CN115536837A - Polyamide material and preparation method thereof - Google Patents
Polyamide material and preparation method thereof Download PDFInfo
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Abstract
The application discloses a polyamide material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, pretreating a waste polyamide material by using an ionic liquid to obtain caprolactam powder; s2, blending caprolactam and modified amino titanium dioxide-carbon fibers, adding deionized water and adipic acid, adjusting the temperature to 220-250 ℃, reacting for 16-20 h under the pressure of 130-170kPa, and drying to obtain a polyamide material; the weight ratio of the caprolactam to the modified amino titanium dioxide-carbon fiber is 62-88. The polyamide material prepared by the method has good mechanical property and ultraviolet resistance, and can meet the performance requirements of automobile safety belts.
Description
Technical Field
The application relates to the field of regenerated polyamide materials, in particular to a polyamide material and a preparation method thereof.
Background
The polyamide is commonly called nylon, has good mechanical property and processability, is a good thermoplastic engineering plastic, and can widely replace wear-resistant parts of mechanical equipment and wear-resistant parts of equipment instead of copper and alloy.
In the automotive field, polyamides are used in a very wide range of applications, both as exterior materials for the production of automotive tail lights, side lights and the like, and for the manufacture of automotive interior parts such as instrument panels, seat belts and the like. However, the light resistance of polyamide is poor, and the chain of polyamide can be broken under long-term illumination, so that aged parts need to be replaced frequently, and a large amount of waste polyamide is formed. The waste polyamide causes pollution to the existing land and ocean due to the non-regenerability of the waste polyamide, and the ecological balance is damaged.
Therefore, recycling of waste polyamide is a hot point of attention of people at present, but in the recycling process of waste polyamide, the physical recycling method is adopted to influence the mechanical properties such as tensile strength, bending strength and the like of polyamide, so that the properties of regenerated polyamide cannot meet the use requirements for manufacturing automobile parts, such as safety belts.
Disclosure of Invention
In order to solve the problem of poor mechanical property of regenerated polyamide, the application provides a polyamide material and a preparation method thereof.
In a first aspect, the present application provides a method for preparing a polyamide material, comprising the steps of:
s1, pretreating a waste polyamide material by using an ionic liquid to obtain caprolactam powder;
s2, blending caprolactam and modified amino titanium dioxide-carbon fiber, adding deionized water and adipic acid, adjusting the temperature to 220-250 ℃, reacting for 16-20 hours under the pressure of 130-170kPa, and drying to obtain a polyamide material;
the weight ratio of the caprolactam to the modified amino titanium dioxide-carbon fiber is 62-88.
By adopting the technical scheme, the waste polyamide is recovered by using the ionic liquid, the ionic liquid contains a large amount of hydrogen ions, the activity of the polyamide in the ionic liquid is high, the depolymerization speed of the polyamide can be accelerated, and on the other hand, the anion in the ionic liquid can weaken the hydrogen bond acting force among polyamide macromolecules, so that in the ionic liquid, the polyamide can be subjected to depolymerization reaction under a mild condition to obtain caprolactam, and the degradation rate of the polyamide in the ionic liquid is high and can generally reach more than 90%; the polyamide is recovered by the ionic liquid without introducing other chemical substances, so that the purity of the obtained caprolactam powder is higher, and the mechanical property of the polyamide regenerated by subsequent reaction is less influenced.
The carbon fiber has higher mechanical strength, the tensile strength of the regenerated polyamide can be improved by adding a small amount of the carbon fiber, the chemical property of the carbon fiber is stable, the carbon fiber has larger load surface area, and the load on the modified amino titanium dioxide can be better completed, but the material has too strong rigidity and insufficient toughness due to excessive addition of the carbon fiber, and the bending strength of the polyamide material is influenced. The titanium dioxide has excellent ultraviolet resistance and certain catalytic capacity under the illumination condition, so that stains can be degraded, the light resistance and antibacterial property of regenerated polyamide can be improved, the service life of the polyamide is prolonged, the titanium dioxide is modified to have amino groups, and in the process of loading the titanium dioxide, the modified amino titanium dioxide can form hydrogen bonds with active groups on the surface of carbon fibers, so that the loading fastness is improved; in the process of synthesizing polyamide, the modified amino titanium dioxide can be grafted to the polyamide through the esterification reaction of amino and carboxyl, and the modified amino titanium dioxide is combined with the polyamide in a chemical bond mode, so that the modified amino titanium dioxide is firmly combined with the polyamide, the modified amino titanium dioxide is more uniformly distributed, the light resistance of the product is improved, and the anti-aging capability of the product is further improved.
