CN112011179A - Titanium dioxide-based ultraviolet-resistant nylon 66 resin and preparation method thereof - Google Patents

Titanium dioxide-based ultraviolet-resistant nylon 66 resin and preparation method thereof Download PDF

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CN112011179A
CN112011179A CN202010800852.4A CN202010800852A CN112011179A CN 112011179 A CN112011179 A CN 112011179A CN 202010800852 A CN202010800852 A CN 202010800852A CN 112011179 A CN112011179 A CN 112011179A
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stirring
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parts
titanium dioxide
silicon particles
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成丹丹
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Abstract

The invention discloses an anti-ultraviolet nylon 66 resin based on titanium dioxide and a preparation method thereof, and discloses the anti-ultraviolet nylon 66 resin based on titanium dioxide and the preparation method thereof, wherein the nylon 66 resin comprises a matrix, the matrix is mainly prepared from nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, a modified additive, glass fiber and the like, the modified additive comprises modified silicon particles, modified cerium dioxide, titanium dioxide and dopamine, the modified silicon particles take crystalline silicon particles as main bodies, and the crystalline silicon particles are inorganic particles with high refractive index, can refract ultraviolet rays and improve the anti-ultraviolet performance of finished products. The invention has reasonable process design and proper component proportion, and the prepared resin material has excellent ultraviolet resistance and mechanical property, is suitable for various fields and has higher practicability.

Description

Titanium dioxide-based ultraviolet-resistant nylon 66 resin and preparation method thereof
Technical Field
The invention relates to the technical field of nylon 66, in particular to titanium dioxide-based ultraviolet-resistant nylon 66 resin and a preparation method thereof.
Background
The polyamide is named polycaprolactam commonly known as nylon, a molecular chain contains a large number of amido bonds, and the nylon material has the characteristics of excellent performance, good initial performance, easy processability and the like, and particularly has excellent friction resistance. The nylon has various types, including nylon 6, nylon 6 and the like, and can be widely applied to the fields of machine manufacturing, automobile parts, textile and the like.
Polyhexamethylene adipamide, commonly known as nylon-66, is used as a mechanical accessory, such as a gear, a lubricated bearing; it can replace non-ferrous metal material to make machine casing, automobile engine blade, etc. Can also be used for preparing synthetic fibers; nowadays, with the intensive research on nylon 66 materials, how to improve the ultraviolet resistance of the materials becomes the focus of the research.
Disclosure of Invention
The invention aims to provide an ultraviolet-resistant nylon 66 resin based on titanium dioxide and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a titanium dioxide-based ultraviolet resistant nylon 66 resin, the nylon 66 resin comprising a substrate, the surface of which is modified by a surface treatment agent; the matrix comprises the following raw materials: by weight, nylon 6640-50 parts, dispersant 1-1.2 parts, ultraviolet absorbent 1-1.5 parts, antioxidant 1-3 parts, modified additive 10-15 parts, and glass fiber 15-18 parts.
According to an optimized scheme, the modified additive comprises the following raw materials in parts by weight: 10-15 parts of modified silicon particles, 10-12 parts of modified cerium dioxide, 6-8 parts of titanium dioxide and 25-30 parts of dopamine.
According to an optimized scheme, the surface treating agent comprises the following raw materials in parts by weight: by weight, 20-25 parts of dopamine, 8-12 parts of graphene oxide and 8-10 parts of filler.
According to an optimized scheme, the filler is mainly prepared from calcium acetate, calcium metavanadate and PVP.
In an optimized scheme, the antioxidant is one or a mixture of diphenylamine, p-phenylenediamine, docosanol ester and trioctyl ester.
According to an optimized scheme, the ultraviolet absorbent is any one of phenyl ortho-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone.
