CN110791241A - Preparation method of resorcinol adhesive with high adhesion for tires - Google Patents
Preparation method of resorcinol adhesive with high adhesion for tires Download PDFInfo
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- CN110791241A CN110791241A CN201910884493.2A CN201910884493A CN110791241A CN 110791241 A CN110791241 A CN 110791241A CN 201910884493 A CN201910884493 A CN 201910884493A CN 110791241 A CN110791241 A CN 110791241A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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Abstract
The invention discloses a preparation method of a resorcinol adhesive with high viscosity for a tire, which comprises the following steps: (1) preparing resorcinol dispersion liquid; (2) preparing a swollen product; (3) post-treating the swelling product; (4) homogenizing and stirring; (5) and (5) dehydrating and drying. The polystyrene with low crosslinking degree is not only easy to be permeated by resorcinol to swell, but also can not be dissolved while keeping the maximum swelling ratio so as to keep high viscosity, and the adhesive force of the adhesive is further improved by combining with the vinyl silicone oil emulsion. In addition, the invention also utilizes the free resorcinol in the sealing agent contrast system to carry out adsorption and blocking, thereby preventing the resorcinol from being decomposed at high temperature and reducing the smoke generation rate.
Description
Technical Field
The invention belongs to the technical field of tire adhesive production, and particularly relates to a preparation method of a resorcinol adhesive with high viscosity for a tire.
Background
With the rapid development of road traffic, more and more high-grade roads provide greater tests for the quality of automobile tires. At present, most tires are compounded with various framework materials and reinforcing materials in rubber base materials so as to meet the strength of the tires. However, metal materials are not easily adhered to rubber, and the adhesion technique is not necessarily small for obtaining a tire made of a rubber-metal frame material with high performance. In the market, the tire adhesive adopts a m-methyl-white adhesive system, however, resorcinol is easy to sublimate during mixing to generate a large amount of irritant smog, which not only affects the environment, but also seriously affects the human health, and easily causes the content reduction of the resorcinol in rubber materials to affect the adhesive effect.
Therefore, the prior art has improved resorcinol to change this situation. The method comprises the steps of taking resorcinol and formaldehyde as raw materials, adding styrene as a modifier, carrying out two-step polymerization reaction in the presence of a composite acid catalyst, heating and melting the resorcinol and the composite acid catalyst, then dropwise adding 50-80% of the modifier and 10-30% of the formaldehyde into the molten liquid for primary polymerization reaction, simultaneously dropwise adding the balance of the modifier and the balance of the formaldehyde into the primary polymerization solution for main polymerization reaction, and finally separating the polymerization reaction liquid to obtain the resorcinol/formaldehyde resin. However, the adhesives described above all focus on reducing free resorcinol, thereby reducing the smoke generation rate, but reduce the adhesion strength while adding resorcinol, so that the adhesives produced cannot meet higher requirements.
Therefore, the research and development of the resorcinol adhesive for the tire, which has high viscosity and low smoke rate, is of great significance, meets the requirements of the current market, and has better application prospect.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing a resorcinol adhesive for a tire, which has high adhesion and low smoke generation rate.
The technical scheme of the invention is as follows: a method for preparing a resorcinol adhesive for a tire with high viscosity comprises the following steps:
(1) preparing resorcinol dispersion liquid: mixing resorcinol and ethanol according to a mass ratio of 1:2, stirring until the resorcinol and the ethanol are dissolved to obtain resorcinol solution, adding a dispersing agent with the mass percentage of 5-7 wt% into the resorcinol solution, and fully stirring to obtain resorcinol dispersion liquid for later use;
(2) preparation of a swollen product: activating polystyrene microspheres, adding the activated polystyrene microspheres into the resorcinol dispersion liquid, wherein the mass ratio of the polystyrene microspheres to the resorcinol dispersion liquid is 1:5-10, stirring for 24-30h at 60-120r/min in a closed environment at 30-35 ℃, and continuously permeating resorcinol into molecular chains of the polystyrene microspheres until swelling balance is achieved, so as to obtain a swelling product;
(3) post-treatment of the swollen product: gradually heating the swelling product to 90 ℃ under the water bath condition to remove ethanol, dropwise adding 10-15 wt% of sealing agent, stirring and mixing uniformly, keeping the temperature at 90 ℃ for 30min, and reducing free resorcinol to obtain a post-treatment swelling product;
(4) homogenizing and stirring: putting the post-treatment swelling product into a homogenizing mixer, dropwise adding 20-25 wt% of vinyl silicone oil emulsion, stirring at the rotation speed of 200-300rpm for 60min, then adding 4-6 wt% of addition agent, and continuously stirring for 30min to obtain a crude adhesive product;
(5) and (3) dehydrating and drying: and under the protection of nitrogen atmosphere, distilling and dehydrating the crude adhesive, and then drying in a vacuum dryer at 50-60 ℃ for 1-3h to finally obtain the finished adhesive.
