CN110551385A - Preparation method of environment-friendly long-acting rubber antioxidant - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K9/00—Use of pretreated ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
the invention discloses a preparation method of an anti-aging agent, in particular to a preparation method of an environment-friendly long-acting rubber anti-aging agent, which comprises the following steps: (1) preparing nano white carbon black; (2) carrying out ultrasonic modification; (3) coating inorganic matters; (4) preparing modified white carbon black; (5) and (3) condensation reaction. The invention can reduce the volatilization and migration phenomena of small molecules in the rubber matrix, can also enhance the strength of rubber, and is simple to operate, energy-saving and environment-friendly in the preparation process.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of an environment-friendly long-acting rubber antioxidant.
background
In the using process, the rubber is aged under the influence of external factors (such as ozone aging, thermal oxidation aging and the like), so that the physical and mechanical properties of the rubber are changed, the elasticity of the rubber is lost, the mechanical properties are reduced, and the service life is shortened. In order to solve the problem of rubber aging, it is necessary to add proper auxiliary agents into the rubber so as to inhibit or delay the aging process and prolong the service life, and the auxiliary agents for preventing the rubber aging are anti-aging agents.
White carbon black is an important reinforcing material in the rubber industry, has poorer processability compared with carbon black, and is limited in application in the rubber industry. The practical silane coupling agent modifies the white carbon black, so that the affinity of the white carbon black and the sizing material is solved, and the processability of the sizing material is improved. Meanwhile, the stress at definite elongation, tensile strength, tearing strength and wear resistance of the rubber material can be improved.
The general formula of the silane coupling agent is RSiX, wherein R is an organic group such as vinyl, epoxy, amino, methacryloxy and the like, and the silane coupling agent can form firm chemical combination with resin; x is an organic group capable of being hydrolyzed, such as methoxy, ethoxy, chlorine and the like, hydrolysis byproducts of the X can volatilize at low temperature, isopropyl and isobutyl require longer reaction time, the reaction byproducts are difficult to remove from the treated inorganic filler, and the X group can be condensed with active hydroxyl on the surface of the white carbon black to form a siloxane bond.
The anti-aging agent 2246 is one of the better varieties of phenol anti-aging agents, has excellent protection effects on thermal oxidation, weather aging, flex aging and variable valence metals, and is suitable for light-colored and colored rubber products. In the plastics industry, the protective effect is provided for heat aging and light aging of chlorinated polyether, impact-resistant PS, ABS resin, polymethyl ether and fiber resin.
The yield and variety of the anti-aging agent are the first of rubber additives. The amine anti-aging agent has good anti-aging performance, is one of the largest varieties with the current yield and dosage, but the molecular structure of the amine anti-aging agent contains amino, which is easy to generate carcinogenic substances, when the dosage reaches a certain value, the amine anti-aging agent is easy to migrate to the surface, and the color of a rubber product is changed or the surface of the rubber product is polluted due to the phenomenon of frost spraying, so the quality of the rubber product is influenced, and the use of the amine anti-aging agent is limited to a certain extent. Other commonly used antioxidants are also mostly toxic or polluting.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a composite component anti-aging agent which is non-toxic, pollution-free, long in validity period, energy-saving and environment-friendly.
The invention is realized by the following technical scheme:
A preparation method of a rubber antioxidant comprises the following steps:
(1) Adding 4-8 parts of hydrated sodium silicate into a beaker, adding 400 parts of distilled water to dissolve sodium silicate powder, slowly dropwise adding dilute sulfuric acid into the beaker until the pH value is 6.5, then adding 1-5 parts of sodium sulfate as a dispersing agent, aging for 1h, filtering and washing the flocculent precipitate by using gauze to obtain SiO 2 crystals, pressing the washed flocculent precipitate into a filter cake, drying the filter cake in an oven at the temperature of 80 ℃, then placing the dried product into a calcining furnace to calcine at the temperature of 450 ℃, and finally placing the calcined product into an ultrafine grinder to grind into 1500-mesh 2000-mesh powder to obtain the nano white carbon black;
(2) Ultrasonic modification: dispersing 5-8 parts of nano white carbon black in 200 parts by mass of ethanol solution, performing ultrasonic treatment at 40-70 ℃ for 30-120min, filtering and removing generated flocculent precipitate, washing and drying to obtain nano white carbon black with reduced surface energy;
(3) Coating inorganic matter, namely dispersing 3-9 parts of the nano white carbon black treated in the step (2) in 200 parts of ethanol solution, adding 3-6 parts of butyl titanate into the solution for pre-dispersion, slowly dropping 8 mass percent sodium silicate solution into the solution at 85-90 ℃ until the pH value of the solution is 8.5, aging for 2h to finish coating of SiO 2 by TiO 2, slowly dropping dilute sulfuric acid solution into the solution until the pH value of the solution is 7.0, aging for 4h, washing with water, filtering, and drying at 100-200 ℃ to obtain SiO 2/TiO 2 particles;
(4) Preparing an intermediate product, namely grinding and uniformly mixing 40-60 parts of SiO 2/TiO 2 particles, adding 8-10 parts of silane coupling agent into a mixer, stirring and reacting for 10-24h at the temperature of 80-120 ℃, washing the prepared reaction product with a solvent, and distilling and drying to obtain the intermediate product;
(5) condensation reaction: putting 2-4 parts by mass of polyurethane prepolymer, 1-3 parts by mass of intermediate product and 4-10 parts by mass of anti-aging agent into a triangular flask to obtain a mixture, adding 5-10% by mass of hydrochloric acid serving as a catalyst into the mixture, heating to 40-60 ℃, and stirring for reacting for 4-6 hours to obtain a final product; the above parts are mass components.