According to an optimized scheme, the preparation method of the titanium dioxide-based ultraviolet-resistant nylon 66 resin comprises the following steps:
1) preparing materials;
2) preparing a modified additive:
a) taking crystalline silicon particles, soaking the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, cooling and separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring, adding a silane coupling agent, stirring and reacting for 20-24h at 70-80 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles;
b) mixing and stirring boric acid, urea, ethanol and deionized water, adding cerium dioxide, ultrasonically stirring, carrying out vacuum drying, calcining under the protection of nitrogen at the calcining temperature of 890-910 ℃, washing, and carrying out vacuum drying to obtain modified cerium dioxide;
c) mixing trihydroxymethyl aminomethane buffer solution and ethanol, stirring for dissolving, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion, adding modified cerium dioxide, stirring at 25-28 deg.C for 2-3h, adding modified silicon particles and titanium dioxide, stirring, washing, and vacuum drying to obtain modified additive;
3) preparing a matrix: mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive by a high-speed mixer, melting, extruding, and processing to obtain a matrix;
4) surface treatment with the surface treating agent:
a) dissolving calcium metavanadate in deionized water, and stirring to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring, adding the material B, continuing stirring, reacting at 190 ℃ for 22-26h at 180 ℃, cooling, performing centrifugal separation, and drying to obtain a filler;
b) mixing trihydroxymethyl aminomethane buffer solution and ethanol, stirring for dissolving, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion, adding matrix, performing ultrasonic oscillation, adding graphene oxide, stirring, adding filler, reacting at 50-60 deg.C for 10-12h, washing, and vacuum drying to obtain the final product.
The optimized scheme comprises the following steps:
1) preparing materials;
2) preparing a modified additive:
a) taking crystalline silicon particles, placing the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, soaking for 30-40min at 80-90 ℃, cooling, separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring for 10-20min, adding a silane coupling agent, stirring and reacting for 20-24h at 70-80 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles;
b) mixing and stirring boric acid, urea, ethanol and deionized water for 10-20min, adding cerium dioxide, ultrasonically stirring for 1-1.5h, vacuum drying at 70-80 ℃, calcining for 5-5.5h under the protection of nitrogen at the calcining temperature of 890-910 ℃, washing, and vacuum drying to obtain modified cerium dioxide;
c) mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 5-10min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 5-8min, adding modified cerium dioxide, stirring for 2-3h at 25-28 ℃, then adding modified silicon particles and titanium dioxide, continuing stirring for 2-3h, washing, and performing vacuum drying at 60-70 ℃ to obtain a modified additive;
3) preparing a matrix: mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive by a high-speed mixer for 30-40min, melting, extruding, and processing to obtain a matrix;
4) surface treatment with the surface treating agent:
a) dissolving calcium metavanadate in deionized water, and stirring for 10-15min to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring for 5-10min, adding the material B, continuously stirring for 10-15min, reacting at 180-190 ℃ for 22-26h, cooling, performing centrifugal separation, and drying at 60-70 ℃ for 12-15h to obtain a filler;
b) mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 5-10min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 5-8min, adding the matrix, performing ultrasonic oscillation for 20-24h, adding graphene oxide, stirring for 10-20min, adding filler, reacting for 10-12h at 50-60 ℃, washing, and vacuum drying to obtain the final product.
In an optimized scheme, in the step 2), the mass ratio of concentrated sulfuric acid to hydrogen peroxide is (7-8): (2-4).
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses an anti-ultraviolet nylon 66 resin based on titanium dioxide and a preparation method thereof, wherein the nylon 66 resin comprises a matrix, the matrix is mainly prepared from nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, a modified additive, glass fiber and the like, wherein the modified additive comprises modified silicon particles, modified cerium dioxide, titanium dioxide and dopamine, the modified silicon particles take crystalline silicon particles as a main body, and the crystalline silicon particles are inorganic particles with high refractive index, can refract ultraviolet rays and improve the anti-ultraviolet performance of a finished product; during preparation, firstly, crystal silicon particles are placed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, the outermost layer of the crystal silicon particles is oxidized into amorphous silicon dioxide after soaking, and then, the amorphous silicon dioxide is subjected to graft modification by using a silane coupling agent, so that the dispersion performance of the crystal silicon particles is improved, and the agglomeration phenomenon of the crystal silicon particles in a matrix is avoided; in the implementation of the embodiment, the silane coupling agent is selected to be KH-550 or KH570, and other types can be selected according to actual requirements.