Further, the dispersant in the step (1) is composed of carbon black powder and an amphiphilic surfactant according to a mass ratio of 1:1-3, the particle size of the carbon black powder is 2-5 μm, and if the carbon black powder is too large, the polystyrene microspheres are easily hindered, and the resorcinol cannot be permeated favorably. Amphiphilic surfactants include, but are not limited to, sodium lauryl sulfate and cetyltrimethylammonium bromide.
Further, the preparation method of the dispersant comprises the following steps: uniformly spraying the amphiphilic surfactant on the surface of the carbon black powder in 3-5 batches at intervals of 20-30min, finally placing the carbon black powder sprayed with the amphiphilic surfactant into a quartz tube with two ends connected with a positive electrode and a negative electrode of a power supply, vacuumizing to a range of not less than-0.08 MPa and not more than-0.05 MPa, introducing nitrogen for protection, and applying a voltage of 1200-1500V to two ends of the quartz tube for plasma treatment for 10-15 min. The amphiphilic surfactant is firmly embedded into the surface of the carbon black powder by using plasma, so that the polystyrene microspheres can keep good dispersibility during swelling, and the contact area with resorcinol is increased.
Further, the polystyrene microspheres in the step (2) are low-crosslinking-degree polystyrene with a crosslinking degree of 8-10%, and the particle size is 8-10 μm. The viscosity increases with the decrease of the crosslinking degree, and the polystyrene having a low crosslinking degree is easily penetrated by resorcinol to be swollen, thereby performing a good dispersion fixation effect on resorcinol, and maintaining high viscosity without being dissolved while maintaining the maximum swelling ratio.
Further, the polystyrene microsphere activation method in the step (2) comprises the following steps: firstly, mixing formic acid, N-dimethylcyclohexylamine and ethanol according to the volume ratio of 2:1:5 to prepare an activating solution; and secondly, filling the polystyrene microspheres into a filler column, continuously refluxing for 1-3h by using the activating solution, taking out the polystyrene microspheres, freeze-drying for 1-2h at-10-20 ℃, taking out the polystyrene microspheres for thawing at room temperature, continuously refluxing, freeze-drying and thawing for 3-5 times by using the activating solution, wherein the surfaces of the polystyrene microspheres can be fully activated by using formic acid and N, N-dimethylcyclohexylamine through repeated freeze thawing, the formic acid has two functional groups of carboxyl and aldehyde, the carboxyl can be used for cleaning the surfaces of the polystyrene microspheres, the aldehyde can be used for carrying out directional adsorption and fixation on resorcinol, and the N, N-dimethylcyclohexylamine can be used as an accelerator for improving the fixation rate of resorcinol in the polystyrene microspheres.
Further, the sealant in the step (3) comprises the following components in parts by weight: 40-45 parts of polyaldehyde sodium alginate, 25-30 parts of nano crystalline cellulose, 8-10 parts of heparin, 1-2 parts of non-silicon antifoaming agent and 150-200 parts of pure water. The polyaldehyde group sodium alginate can be prepared by adopting a preparation method disclosed in the patent number CN 201110213723.6.
Further, the preparation method of the sealant comprises the following steps: heating 25-30 parts of the nanocrystalline cellulose to 150-200 ℃ under the protection of nitrogen atmosphere, and preserving heat for 30min to obtain a product A; adding 40-45 parts of the multi-aldehyde sodium alginate into 50-80 parts of pure water, uniformly stirring, adding the product A, heating in a water bath to 85-90 ℃, mechanically stirring for 30-40min, cooling to 10-15 ℃ at the speed of 10 ℃/min to obtain a product B, heating to melt the multi-aldehyde sodium alginate so as to disorder the molecular structure of the multi-aldehyde sodium alginate, and enabling the linear structure of the molecules to shrink to form a spiral structure after rapid cooling, so that the multi-aldehyde sodium alginate is organically combined with the nano crystalline cellulose activated at high temperature, and free resorcinol can be blocked to prevent the resorcinol from being decomposed at high temperature; and finally, mixing the product A and the product B, adding 8-10 parts of heparin, 1-2 parts of non-silicon defoaming agent and the rest pure water, dispersing by using a high-speed dispersion machine, controlling the rotating speed at 3000r/min for 2000 and 3000r/min, and stopping after 30min to obtain the sealing agent. Wherein, the heparin with high negative charge can adsorb free resorcinol, thereby reducing the smoke rate.
