CN115197659A - Method for preparing pre-reaction liquid for adhesive containing hydrotalcite compound - Google Patents
Method for preparing pre-reaction liquid for adhesive containing hydrotalcite compound Download PDFInfo
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- CN115197659A CN115197659A CN202210794178.2A CN202210794178A CN115197659A CN 115197659 A CN115197659 A CN 115197659A CN 202210794178 A CN202210794178 A CN 202210794178A CN 115197659 A CN115197659 A CN 115197659A
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- hydrotalcite
- sodium phenolate
- magnesium oxide
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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
- 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
- C09J115/00—Adhesives based on rubber derivatives
- C09J115/02—Rubber derivatives containing halogen
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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
Abstract
The invention provides a preparation method of a pre-reaction liquid for an adhesive containing a hydrotalcite compound, which is characterized in that magnesium-aluminum hydrotalcite is prepared from magnesium nitrate and aluminum nitrate, and then a layered hydrotalcite-sodium phenolate compound is prepared. The pre-reaction liquid prepared by the invention can be applied to the preparation of the adhesive of the chlorinated rubber, the adhesive force, the heat resistance and the storage stability of the adhesive are improved, and the pre-reaction liquid is easy to prepare and is suitable for popularization and application.
Description
The technical field is as follows:
the invention provides a pre-reaction liquid for an adhesive containing a hydrotalcite compound, and a preparation method of the pre-reaction liquid, belonging to the technical field of chlorinated rubber adhesives.
Background art:
the chlorinated rubber adhesive is one of the commonly used adhesives in material bonding, a pre-reaction liquid is required to be added in the preparation process of the chlorinated rubber adhesive, and the pre-reaction liquid with good performance can obviously improve the adhesion of the adhesive to the surface of materials (such as glass, metal, cloth and the like) and improve the high-temperature adhesive property of the adhesive. The pre-reaction liquid is generally obtained by the reaction of magnesium oxide solid powder and tert-butyl phenolic resin, but the phenomenon of phase separation of the pre-reaction liquid, namely the phenomenon of solid-liquid delamination of the pre-reaction liquid is often encountered in production, storage and application (document 1: chendenlong, how to overcome the delamination phenomenon of the pre-reaction liquid of the neoprene adhesive and remedy after delamination, china adhesive, 2003, 12 (2), 38-40). The solid-liquid layering of the pre-reaction liquid not only reduces the performance of an adhesive product and brings much inconvenience to a user, but also causes distrust of the user to a manufacturer due to the white precipitate at the bottom of the barrel due to the non-uniform appearance, thereby influencing the market sale of the adhesive. The main reason why the solid-liquid separation phenomenon occurs in the pre-reaction solution is that the polar low molecular weight resin contained in the phenolic resin is preferentially adsorbed on the surface of the magnesium oxide particles, thereby preventing the formation of a thick adsorbed layer of chlorinated rubber on the suspended magnesium oxide particles, or the chlorinated rubber adsorbed on the surface of the magnesium oxide particles is replaced by the low molecular weight resin having a molecular chain length insufficient to form a sufficiently thick adsorbed layer on the surface of the magnesium oxide particles, so that the magnesium oxide suspended particles lose stability and gradually undergo flocculent precipitation, and finally the solid-liquid separation phenomenon occurs (document 2: guoji, phenolic resin for chloroprene adhesives, binder, 1983,2 (7), 23-31).
The invention content is as follows:
in order to solve the problems in the prior art, the invention provides a pre-reaction liquid for a chlorinated rubber adhesive, which is not easy to generate solid-liquid layering phenomenon
The invention also aims to provide a preparation method of the pre-reaction liquid for the chlorinated rubber adhesive, which is simple, has easily obtained raw materials and is easy to popularize and apply in the market.
The invention also provides application of the pre-reaction liquid for the chlorinated rubber adhesive in the field of adhesives.
