CN117820855B - Aging-resistant hydrolysis-resistant PA6T composite material and preparation method and application thereof - Google Patents
Aging-resistant hydrolysis-resistant PA6T composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anti-aging hydrolysis-resistant PA6T composite material, and a preparation method and application thereof. The composite material comprises the following raw material components in parts by weight: 40-80 parts of PA6T, 10-50 parts of hydrolysis-resistant glass fiber, 0.5-5 parts of hydrolysis-resistant agent, 0.2-2 parts of antioxidant, 0.2-2 parts of lubricant, 0.2-2 parts of surface modifier and 0.2-2 parts of anti-aging agent; the hydrolysis-resistant glass fiber is glass fiber pretreated by a coupling agent and a surfactant. The composite material obviously improves the hydrolysis resistance of the PA6T material, has excellent processing performance, mechanical performance and ageing resistance, can be used for manufacturing the electronic water pump shell material of the new energy automobile, and meets the requirements of hydrolysis resistance, ageing resistance and high temperature resistance of the use environment.
Description
Technical Field
The invention relates to the technical field of resin high polymer materials, in particular to an anti-aging hydrolysis-resistant PA6T composite material, a preparation method and application thereof.
Background
With the rapid development of light automobiles, new energy automobiles and high-end electronic information industry, people put forward higher requirements on the heat resistance of polymer materials, and enterprises at home and abroad develop high-temperature resistant nylon through intensive research. The high temperature resistant nylon is mainly classified into semi-aromatic nylon and wholly aromatic nylon, wherein the semi-aromatic nylon has better comprehensive performance, and is a typical representative of the development of the high temperature resistant nylon, such as PA6T, PA9T, PA10T, MXD6, HTN and the like. The copolymerization type semi-aromatic nylon has strong designability, low cost, easily available raw materials and easily regulated and controlled product performance, and becomes a hot spot for domestic and foreign research. However, the semi-aromatic nylon industry in China starts late, the dependency is over 70% at present, the market demand is large, and the pure resin and high-end modified products of foreign companies are limited to be sold in China. Therefore, the development of domestic high-temperature resistant nylon resin and functional modified materials thereof has very important supporting effect on the development of industries such as automobiles, electronics, electric appliances and the like.
The functional modification of the high-temperature resistant nylon mainly comprises the steps of introducing a filler with a certain function into a nylon resin system in a physical or chemical mixing mode, wherein the filler has good heat resistance, and can also introduce a new function to form a multifunctional high-temperature resistant nylon material. The functional modification mainly comprises fiber reinforcement, toughening modification, low dielectric modification, halogen-free flame retardance, super chemical resistance modification and the like. The filler modification process is relatively mature, but still has the problem of unstable quality.
Whether aliphatic or aromatic, the amide groups present to varying degrees exhibit water-absorbing properties that tend to result in dimensional stability problems in the product parts, fatigue after absorption of water, and reduced mechanical properties. Even the glass fiber reinforced nylon 66 has strength reduced by more than 50% after being boiled, so that the application of the nylon 66 in a water-contact environment is greatly limited. To overcome this problem, researchers have made many efforts, for example, chinese patent ZL201210574132.6 discloses the use of a mixture of copper compound, halogen synergist and lubricant (i.e. a bragg mann stabilizer) to improve the hydrolysis resistance of PA66, but such a stabilizer is only suitable for aliphatic nylon systems at use temperatures up to 180 ℃ and not for high temperature nylon systems. For example, chinese patent ZL201710830811.8 discloses a technical scheme for improving hydrolysis resistance of aliphatic nylon and aromatic nylon by adopting polycarbodiimides, but the polycarbodiimides have the defects of large molecular weight, difficult volatilization, difficult extraction and low toxicity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an anti-aging hydrolysis-resistant PA6T composite material, and a preparation method and application thereof. The composite material obviously improves the hydrolysis resistance of the PA6T material, has excellent processing performance, mechanical performance and ageing resistance, can be used for manufacturing the electronic water pump shell material of the new energy automobile, and meets the requirements of hydrolysis resistance, ageing resistance and high temperature resistance of the use environment.