Preferably, the pretreatment comprises the following steps:
step one, infiltrating a waste polyamide material with an ionic liquid, adding a catalyst accounting for 5-8 wt% of the ionic liquid, stirring and catalyzing for 0.5-4 h, and filtering to obtain filter residue and a caprolactam solution;
step two: and (3) microwave heating the caprolactam solution in the step one at 220-260 ℃ for 0.5-1 h, cooling to room temperature, extracting, filtering and drying to obtain caprolactam powder.
By adopting the technical scheme, the catalyst is added to accelerate the depolymerization rate of the waste polyamide in the ionic liquid; the microwave heating is used for controlling the temperature, improving the depolymerization rate, controlling the side reaction and improving the yield and the purity of the caprolactam.
Typically, but not by way of limitation, the catalyst is 4-dimethylaminopyridine.
Preferably, the ionic liquid is one or more of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-hydroxyethyl-2,3-dimethylimidazole tetrafluoroborate and 1-hydroxyethyl-2,3-dimethylimidazole chloride salt.
By adopting the technical scheme, the ionic liquid with imidazole and imidazole groups in the ionic liquid cations has higher reaction activity, so that the depolymerization speed of the polyamide in the ionic liquid is higher, and the time for degrading the waste polyamide is shortened. The ionic liquid has a low melting point and is liquid at normal temperature.
Preferably, the preparation method of the modified amino titanium dioxide comprises the following steps:
step 1: mixing butyl titanate and absolute ethyl alcohol, then adding 0.1-0.3 mol/L silver ion solution, and continuously mixing to prepare reaction solution;
and 2, step: mixing an ethanol aqueous solution, glacial acetic acid and a reducing agent, then dropwise adding the mixture into the reaction solution, and uniformly stirring to obtain mixed gel; drying the mixed gel, grinding into powder, and calcining in a chlorine environment to obtain silver-doped titanium dioxide;
step 3, blending the silver-doped titanium dioxide obtained in the step 2 with an aminosilane coupling agent, dissolving the mixture into an alcohol-water mixture, and drying the mixture after ultrasonic oscillation for 20-40 min to obtain modified amino titanium dioxide;
the weight ratio of the aminosilane coupling agent to the butyl titanate is 1:2-4.
Typically, but not by way of limitation, the reducing agent is NaBH 4 。
By adopting the technical scheme, the nano silver has excellent light reflectivity, better ultraviolet resistance can be provided under the synergy of the nano silver and the titanium dioxide, and the nano silver and the titanium dioxide can form a long and compact crystal structure, so that the wear resistance and the bending strength of the polyamide can be improved, and the service life of the product is further prolonged. Amino groups are introduced on titanium dioxide by using an aminosilane coupling agent, so that the bonding fastness of subsequent modified amino titanium dioxide and carbon fibers is improved, and when polyamide is synthesized, the modified amino titanium dioxide can be grafted to the polyamide, so that the light resistance and the mechanical property of the polyamide material are improved.
Preferably, the preparation material of the modified amino titanium dioxide-carbon fiber comprises the modified amino titanium dioxide and the carbon fiber in a weight ratio of 1:1-15.
The carbon fiber has better strength, but the excessive addition of the carbon fiber can influence the toughness and elasticity of the polyamide material, the titanium dioxide can improve the toughness and elasticity of the polyamide material, and the excessive titanium dioxide can accelerate the aging of the polyamide material due to the excessively strong photocatalytic performance; in the process of manufacturing automobile interiors such as safety belts and the like, the polyamide material is required to have better elasticity and bending property, so the doping amount of the modified amino titanium dioxide-carbon fiber is preferably selected to meet the polyamide property for producing the safety belts.
Preferably, the preparation material of the modified amino titanium dioxide-carbon fiber comprises the modified amino titanium dioxide and the carbon fiber in the weight ratio of 1:4-10.