The modified cerium dioxide is an inorganic ultraviolet shielding component which has excellent ultraviolet absorption capacity and can effectively shield ultraviolet rays, but the cerium dioxide has stronger ultraviolet catalytic activity and can catalyze and oxidize matrix resin so as to reduce the comprehensive performance of the material, so that boron nitride is generated by utilizing the components such as boric acid, urea, ethanol and the like and is coated on the surface of the cerium dioxide, and charge carriers are effectively isolated and transferred so as to reduce the catalytic activity of the boron nitride; according to the scheme, titanium dioxide is used as an ultraviolet absorption component, the ultraviolet resistance of the product is further improved, meanwhile, dopamine is used for carrying out an autoxidation reaction to generate polydopamine, and the polydopamine is coated on the surfaces of the modified cerium dioxide, the modified silicon particles and the titanium dioxide, so that the catalytic activity of the modified cerium dioxide and the titanium dioxide is further reduced, and the compatibility between each component and the matrix resin is improved.
The matrix material is prepared from the modified additive, the nylon 66, the dispersing agent, the ultraviolet absorbent, the antioxidant and the glass fiber, and the matrix has excellent ultraviolet resistance due to the synergistic effect of the modified additive and the ultraviolet absorbent, and meanwhile, the modified additive and the glass fiber can play a reinforcing role so as to improve the mechanical property of the matrix.
According to the scheme, the surface modification treatment is carried out on the matrix through the surface treatment agent, sodium metavanadate and calcium acetate are used as raw materials, PVP (polyvinylpyrrolidone) is used as a dispersing agent, the reaction is carried out to synthesize the filler, the filler is vanadic acid with a polycrystalline flower cluster structure, ultraviolet rays can be effectively absorbed, meanwhile, due to the polycrystalline flower cluster structure, the filler can refract and reflect the ultraviolet rays, and the ultraviolet resistance of the product is further improved; according to the invention, a layer of dopamine is deposited on the surface of the substrate, a polydopamine layer is generated through self-polymerization, the filler is deposited and adsorbed through the polydopamine layer, meanwhile, graphene oxide is added in the process, the graphene oxide and the filler can be uniformly distributed on the surface of the substrate, the graphene oxide and the filler are mutually synergistic to improve the ultraviolet resistance of the product, and meanwhile, each material and the substrate are adhered through the polydopamine layer, so that the mechanical property of the product can be improved.
The invention discloses an anti-ultraviolet nylon 66 resin based on titanium dioxide and a preparation method thereof, the process design is reasonable, the component proportion is proper, the prepared resin material has excellent anti-ultraviolet performance, and meanwhile, the mechanical property is excellent, so that the anti-ultraviolet nylon 66 resin is suitable for various fields and has high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
step 1: preparing materials;
step 2: preparing a modified additive:
taking crystalline silicon particles, placing the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, soaking for 30min at 80 ℃, cooling, separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring for 10min, adding a silane coupling agent, stirring and reacting for 20h at 70 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles; wherein the mass ratio of concentrated sulfuric acid to hydrogen peroxide is 7: 2.
