely soaking the pretreated glass fiber in a hydrochloric acid solution of 3 mol/L for 85 minutes, wherein the solid-to-liquid ratio of the glass fiber to the hydrochloric acid solution is 1 g: 5m L, washing with water until the washing liquid is neutral, and drying at 85 ℃ to constant weight to obtain acidified glass fiber;
(3) the first modification is that 220m L of toluene is added into a 500m L flask, 4g of 1, 4-p-phenylene diisocyanate is added, the mixture is stirred for 30 minutes at 25 ℃ at 400 rpm, 8g of acidified glass fiber and 0.5g of dibutyltin dilaurate are added, the mixture is stirred for 5 hours at 40 ℃ at 200 rpm, the mixture is filtered by a 300-mesh filter cloth, the obtained solid is washed three times by toluene and dried to constant weight at 75 ℃, and the primary modified glass fiber is obtained, and the second modification is that 2g of silicon dioxide and 200m L1, 4-dioxane are mixed, the mixture is stirred for 30 minutes at 25 ℃ at 400 rpm, 0.5g of primary modified glass fiber and triethylamine are added, the mixture is reacted for 20 hours at 40 ℃, the filter cloth is filtered by a 300-mesh filter cloth, the obtained solid is washed three times by 1, 4-dioxane and dried to constant weight at 85 ℃, and the modified glass fiber is obtained.
A preparation method of a nylon 66 and semi-aromatic nylon composite material comprises the following steps:
(1) respectively drying the semi-aromatic nylon and the nylon 66 at 85 ℃ for 8 hours, respectively drying the modified glass fiber at 70 ℃ for 5 hours, weighing the semi-aromatic nylon, the nylon 66, the flame retardant, the heat stabilizer, the lubricant and the antioxidant 168 according to parts by weight, putting the materials into a stirrer, and stirring the materials at 400 revolutions per minute for 6 minutes to obtain a mixture;
(2) putting the mixture into a main feeding port in a double-screw extruder, introducing the modified glass fiber into a long fiber feeding port of the double-screw extruder, and performing extrusion, traction and granulation to obtain the nylon 66 and semi-aromatic nylon composite material, wherein the temperature of the double-screw extruder is as follows: 260 ℃ in the first zone, 270 ℃ in the second zone, 280 ℃ in the third zone, 285 ℃ in the fourth zone, 290 ℃ in the fifth zone, 290 ℃ in the sixth zone, 295 ℃ in the seventh zone, 295 ℃ in the eighth zone, 295 ℃ in the ninth zone, 295 ℃ in the tenth zone, 290 ℃ in the head temperature and 200r/min in the screw rotation speed.
The limit oxygen index test result of the obtained nylon 66 and semi-aromatic nylon composite material is as follows: 24.9 percent; the mechanical property test result is as follows: tensile strength 242MPa, notched Izod impact strength 15.7KJ/m2Water absorption 0.11% and heat distortion temperature 285 ℃.
Example 7
Raw materials (parts by weight) of the nylon 66 and semi-aromatic nylon composite material are as follows: 60 parts of semi-aromatic nylon, 6640 parts of nylon, 45 parts of modified glass fiber, 3 parts of flame retardant, 1.5 parts of heat stabilizer, 1.5 parts of lubricant and 1680.8 parts of antioxidant.
The semi-aromatic nylon is nylon 10T.
The heat stabilizer is a mixture of lanthanum stearate and zirconium stearate, and the mass ratio of the lanthanum stearate to the zirconium stearate is 10: 1.
the lubricant is pentaerythritol stearate.
The flame retardant is a mixture of modified magnesium hydroxide and magnesium phytate, and the mass ratio of the modified magnesium hydroxide to the magnesium phytate is 5: 1.
the modified magnesium hydroxide is prepared by the following method: 10g of magnesium hydroxide and 0.05 g of sodium hexametaphosphate are weighed, added into 220g of water, stirred for 75 minutes at the temperature of 25 ℃ at 400 rpm, 0.8g of lauric acid is added, stirred for 75 minutes at the temperature of 85 ℃ at 200 rpm, centrifuged for 25 minutes at 4000 rpm, and the obtained solid is dried to constant weight at the temperature of 105 ℃ to obtain the modified magnesium hydroxide.