Further, the vinyl silicone oil emulsion in the step (4) is composed of vinyl silicone oil, an emulsifier and pure water according to a mass ratio of 80:3: 100.
Further, the addition auxiliary agent in the step (4) is composed of an antioxidant, an anti-aging agent and a promoter according to the mass ratio of 2:1: 1.
The invention has the beneficial effects that: the method utilizes an activating solution consisting of formic acid, N, N-dimethylcyclohexylamine and ethanol to carry out reflux-freeze drying-unfreezing circulation on the polystyrene microspheres with low crosslinking degree, wherein the formic acid has two functional groups of carboxyl and aldehyde groups, the carboxyl can be used for cleaning the surfaces of the polystyrene microspheres, the aldehyde groups can be used for carrying out directional adsorption and fixation on resorcinol, and the N, N-dimethylcyclohexylamine as an accelerant can improve the fixation rate of the resorcinol in the polystyrene microspheres. And the sealing agent is also used for adsorbing and blocking free resorcinol in the system, so that the resorcinol is prevented from being decomposed at high temperature, and the smoke generation rate is reduced. In addition, the polystyrene with low crosslinking degree is not only easy to be permeated by resorcinol to swell, but also can not be dissolved while the maximum swelling ratio is kept, so that high viscosity is kept, and the adhesive force of the adhesive is further improved by combining with the vinyl silicon oil emulsion.
Detailed Description
The reagents used in the present invention are all commercially available products unless otherwise specified.
Example 1
(1) Preparing resorcinol dispersion liquid: mixing resorcinol and ethanol according to a mass ratio of 1:2, stirring until the resorcinol and the ethanol are dissolved to obtain resorcinol solution, adding a dispersing agent with the mass percentage of 6 wt% into the resorcinol solution, wherein the dispersing agent is formed by mixing carbon black powder with the particle size of 5 mu m and sodium dodecyl sulfate according to the mass ratio of 1:2, and fully stirring to obtain resorcinol dispersion liquid for later use.
(2) Preparation of a swollen product: since the viscosity increases with the decrease in the degree of crosslinking, polystyrene having a low degree of crosslinking is easily penetrated by resorcinol to be swollen, and thus can exert a good dispersion-fixing effect on resorcinol, and can maintain the maximum swelling ratio without being dissolved to maintain high viscosity. Therefore, in the embodiment, low-crosslinking-degree polystyrene microspheres with a particle size of 10 μm and a crosslinking degree of 8% are selected, formic acid, N-dimethylcyclohexylamine and ethanol are mixed according to a volume ratio of 2:1:5 to prepare an activation solution, the activation solution is subjected to continuous reflux for 3 hours to activate the polystyrene microspheres, the polystyrene microspheres are added into resorcinol dispersion liquid after being activated, the mass ratio of the polystyrene microspheres to the resorcinol dispersion liquid is 1:8, the polystyrene microspheres are stirred for 24 hours at 90r/min in a closed environment at 32 ℃, resorcinol continuously permeates into molecular chains of the polystyrene microspheres to reach swelling balance, and finally a swelling product is obtained;
(3) post-treatment of the swollen product: gradually heating the swelling product to 90 ℃ under the water bath condition to remove ethanol, dropwise adding 12 wt% of sealing agent, stirring and mixing uniformly, keeping the temperature at 90 ℃ for 30min, and reducing free resorcinol to obtain a post-treatment swelling product; the sealant is prepared by mixing 43 parts of polyaldehyde sodium alginate, 26 parts of nano crystalline cellulose, 9 parts of heparin, 1.5 parts of non-silicon defoaming agent (Dow Corning B-2030 defoaming agent) and 180 parts of pure water according to weight components. The polyaldehyde group sodium alginate can be prepared by adopting a preparation method disclosed in the patent number CN 201110213723.6.