In order to achieve the purpose, the first aspect of the invention discloses an anti-aging hydrolysis-resistant PA6T composite material, which comprises the following raw material components in parts by weight:
the hydrolysis-resistant glass fiber is glass fiber pretreated by a coupling agent and a surfactant.
Preferably, the preparation method of the hydrolysis-resistant glass fiber comprises the following steps:
1) Sequentially adding a coupling agent and a surfactant into a deionized water tank, heating the liquid to 40-50 ℃ and maintaining uniform stirring;
2) Immersing the glass fiber into the liquid of the water tank obtained in the step 1), immersing for 10-200 min, discharging from the water tank, and drying to obtain the hydrolysis-resistant glass fiber.
Preferably, the glass fiber pretreated in the step 1) is 100 parts by weight, the coupling agent is used in an amount of 0.1 to 5 parts by weight, and the surfactant is used in an amount of 1 to 10 parts by weight.
Preferably, the step 1) is performed with pretreatment of 100 parts by weight of glass fiber, and the weight part of the coupling agent is 0.5-3 parts; the weight portion of the surfactant is 2-8 portions.
Preferably, the coupling agent is one or more of titanate coupling agent, aluminate coupling agent and zirconate coupling agent.
Preferably, the surfactant is alkylphenol polyoxyethylene ether carboxylate, and the carboxylate is alkali metal salt, alkaline earth metal salt or ammonium salt.
Preferably, the aging-resistant hydrolysis-resistant PA6T composite material comprises the following raw material components in parts by weight: 68.5 parts of PA6T, 30 parts of hydrolysis-resistant glass fiber, 3 parts of hydrolysis-resistant agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 2 parts of anti-aging agent; the preparation method of the hydrolysis-resistant glass fiber comprises the following steps:
1) Sequentially adding 10 parts of coupling agent and 30 parts of surfactant into a deionized water tank, and heating the liquid to 45 ℃ and maintaining uniform stirring;
2) And (3) unreeling 500 parts of glass fiber by a winding ring, pulling and immersing the glass fiber in a water tank, setting the residence time to be 60min, discharging the glass fiber from the water tank, and blowing and reeling by hot air to obtain the hydrolysis-resistant glass fiber.
Preferably, the PA6T is PA6T homopolymer or PA6T copolymer, and the PA6T copolymer is one or more of PA6T/6, PA6T/66, PA6T/56, PA6T/610, PA6T/612, PA6T/1010, PA6T/1111, PA6T/1012, PA6T/1212, and PA 6T/1313.
Preferably, the hydrolysis inhibitor is an isocyanate compound.
Preferably, the antioxidant is one or more of Irganox 168, irganox 1010 and Irganox 1076.
Preferably, the lubricant is one or more of long carbon chain fatty acid ester, long carbon chain fatty acid amide and long carbon chain fatty acid soap.
Preferably, the surface modifier is selected from silicone compounds.
Preferably, the anti-aging agent is one or more of 2- [2, 4-bis (2, 4-xylyl) -2- (1, 3, 5-triazinyl) 5-octyloxyphenol and 2,2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol).
The second aspect of the invention discloses a preparation method of the aging-resistant hydrolysis-resistant PA6T composite material, which comprises the following steps:
s1: weighing raw materials of all the components according to parts by weight, and uniformly mixing PA6T, hydrolysis inhibitor, antioxidant, lubricant, surface modifier and anti-aging agent in a high-speed mixer to obtain a stirring mixture
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, the hydrolysis-resistant glass fiber is fed into a fiber inlet of the double-screw extruder, and the materials are mixed and extruded by the double-screw extruder;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Preferably, in the step S2, the temperature of each zone of the twin-screw extruder is set to 280-340 ℃ and the rotation speed of the main machine is set to 350-800 rpm.