mixing boric acid, urea, ethanol and deionized water, stirring for 10min, adding cerium dioxide, ultrasonically stirring for 1h, vacuum drying at 70 ℃, calcining for 5h under the protection of nitrogen at the calcining temperature of 890 ℃, washing, and vacuum drying to obtain modified cerium dioxide;
mixing a trihydroxymethyl aminomethane buffer solution and ethanol, stirring and dissolving for 5min, adding a dopamine hydrochloric acid solution, performing ultrasonic dispersion for 5min, adding modified cerium dioxide, stirring for 2h at 25 ℃, adding modified silicon particles and titanium dioxide, continuing stirring for 2h, washing, and performing vacuum drying at 60 ℃ to obtain a modified additive;
and step 3: preparing a matrix:
mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive by a high-speed mixer for 30min, melting, extruding, and processing to obtain a matrix;
and 4, step 4: surface treatment with the surface treating agent:
dissolving calcium metavanadate in deionized water, and stirring for 10min to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring for 5min, adding the material B, continuously stirring for 10min, reacting at 180 ℃ for 22h, cooling, performing centrifugal separation, and drying at 60 ℃ for 12h to obtain a filler;
mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 5min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 5min, adding the matrix, performing ultrasonic oscillation for 20h, adding graphene oxide, stirring for 10min, adding filler, reacting for 10h at 50 ℃, washing, and vacuum drying to obtain the final product.
In this embodiment, the nylon 66 resin includes a matrix, and the surface of the matrix is modified by a surface treatment agent; the matrix comprises the following raw materials: by weight, nylon 6640 parts, dispersant 1 part, ultraviolet absorbent 1 part, antioxidant 1 part, modified additive 10 parts, and glass fiber 15 parts.
Wherein the modified additive comprises the following raw materials in parts by weight: 10 parts of modified silicon particles, 10 parts of modified cerium dioxide, 6 parts of titanium dioxide and 25 parts of dopamine by weight; the surface treating agent comprises the following raw materials: by weight, 20 parts of dopamine, 8 parts of graphene oxide and 8 parts of filler. The antioxidant is diphenylamine. The ultraviolet absorbent is phenyl ortho-hydroxybenzoate.
Example 2:
step 1: preparing materials;
step 2: preparing a modified additive:
taking crystalline silicon particles, placing the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, soaking for 35min at 85 ℃, cooling, separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring for 15min, adding a silane coupling agent, stirring and reacting for 22h at 75 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles; wherein the mass ratio of concentrated sulfuric acid to hydrogen peroxide is 8: 2.
mixing and stirring boric acid, urea, ethanol and deionized water for 15min, adding cerium dioxide, ultrasonically stirring for 1.2h, vacuum drying at 75 ℃, calcining for 5.2h under the protection of nitrogen at the calcining temperature of 900 ℃, washing, and vacuum drying to obtain modified cerium dioxide;
mixing a trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 8min, adding a dopamine hydrochloric acid solution, performing ultrasonic dispersion for 7min, adding modified cerium dioxide, stirring for 2.5h at 27 ℃, adding modified silicon particles and titanium dioxide, continuing stirring for 2.5h, washing, and performing vacuum drying at 65 ℃ to obtain a modified additive;
and step 3: preparing a matrix:
mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive for 35min by a high-speed mixer, and carrying out melt extrusion and processing molding to obtain a matrix;
and 4, step 4: surface treatment with the surface treating agent:
dissolving calcium metavanadate in deionized water, and stirring for 12min to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring for 8min, adding the material B, continuously stirring for 12min, reacting at 185 ℃ for 24h, cooling, performing centrifugal separation, and drying at 65 ℃ for 14h to obtain a filler;
mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 8min, adding a dopamine hydrochloric acid solution, performing ultrasonic dispersion for 7min, adding a matrix, performing ultrasonic oscillation for 22h, adding graphene oxide, stirring for 15min, adding a filler, reacting for 11h at 55 ℃, washing, and performing vacuum drying to obtain a finished product.
In this embodiment, the nylon 66 resin includes a matrix, and the surface of the matrix is modified by a surface treatment agent; the matrix comprises the following raw materials: by weight, nylon 6645 parts, dispersant 1.1 parts, ultraviolet absorbent 1.2 parts, antioxidant 2 parts, modified additive 12 parts, and glass fiber 17 parts.