(4) Homogenizing and stirring: putting the post-treated swelling product into a homogenizing mixer, dropwise adding 22 wt% of vinyl silicon oil emulsion, stirring at the rotating speed of 250rpm for 60min, then adding 5 wt% of addition agent, and continuously stirring for 30min to obtain a crude adhesive product; the vinyl silicone oil emulsion is composed of vinyl silicone oil, an emulsifier (sodium alkyl benzene sulfonate) and pure water according to a mass ratio of 80:3:100, and the additive auxiliary agent is composed of an antioxidant (AT-10 type antioxidant), an anti-aging agent (N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine) and an accelerator (rubber accelerator M) according to a mass ratio of 2:1: 1.
(5) And (3) dehydrating and drying: and (3) distilling and dehydrating the crude adhesive under the protection of nitrogen atmosphere, and then drying the crude adhesive in a vacuum dryer at 55 ℃ for 3h to finally obtain a finished adhesive.
Example 2
(1) Preparing resorcinol dispersion liquid: mixing resorcinol and ethanol according to a mass ratio of 1:2, stirring until the mixture is dissolved to obtain a resorcinol solution, adding a dispersing agent with the mass percentage of 6 wt% into the resorcinol solution, wherein the dispersing agent is carbon black powder with the particle size of 4 mu m and an amphiphilic surfactant, the polystyrene microspheres are easily hindered by the overlarge carbon black powder and are not beneficial to the permeation of resorcinol, the amphiphilic surfactant can be cetyl trimethyl ammonium bromide, and the preparation method of the dispersing agent comprises the following steps: uniformly spraying a hexadecyl trimethyl ammonium bromide solution with mass twice that of the carbon black powder on the surface of the carbon black powder in 3 batches, wherein the interval between each batch is 20-30min, finally putting the carbon black powder sprayed with the hexadecyl trimethyl ammonium bromide solution into a quartz tube with two ends connected with a positive electrode and a negative electrode of a power supply, vacuumizing to the range of ≧ 0.08MPa and ≦ 0.05MPa, introducing nitrogen for protection, applying a voltage of 1200-1500V at two ends of the quartz tube, and carrying out plasma treatment for 10-15 min. The amphiphilic surfactant is firmly embedded into the surface of the carbon black powder by using plasma, so that the polystyrene microspheres can keep good dispersibility during swelling, and the contact area with resorcinol is increased.
(2) Preparation of a swollen product: since the viscosity increases with the decrease in the degree of crosslinking, polystyrene having a low degree of crosslinking is easily penetrated by resorcinol to be swollen, and thus can exert a good dispersion-fixing effect on resorcinol, and can maintain the maximum swelling ratio without being dissolved to maintain high viscosity. Therefore, in the embodiment, low-crosslinking-degree polystyrene microspheres with a particle size of 10 μm and a crosslinking degree of 8% are selected, formic acid, N-dimethylcyclohexylamine and ethanol are mixed according to a volume ratio of 2:1:5 to prepare an activation solution, the activation solution is subjected to continuous reflux for 3 hours to activate the polystyrene microspheres, the polystyrene microspheres are added into resorcinol dispersion liquid after being activated, the mass ratio of the polystyrene microspheres to the resorcinol dispersion liquid is 1:8, the polystyrene microspheres are stirred for 24 hours at 90r/min in a closed environment at 32 ℃, resorcinol continuously permeates into molecular chains of the polystyrene microspheres to reach swelling balance, and finally a swelling product is obtained;
(3) post-treatment of the swollen product: gradually heating the swelling product to 90 ℃ under the water bath condition to remove ethanol, dropwise adding 12 wt% of sealing agent, stirring and mixing uniformly, keeping the temperature at 90 ℃ for 30min, and reducing free resorcinol to obtain a post-treatment swelling product; the sealant is prepared by mixing 43 parts of polyaldehyde sodium alginate, 26 parts of nano crystalline cellulose, 9 parts of heparin, 1.5 parts of non-silicon defoaming agent (Dow Corning B-2030 defoaming agent) and 180 parts of pure water according to weight components. The polyaldehyde group sodium alginate can be prepared by adopting a preparation method disclosed in the patent number CN 201110213723.6.
(4) Homogenizing and stirring: putting the post-treated swelling product into a homogenizing mixer, dropwise adding 22 wt% of vinyl silicon oil emulsion, stirring at the rotating speed of 250rpm for 60min, then adding 5 wt% of addition agent, and continuously stirring for 30min to obtain a crude adhesive product; the vinyl silicone oil emulsion is composed of vinyl silicone oil, an emulsifier (sodium alkyl benzene sulfonate) and pure water according to a mass ratio of 80:3:100, and the additive auxiliary agent is composed of an antioxidant (AT-10 type antioxidant), an anti-aging agent (N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine) and an accelerator (rubber accelerator M) according to a mass ratio of 2:1: 1.