The specific technical scheme of the invention is as follows:
a pre-reaction liquid for a chlorinated rubber adhesive is prepared by the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 7.0-10.0 by using alkali liquor under the stirring condition of the rotating speed of 100-1000r/min, then reacting for 0.5-3h under the protection of nitrogen and the stirring condition of the rotating speed of 500-1500r/min, placing the obtained mixture in a closed reaction kettle for reacting for 2-24h at 70-120 ℃, filtering the obtained mixture, washing by using the distilled water for removing the carbon dioxide until filtrate is neutral, and reserving the filtered jelly for later use;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water without carbon dioxide at room temperature, then reacting for 10-48h under the protection of nitrogen and stirring at the rotating speed of 200-1200r/min, filtering the obtained product, washing the filtrate with distilled water without carbon dioxide until the filtrate is neutral, drying the filtered precipitate at 80-115 ℃ for 10-48h, and grinding the dried solid into (300-500) mesh white hydrotalcite-sodium phenolate composite powder for later use;
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture for 3-6h at the temperature of 45-70 ℃ and under the stirring condition of the rotating speed of 200-3000r/min, and then standing for 12-36h to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite;
(4) Adding p-tert-butylphenol formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and carrying out reflux reaction on the obtained mixture for 6-10h at the temperature of 25-60 ℃ and under the stirring condition of the rotating speed of 200-1200r/min to obtain the pre-reaction liquid for the chlorinated rubber adhesive.
The invention is further designed in that:
the alkali liquor in the step (1) adopts 5-25wt% NaOH solution.
In the step (1), the weight ratio of the magnesium nitrate hexahydrate, the aluminum nitrate nonahydrate and the carbon dioxide-removed water is (1-1.06): (0.32-0.43): (15-30).
The weight ratio of the jelly obtained in the step (2) to the sodium phenolate to the distilled water from which the carbon dioxide is removed is 1: (0.22-0.46): (5-14).
The weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3), the magnesium oxide, the ethyl acetate and the cyclohexane is (0.5-1.5): (2-3.8): (1.2-2): (20-38).
The weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite prepared in the step (3) to the p-tert-butylphenol formaldehyde resin is (24-46): (22-40).
The invention also provides a pre-reaction liquid for the chlorinated rubber adhesive and application of the pre-reaction liquid in the chlorinated rubber adhesive.
Compared with the prior art, the invention has the following working principle and advantages:
step 1 of the invention is to prepare the layered magnesium aluminum hydrotalcite by using aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide as raw materials, wherein the molecular formula of the hydrotalcite is [ Mg 1-x Al x (OH) 2 ](NO 3 ) x And x:0.17-0.22. The hydrotalcite is brucite [ Mg (OH) 2 ]On the basis of structure, is made of MgO 6 Mg in unit layers formed by octahedral common edges 2+ Can be coated with Al within a certain range 3+ Isomorphous substitution to give positive charge to the laminate with exchangeable NO between layers 3 - Balancing with positive charges on the laminate to make the whole structure of the hydrotalcite be electrically neutral. The surface of the magnesium-aluminum hydrotalcite inorganic layer plate is positively charged, metal ions at the edge of the hydrotalcite inorganic layer plate are in an unsaturated coordination state, so that the magnesium-aluminum hydrotalcite inorganic layer plate has strong activity, and flat hydroxyl groups at the edge of the hydrotalcite layer plate are easy to provide electrons, so that the magnesium-aluminum hydrotalcite inorganic layer plate is favorable for attracting other surrounding positively charged particles (document 3: zhonghui et al, theoretical research on adsorption of azo dye acid orange in hydrotalcite layers, industrial catalysis, 20)08, 16 (10),180-183). The interaction between nitrate ions and inorganic laminates in the hydrotalcite structure is weak, so that the nitrate ions between layers can perform interlayer exchange reaction with other ions and molecules to form a new compound with a layered structure, and the new compound with the layered structure has different physical and chemical properties from the original hydrotalcite compound.
In the step 2 of the invention, the Mg-Al hydrotalcite embedded with nitrate ions among the inorganic laminates prepared in the step 1 and sodium phenolate are subjected to interlayer ion exchange reaction to prepare a hydrotalcite-sodium phenolate compound, sodium phenolate can ionize phenol radical ions with negative charges in aqueous solution, the volume of the phenol radical ions is far larger than that of the nitrate ions, and when the phenol radical ions are embedded among the hydrotalcite laminates, the spacing among the hydrotalcite laminates is increased, the specific surface area of the hydrotalcite inorganic laminates is also enlarged, and more active sites are exposed. In addition, phenol anions are adsorbed on the surface of the hydrotalcite inorganic layer plate, and the hydrophilic surface of the hydrotalcite inorganic layer plate is modified into a hydrophobic surface, so that the hydrotalcite layer plate is easily dispersed in a hydrophobic mixed organic solvent formed by ethyl acetate and cyclohexane; otherwise, the unmodified hydrotalcite inorganic layer plate with the strong hydrophilic surface in the hydrophobic organic solvent can cause polymerization and precipitation among hydrotalcite particles because the properties of the two are completely opposite.