Preferably, in the step S2, the temperatures of each section of the twin-screw extruder are as follows: first zone 295, second zone 305, third zone 315, fourth zone 325, fifth zone 325, sixth zone 325, seventh zone 315, eighth zone 315, ninth zone 315, tenth zone 315, die 310, residence time 55s.
The third aspect of the invention discloses application of the anti-aging hydrolysis-resistant PA6T composite material in new energy automobiles.
Compared with the prior art, the invention has the advantages and positive effects that: provides an anti-aging hydrolysis-resistant PA6T composite material, a preparation method and application thereof. The composite material remarkably improves the hydrolysis resistance of the PA6T material, has excellent processing performance, mechanical performance, ageing resistance and the like, can be used for manufacturing new energy automobile electronic water pump shell materials, can still maintain excellent performance in a high-temperature and high-humidity environment, and better meets the hydrolysis resistance, ageing resistance and high-temperature resistance requirements of the use environment. Specifically:
(1) The fiber used in the composite material is hydrolysis-resistant glass fiber obtained through hydrolysis-resistant and surface modification pretreatment, and the hydrolysis-resistant glass fiber is added according to the raw material proportion of the application, so that the mechanical property of the composite material can be effectively improved. Meanwhile, the compatibility between the fiber and the PA6T resin can be effectively improved through pretreatment.
(2) The invention can obviously improve the surface performance, the thermal stability and the ageing resistance of the obtained composite material product by excellent combination of the ageing resistance agent, the lubricant, the surface modifier and the antioxidant, better adapt to the material requirements of products such as electronic water pump shell materials of new energy automobile parts, and meet the performance requirements of hydrolysis resistance, ageing resistance, high temperature resistance and the like.
(3) In the preferred scheme, the composite material adopts isocyanate hydrolysis-resistant agent, and can catch active groups generated by nylon decomposition, so that the material is slowed down or prevented from further hydrolysis, the hydrolysis-resistant capability is improved, and the material is more suitable for use in a water-contact environment.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific structures, process conditions, and results thereof described in the examples are only illustrative of the invention and should not be nor should they be construed to limit the invention as detailed in the claims.
An anti-aging hydrolysis-resistant PA6T composite material comprises the following raw material components in parts by weight:
wherein, the hydrolysis-resistant glass fiber is glass fiber pretreated by a coupling agent and a surfactant.
The preparation method of the aging-resistant hydrolysis-resistant PA6T composite material comprises the following steps:
s1: weighing raw materials of all the components according to parts by weight, and uniformly mixing PA6T, hydrolysis inhibitor, antioxidant, lubricant, surface modifier and anti-aging agent in a high-speed mixer to obtain a stirring mixture
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder, and materials are mixed and extruded by the double-screw extruder;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
The anti-aging hydrolysis-resistant PA6T composite material has excellent hydrolysis resistance, and also has excellent processability, mechanical properties and aging resistance, and the fibers used in the composite material are hydrolysis-resistant glass fibers obtained through hydrolysis resistance and surface modification pretreatment. Meanwhile, the compatibility between the fiber and the PA6T resin can be effectively improved through pretreatment. According to the embodiment, through the excellent combination of the PA6T resin, the fiber, the anti-aging agent, the lubricant, the surface modifier and the antioxidant, the surface performance, the thermal stability and the aging resistance of the obtained composite material product can be obviously improved, so that the obtained composite material can be better adapted to the material requirements of products such as new energy automobile parts, e.g. electronic water pump shells and the like, and the requirements of hydrolysis resistance, aging resistance, high temperature resistance and the like of the composite material product are met.
The aging-resistant hydrolysis-resistant PA6T composite material preferably comprises the following raw material components in parts by weight: 68.5 parts of PA6T, 30 parts of hydrolysis-resistant glass fiber, 3 parts of hydrolysis-resistant agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 2 parts of anti-aging agent.