(5) And (3) dehydrating and drying: and (3) distilling and dehydrating the crude adhesive under the protection of nitrogen atmosphere, and then drying the crude adhesive in a vacuum dryer at 55 ℃ for 3h to finally obtain a finished adhesive.
Example 3
(1) Preparing resorcinol dispersion liquid: mixing resorcinol and ethanol according to a mass ratio of 1:2, stirring until the mixture is dissolved to obtain a resorcinol solution, adding a dispersing agent with the mass percentage of 6 wt% into the resorcinol solution, wherein the dispersing agent is carbon black powder with the particle size of 4 mu m and an amphiphilic surfactant, the polystyrene microspheres are easily hindered by the overlarge carbon black powder and are not beneficial to the permeation of resorcinol, the amphiphilic surfactant can be cetyl trimethyl ammonium bromide, and the preparation method of the dispersing agent comprises the following steps: and uniformly spraying a hexadecyl trimethyl ammonium bromide solution with the mass twice that of the carbon black powder on the surface of the carbon black powder in 3 batches, wherein the interval between each batch is 25min, finally putting the carbon black powder sprayed with the hexadecyl trimethyl ammonium bromide solution into a quartz tube with two ends connected with a positive electrode and a negative electrode of a power supply, vacuumizing to-0.06 MPa, introducing nitrogen for protection, applying a voltage of 1200-1500V to two ends of the quartz tube, and carrying out plasma treatment for 10-15 min. The amphiphilic surfactant is firmly embedded into the surface of the carbon black powder by using plasma, so that the polystyrene microspheres can keep good dispersibility during swelling, and the contact area with resorcinol is increased.
(2) Preparation of a swollen product: since the viscosity increases with the decrease in the degree of crosslinking, polystyrene having a low degree of crosslinking is easily penetrated by resorcinol to be swollen, and thus can exert a good dispersion-fixing effect on resorcinol, and can maintain the maximum swelling ratio without being dissolved to maintain high viscosity. Therefore, the present example selects the low crosslinking degree polystyrene microsphere with the particle size of 10 μm and the crosslinking degree of 8%, mixing formic acid, N, N-dimethylcyclohexylamine and ethanol according to a volume ratio of 2:1:5 to prepare an activation solution, continuously refluxing for 3 hours, taking out the polystyrene microspheres, freeze-drying for 1.5 hours at-15 ℃, taking out the polystyrene microspheres, thawing at room temperature, continuously refluxing, freeze-drying and thawing for 3 times by using the activation solution, and promoting the formic acid and the N, N-dimethylcyclohexylamine to fully activate the polystyrene surfaces by using repeated freeze thawing, wherein the formic acid has carboxyl and aldehyde groups, so that the surfaces of the polystyrene microspheres can be cleaned by using the carboxyl groups, and resorcinol can be directionally adsorbed and fixed by using the aldehyde groups, and the fixing rate of resorcinol in the polystyrene microspheres can be improved by using the N, N-dimethylcyclohexylamine as an accelerant. And finally, adding the activated polystyrene microspheres into resorcinol dispersion liquid, wherein the mass ratio of the polystyrene microspheres to the resorcinol dispersion liquid is 1:8, stirring at 90r/min for 24h in a closed environment at 32 ℃, and continuously permeating resorcinol into molecular chains of the polystyrene microspheres until swelling balance is achieved, so as to finally obtain a swelling product.
(3) Post-treatment of the swollen product: gradually heating the swelling product to 90 ℃ under the water bath condition to remove ethanol, dropwise adding 12 wt% of sealing agent, stirring and mixing uniformly, keeping the temperature at 90 ℃ for 30min, and reducing free resorcinol to obtain a post-treatment swelling product; the sealant is prepared by mixing 43 parts of polyaldehyde sodium alginate, 26 parts of nano crystalline cellulose, 9 parts of heparin, 1.5 parts of non-silicon defoaming agent (Dow Corning B-2030 defoaming agent) and 180 parts of pure water according to weight components. The polyaldehyde group sodium alginate can be prepared by adopting a preparation method disclosed in the patent number CN 201110213723.6.