By adopting the technical scheme, the proportion of the modified amino titanium dioxide and the carbon fiber is further optimized, so that the prepared polyamide material has better tensile strength, bending strength, light resistance and service life, and the safety belt with better performance is prepared.
Preferably, the preparation of the modified amino titanium dioxide-carbon fiber comprises the following steps:
a1, soaking carbon fibers in an acid solution, stirring for 1-2 h, adjusting the temperature to 90-100 ℃, carrying out hydrothermal reaction for 20-24 h, taking out the carbon fibers, cleaning, filtering and drying to obtain functional carbon fibers;
a2, adding the modified amino titanium dioxide and glacial acetic acid into absolute ethyl alcohol, and stirring and dispersing to obtain a modified amino titanium dioxide solution; soaking the functional carbon fiber obtained in the step A1 into a modified amino titanium dioxide solution, adjusting the temperature to 160-200 ℃, the pressure to 150-200kPa, and reacting for 24-36 h; and then cooling to room temperature, taking out the carbon fiber and drying to obtain the modified amino titanium dioxide-carbon fiber.
By adopting the technical scheme, impurities on the surface of the carbon fiber are removed by using the acid solution, and meanwhile, hydroxyl groups are introduced into the surface of the carbon fiber, so that the load capacity of the carbon fiber is improved, and when polyamide is synthesized subsequently, the hydroxyl groups of the carbon fiber can form hydrogen bonds with active groups such as hydroxyl groups on the polyamide, so that the tensile strength of the prepared polyamide material is improved;
compared with the conventional titanium dioxide loaded, the modified amino titanium dioxide loaded on the functional carbon fiber under the acidic condition is combined by hydrogen bonds, and is more tightly arranged on the surface of the carbon fiber, so that the loading amount and the light resistance of the carbon fiber in unit area are improved.
Preferably, the carbon fiber is a chopped carbon fiber having a thickness of 6 to 10um, a length of 1 to 20mm, and a tensile strength of 3500MPa to 3800 MPa.
Typically, but not by way of limitation, the acid solution is a nitric acid solution.
In summary, the present application has the following beneficial effects:
1. the waste polyamide is recovered through the ionic liquid, the polyamide degradation rate is high, the reaction condition is mild, the reaction is rapid, and the obtained caprolactam powder contains less impurities.
2. The blend of the modified amino titanium dioxide-carbon fiber in the polymerization process of caprolactam improves the tensile strength, bending strength and light resistance of regenerated polyamide, so that automobile parts such as safety belts made of the polyamide material have better elasticity, tensile strength and service life.
3. By modifying the carbon fiber and the titanium dioxide, the tensile strength, the bending strength and the light resistance of the prepared polyamide are improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples of preparation of raw materials and/or intermediates
Preparation of modified amino titanium dioxide
Preparation example 0-1, a modified amino titanium dioxide, was prepared according to the following procedure:
step 1: mixing 3kg of butyl titanate and 1L of absolute ethyl alcohol, then adding 1L of 0.2mol/L silver nitrate solution, and uniformly mixing to obtain a reaction solution;
step 2: 970g of ethanol aqueous solution (the mass of water is 70 g), 20g of glacial acetic acid and 10g of NaBH 4 After mixing, dropwise adding the mixture into the reaction solution, and uniformly stirring to obtain mixed gel; and (3) drying the mixed gel, grinding the mixed gel into powder, and calcining the powder for 2 hours at 600 ℃ in a chlorine environment to obtain the silver-doped titanium dioxide.
And 3, blending all the silver-doped titanium dioxide obtained in the step 2 and 1kg of gamma-aminoethyl aminopropyltrimethoxysilane, dissolving the mixture in 1kg of alcohol-water mixture (900 g of ethanol and 100g of water), ultrasonically oscillating for 30min, and drying to obtain the modified amino titanium dioxide.
Preparation examples 0 to 2, a modified amino titanium dioxide, was prepared according to the following steps:
step 1: mixing 4kg of butyl titanate and 1L of absolute ethyl alcohol, then adding 1L of 0.15mol/L silver nitrate solution, and uniformly mixing to obtain a reaction solution;
step 2: mixing 960g of ethanol aqueous solution (the mass of water is 70 g), 25g of glacial acetic acid and 15g of NaBH4, then dropwise adding the mixture into the reaction solution, and uniformly stirring to obtain mixed gel; and (3) drying the mixed gel, grinding the mixed gel into powder, and calcining the powder for 1h at the temperature of 650 ℃ in a chlorine environment to obtain the silver-doped titanium dioxide.