Preferably, the PA6T is PA6T homopolymer or PA6T copolymer, and the PA6T copolymer is one or more of PA6T/6, PA6T/66, PA6T/56, PA6T/610, PA6T/612, PA6T/1010, PA6T/1111, PA6T/1012, PA6T/1212, and PA 6T/1313.
In order to further enhance the water-washing resistance of the composite material, the hydrolysis-resistant agent is isocyanate compound, which can catch active groups generated by nylon decomposition, thereby slowing down or preventing the material from further hydrolysis, improving the hydrolysis-resistant capability and enabling the material to be more suitable for use in a water-contact environment.
Wherein the antioxidant is one or more of Irganox 168, irganox 1010 and Irganox 1076; the lubricant is one or more of long carbon chain fatty acid ester, long carbon chain fatty acid amide and long carbon chain fatty acid soap. The surface modifier is selected from silicone compounds. The anti-aging agent is one or more of 2- [2, 4-bis (2, 4-xylyl) -2- (1, 3, 5-triazinyl) 5-octoxyphenol and 2,2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol).
The preparation method of the hydrolysis-resistant glass fiber comprises the following steps:
1) Sequentially adding a coupling agent and a surfactant into a deionized water tank, heating the liquid to 40-50 ℃ and maintaining uniform stirring; pretreating 100 parts by weight of glass fiber, wherein the weight part of the used coupling agent is 0.1-5 parts, and the weight part of the used surfactant is 1-10 parts;
2) Immersing the glass fiber into the liquid of the water tank obtained in the step 1), immersing for 10-200 min, discharging from the water tank, and drying to obtain the hydrolysis-resistant glass fiber.
The hydrolysis-resistant glass fiber prepared by the method can be used as a raw material to be added into the PA6T resin, so that the mechanical property of the composite material can be effectively improved, and meanwhile, the compatibility between the fiber and the PA6T resin can be effectively improved through pretreatment.
Specifically, the glass fiber with the weight portion of 100 parts is pretreated in the step 1), and the weight portion of the coupling agent is 0.5 to 3 parts; the weight portion of the surfactant is 2-8 portions.
Specifically, the coupling agent used in the step 1) is one or more of titanate coupling agent, aluminate coupling agent and zirconate coupling agent; the surfactant is alkylphenol polyoxyethylene ether carboxylate, and the carboxylate is alkali metal salt, alkaline earth metal salt or ammonium salt.
In the step S2, the temperature of each area of the double-screw extruder is set to be 280-340 ℃, the rotating speed of a main machine is set to be 350-800 rpm, the main feeding rotating speed is regulated to control the adding amount of the mixture, and the rotating speed of the glass fiber roll is regulated to control the adding amount of the hydrolysis-resistant glass fiber. Specifically, in step S2, the temperatures of each section of the twin-screw extruder are: first zone 295, second zone 305, third zone 315, fourth zone 325, fifth zone 325, sixth zone 325, seventh zone 315, eighth zone 315, ninth zone 315, tenth zone 315, die 310, residence time 55s.
The following raw materials were used in the examples: PA6T is dupont FR52G30BL; the glass fiber is ECDR-2000-SL 810 manufactured by Chongqing three-epitaxy glass fiber Co., ltd; the coupling agent is an epoxy silane coupling agent (Japanese Kossa KBE-403); the surfactant is APEC-Na (manufactured by WU Kang Qiong biological medicine technology Co., ltd.); the hydrolysis-resistant agent is 1, 5-naphthalene diisocyanate (manufactured by Wohan Ji Xinyi, inc. of Biotechnology Co., ltd.); the antioxidant is a mixture of the Pasteur Irganox 168 and the Irganox 1076 according to the mass ratio of 1:1; the lubricant is lauric acid diethanolamide (Jinan Cheng Shi Biotechnology Co., ltd.) 6501; the surface modifier is bio-polydimethylsiloxane (produced by Jining Sanshi Biotechnology Co., ltd.); the anti-aging agent is 2,2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol) (produced by Henz new polymer materials Co., ltd.).