(4) Homogenizing and stirring: putting the post-treated swelling product into a homogenizing mixer, dropwise adding 22 wt% of vinyl silicon oil emulsion, stirring at the rotating speed of 250rpm for 60min, then adding 5 wt% of addition agent, and continuously stirring for 30min to obtain a crude adhesive product; the vinyl silicone oil emulsion is composed of vinyl silicone oil, an emulsifier (sodium alkyl benzene sulfonate) and pure water according to a mass ratio of 80:3:100, and the additive auxiliary agent is composed of an antioxidant (AT-10 type antioxidant), an anti-aging agent (N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine) and an accelerator (rubber accelerator M) according to a mass ratio of 2:1: 1.
(5) And (3) dehydrating and drying: and (3) distilling and dehydrating the crude adhesive under the protection of nitrogen atmosphere, and then drying the crude adhesive in a vacuum dryer at 55 ℃ for 3h to finally obtain a finished adhesive.
Example 4
(1) Preparing resorcinol dispersion liquid: mixing resorcinol and ethanol according to a mass ratio of 1:2, stirring until the mixture is dissolved to obtain a resorcinol solution, adding a dispersing agent with the mass percentage of 6 wt% into the resorcinol solution, wherein the dispersing agent is carbon black powder with the particle size of 4 mu m and an amphiphilic surfactant, the polystyrene microspheres are easily hindered by the overlarge carbon black powder and are not beneficial to the permeation of resorcinol, the amphiphilic surfactant can be cetyl trimethyl ammonium bromide, and the preparation method of the dispersing agent comprises the following steps: and uniformly spraying a hexadecyl trimethyl ammonium bromide solution with the mass twice that of the carbon black powder on the surface of the carbon black powder in 3 batches, wherein the interval between each batch is 25min, finally putting the carbon black powder sprayed with the hexadecyl trimethyl ammonium bromide solution into a quartz tube with two ends connected with a positive electrode and a negative electrode of a power supply, vacuumizing to-0.06 MPa, introducing nitrogen for protection, applying a voltage of 1200-1500V to two ends of the quartz tube, and carrying out plasma treatment for 10-15 min. The amphiphilic surfactant is firmly embedded into the surface of the carbon black powder by using plasma, so that the polystyrene microspheres can keep good dispersibility during swelling, and the contact area with resorcinol is increased.
(3) Preparation of a swollen product: since the viscosity increases with the decrease in the degree of crosslinking, polystyrene having a low degree of crosslinking is easily penetrated by resorcinol to be swollen, and thus can exert a good dispersion-fixing effect on resorcinol, and can maintain the maximum swelling ratio without being dissolved to maintain high viscosity. Therefore, the present example selects the low crosslinking degree polystyrene microsphere with the particle size of 10 μm and the crosslinking degree of 8%, mixing formic acid, N, N-dimethylcyclohexylamine and ethanol according to a volume ratio of 2:1:5 to prepare an activation solution, continuously refluxing for 3 hours, taking out the polystyrene microspheres, freeze-drying for 1.5 hours at-15 ℃, taking out the polystyrene microspheres, thawing at room temperature, continuously refluxing, freeze-drying and thawing for 3 times by using the activation solution, and promoting the formic acid and the N, N-dimethylcyclohexylamine to fully activate the polystyrene surfaces by using repeated freeze thawing, wherein the formic acid has carboxyl and aldehyde groups, so that the surfaces of the polystyrene microspheres can be cleaned by using the carboxyl groups, and resorcinol can be directionally adsorbed and fixed by using the aldehyde groups, and the fixing rate of resorcinol in the polystyrene microspheres can be improved by using the N, N-dimethylcyclohexylamine as an accelerant. And finally, adding the activated polystyrene microspheres into resorcinol dispersion liquid, wherein the mass ratio of the polystyrene microspheres to the resorcinol dispersion liquid is 1:8, stirring at 90r/min for 24h in a closed environment at 32 ℃, and continuously permeating resorcinol into molecular chains of the polystyrene microspheres until swelling balance is achieved, so as to finally obtain a swelling product.