And 3, blending all the silver-doped titanium dioxide obtained in the step 2 with 1kg of diethylenetriaminopropyltrimethoxysilane, dissolving the mixture in 1kg of alcohol-water mixture (900 g of ethanol and 100g of water), carrying out ultrasonic oscillation for 40min, and drying to obtain the modified amino titanium dioxide.
Preparation examples 0 to 3, a modified amino titanium dioxide, was prepared according to the following steps:
step 1: mixing 2kg of butyl titanate and 1L of absolute ethyl alcohol, then adding 1L of 0.1mol/L silver nitrate solution, and uniformly mixing to obtain a reaction solution;
step 2: 965g of ethanol aqueous solution (the mass of water is 70 g), 30g of glacial acetic acid and 5g of NaBH4 are mixed and then are dripped into the reaction solution, and the mixture is stirred uniformly to prepare mixed gel; and (3) drying the mixed gel, grinding the mixed gel into powder, and calcining the powder for 1.5 hours at the temperature of 650 ℃ in a chlorine environment to obtain the silver-doped titanium dioxide.
And 3, blending all the silver-doped titanium dioxide obtained in the step 2 and 1kg of diethylenetriaminopropyltrimethoxysilane, dissolving the mixture in 1kg of alcohol-water mixture (900 g of ethanol and 100g of water), ultrasonically oscillating for 20min, and drying to obtain the modified amino titanium dioxide.
Preparation examples 0 to 4, a modified amino titanium dioxide was prepared, differing from preparation examples 0 to 1 in that: the amount of butyl titanate added was 6kg.
Preparation examples 0 to 5, a modified amino titanium dioxide was prepared, differing from preparation examples 0 to 1 in that: the amount of butyl titanate added was 0.5kg.
Preparation of modified amino titanium dioxide-carbon fiber
Preparation example 1-1, a modified amino titanium dioxide-carbon fiber, was prepared according to the following steps:
a1, taking 7kg of carbon fiber, immersing the carbon fiber into 10L of 0.5mol/L nitric acid solution, stirring for 2 hours, adjusting the temperature to 90 ℃, reacting for 24 hours, taking out the carbon fiber, alternately washing the carbon fiber with deionized water and acetic acid for three times, filtering, and drying in an oven at 80 ℃ for 1.5 hours to obtain functional carbon fiber;
a2, adding 1kg of modified amino titanium dioxide and 500g of acetic acid into 10L of absolute ethyl alcohol, and stirring and dispersing to obtain a modified amino titanium dioxide solution; soaking the functional carbon fiber obtained in the step A1 into a modified amino titanium dioxide solution, and reacting for 30 hours at 180 ℃ under 180 kPa; and then cooling to room temperature, taking out the carbon fiber and drying to obtain the modified amino titanium dioxide-carbon fiber.
Among them, modified amino titanium dioxide was obtained from preparation example 0-1.
Preparation examples 1 to 2, a modified amino titanium dioxide-carbon fiber, was prepared according to the following steps:
a1, immersing 10kg of carbon fiber into 10L of 0.5mol/L nitric acid solution, stirring for 1h, adjusting the temperature to 100 ℃, reacting for 20h, taking out the carbon fiber, alternately washing the carbon fiber with deionized water and acetic acid for three times, filtering, and drying in an oven at 75 ℃ for 2h to obtain functional carbon fiber;
a2, adding 1kg of modified amino titanium dioxide and 600g of acetic acid into 10L of absolute ethyl alcohol, and stirring and dispersing to obtain a modified amino titanium dioxide solution; soaking the functional carbon fiber obtained in the step A1 into a modified amino titanium dioxide solution, and reacting for 24 hours at 200 ℃ under the pressure of 200 kPa; and then cooling to room temperature, taking out the carbon fiber and drying to obtain the modified amino titanium dioxide-carbon fiber.
Among them, modified amino titanium dioxide was obtained from preparation examples 0 to 2.