The preparation method of the hydrolysis-resistant glass fiber used in the following example comprises the following steps:
2) Sequentially adding 10 parts of coupling agent and 30 parts of surfactant into a deionized water tank, and heating the liquid to 45 ℃ and maintaining uniform stirring;
3) And (3) unreeling 500 parts of glass fiber by a winding ring, pulling and immersing the glass fiber in a water tank, setting the residence time to be 60min, discharging the glass fiber from the water tank, and blowing and reeling by hot air to obtain the hydrolysis-resistant glass fiber.
Example 1
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
s1: weighing raw materials of the components according to parts by weight, and uniformly mixing 70 parts of PA6T, 3 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperature of each zone of the twin-screw extruder is set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
And obtaining the aging-resistant hydrolysis-resistant PA6T material through melt extrusion, water cooling, air cooling, drying, granulating, vibration screening, homogenization and drying.
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 2
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 68 parts of PA6T, 5 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperature of each zone of the twin-screw extruder is set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 3
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 72.2 parts of PA6T, 0.8 part of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperature of each zone of the twin-screw extruder is set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 4
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of all the components according to parts by weight, and uniformly mixing 69.3 parts of PA6T, 3 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 1.2 parts of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 5
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
s1: weighing raw materials of the components according to parts by weight, and uniformly mixing 68.5 parts of PA6T, 3 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 2 parts of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 6
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 55 parts of PA6T, 3 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
s2: putting the stirring mixture obtained in the step S1 into a main feeding hopper of a double-screw extruder, and feeding 45 parts of hydrolysis-resistant glass fibers into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: 300 ℃ in the first area, 315 ℃ in the second area, 325 ℃ in the third area, 330 ℃ in the fourth area, 330 ℃ in the fifth area, 330 ℃ in the sixth area, 325 ℃ in the seventh area, 325 ℃ in the eighth area, 325 ℃ in the ninth area, 325 ℃ in the tenth area, 320 ℃ in the die opening, the residence time is 55s, the host machine rotating speed is 500rpm, the main feeding rotating speed is regulated to control the adding amount of the mixture, and the glass fiber winding rotating speed is regulated to control the adding amount of the hydrolysis resistant glass fibers;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 7
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 40 parts of PA6T, 0.5 part of hydrolysis inhibitor, 0.2 part of antioxidant, 0.2 part of lubricant, 0.2 part of surface modifier and 0.2 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
s2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 10 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: 300 ℃ in the first area, 315 ℃ in the second area, 325 ℃ in the third area, 330 ℃ in the fourth area, 330 ℃ in the fifth area, 330 ℃ in the sixth area, 325 ℃ in the seventh area, 325 ℃ in the eighth area, 325 ℃ in the ninth area, 325 ℃ in the tenth area, 320 ℃ in the die opening, 55 seconds in the stay time, 350rpm in the main machine, adjusting the main feeding rotating speed to control the adding amount of the mixture, and adjusting the rotating speed of the glass fiber roll to control the adding amount of the hydrolysis-resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 8
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 80 parts of PA6T, 5 parts of hydrolysis resistance agent, 2 parts of antioxidant, 2 parts of lubricant, 2 parts of surface modifier and 2 parts of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
s2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 50 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: 300 ℃ in the first area, 315 ℃ in the second area, 325 ℃ in the third area, 330 ℃ in the fourth area, 330 ℃ in the fifth area, 330 ℃ in the sixth area, 325 ℃ in the seventh area, 325 ℃ in the eighth area, 325 ℃ in the ninth area, 325 ℃ in the tenth area, 320 ℃ in the die opening, the residence time is 55s, the rotating speed of the host machine is 800rpm, the main feeding rotating speed is regulated to control the adding amount of the mixture, and the rotating speed of the glass fiber roll is regulated to control the adding amount of the hydrolysis-resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 9