(3) Post-treatment of the swollen product: gradually heating the swelling product to 90 ℃ under the water bath condition to remove ethanol, dropwise adding 12 wt% of sealing agent, stirring and mixing uniformly, keeping the temperature at 90 ℃ for 30min, and reducing free resorcinol to obtain a post-treatment swelling product; the sealant comprises 43 parts of polyaldehyde sodium alginate, 26 parts of nano crystalline cellulose, 9 parts of heparin, 1.5 parts of non-silicon defoaming agent (Dow Corning B-2030 defoaming agent) and 180 parts of pure water according to weight components. The polyaldehyde group sodium alginate can be prepared by adopting a preparation method disclosed in the patent number CN 201110213723.6. The sealing agent is prepared by a method comprising the following steps of heating 28 parts of nano crystalline cellulose to 180 ℃ under the protection of nitrogen atmosphere, and preserving heat for 30min to obtain a product A; adding 42 parts of polyaldehyde group sodium alginate into 60 parts of pure water, uniformly stirring, adding a product A, heating in a water bath to 88 ℃, mechanically stirring for 35min, cooling to 12 ℃ at the speed of 10 ℃/min to obtain a product B, heating to melt the polyaldehyde group sodium alginate so as to disorder the molecular structure of the polyaldehyde group sodium alginate, shrinking the linear structure of the molecules after rapid cooling to form a spiral structure, organically combining with the nano crystalline cellulose activated at high temperature, and blocking free resorcinol to prevent high-temperature decomposition of the free resorcinol; and finally, mixing the product A and the product B, adding 9 parts of heparin, 1.5 parts of non-silicon antifoaming agent (Dow Corning B-2030 antifoaming agent) and the rest pure water, dispersing by using a high-speed dispersion machine, controlling the rotating speed at 3000r/min for 2000 plus materials, and stopping after 30min to obtain the sealing agent. Wherein, the heparin with high negative charge can adsorb free resorcinol, thereby reducing the smoke rate.
(4) Homogenizing and stirring: putting the post-treated swelling product into a homogenizing mixer, dropwise adding 22 wt% of vinyl silicon oil emulsion, stirring at the rotating speed of 250rpm for 60min, then adding 5 wt% of addition agent, and continuously stirring for 30min to obtain a crude adhesive product; the vinyl silicone oil emulsion is composed of vinyl silicone oil, an emulsifier (sodium alkyl benzene sulfonate) and pure water according to a mass ratio of 80:3:100, and the additive auxiliary agent is composed of an antioxidant (AT-10 type antioxidant), an anti-aging agent (N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine) and an accelerator (rubber accelerator M) according to a mass ratio of 2:1: 1.
(5) And (3) dehydrating and drying: and (3) distilling and dehydrating the crude adhesive under the protection of nitrogen atmosphere, and then drying the crude adhesive in a vacuum dryer at 55 ℃ for 3h to finally obtain a finished adhesive.
Test examples
The results of the comparisons of the properties of inventive examples 1-4 with prior art tire adhesives (resorcinol-formaldehyde resin RF-90 and resorcinol-formaldehyde resin SL3022) are shown in Table 1.
Table 1 table comparing the performance of the examples 1-4 with prior art tire adhesives
As can be seen from Table 1, the adhesive prepared in example 4 of the present invention exhibited the best performance, substantially eliminated free resorcinol, and the wire drawing treatment was improved by 65.8% and 52.0% over resorcinol-formaldehyde resin RF-90 and resorcinol-formaldehyde resin SL3022, respectively, and the adhesion strength was improved by 63.5% and 56.2%, respectively.
Claims (8)
1. A preparation method of a resorcinol adhesive with high viscosity for a tire is characterized by comprising the following steps:
(1) preparing resorcinol dispersion liquid: mixing resorcinol and ethanol according to a mass ratio of 1:2, stirring until the resorcinol and the ethanol are dissolved to obtain resorcinol solution, adding a dispersing agent with the mass percentage of 5-7 wt% into the resorcinol solution, and fully stirring to obtain resorcinol dispersion liquid for later use;
(2) preparation of a swollen product: activating polystyrene microspheres, adding the activated polystyrene microspheres into the resorcinol dispersion liquid, wherein the mass ratio of the polystyrene microspheres to the resorcinol dispersion liquid is 1:5-10, stirring for 24-30h at 60-120r/min in a closed environment at 30-35 ℃, and continuously permeating resorcinol into molecular chains of the polystyrene microspheres until swelling balance is achieved, so as to obtain a swelling product;
(3) post-treatment of the swollen product: gradually heating the swelling product to 90 ℃ under the water bath condition to remove ethanol, dropwise adding 10-15 wt% of sealing agent, stirring and mixing uniformly, keeping the temperature at 90 ℃ for 30min, and reducing free resorcinol to obtain a post-treatment swelling product;
(4) homogenizing and stirring: putting the post-treatment swelling product into a homogenizing mixer, dropwise adding 20-25 wt% of vinyl silicone oil emulsion, stirring at the rotation speed of 200-300rpm for 60min, then adding 4-6 wt% of addition agent, and continuously stirring for 30min to obtain a crude adhesive product;
(5) and (3) dehydrating and drying: and under the protection of nitrogen atmosphere, distilling and dehydrating the crude adhesive, and then drying in a vacuum dryer at 50-60 ℃ for 1-3h to finally obtain the finished adhesive.