Step 3 of the present invention is to react the hydrotalcite-sodium phenolate composite prepared in step 2 with magnesium oxide (active light magnesium oxide) particles. The active light magnesium oxide has high activity, the particle surface can easily absorb moisture in the environment to form a magnesium hydroxide layer, and the surface of the magnesium hydroxide layer is positively charged (document 4: zhangdong. Surface modification research of magnesium hydroxide [ D ]. Shaanxi: university of electronic science and technology of Xian, 2013). Therefore, electron-donating hydroxyl groups at the edge of a hydrotalcite inorganic layer plate in the hydrotalcite-sodium phenolate compound interact with the positively charged surfaces of the active light magnesium oxide particles to form the magnesium oxide-hydrotalcite-sodium phenolate compound, and the magnesium oxide particles in the compound are coated by the hydrotalcite-sodium phenolate compound, so that the independent magnesium oxide particles are not easy to agglomerate and precipitate.
Step 4 of the invention is to react the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in step 3 with p-tert-butyl phenol formaldehyde resin. When the p-tert-butylphenol formaldehyde resin is added, the migration speed of the small-molecular-weight p-tert-butylphenol formaldehyde resin is faster than that of the large-molecular-weight p-tert-butylphenol formaldehyde resin due to the fact that the molecular chain of the small-molecular-weight p-tert-butylphenol formaldehyde resin is smaller, therefore, the small-molecular-weight p-tert-butylphenol formaldehyde resin can firstly contact the hydrotalcite-sodium phenolate compound wrapped outside the magnesium oxide particles, and the small-molecular-weight p-tert-butylphenol formaldehyde resin also contains the same phenol groups as those in the hydrotalcite-sodium phenolate compound, and is adsorbed by a hydrotalcite-sodium phenolate compound laminate due to the principle of same polarity adsorption, so that the molecular weight loaded by the laminate of the hydrotalcite-sodium phenolate compound is too large, the interaction between the hydrotalcite-sodium phenolate compound and the surface of the magnesium oxide is weakened, namely, the hydrotalcite-sodium phenolate compound can be separated from the surface of the magnesium oxide particles, and active sites on the surface of the magnesium oxide are exposed; the p-tert-butylphenol formaldehyde resin with large molecular weight can replace hydrotalcite-sodium phenolate compound to act with the surface of magnesium oxide, namely the p-tert-butylphenol formaldehyde resin with large molecular weight replaces hydrotalcite-sodium phenolate compound to be wrapped on the surface of magnesium oxide particles, so that a sufficiently thick p-tert-butylphenol formaldehyde resin adsorption layer with large molecular weight is formed on the surface of the magnesium oxide particles, the suspension property of the p-tert-butylphenol formaldehyde resin with large molecular weight is excellent, and the magnesium oxide particles are suspended in the solution and keep sufficient stability.
In the pre-reaction liquid prepared by the invention, due to the existence of the hydrotalcite-sodium phenolate compound, low molecular weight resin contained in the p-tert-butylphenol formaldehyde resin can not be preferentially adsorbed on the surfaces of magnesium oxide particles, and finally the p-tert-butylphenol formaldehyde resin with large molecular weight is adsorbed on the surfaces of the magnesium oxide particles, so that the suspension property of the p-tert-butylphenol formaldehyde resin with large molecular weight is good, the coated magnesium oxide particles can be suspended in the solution, the magnesium oxide particles are separated by the large molecular weight resin, the magnesium oxide particles are prevented from being condensed with each other to form precipitates, and further, the pre-reaction liquid is prevented from generating a solid-liquid stratification phenomenon.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow chart of a preparation process of a pre-reaction liquid for a chlorinated rubber adhesive.
FIG. 2 is an X-ray powder diffraction pattern of a sample; in fig. 2, a is a dried sample of the jelly prepared in step (1) of example 3, and b is a hydrotalcite-sodium phenolate composite powder prepared in step (2) of example 3 according to the present invention.