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 50 parts of PA6T, 1 part of hydrolysis resistance agent, 0.5 part of antioxidant, 0.5 part of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, and 20 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: 300 ℃ in the first area, 315 ℃ in the second area, 325 ℃ in the third area, 330 ℃ in the fourth area, 330 ℃ in the fifth area, 330 ℃ in the sixth area, 325 ℃ in the seventh area, 325 ℃ in the eighth area, 325 ℃ in the ninth area, 325 ℃ in the tenth area, 320 ℃ in the die opening, the residence time is 55s, the host machine rotating speed is 500rpm, the main feeding rotating speed is regulated to control the adding amount of the mixture, and the glass fiber winding rotating speed is regulated to control the adding amount of the hydrolysis resistant glass fibers;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 10
A preparation method of an anti-aging hydrolysis-resistant PA6T composite material comprises the following steps:
s1: weighing raw materials of the components according to parts by weight, and uniformly mixing 70 parts of PA6T, 3.5 parts of hydrolysis resistance agent, 1.5 parts of antioxidant, 1.5 parts of lubricant, 1.5 parts of surface modifier and 1.5 parts of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
s2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 40 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: the method comprises the steps of 300 ℃ in a first area, 315 ℃ in a second area, 325 ℃ in a third area, 330 ℃ in a fourth area, 330 ℃ in a fifth area, 330 ℃ in a sixth area, 325 ℃ in a seventh area, 325 ℃ in an eighth area, 325 ℃ in a ninth area, 325 ℃ in a tenth area, 320 ℃ in a die, and the residence time is 55 seconds, and the main machine rotating speed is 600rpm, so that the adding amount of a mixture is controlled by adjusting the main feeding rotating speed, and the adding amount of hydrolysis-resistant glass fibers is controlled by adjusting the rotating speed of a glass fiber roll;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Comparative example 1
The preparation method of the PA6T composite material comprises the following steps:
S1: weighing raw materials of all the components according to parts by weight, and uniformly mixing 73 parts of PA6T, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Comparative example 2
The preparation method of the PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 70.5 parts of PA6T, 3 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant and 0.5 part of surface modifier in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 30 parts of hydrolysis-resistant glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: first region 295 deg.c, second region 305 deg.c, third region 315 deg.c, fourth region 325 deg.c, fifth region 325 deg.c, sixth region 325 deg.c, seventh region 315 deg.c, eighth region 315 deg.c, ninth region 315 deg.c, tenth region 315 deg.c, die opening 310 deg.c, residence time 55s, main machine rotation speed 500rpm, main feeding rotation speed to control the amount of mixture, and glass fiber roll rotation speed to control the amount of hydrolysis resistant glass fiber;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Comparative example 3
The preparation method of the PA6T composite material comprises the following steps:
S1: weighing raw materials of the components according to parts by weight, and uniformly mixing 55 parts of PA6T, 3 parts of hydrolysis resistance agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 0.5 part of anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, 45 parts of glass fibers are fed into a fiber inlet of the double-screw extruder; the temperatures of all sections of the twin-screw extruder are set as follows: 300 ℃ in the first area, 315 ℃ in the second area, 325 ℃ in the third area, 330 ℃ in the fourth area, 330 ℃ in the fifth area, 330 ℃ in the sixth area, 325 ℃ in the seventh area, 325 ℃ in the eighth area, 325 ℃ in the ninth area, 325 ℃ in the tenth area, 320 ℃ in the die opening, the residence time is 55s, the host machine rotating speed is 500rpm, the main feeding rotating speed is regulated to control the adding amount of the mixture, and the glass fiber winding rotating speed is regulated to control the adding amount of the hydrolysis resistant glass fibers;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
Example 11 Performance test experiments
The pellets prepared in the 10 examples and 3 comparative examples were injection molded on an injection molding machine, and the bars were placed in a constant temperature and humidity oven at 100% humidity and room temperature for 48 hours, then placed in a 185 ℃ oven for 720 hours, and then tested.