Further, the ultrasonic frequency in the step (2) is 25-50KHz, the ultrasonic wave in the range has a cavitation effect, so that the white carbon black aggregates can be disintegrated and uniformly dispersed in the solution, the dispersion effect on the white carbon black aggregates is not good when the frequency is less than the range, and the heating effect is significant when the frequency is more than the range, so that the components are changed.
Further, the mass ratio of the SiO 2 to the TiO 2 in the step (3) is 2% -3%, and the white carbon black with a little excess content of TiO 2 can form a coating layer on the surface of the white carbon black particles.
Further, the catalyst in step (5) is a concentrated hydrochloric acid solution with a mass fraction of 60%, a hydrochloric acid solution with a concentration higher than this has a poor dissolution effect, and a hydrochloric acid solution with a concentration lower than this brings excessive water, which is not favorable for accelerating the condensation reaction.
Further, the model of the anti-aging agent in the step (5) is 2246. The micromolecule anti-aging agent 2246 can be subjected to graft reaction with the modified white carbon black to form a load type anti-aging agent component.
Further, the white carbon black in the step (1) may also be one of kaolin, montmorillonite, halloysite nanotube, talcum powder and mica powder zinc oxide.
further, the silane coupling agent in the step (1) is one of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, bis (gamma-triethoxysilylpropyl) tetrasulfide and 3- (trimethoxysilyl) -1-propanethiol, and is preferably gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH 560).
compared with the prior art, the invention has the beneficial effects that: according to the invention, the nano white carbon black is modified by ultrasonic waves and then coated with an inorganic substance to prepare modified white carbon black, the modified white carbon black is subjected to condensation reaction with the anti-aging agent 2246 and the polyurethane prepolymer to obtain the environment-friendly anti-aging agent, and compared with a directly grafted load type anti-aging agent, the anti-aging agent disclosed by the invention can obviously improve the dispersion between a rubber matrix and a filler, improve the interaction between the rubber and the filler and achieve the effect of improving the mechanical property of the matrix. In addition, the invention has the same advantages as the anti-aging agent obtained by direct solid-phase reaction, such as reducing the volatilization and migration phenomenon of small molecules in a rubber matrix, reducing the dust flying and volatilization of the anti-aging agent and the filler in the processing processes of rubber mixing, vulcanization and the like, being beneficial to the environmental protection of workshops, reducing the dust and explosion hazard of a small molecule promoter causing fire, greatly reducing the migration and volatilization of the residue of the anti-aging agent in vulcanized rubber, improving the grinding performance, oil resistance, low temperature resistance and ozone aging resistance of the rubber by adding the polyurethane prepolymer, and prolonging the service life. In a word, the invention has the advantages of simple process, no toxicity or pollution, high product recovery rate, energy conservation and environmental protection.