Preparation examples 1 to 3, a modified amino titanium dioxide-carbon fiber, was prepared according to the following steps:
a1, soaking 4kg of carbon fiber into 10L of 0.5mol/L nitric acid solution, stirring for 1.5h, adjusting the temperature to 95 ℃, reacting for 22h, taking out the carbon fiber, washing the carbon fiber with deionized water and acetic acid for three times respectively, filtering, and drying in an oven at 85 ℃ to obtain functional carbon fiber;
a2, adding 1kg of modified amino titanium dioxide and 500g of acetic acid into 10L of absolute ethyl alcohol, and stirring and dispersing to obtain a modified amino titanium dioxide solution; soaking the functional carbon fiber obtained in the step A1 into a modified amino titanium dioxide solution, and reacting for 36 hours under the pressure of 150kPa at 160 ℃; and then cooling to room temperature, taking out the carbon fiber and drying to obtain the modified amino titanium dioxide-carbon fiber.
Among them, modified amino titanium dioxide was obtained from preparation examples 0 to 3.
Preparation examples 1 to 4, preparation of a modified amino titanium dioxide-carbon fiber, which is different from preparation example 1 to 1 in that: among them, modified amino titanium dioxide was obtained from preparation examples 0 to 4.
Preparation examples 1 to 5, preparation of a modified amino titanium dioxide-carbon fiber, different from preparation example 1 to 1, were: wherein the modified amino titanium dioxide is obtained from preparation examples 0 to 5.
Preparation examples 1 to 6, preparation of a modified amino titanium dioxide-carbon fiber, was different from the preparation example 1 to 1 in that: the amount of carbon fibers added was 15kg.
Preparation examples 1 to 7, preparation of a modified amino titanium dioxide-carbon fiber, was different from the preparation example 1 to 1 in that: the amount of carbon fibers added was 1kg.
Preparation examples 1 to 8, preparation of a modified amino titanium dioxide-carbon fiber, which is different from preparation example 1 to 1 in that: the carbon fiber is not subjected to the acidification treatment in the step A1, and the carbon fiber is directly immersed into the modified amino titanium dioxide solution in the step A2.
Preparation examples 1 to 9, preparation of a modified amino titanium dioxide-carbon fiber, was different from the preparation example 1 to 1 in that: and cooling the carbon fiber to room temperature, washing with deionized water and drying.
Examples
Example 1, a polyamide material, prepared as follows:
step one, 1kg of waste polyamide material is soaked by 10kg of 1-ethyl-3-methylimidazolium tetrafluoroborate, 0.65kg of 4-dimethylaminopyridine is added, stirring and catalysis are carried out for 2 hours, and filtering is carried out to obtain filter residue and caprolactam solution;
step two: and (2) heating the caprolactam solution in the step (I) for 0.8h at 240 ℃ by microwave, cooling to room temperature, extracting by using deionized water, filtering, and drying in an oven at 80 ℃ for 2h to obtain caprolactam powder.
And step three, taking 75g of caprolactam and 1g of modified amino titanium dioxide-carbon fiber, mixing, adding 950mL of deionized water and 50ml of 1g/mL adipic acid, adjusting the temperature to 240 ℃, reacting for 18h under the pressure of 150kPa, and drying to obtain the polyamide material.
Wherein, the modified amino titanium dioxide-carbon fiber is obtained from preparation example 1-1.
Example 2, a polyamide material, prepared as follows:
step one, 1kg of waste polyamide material is soaked by 10kg of 1-hydroxyethyl-2,3-dimethyl imidazole tetrafluoroborate, 0.8kg of 4-dimethylamino pyridine is added, stirring and catalyzing are carried out for 0.5h, and filtering is carried out to obtain filter residue and caprolactam solution;
step two: and (2) heating the caprolactam solution in the step (I) for 0.5h at 260 ℃ by microwave, cooling to room temperature, extracting by using deionized water, filtering, and drying in an oven at 120 ℃ for 1h to obtain caprolactam powder.
And step three, blending 62g of caprolactam and 1g of modified amino titanium dioxide-carbon fiber, adding 970mL of deionized water and 30ml of 1g/mL of adipic acid, adjusting the temperature to 250 ℃, reacting for 20 hours under the pressure of 170kPa, and drying to obtain the polyamide material.