Modulus of elasticity: the stretching speed is 2mm/min according to ISO 527 standard;
Flexural strength: bending speed was 2mm/min as tested according to ISO 178 standard;
notched impact strength: tested according to ISO 179 standard;
Heat distortion temperature: the load was 1.80MPa according to ISO 75-2 standard.
The properties of examples 1 to 10 and comparative examples 1 to 3 are shown in the following table:
As can be seen from the comparison of the data in the table, when the hydrolysis-resistant agent is not added, after the material is subjected to constant temperature, constant humidity and thermal aging treatment, the retention rate of mechanical property and heat resistance is far lower than that of the PA6T composite material modified by the hydrolysis-resistant agent, which indicates that the hydrolysis-resistant agent inhibits the decomposition of the material under the conditions of high humidity and high temperature; the aging resistance of the PA6T composite material is improved to a certain extent by reasonably matching the aging resistance agent with other components; in addition, the glass fiber is subjected to surface coupling pretreatment, so that the interfacial adhesion between the fiber and the PA6T can be effectively improved, and the performance retention rate is superior to that of an untreated fiber system.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The aging-resistant hydrolysis-resistant PA6T composite material is characterized by comprising the following raw material components in parts by weight: 68.5 parts of PA6T, 30 parts of hydrolysis-resistant glass fiber, 3 parts of hydrolysis-resistant agent, 0.8 part of antioxidant, 1.2 parts of lubricant, 0.5 part of surface modifier and 2 parts of anti-aging agent; the hydrolysis-resistant glass fiber is glass fiber pretreated by a coupling agent and a surfactant; the hydrolysis inhibitor is 1, 5-naphthalene diisocyanate; pretreating 100 parts by weight of glass fiber, wherein the weight part of the coupling agent is 0.1-5 parts, and the weight part of the surfactant is 1-10 parts; the surfactant is alkylphenol polyoxyethylene ether carboxylate, and the salt is alkali metal salt, alkaline earth metal salt or ammonium salt; the surface modifier is selected from silicone compounds; the anti-aging agent is 2,2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol).
2. The anti-aging hydrolysis-resistant PA6T composite material as claimed in claim 1, wherein the preparation method of the hydrolysis-resistant glass fiber comprises the following steps:
1) Sequentially adding a coupling agent and a surfactant into a deionized water tank, heating the liquid to 40-50 ℃ and maintaining uniform stirring;
2) Immersing the glass fiber into the liquid of the water tank obtained in the step 1), immersing for 10-200 min, discharging from the water tank, and drying to obtain the hydrolysis-resistant glass fiber.
3. The anti-aging hydrolysis-resistant PA6T composite material according to claim 2, wherein the glass fiber is pretreated in the step 1) in 100 parts by weight, and the coupling agent is 0.5-3 parts by weight; the weight portion of the surfactant is 2-8 portions.
4. The anti-aging hydrolysis-resistant PA6T composite material of claim 3, wherein the coupling agent is one or more of a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent.
5. The anti-aging hydrolysis-resistant PA6T composite material as claimed in claim 1, wherein the preparation method of the hydrolysis-resistant glass fiber comprises the following steps:
1) Sequentially adding 10 parts of coupling agent and 30 parts of surfactant into a deionized water tank, and heating the liquid to 45 ℃ and maintaining uniform stirring;
2) And (3) unreeling 500 parts of glass fiber by a winding ring, pulling and immersing the glass fiber into a water tank, setting the residence time to be 60 min, discharging the glass fiber from the water tank, and carrying out hot air blowing and reeling to obtain the hydrolysis-resistant glass fiber.
6. The anti-aging hydrolysis-resistant PA6T composite material of claim 1, wherein the antioxidant is one or more of Irganox 168, irganox 1010, irganox 1076; the lubricant is one or more of long carbon chain fatty acid ester, long carbon chain fatty acid amide and long carbon chain fatty acid soap.