2. The method for preparing a resorcinol adhesive for a tire having a high degree of adhesion according to claim 1, wherein the dispersant in the step (1) is carbon black powder having a particle size of 2 to 5 μm and an amphiphilic surfactant in a mass ratio of 1:1 to 3.
3. The method for preparing resorcinol adhesive for tire with high viscosity according to claim 1, wherein the polystyrene microspheres in the step (2) are low crosslinking degree polystyrene with crosslinking degree of 8-10% and particle size of 8-10 μm.
4. The method for preparing resorcinol adhesive for tire with high viscosity according to claim 1, wherein the polystyrene microsphere activation method in the step (2) comprises: firstly, mixing formic acid, N-dimethylcyclohexylamine and ethanol according to the volume ratio of 2:1:5 to prepare an activating solution; and secondly, filling the polystyrene microspheres into a filler column, continuously refluxing for 1-3h by using the activating solution, taking out the polystyrene microspheres, freeze-drying for 1-2h at-10-20 ℃, taking out the polystyrene microspheres, thawing at room temperature, and continuously performing reflux-freeze drying-thawing circulation for 3-5 times by using the activating solution to finally obtain the activated polystyrene microspheres.
5. The method for preparing a resorcinol adhesive for a tire having a high adhesion degree according to claim 1, wherein the blocking agent in the step (3) comprises, in terms of weight components: 40-45 parts of polyaldehyde sodium alginate, 25-30 parts of nano crystalline cellulose, 8-10 parts of heparin, 1-2 parts of non-silicon antifoaming agent and 150-200 parts of pure water.
6. The method for preparing a resorcinol adhesive for a tire with a high viscosity according to claim 5, wherein the blocking agent is prepared by: heating 25-30 parts of the nanocrystalline cellulose to 150-200 ℃ under the protection of nitrogen atmosphere, and preserving heat for 30min to obtain a product A; adding 40-45 parts of the multi-aldehyde sodium alginate into 50-80 parts of pure water, uniformly stirring, adding the product A, heating to 85-90 ℃ in a water bath, mechanically stirring for 30-40min, and cooling to 10-15 ℃ at the speed of 10 ℃/min to obtain a product B; and finally, mixing the product A and the product B, adding 8-10 parts of heparin, 1-2 parts of non-silicon defoaming agent and the rest pure water, dispersing by using a high-speed dispersion machine, controlling the rotating speed at 3000r/min for 2000 and 3000r/min, and stopping after 30min to obtain the sealing agent.
7. The method of claim 1, wherein the vinyl silicone oil emulsion in step (4) comprises vinyl silicone oil, an emulsifier, and pure water at a mass ratio of 80:3: 100.
8. The method for preparing a resorcinol adhesive for a tire having a high adhesion degree according to claim 1, wherein the additive auxiliary agent in the step (4) is composed of an antioxidant, an anti-aging agent and an accelerator in a mass ratio of 2:1: 1.
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| CA1335312C (en) * | 1988-03-09 | 1995-04-18 | Axel W. Anderson | Phenol formaldehyde adhesive for bonding wood pieces of high moisture content and composite board and wood veneers bonded with such adhesives |
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| CN109135528A (en) * | 2018-08-17 | 2019-01-04 | 佛山市森昂生物科技有限公司 | A kind of waterborne anti-rust sealer |
| CN109575787A (en) * | 2018-12-12 | 2019-04-05 | 合众（佛山）化工有限公司 | A kind of double-component aqueous wood paint that polystyrene microsphere is modified |
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| CA1335312C (en) * | 1988-03-09 | 1995-04-18 | Axel W. Anderson | Phenol formaldehyde adhesive for bonding wood pieces of high moisture content and composite board and wood veneers bonded with such adhesives |
| JP2005263887A (en) * | 2004-03-17 | 2005-09-29 | Bridgestone Corp | Adhesive composition, method for producing the same, resin material, rubber member, and tire |
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