Wherein, the modified amino titanium dioxide-carbon fiber is obtained from preparation examples 1-2.
Example 3, a polyamide material, prepared as follows:
step one, 1kg of waste polyamide material is soaked by 10kg of 1-hydroxyethyl-2,3-dimethyl imidazole chloride salt, 0.5kg of 4-dimethylamino pyridine is added, stirring and catalyzing are carried out for 4 hours, and filtering is carried out to obtain filter residue and caprolactam solution;
step two: and (2) heating the caprolactam solution in the step (I) for 1h at 220 ℃ by microwave, cooling to room temperature, extracting by using deionized water, filtering, and drying in an oven at 100 ℃ for 1.5h to obtain caprolactam powder.
And step three, blending 88g of caprolactam and 1g of modified amino titanium dioxide-carbon fiber, adding 900mL of deionized water and 100ml of 1g/mL of adipic acid, adjusting the temperature to 220 ℃, reacting for 16 hours under the pressure of 130kPa, and drying to obtain the polyamide material.
Wherein, the modified amino titanium dioxide-carbon fiber comes from preparation examples 1 to 3.
Example 4, a polyamide material was prepared, differing from example 1 in that: modified amino titanium dioxide-carbon fibers were obtained from preparation examples 1 to 4.
Example 5, a polyamide material was prepared, differing from example 1 in that: modified amino titanium dioxide-carbon fibers were obtained from preparation examples 1 to 5.
Example 6, a polyamide material was prepared, differing from example 1 in that: modified amino titanium dioxide-carbon fibers were obtained from preparation examples 1 to 6.
Example 7, a polyamide material was prepared, differing from example 1 in that: modified amino titanium dioxide-carbon fibers were obtained from preparation examples 1 to 7.
Example 8, a polyamide material was prepared, differing from example 1 in that: modified amino titanium dioxide-carbon fibers were obtained from preparation examples 1 to 8.
Example 9, the preparation of a polyamide material, differs from example 1 in that: modified amino titanium dioxide-carbon fibers were obtained from preparation examples 1 to 9.
Example 10, preparation of a polyamide material, differs from example 1 in that: the mass of the modified amino titanium dioxide-carbon fiber is 2g, namely the mass ratio of the modified amino titanium dioxide-carbon fiber to caprolactam is 2.
Example 11, a polyamide material was prepared, differing from example 1 in that: the mass of the modified amino titanium dioxide-carbon fiber is 0.5g, namely the mass ratio of the modified amino titanium dioxide-carbon fiber to caprolactam is 0.5.
Comparative example
Comparative example 1, a polyamide material (prepared by physical recycling) comprising the following preparation steps: soaking 5g of waste polyamide material in 85g of CEW for 24-30 h, filtering, extracting with deionized water, and drying in an oven at 80 ℃ for 2h to obtain the polyamide material, wherein the CEW comprises the following components: 12.5% CaCl 2 82.5% ethanol and 5% deionized water.
Comparative example 2, a polyamide material, differs from example 1-1 in that: the modified amino titanium dioxide-carbon fibers were replaced with an equal amount of unmodified carbon fibers.
Comparative example 3, a polyamide material, differs from example 1-1 in that: the modified amino titanium dioxide-carbon fiber is replaced by the same amount of modified amino titanium dioxide.
Comparative example 4, a polyamide material, differs from example 1-1 in that: the modified amino titanium dioxide-carbon fiber is replaced by a blend of the modified amino titanium dioxide and the carbon fiber with the mass ratio of 7:1.
Comparative example 5, preparation of a polyamide material comprising the steps of: 100kg of crushed and cleaned fishing net thread polyamide and 2kg of anhydrous CaCl 2 Adding the mixture into ionic liquid 1-butyl-3-methylimidazole trifluoromethanesulfonate, heating to 150 ℃ under the protection of nitrogen atmosphere, and stirring for 1h to dissolve. Then, impurities and drying agents are removed by vacuum filtration while the polyamide is hot, and pure polyamide solution is obtained. Then 0.5kg of chain extender ADR4400 is added into the polyamide solution, stirred and dissolved under the protection of nitrogen, and simultaneously the temperature is increased to 180 ℃. Stirring at 180 deg.C for 30min, and slowly cooling. And after the temperature is reduced to be below 80 ℃, adding the polyamide into deionized water, and precipitating the polyamide. Filtering, washing the filtrate with deionized water for 3 times to remove residual ionic liquid on the surface, and oven drying at 80 deg.C for 6h to obtain recovered ADR4400 chain extensionTreated polyamide powder.