7. The method for producing an aging-resistant hydrolysis-resistant PA6T composite material according to any one of claims 1 to 6, comprising the steps of:
S1: weighing raw materials of all the components according to parts by weight, and uniformly mixing PA6T, hydrolysis inhibitor, antioxidant, lubricant, surface modifier and anti-aging agent in a high-speed mixer to obtain a stirring mixture;
S2: the stirring mixture obtained in the step S1 is put into a main feeding hopper of a double-screw extruder, the hydrolysis-resistant glass fiber is fed into a fiber inlet of the double-screw extruder, and the materials are mixed and extruded by the double-screw extruder;
S3: and (3) carrying out water cooling, air cooling, drying, granulating, vibration screening, homogenizing and drying on a product obtained through melt extrusion by a double-screw extruder to obtain the aging-resistant hydrolysis-resistant PA6T composite material.
8. The method according to claim 7, wherein in the step S2, the temperature of each zone of the twin-screw extruder is set to 280-340 ℃ and the rotation speed of the main machine is set to 350-800 rpm.
9. The method according to claim 8, wherein in the step S2, the temperatures of each section of the twin-screw extruder are as follows: first zone 295, second zone 305, third zone 315, fourth zone 325, fifth zone 325, sixth zone 325, seventh zone 315, eighth zone 315, ninth zone 315, tenth zone 315, die 310, residence time 55s.
10. The use of an anti-aging hydrolysis-resistant PA6T composite material according to any one of claims 1 to 6 in new energy automobiles.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914278A (en) * | 2003-12-02 | 2007-02-14 | 索尼株式会社 | Resin composition, molded product, and method for producing the resin composition |
| CN101675839A (en) * | 2008-09-18 | 2010-03-24 | E.I.内穆尔杜邦公司 | Industrial brush bristles and brush comprising same |
| CN107446349A (en) * | 2017-07-05 | 2017-12-08 | 惠州市华聚塑化科技有限公司 | A kind of ultraviolet aging resistance fire-retardant nylon composite and preparation method thereof |
| CN108373273A (en) * | 2018-02-26 | 2018-08-07 | 巨石集团有限公司 | A kind of fiberglas chopped strand size and its preparation method and application |
| CN109796752A (en) * | 2019-01-22 | 2019-05-24 | 重庆鑫翎创福光电科技股份有限公司 | A kind of anti-aging daiamid composition and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL130570C (en) * | 1963-12-12 | |||
| CN102382467A (en) * | 2011-11-25 | 2012-03-21 | 深圳市科聚新材料有限公司 | High-temperature and heat-ageing resistant PA66 material and preparation method thereof |
| CN108726898B (en) * | 2017-04-20 | 2021-08-13 | 巨石集团有限公司 | Impregnating compound for glass fiber of reinforced nylon resin and preparation method thereof |
| CN108503238B (en) * | 2018-04-19 | 2021-06-18 | 巨石集团有限公司 | Glass fiber impregnating compound for pipeline and preparation method and application thereof |
| CN111621147B (en) * | 2019-02-28 | 2024-02-23 | 艾曼斯（苏州）工程塑料有限公司 | Polyamide composition, preparation method and application thereof |
-
2023
- 2023-12-31 CN CN202311869349.4A patent/CN117820855B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914278A (en) * | 2003-12-02 | 2007-02-14 | 索尼株式会社 | Resin composition, molded product, and method for producing the resin composition |
| CN101675839A (en) * | 2008-09-18 | 2010-03-24 | E.I.内穆尔杜邦公司 | Industrial brush bristles and brush comprising same |
| CN107446349A (en) * | 2017-07-05 | 2017-12-08 | 惠州市华聚塑化科技有限公司 | A kind of ultraviolet aging resistance fire-retardant nylon composite and preparation method thereof |
| CN108373273A (en) * | 2018-02-26 | 2018-08-07 | 巨石集团有限公司 | A kind of fiberglas chopped strand size and its preparation method and application |
| CN109796752A (en) * | 2019-01-22 | 2019-05-24 | 重庆鑫翎创福光电科技股份有限公司 | A kind of anti-aging daiamid composition and preparation method thereof |
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