Wherein the modified additive comprises the following raw materials in parts by weight: 13 parts of modified silicon particles, 11 parts of modified cerium dioxide, 7 parts of titanium dioxide and 28 parts of dopamine by weight; the surface treating agent comprises the following raw materials: 23 parts of dopamine, 10 parts of graphene oxide and 9 parts of filler. The antioxidant is p-phenylenediamine; the ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
Example 3:
step 1: preparing materials;
step 2: preparing a modified additive:
taking crystalline silicon particles, placing the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, soaking for 40min at 90 ℃, cooling, separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring for 20min, adding a silane coupling agent, stirring and reacting for 24h at 80 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles; wherein the mass ratio of concentrated sulfuric acid to hydrogen peroxide is 8: 4.
mixing and stirring boric acid, urea, ethanol and deionized water for 20min, adding cerium dioxide, ultrasonically stirring for 1.5h, vacuum drying at 80 ℃, calcining for 5.5h under the protection of nitrogen at the calcining temperature of 910 ℃, washing, and vacuum drying to obtain modified cerium dioxide;
mixing a trihydroxymethyl aminomethane buffer solution and ethanol, stirring and dissolving for 10min, adding a dopamine hydrochloric acid solution, performing ultrasonic dispersion for 8min, adding modified cerium dioxide, stirring for 3h at 28 ℃, adding modified silicon particles and titanium dioxide, continuing stirring for 3h, washing, and performing vacuum drying at 70 ℃ to obtain a modified additive;
and step 3: preparing a matrix:
mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive by a high-speed mixer for 40min, and carrying out melt extrusion and processing molding to obtain a matrix;
and 4, step 4: surface treatment with the surface treating agent:
dissolving calcium metavanadate in deionized water, and stirring for 15min to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring for 10min, adding the material B, continuously stirring for 15min, reacting for 26h at 190 ℃, cooling, performing centrifugal separation, and drying at 70 ℃ for 15h to obtain a filler;
mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 10min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 8min, adding the matrix, performing ultrasonic oscillation for 24h, adding graphene oxide, stirring for 20min, adding filler, reacting for 12h at 60 ℃, washing, and vacuum drying to obtain the final product.
In this embodiment, the nylon 66 resin includes a matrix, and the surface of the matrix is modified by a surface treatment agent; the matrix comprises the following raw materials: by weight, nylon 6650 parts, dispersant 1.2 parts, ultraviolet absorbent 1.5 parts, antioxidant 3 parts, modified additive 15 parts, and glass fiber 18 parts.
Wherein the modified additive comprises the following raw materials in parts by weight: 15 parts of modified silicon particles, 12 parts of modified cerium dioxide, 8 parts of titanium dioxide and 30 parts of dopamine by weight; the surface treating agent comprises the following raw materials: 25 parts of dopamine, 12 parts of graphene oxide and 10 parts of filler. The antioxidant is didodecanol ester; the ultraviolet absorbent is 2-hydroxy-4-n-octoxy benzophenone.
Comparative example 1:
comparative example 1 was modified on the basis of example 2, no graphene oxide was added in the surface modifier treatment step, and the remaining step parameters and component contents were in accordance with example 2.
The method comprises the following specific steps:
and 4, step 4: surface treatment with the surface treating agent:
dissolving calcium metavanadate in deionized water, and stirring for 12min to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring for 8min, adding the material B, continuously stirring for 12min, reacting at 185 ℃ for 24h, cooling, performing centrifugal separation, and drying at 65 ℃ for 14h to obtain a filler;
mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 8min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 7min, adding matrix, performing ultrasonic oscillation for 22h, adding filler, reacting at 55 deg.C for 11h, washing, and vacuum drying to obtain the final product.
Comparative example 2:
comparative example 2 was modified on the basis of comparative example 1 without surface modification treatment, and the remaining step parameters and component contents were identical to those of example 2.
Comparative example 3:
comparative example 3 was modified on the basis of comparative example 2 without adding modified silicon particles, and the remaining process parameters and component contents were in accordance with example 2.