The preparation method of the modified glass fiber comprises the following steps:
(1) pretreatment: keeping the temperature of the glass fiber at 450 ℃ for 30 minutes, cleaning the glass fiber with water, and drying the glass fiber at 85 ℃ to constant weight to obtain pretreated glass fiber;
(2) acidifying, namely soaking the pretreated glass fiber in a hydrochloric acid solution of 3 mol/L for 85 minutes, wherein the solid-to-liquid ratio of the glass fiber to the hydrochloric acid solution is 1 g: 5m L, washing with water until the washing liquid is neutral, and drying at 85 ℃ to constant weight to obtain acidified glass fiber;
(3) the first modification is that 220m L of toluene is added into a 500m L flask, 4g of 1, 4-p-phenylene diisocyanate is added, the mixture is stirred for 30 minutes at 25 ℃ at 400 rpm, 8g of acidified glass fiber and 0.5g of dibutyltin dilaurate are added, the mixture is stirred for 5 hours at 40 ℃ at 200 rpm, the mixture is filtered by a 300-mesh filter cloth, the obtained solid is washed three times by toluene and dried to constant weight at 75 ℃, and the primary modified glass fiber is obtained, and the second modification is that 2g of silicon dioxide and 200m L1, 4-dioxane are mixed, the mixture is stirred for 30 minutes at 25 ℃ at 400 rpm, 0.5g of primary modified glass fiber and triethylamine are added, the mixture is reacted for 20 hours at 40 ℃, the filter cloth is filtered by a 300-mesh filter cloth, the obtained solid is washed three times by 1, 4-dioxane and dried to constant weight at 85 ℃, and the modified glass fiber is obtained.
A preparation method of a nylon 66 and semi-aromatic nylon composite material comprises the following steps:
(1) respectively drying the semi-aromatic nylon and the nylon 66 at 85 ℃ for 8 hours, respectively drying the modified glass fiber at 70 ℃ for 5 hours, weighing the semi-aromatic nylon, the nylon 66, the flame retardant, the heat stabilizer, the lubricant and the antioxidant 168 according to parts by weight, putting the materials into a stirrer, and stirring the materials at 400 revolutions per minute for 6 minutes to obtain a mixture;
(2) putting the mixture into a main feeding port in a double-screw extruder, introducing the modified glass fiber into a long fiber feeding port of the double-screw extruder, and performing extrusion, traction and granulation to obtain the nylon 66 and semi-aromatic nylon composite material, wherein the temperature of the double-screw extruder is as follows: 260 ℃ in the first zone, 270 ℃ in the second zone, 280 ℃ in the third zone, 285 ℃ in the fourth zone, 290 ℃ in the fifth zone, 290 ℃ in the sixth zone, 295 ℃ in the seventh zone, 295 ℃ in the eighth zone, 295 ℃ in the ninth zone, 295 ℃ in the tenth zone, 290 ℃ in the head temperature and 200r/min in the screw rotation speed.
The limit oxygen index test result of the obtained nylon 66 and semi-aromatic nylon composite material is as follows: 28.8 percent; the mechanical property test result is as follows: tensile strength 277MPa, Izod notched impact strength 18.5KJ/m2Water absorption of 0.08% and heat distortion temperature 323 ℃.
Test example 1
The limited oxygen indexes of the nylon 66 and semi-aromatic nylon composite materials obtained in the examples 1 to 5 are tested, and the specific results are shown in the table 1.
TABLE 1 test results of limiting oxygen index
| Limit oxygen index% | |
| Example 1 | 21.6 |
| Example 2 | 22.7 |
| Example 3 | 23.6 |
| Example 4 | 23.1 |
| Example 5 | 25.8 |
Test example 2
The mechanical properties of the nylon 66 and semi-aromatic nylon composite materials obtained in examples 1 to 5 were measured. The specific results are shown in Table 2.
TABLE 2 mechanical property test result table for nylon 66 and semi-aromatic nylon composite material
Test example 3
The water absorption and heat distortion temperature of the nylon 66 and semi-aromatic nylon composite obtained in examples 1 to 5 were measured. The specific results are shown in Table 3.
TABLE 3 mechanical property test result table for nylon 66 and semi-aromatic nylon composite material
The composite material of nylon 66 and semi-aromatic nylon obtained in example 2 has better flame retardancy, mechanical properties, water absorption and heat resistance than those of example 1, because the surface of the glass fiber is smooth, the active group is less, and the interface bonding between the glass fiber and the resin matrix in the composite material is weak, thereby affecting the performance of the composite material. Through primary modification, the surface of the glass fiber is coated to form an isocyanate layer, so that the reactivity of the surface of the glass fiber is improved. After the secondary modification, the glass fiber with the surface coated with the polyisocyanate layer is subjected to grafting reaction with silicon dioxide to obtain the silicon dioxide modified glass fiber. Silicon hydroxyl on the surface of the silicon dioxide is easy to generate physical and chemical actions with a high polymer material, so that the effects of strengthening and toughening are achieved, the heat resistance is improved, and the mechanical property is improved.