Detailed Description
Example 1:
adding 4 parts of hydrated sodium silicate into a beaker, adding 400 parts of distilled water to dissolve sodium silicate powder, slowly dropwise adding dilute sulfuric acid into the beaker until the pH value is 6.5, then adding 1 part of sodium sulfate as a dispersing agent, aging for 1 hour, filtering and washing flocculent precipitate by using gauze to obtain SiO 2 crystals, pressing the washed flocculent precipitate into a filter cake, drying the filter cake in an oven at the temperature of 80 ℃, then placing the dried product into a calcining furnace to calcine at the temperature of 450 ℃, and finally placing the calcined product into an ultrafine grinder to grind into 1500-mesh powder to obtain the nano white carbon black;
Dispersing 5 parts of nano white carbon black in 200 parts of ethanol solution, treating for 30min at 40 ℃ by using 25KHz ultrasonic waves, filtering and removing generated flocculent precipitate, washing and drying to obtain nano white carbon black with reduced surface energy;
Taking 3 parts of treated nano white carbon black, dispersing in 200 parts of ethanol solution, adding 3 parts of butyl titanate into the solution, pre-dispersing, slowly dropping 8% sodium silicate solution by mass fraction into the solution at 85 ℃ until the pH value of the solution is 8.5, aging for 2h to finish coating of SiO 2 by TiO 2, slowly dropping dilute sulfuric acid solution into the solution until the pH value of the solution is 7.0, aging for 4h, washing with water, filtering, and drying at 100 ℃ to obtain SiO 2/TiO 2 particles;
grinding 40 parts of SiO 2/TiO 2 particles, uniformly mixing, adding 8 parts of gamma-methacryloxypropyltrimethoxysilane into a mixer, stirring and reacting for 10 hours at 80 ℃, washing the prepared reaction product with a solvent, and distilling and drying to obtain an intermediate product;
putting 2 parts of polyurethane prepolymer, 1 part of intermediate product and 4 parts of anti-aging agent 2246 into a triangular flask to obtain a mixture, adding 5% by mass of concentrated hydrochloric acid solution serving as a catalyst into the mixture, heating to 40 ℃, and stirring for reaction for 4 hours to obtain a final product; the above parts are mass components.
Example 2:
Adding 6 parts of sodium silicate hydrate into a beaker, adding 400 parts of distilled water to dissolve sodium silicate powder, slowly dropwise adding a dilute sulfuric acid solution into the beaker until the pH value is 6.5, then adding 3 parts of sodium sulfate as a dispersing agent, aging for 1h, filtering and washing flocculent precipitates by using gauze to obtain SiO 2 crystals, pressing the washed flocculent precipitates into a filter cake, drying the filter cake in an oven at the temperature of 80 ℃, then placing the dried product into a calcining furnace to calcine at the temperature of 450 ℃, and finally placing the calcined product into an ultrafine grinder to grind into 1700-mesh powder to obtain the nano white carbon black;
dispersing 6 parts of nano white carbon black in 200 parts of ethanol solution, treating for 75min at 55 ℃ by using 36KHz ultrasonic waves, filtering and removing generated flocculent precipitate, washing and drying to obtain nano white carbon black with reduced surface energy;
taking 6 parts of treated nano white carbon black, dispersing in 200 parts of ethanol solution, adding 5 parts of butyl titanate into the solution, pre-dispersing, slowly dropping 8% sodium silicate solution by mass fraction into the solution at 87 ℃ until the pH value of the solution is 8.5, aging for 2h to finish coating of SiO 2 by TiO 2, slowly dropping dilute sulfuric acid solution into the solution until the pH value of the solution is 7.0, aging for 4h, washing with water, filtering, and drying at 150 ℃ to obtain SiO 2/TiO 2 particles;
Grinding 50 parts of SiO 2/TiO 2 particles, uniformly mixing, adding 9 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a mixer, stirring and reacting for 17 hours at the temperature of 100 ℃, washing the obtained reaction product with a solvent, and distilling and drying to obtain an intermediate product;
putting 3 parts of polyurethane prepolymer, 2 parts of intermediate product and 7 parts of anti-aging agent 2246 into a triangular flask to obtain a mixture, adding 7% by mass of hydrochloric acid serving as a catalyst into the mixture, heating to 50 ℃, and stirring for reaction for 5 hours to obtain a final product; the above parts are mass components.
example 3:
adding 8 parts of hydrated sodium silicate into a beaker, adding 400 parts of distilled water to dissolve sodium silicate powder, slowly dropwise adding a dilute sulfuric acid solution into the beaker until the pH value is 6.5, then adding 5 parts of sodium sulfate serving as a dispersing agent, aging for 1 hour, filtering and washing flocculent precipitate by using gauze to obtain SiO 2 crystals, pressing the washed flocculent precipitate into a filter cake, drying the filter cake in an oven at the temperature of 80 ℃, then placing the dried product into a calcining furnace to calcine at the temperature of 450 ℃, and finally placing the calcined product into a superfine grinder to grind into 2000-mesh powder to obtain the nano white carbon black;
Dispersing 8 parts of nano white carbon black in 200 parts of ethanol solution, treating for 120min at 70 ℃ by using 50KHz ultrasonic waves, filtering and removing generated flocculent precipitate, washing and drying to obtain nano white carbon black with reduced surface energy;
Taking 9 parts of treated nano white carbon black, dispersing in 200 parts of ethanol solution, adding 6 parts of butyl titanate into the solution, pre-dispersing, slowly dropping 8% sodium silicate solution by mass fraction into the solution at 90 ℃ until the pH value of the solution is 8.5, aging for 2h to finish coating of SiO 2 by TiO 2, slowly dropping dilute sulfuric acid solution into the solution until the pH value of the solution is 7.0, aging for 4h, washing with water, filtering, and drying at 200 ℃ to obtain SiO 2/TiO 2 particles;
Grinding 60 parts of SiO 2/TiO 2 particles, uniformly mixing, adding 10 parts of gamma-aminopropyltriethoxysilane into a mixer, stirring and reacting for 24 hours at 120 ℃, washing the obtained reaction product with a solvent, and distilling and drying to obtain an intermediate product;
Putting 4 parts of polyurethane prepolymer, 3 parts of intermediate product and 10 parts of anti-aging agent 2246 into a triangular flask to obtain a mixture, adding 10% by mass of hydrochloric acid serving as a catalyst into the mixture, heating to 60 ℃, and stirring for reacting for 6 hours to obtain a final product; the above parts are mass components.
finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a rubber antioxidant is characterized by comprising the following steps:
(1) adding 4-8 parts of hydrated sodium silicate into a beaker, adding 400 parts of distilled water to dissolve sodium silicate powder, slowly dropwise adding dilute sulfuric acid into the beaker until the pH value is 6.5, then adding 1-5 parts of sodium sulfate as a dispersing agent, aging for 1h, filtering and washing the flocculent precipitate by using gauze to obtain SiO 2 crystals, pressing the washed flocculent precipitate into a filter cake, drying the filter cake in an oven at the temperature of 80 ℃, then placing the dried product into a calcining furnace to calcine at the temperature of 450 ℃, and finally placing the calcined product into an ultrafine grinder to grind into 1500-mesh 2000-mesh powder to obtain the nano white carbon black;
(2) ultrasonic modification: dispersing 5-8 parts of nano white carbon black in 200 parts of ethanol solution, treating for 30-120min at 40-70 ℃ by using ultrasonic waves, filtering and removing generated flocculent precipitate, washing and drying to obtain nano white carbon black with reduced surface energy;
(3) coating inorganic matter, namely dispersing 3-9 parts of the nano white carbon black treated in the step (2) in 200 parts of ethanol solution, adding 3-6 parts of butyl titanate into the solution for pre-dispersion, slowly dropping 8 mass percent sodium silicate solution into the solution at 85-90 ℃ until the pH value of the solution is 8.5, aging for 2h to finish coating of SiO 2 by TiO 2, slowly dropping dilute sulfuric acid solution into the solution until the pH value of the solution is 7.0, aging for 4h, washing with water, filtering, and drying at 100-200 ℃ to obtain SiO 2/TiO 2 particles;
(4) Preparing an intermediate product, namely grinding and uniformly mixing 40-60 parts of SiO 2/TiO 2 particles, adding 8-10 parts of silane coupling agent into a mixer, stirring and reacting for 10-24h at the temperature of 80-120 ℃, washing the prepared reaction product with a solvent, and distilling and drying to obtain the intermediate product;
(5) Condensation reaction: putting 2-4 parts of polyurethane prepolymer, 1-3 parts of intermediate product and 4-10 parts of anti-aging agent into a triangular flask to obtain a mixture, adding 5-10% by mass of hydrochloric acid serving as a catalyst into the mixture, heating to 40-60 ℃, and stirring for reacting for 4-6 hours to obtain a final product; the above parts are mass components.
2. the method for preparing the environment-friendly long-acting rubber antioxidant according to claim 1, wherein the ultrasonic frequency in the step (2) is 25 to 50 KHz.
3. The method for preparing the environment-friendly long-acting rubber antioxidant as claimed in claim 1, wherein the mass ratio of SiO 2 to TiO 2 in step (3) is 2-3%.
4. The method for preparing an environment-friendly long-acting rubber antioxidant according to claim 1, wherein the catalyst in the step (5) is a concentrated hydrochloric acid solution having a concentration of 60%.
5. the method for preparing the environment-friendly long-acting rubber antioxidant as claimed in claim 1, wherein the antioxidant in the step (5) has a model of 2246.
6. The method for preparing the environment-friendly long-acting rubber antioxidant as claimed in claim 1, wherein the white carbon black in the step (1) can be any one of kaolin, montmorillonite, halloysite nanotube, talcum powder or mica powder zinc oxide.
7. the method for preparing the environment-friendly long-acting rubber antioxidant as claimed in claim 1, wherein any one of mica powder, zinc oxide, montmorillonite, halloysite nanotube, talcum powder or kaolin is used to replace the white carbon black in the step (1).
8. the method for preparing the environment-friendly long-acting rubber antioxidant according to claim 1, wherein the silane coupling agent in the step (1) is any one of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, bis (gamma-triethoxysilylpropyl) tetrasulfide and 3- (trimethoxysilyl) -1-propanethiol.
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Application publication date: 20191210 |