The method comprises the following specific steps:
step 2: preparing a modified additive:
mixing and stirring boric acid, urea, ethanol and deionized water for 15min, adding cerium dioxide, ultrasonically stirring for 1.2h, vacuum drying at 75 ℃, calcining for 5.2h under the protection of nitrogen at the calcining temperature of 900 ℃, washing, and vacuum drying to obtain modified cerium dioxide;
mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 8min, adding dopamine hydrochloric acid solution, ultrasonically dispersing for 7min, adding modified cerium dioxide and titanium dioxide, stirring for 2.5h at 27 ℃, washing, and vacuum drying at 65 ℃ to obtain the modified additive.
Comparative example 4:
comparative example 4 was modified from comparative example 3, without the addition of modifying additives, and the remaining process parameters and component contents were identical to those of example 2.
And step 3: preparing a matrix:
mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant and glass fiber for 35min by a high-speed mixer, melting, extruding, and processing to obtain the matrix.
Experiment:
the tensile strength of each sample prepared in examples 1 to 3 and comparative examples 1 to 4 was measured according to ASTM D638-2003, method for measuring tensile properties of plastics, and the flexural strength of each sample was measured according to ASTM D790, method for testing flexural properties of reinforced and unreinforced plastics and electrical insulating materials.
Xenon lamp test conditions: the illumination intensity is 0.35W/nm.m2Irradiation of1000 hours; the tensile strength of each specimen was re-measured after the xenon lamp test.
Figure BDA0002627331330000131
Figure BDA0002627331330000141
And (4) conclusion:
comparative example 1 was modified on the basis of example 2, no graphene oxide was added in the surface modifier treatment step, and the remaining step parameters and component contents were in accordance with example 2.
Comparative example 2 was modified on the basis of comparative example 1 without surface modification treatment, and the remaining step parameters and component contents were identical to those of example 2.
Comparative example 3 was modified on the basis of comparative example 2 without adding modified silicon particles, and the remaining process parameters and component contents were in accordance with example 2.
Comparative example 4 was modified from comparative example 3, without the addition of modifying additives, and the remaining process parameters and component contents were identical to those of example 2.
Examples 1-3 were prepared according to the disclosed protocol, comparative examples 1-4 were compared with example 2, and it can be seen from the above data that the UV resistance of examples 1-3 was significantly superior to that of comparative examples 1-4, and the UV resistance of comparative examples 1-4 was sequentially reduced.
Namely: the invention has reasonable process design and proper component proportion, and the prepared resin material has excellent ultraviolet resistance and mechanical property, is suitable for various fields and has higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (9)

1. The titanium dioxide-based ultraviolet-resistant nylon 66 resin is characterized in that: the nylon 66 resin comprises a matrix, wherein the surface of the matrix is modified by a surface treatment agent; the matrix comprises the following raw materials: by weight, nylon 6640-50 parts, dispersant 1-1.2 parts, ultraviolet absorbent 1-1.5 parts, antioxidant 1-3 parts, modified additive 10-15 parts, and glass fiber 15-18 parts.
2. The titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 1, wherein: the modified additive comprises the following raw materials in parts by weight: 10-15 parts of modified silicon particles, 10-12 parts of modified cerium dioxide, 6-8 parts of titanium dioxide and 25-30 parts of dopamine.
3. The titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 1, wherein: the surface treating agent comprises the following raw materials: by weight, 20-25 parts of dopamine, 8-12 parts of graphene oxide and 8-10 parts of filler.
4. The titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 3, wherein: the filler is mainly prepared from calcium acetate, calcium metavanadate and PVP.
5. The titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 1, wherein: the antioxidant is one or a mixture of diphenylamine, p-phenylenediamine, docosanol ester and trioctyl ester.
6. The titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 1, wherein: the ultraviolet absorbent is any one of phenyl ortho-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone.