Performance test
The polyamide materials of examples 1 to 11 and comparative examples 1 to 5 were subjected to performance tests, and 6 parallel tests of each test were averaged.
Test 1: the tensile yield strength and elongation at break test method adopts ISO527:2012 standard;
test 2: the test methods for flexural strength and flexural modulus adopt ISO178:2001 standard;
test 3: according to the type 1 of the exposure period in the table C.1 of the appendix C of the GB/T14522.2008 standard, the tube is aged for 96 hours by using an ultraviolet UV340 lamp tube and then taken out, and then the test 1 and the test 2 are respectively repeated.
The test results are shown in table 1:
it can be seen from the combination of examples 1-5, examples 6-7, examples 10-11 and comparative example 1 and table 1 that the polyamide material of the present application has greatly improved performance compared with the physical method for recycling polyamide material, and the present application can prepare polyamide materials with different performance according to the actual manufacturing requirements (such as safety belts with higher requirements on tensile property and bending strength), because during the synthesis of polyamide from caprolactam, carbon fiber can provide better tensile strength, and modified amino titanium dioxide can also improve the bending strength of polyamide, and the addition of modified amino titanium dioxide can provide good light resistance to polyamide, and can prolong the service life of the actual product.
It can be seen from the combination of example 1 and example 8 and table 1 that the polyamide material obtained by treating the carbon fiber without the step A1 has reduced tensile strength, bending strength and light resistance because the impurities on the surface of the carbon fiber are removed by using the acid solution and hydroxyl groups are introduced on the surface of the carbon fiber, so that the load capacity of the carbon fiber is improved, and the hydroxyl groups of the carbon fiber can form hydrogen bonds with active groups such as hydroxyl groups on the polyamide when the polyamide is subsequently synthesized, so that the tensile strength of the obtained polyamide material is improved. The reason for the performance degradation is that the bending strength and light resistance of the polyamide material are also degraded due to the decrease in the supported modified amino titanium dioxide.
As can be seen from the combination of examples 1 and 9 and Table 1, the obtained carbon fibers are washed before being dried, and the flexural strength and light resistance of the obtained polyamide material are reduced because the modified amino titanium dioxide is not completely supported on the carbon fibers by chemical bonds, some modified amino titanium dioxide may be bonded with each other by Van der Waals force and electrostatic force, and the modified amino titanium dioxide in the part can also improve the performance of the polyamide in the subsequent grafting process on the polyester fibers.
It can be seen from the combination of example 1, comparative example 1 and comparative example 5 and the combination of table 1 that the polyamide prepared by the method has stronger improvement in tensile strength and bending strength compared with the polyamide recovered by a physical method and a conventional ionic liquid method, and the polyamide prepared by the method has better light resistance because the performance of the polyamide material is improved by adding the modified amino titanium dioxide-carbon fiber in the process of synthesizing the polyamide by caprolactam, the carbon fiber has higher strength, the mechanical strength of the regenerated polyamide can be improved by adding a small amount of the modified amino titanium dioxide-carbon fiber, and the carbon fiber has stable chemical properties, better conductivity and larger loading surface area, and can better complete the loading of the modified amino titanium dioxide. The titanium dioxide has good impact resistance, can reduce the impact reduction of the impact resistance of the polyamide after the carbon fiber is doped, has excellent ultraviolet resistance and certain catalytic capability under the illumination condition, can degrade stains and bacteria, and can improve the light resistance of the regenerated polyamide.
Combining example 1 and comparative examples 2-3 with table 1, it can be seen that the addition of modified amino titanium dioxide and carbon fiber alone does not balance the tensile and flexural properties of the polyamide material.