Detailed Description
The chemical starting materials used in the following examples: sodium phenolate was from the chemical company of jingningchengtai; the chlorinated rubber is produced by Jiangsu Rui and New materials, and CR600 type chlorinated rubber is used; the magnesium oxide is active light magnesium oxide produced by Japan Shendao chemical company, and the product model is 150; the p-tert-butyl phenol formaldehyde resin is produced by chemical technology Limited in the Shanghai of Jinan, and the product model is 2402; the anti-aging agent 264 is from Zhengzhou Penny chemical reagent factory; 120# solvent oil from landish petrochemicals ltd; the other chemical reagents are all commercially available, chemically pure reagents.
Example 1
A pre-reaction liquid for a chlorinated rubber adhesive is prepared by the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 7.0 by using alkali liquor under the stirring condition of the rotating speed of 100r/min, then reacting for 0.5h under the protection of nitrogen and the stirring condition of the rotating speed of 500r/min, placing the obtained mixture in a sealed reaction kettle, reacting for 2h at 70 ℃, filtering the obtained mixture, washing the obtained mixture by using distilled water for removing carbon dioxide until the filtrate is neutral, and filtering jelly for later use; the alkali solution in step (1) was used to 5wt% of the NaOH solution, the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removing water in step (1) was 1:0.32:15;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water without carbon dioxide at room temperature, then reacting for 10 hours under the protection of nitrogen and stirring at the rotating speed of 200r/min, filtering the obtained product, washing with distilled water without carbon dioxide until the filtrate is neutral, drying the filtered precipitate at 80 ℃ for 10 hours, and grinding the dried solid into 300-mesh white hydrotalcite-sodium phenolate compound powder for later use; the weight ratio of the jelly obtained in the step (2) to the sodium phenolate to the distilled water from which the carbon dioxide is removed is 1:0.22:5;
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture for 3 hours at the temperature of 45 ℃ under the stirring condition of the rotation speed of 200r/min, and then standing for 12 hours to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite; the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3), magnesium oxide, ethyl acetate and cyclohexane is 0.5:2:1.2:20;
(4) Adding p-tert-butylphenol formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and carrying out reflux reaction on the obtained mixture for 6 hours at the temperature of 25 ℃ and under the stirring condition of the rotating speed of 200r/min to obtain a pre-reaction liquid for the chlorinated rubber adhesive; the weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (4) to the p-tert-butylphenol formaldehyde resin is 24:22.
example 2
A pre-reaction liquid for a chlorinated rubber adhesive is prepared by the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 8.0 by using alkali liquor under the stirring condition of the rotating speed of 300r/min, then reacting for 1h under the protection of nitrogen and the stirring condition of the rotating speed of 700r/min, placing the obtained mixture in a closed reaction kettle for reacting for 7h at the temperature of 80 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using distilled water for removing the carbon dioxide, and reserving the filtered jelly for later use; the alkali liquor in the step (1) adopts a 10wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removed water in the step (1) is 1.02:0.34:18;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water without carbon dioxide at room temperature, then reacting for 20 hours under the protection of nitrogen and stirring at the rotating speed of 500r/min, filtering the obtained product, washing the filtrate with distilled water without carbon dioxide until the filtrate is neutral, drying the filtered precipitate for 20 hours at 90 ℃, and grinding the dried solid into 300-mesh white hydrotalcite-sodium phenolate compound powder for later use; the weight ratio of the jelly obtained in the step (2) to the sodium phenolate to the distilled water from which the carbon dioxide is removed is 1:0.28:7;
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture for 3 hours at 50 ℃ under the stirring condition of the rotating speed of 1000r/min, and then standing for 18 hours to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite; the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3), the magnesium oxide, the ethyl acetate and the cyclohexane is 0.75:2.4:1.4:25;
(4) Adding p-tert-butylphenol formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and carrying out reflux reaction on the obtained mixture for 7 hours at 35 ℃ under the stirring condition of the rotating speed of 500r/min to obtain a pre-reaction liquid for the chlorinated rubber adhesive; the weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (4) to the p-tert-butylphenol formaldehyde resin is 29:27.