7. A preparation method of titanium dioxide-based ultraviolet-resistant nylon 66 resin is characterized by comprising the following steps: the method comprises the following steps:
1) preparing materials;
2) preparing a modified additive:
a) taking crystalline silicon particles, soaking the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, cooling and separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring, adding a silane coupling agent, stirring and reacting for 20-24h at 70-80 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles;
b) mixing and stirring boric acid, urea, ethanol and deionized water, adding cerium dioxide, ultrasonically stirring, carrying out vacuum drying, calcining under the protection of nitrogen at the calcining temperature of 890-910 ℃, washing, and carrying out vacuum drying to obtain modified cerium dioxide;
c) mixing trihydroxymethyl aminomethane buffer solution and ethanol, stirring for dissolving, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion, adding modified cerium dioxide, stirring at 25-28 deg.C for 2-3h, adding modified silicon particles and titanium dioxide, stirring, washing, and vacuum drying to obtain modified additive;
3) preparing a matrix: mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive by a high-speed mixer, melting, extruding, and processing to obtain a matrix;
4) surface treatment with the surface treating agent:
a) dissolving calcium metavanadate in deionized water, and stirring to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring, adding the material B, continuing stirring, reacting at 190 ℃ for 22-26h at 180 ℃, cooling, performing centrifugal separation, and drying to obtain a filler;
b) mixing trihydroxymethyl aminomethane buffer solution and ethanol, stirring for dissolving, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion, adding matrix, performing ultrasonic oscillation, adding graphene oxide, stirring, adding filler, reacting at 50-60 deg.C for 10-12h, washing, and vacuum drying to obtain the final product.
8. The method for preparing the titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 7, wherein: the method comprises the following steps:
1) preparing materials;
2) preparing a modified additive:
a) taking crystalline silicon particles, placing the crystalline silicon particles in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, soaking for 30-40min at 80-90 ℃, cooling, separating, washing and drying to obtain a material A; dissolving the material A in absolute ethyl alcohol, stirring for 10-20min, adding a silane coupling agent, stirring and reacting for 20-24h at 70-80 ℃, cooling and centrifuging, washing and drying to obtain modified silicon particles;
b) mixing and stirring boric acid, urea, ethanol and deionized water for 10-20min, adding cerium dioxide, ultrasonically stirring for 1-1.5h, vacuum drying at 70-80 ℃, calcining for 5-5.5h under the protection of nitrogen at the calcining temperature of 890-910 ℃, washing, and vacuum drying to obtain modified cerium dioxide;
d) mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 5-10min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 5-8min, adding modified cerium dioxide, stirring for 2-3h at 25-28 ℃, then adding modified silicon particles and titanium dioxide, continuing stirring for 2-3h, washing, and performing vacuum drying at 60-70 ℃ to obtain a modified additive;
3) preparing a matrix: mixing nylon 66, a dispersing agent, an ultraviolet absorbent, an antioxidant, glass fiber and a modified additive by a high-speed mixer for 30-40min, melting, extruding, and processing to obtain a matrix;
4) surface treatment with the surface treating agent:
a) dissolving calcium metavanadate in deionized water, and stirring for 10-15min to obtain a material B; dissolving calcium acetate, PVP and ethylene glycol, stirring for 5-10min, adding the material B, continuously stirring for 10-15min, reacting at 180-190 ℃ for 22-26h, cooling, performing centrifugal separation, and drying at 60-70 ℃ for 12-15h to obtain a filler;
b) mixing the trihydroxymethyl aminomethane buffer solution with ethanol, stirring for dissolving for 5-10min, adding dopamine hydrochloric acid solution, performing ultrasonic dispersion for 5-8min, adding the matrix, performing ultrasonic oscillation for 20-24h, adding graphene oxide, stirring for 10-20min, adding filler, reacting for 10-12h at 50-60 ℃, washing, and vacuum drying to obtain the final product.
9. The method for preparing the titanium dioxide-based ultraviolet resistant nylon 66 resin as claimed in claim 8, wherein: in the step 2), the mass ratio of concentrated sulfuric acid to hydrogen peroxide is (7-8): (2-4).
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