By combining example 1 and comparative example 4 and table 1, it can be seen that the performance of the prepared polyamide material is better when the modified amino titanium dioxide is loaded on the carbon fiber than when blending, because the modified amino titanium dioxide is loaded on the carbon fiber, the dispersibility of the modified amino titanium dioxide can be improved, and the loaded modified amino titanium dioxide can be combined with the carbon fiber through hydrogen bonds, so that the combination is firmer.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A preparation method of a polyamide material is characterized by comprising the following steps:
s1, pretreating a waste polyamide material by using an ionic liquid to obtain caprolactam powder;
s2, blending caprolactam and modified amino titanium dioxide-carbon fibers, adding deionized water and adipic acid, adjusting the temperature to 220-250 ℃, reacting for 16-20 h under the pressure of 130-170kPa, and drying to obtain a polyamide material;
according to the weight, the dosage ratio of the caprolactam to the modified amino titanium dioxide-carbon fiber is 62-88; wherein the waste polyamide material contains more than 60wt% of polyamide.
2. The method for preparing a polyamide material as claimed in claim 1, wherein the pretreatment comprises the steps of:
step one, infiltrating a waste polyamide material with an ionic liquid, adding a catalyst accounting for 5-8 wt% of the ionic liquid, stirring and catalyzing for 0.5-4 h, and filtering to obtain filter residue and a caprolactam solution;
step two: and (3) heating the caprolactam solution in the step one for 0.5-1 h at 220-260 ℃ by microwave, cooling to room temperature, extracting, filtering and drying to obtain caprolactam powder.
3. A polyamide material according to claim 1, characterized in that: the ionic liquid is one or more of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-hydroxyethyl-2,3-dimethylimidazole tetrafluoroborate and 1-hydroxyethyl-2,3-dimethylimidazole chloride.
4. A polyamide material according to claim 1, characterized in that: the preparation method of the modified amino titanium dioxide comprises the following steps:
step 1: mixing butyl titanate and absolute ethyl alcohol, then adding 0.1-0.3 mol/L silver ion solution, and continuously mixing to prepare reaction solution;
and 2, step: mixing an ethanol aqueous solution, glacial acetic acid and a reducing agent, then dropwise adding the mixture into the reaction solution, and uniformly stirring to obtain mixed gel; drying the mixed gel, grinding into powder, and calcining in a chlorine environment to obtain silver-doped titanium dioxide;
step 3, blending the silver-doped titanium dioxide obtained in the step 2 with an aminosilane coupling agent, dissolving the mixture in an alcohol-water mixture, performing ultrasonic oscillation for 20-40 min, and drying to obtain modified amino titanium dioxide;
the weight ratio of the aminosilane coupling agent to the butyl titanate is 1:2-4.
5. A polyamide material according to claim 4, characterized in that: the weight ratio of the modified amino titanium dioxide-carbon fiber preparation material is 1:1-15.
6. A polyamide material according to claim 5, characterized in that: the weight ratio of the modified amino titanium dioxide-carbon fiber preparation material is 1:4-10.
7. The polyamide material as claimed in claim 5, wherein the preparation of the modified amino titanium dioxide-carbon fiber comprises the following steps:
a1, soaking carbon fibers in an acid solution, stirring for 1-2 h, adjusting the temperature to 90-100 ℃, reacting for 20-24 h, taking out the carbon fibers, cleaning, filtering and drying to obtain functional carbon fibers;
a2, adding the modified amino titanium dioxide and glacial acetic acid into absolute ethyl alcohol, and stirring and dispersing to obtain a modified amino titanium dioxide solution; soaking the functional carbon fiber obtained in the step A1 into a modified amino titanium dioxide solution, and reacting for 24-36 h under the conditions that the temperature is 160-200 ℃ and the pressure is 150-200 kPa; and then cooling to room temperature, taking out the carbon fiber and drying to obtain the modified amino titanium dioxide-carbon fiber.
8. Polyamide material obtainable by a process according to any one of claims 1 to 7.
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| JP2007246583A (en) * | 2006-03-14 | 2007-09-27 | Asahi Kasei Chemicals Corp | Polyamide resin composition and its production method |
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| JP2007246583A (en) * | 2006-03-14 | 2007-09-27 | Asahi Kasei Chemicals Corp | Polyamide resin composition and its production method |
| CN109762162A (en) * | 2018-12-25 | 2019-05-17 | 中国纺织科学研究院有限公司 | Functionality polyamide and its continuous producing method |
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