example 3
A pre-reaction liquid for a chlorinated rubber adhesive is prepared by the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 9.5 by using alkali liquor under the stirring condition of the rotation speed of 550r/min, then reacting for 2 hours under the protection of nitrogen and the stirring condition of the rotation speed of 1000r/min, placing the obtained mixture in a closed reaction kettle, reacting for 24 hours at the temperature of 100 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water for removing the carbon dioxide, and keeping the filtered jelly for later use; the alkali liquor in the step (1) adopts a 15wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removed water in the step (1) is 1.04:0.37:22;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water without carbon dioxide at room temperature, then reacting for 30 hours under the protection of nitrogen and stirring at the rotating speed of 800r/min, filtering the obtained product, washing the filtrate with distilled water without carbon dioxide until the filtrate is neutral, drying the filtered precipitate for 30 hours at 100 ℃, and grinding the dried solid into white hydrotalcite-sodium phenolate composite powder of 500 meshes for later use; the weight ratio of the jelly obtained in the step (2) to the sodium phenolate to the distilled water from which the carbon dioxide is removed is 1:0.34:10;
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture at 56 ℃ under the stirring condition of a rotating speed of 1700r/min for 5 hours, and then standing for 24 hours to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite; the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3) to the magnesium oxide, ethyl acetate and cyclohexane is 1:2.9:1.6:29;
(4) Adding p-tert-butylphenol-formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and performing reflux reaction on the obtained mixture for 8 hours at 50 ℃ under the stirring condition of the rotating speed of 700r/min to obtain pre-reaction liquid for the chlorinated rubber adhesive; the weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3) to the p-tert-butylphenol formaldehyde resin in the step (4) is 35:31.
the samples prepared in steps (1) and (2) of this example were subjected to X-ray powder diffraction analysis, which is an ideal Rigaku D/MAX X-ray diffractionThe method is carried out on a shooter, and the instrument adopts CuKa: (
Tubing pressure 40.0kV, tubing flow 30.0 mA), test results are shown in fig. 2.
In FIG. 2, a is the powder of the jelly prepared in step (1) of example 3 after drying at 100 ℃ for 48 hours, and b is the powder of the hydrotalcite-sodium phenolate composite prepared in step (2) of example 3. Example 3 the dried sample of the jelly prepared in step (1) is a characteristic X-ray diffraction pattern of magnesium aluminum hydrotalcite, and the first diffraction peak of the X-ray powder diffraction pattern represents the interlayer spacing between adjacent layers of hydrotalcite. The first diffraction peak of the X-ray powder diffraction of the hydrotalcite-sodium phenolate composite prepared in example 3 was shifted in the direction of the small angle diffraction compared to the powder sample after drying of the jelly prepared in step (1) of example 3, indicating that there were phenolate ions intercalated between the hydrotalcite laminate plates in the hydrotalcite-sodium phenolate composite.
Example 4
A pre-reaction liquid for a chlorinated rubber adhesive is prepared by the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 9.0 by using alkali liquor under the stirring condition of the rotating speed of 750r/min, then reacting for 2.5 hours under the protection of nitrogen and the stirring condition of the rotating speed of 1300r/min, placing the obtained mixture in a closed reaction kettle for reacting for 12 hours at the temperature of 90 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water for removing the carbon dioxide, and reserving the filtered jelly for later use; the alkali solution in the step (1) was a 20wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removing water in the step (1) was 1.05:0.4:26;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water without carbon dioxide at room temperature, then reacting for 40 hours under the protection of nitrogen and stirring at the rotating speed of 1000r/min, filtering the obtained product, washing the filtrate with distilled water without carbon dioxide until the filtrate is neutral, drying the filtered precipitate for 40 hours at 108 ℃, and grinding the dried solid into white hydrotalcite-sodium phenolate composite powder of 500 meshes for later use; the weight ratio of the jelly obtained in the step (2) in the step (1), sodium phenolate and distilled water without carbon dioxide is 1:0.4:12;
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture at 64 ℃ under the stirring condition of the rotating speed of 2200r/min for 4 hours, and then standing for 30 hours to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite; the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3), the magnesium oxide, the ethyl acetate and the cyclohexane is 1.25:3.4:1.8:33;
(4) Adding p-tert-butylphenol-formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and carrying out reflux reaction on the obtained mixture for 9 hours at the temperature of 55 ℃ under the stirring condition of the rotating speed of 1000r/min to obtain pre-reaction liquid for the chlorinated rubber adhesive; the weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3) to the p-tert-butylphenol formaldehyde resin in the step (4) is 41:36.