Different heat stabilizers are respectively adopted in examples 2 to 4, and the fact that lanthanum stearate is adopted in example 3 is found that the comprehensive performance of the obtained nylon 66 and semi-aromatic nylon composite material is good.
Claims (8)
1. The composite material of nylon 66 and semi-aromatic nylon is characterized by comprising the following raw materials in parts by weight: 50-70 parts of semi-aromatic nylon, 0-50 parts of nylon 6630-60 parts of modified glass fiber, 2-4 parts of flame retardant, 1-2 parts of heat stabilizer, 1-2 parts of lubricant and 1680.5-1 part of antioxidant;
the flame retardant is modified magnesium hydroxide, and the modified magnesium hydroxide is prepared by the following method: weighing 10g of magnesium hydroxide and 0.01-0.1g of sodium hexametaphosphate, adding the magnesium hydroxide and the sodium hexametaphosphate into 240g of water of 200-.
2. The composite material of nylon 66 and semi-aromatic nylon of claim 1, wherein the semi-aromatic nylon is selected from one or more of nylon 4T, nylon 5T, nylon 8T, nylon 9T, nylon 10T, nylon 11T and nylon 12T.
3. The composite material of nylon 66 and semi-aromatic nylon as claimed in claim 1, wherein the heat stabilizer is one or more of calcium stearate, lanthanum stearate and zirconium stearate.
4. The nylon 66 and semi-aromatic nylon composite material of claim 1, wherein the thermal stabilizer is lanthanum stearate.
5. The nylon 66 and semi-aromatic nylon composite material of claim 3, wherein the heat stabilizer is a mixture of lanthanum stearate and zirconium stearate, and the mass ratio of the lanthanum stearate to the zirconium stearate is (8-12): 1.
6. the composite of nylon 66 and semi-aromatic nylon as claimed in claim 1, wherein the lubricant is one of pentaerythritol stearate, glycerol monostearate and oleamide.
7. The nylon 66 and semi-aromatic nylon composite material of claim 1, wherein the preparation method of the modified glass fiber comprises the following steps:
(1) pretreatment: keeping the temperature of the glass fiber at 400-500 ℃ for 20-40 minutes, cleaning with water, and drying at 80-90 ℃ to constant weight to obtain pretreated glass fiber;
(2) acidifying, namely soaking the pretreated glass fiber in a hydrochloric acid solution of 3 mol/L for 80-90 minutes, washing with water until the washing liquid is neutral, and drying at 80-90 ℃ to constant weight to obtain acidified glass fiber;
(3) the first modification comprises the steps of adding 200-240m L toluene into a flask, adding 2-5g of 1, 4-p-phenylene diisocyanate, stirring for 20-40 minutes at 20-30 ℃, adding 6-10g of acidified glass fiber and 0.1-1g of dibutyltin dilaurate, stirring for 4-6 hours at 30-50 ℃, filtering by a 300-mesh filter cloth, washing the obtained solid with toluene for three times, and drying at 65-85 ℃ to constant weight to obtain the first modified glass fiber;
(4) and (2) secondary modification, namely mixing 1-3g of silicon dioxide and 180-120m of L1-1, 4-dioxane, stirring for 20-40 minutes at 20-30 ℃, adding 0.1-1g of primary modified glass fiber and triethylamine, reacting for 18-22 hours at 30-50 ℃, filtering by using 300-mesh filter cloth, washing the obtained solid by using 1, 4-dioxane for three times, and drying at 80-90 ℃ to constant weight to obtain the modified glass fiber.
8. A method for preparing the nylon 66 and semi-aromatic nylon composite material of any one of claims 1-7, comprising the steps of:
(1) respectively drying the semi-aromatic nylon and the nylon 66 at 80-90 ℃ for 6-10 hours, respectively drying the modified glass fiber at 60-80 ℃ for 4-6 hours, weighing the semi-aromatic nylon, the nylon 66, the flame retardant, the heat stabilizer, the lubricant and the antioxidant 168 according to parts by weight, putting the materials into a stirrer, and stirring the materials at 300-500 r/min for 3-8 minutes to obtain a mixture;
(2) and (3) putting the mixture into a main feeding port in a double-screw extruder, introducing the modified glass fiber into a long fiber feeding port of the screw extruder, and performing extrusion, traction and granulation to obtain the nylon 66 and semi-aromatic nylon composite material.
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| 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 |
| 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 |
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| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| 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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| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| 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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