example 5
A pre-reaction liquid for a chlorinated rubber adhesive is prepared by the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 10.0 by using alkali liquor under the stirring condition of the rotating speed of 1000r/min, then reacting for 3 hours under the protection of nitrogen and the stirring condition of the rotating speed of 1500r/min, placing the obtained mixture in a closed reaction kettle for reacting for 18 hours at the temperature of 120 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water for removing the carbon dioxide, and using the filtered jelly for later use; the alkali liquor in the step (1) adopts 25wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removed water in the step (1) is 1.06:0.43:30, of a nitrogen-containing gas;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water with carbon dioxide removed at room temperature, reacting for 48 hours under the protection of nitrogen and stirring at the rotating speed of 1200r/min, filtering the obtained product, washing the filtrate with distilled water with carbon dioxide removed until the filtrate is neutral, drying the filtered precipitate for 48 hours at 115 ℃, and grinding the dried solid into white hydrotalcite-sodium phenolate compound powder of 400 meshes for later use; the weight ratio of the jelly obtained in the step (2) in the step (1), sodium phenolate and distilled water without carbon dioxide is 1:0.46:14;
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture for 6 hours at 70 ℃ under the stirring condition of a rotating speed of 3000r/min, and then standing for 36 hours to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite; the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3), the magnesium oxide, the ethyl acetate and the cyclohexane is 1.5:3.8:2:38;
(4) Adding p-tert-butylphenol formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and carrying out reflux reaction on the obtained mixture at the temperature of 60 ℃ for 10 hours under the stirring condition of the rotating speed of 1200r/min to obtain a pre-reaction liquid for the chlorinated rubber adhesive; the weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3) to the p-tert-butylphenol formaldehyde resin in the step (4) is 46:40.
comparative example 6
This example illustrates the effect of hydrotalcite-sodium phenolate complex on the performance of pre-reaction solution, wherein only hydrotalcite and no sodium phenolate are present in the preparation process; that is, compared with example 3, this example does not have step (2) of example 3, the preparation process does not involve the preparation of hydrotalcite-sodium phenolate complex, other preparation steps and the amounts of reagents are the same as those of example 3, and the specific test steps are as follows:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 9.5 by using alkali liquor under the stirring condition of the rotation speed of 550r/min, then reacting for 2 hours under the protection of nitrogen and the stirring condition of the rotation speed of 1000r/min, placing the obtained mixture in a closed reaction kettle, reacting for 24 hours at the temperature of 100 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water for removing the carbon dioxide, and keeping the filtered jelly for later use; the alkali solution in step (1) was used as a solution which was 1.5% by weight of NaOH, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removed water in step (1) was 1.04:0.37:22;
(2) Adding the jelly prepared in the step (1) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture for 5 hours at 56 ℃ under the stirring condition of the rotation speed of 1700r/min, standing for 24 hours to obtain a solution containing the jelly and the magnesium oxide, wherein the weight ratio of the jelly prepared in the step (1) to the magnesium oxide to the ethyl acetate to the cyclohexane is 1:2.9:1.6:29;
(3) Adding p-tert-butylphenol formaldehyde resin into the solution containing the colloid and the magnesium oxide prepared in the step (2), and carrying out reflux reaction on the obtained mixture for 8 hours at the temperature of 50 ℃ and under the stirring condition of the rotating speed of 700r/min to obtain a mixed solution, wherein the weight ratio of the solution containing the colloid and the magnesium oxide prepared in the step (2) to the p-tert-butylphenol formaldehyde resin in the step (3) is 35:31.
comparative example 7
This example is to illustrate the effect of hydrotalcite-sodium phenolate complex on the performance of pre-reaction solution, and no hydrotalcite or sodium phenolate was present in the preparation process; compared with example 3, this example does not have step (1) and step (2) of example 3, does not involve the preparation of hydrotalcite-sodium phenolate complexes, and the other preparation steps and the amounts of reagents are the same as those of example 3, and the specific test steps are as follows:
(1) Adding magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture for 5 hours at the temperature of 56 ℃ under the stirring condition of the rotating speed of 1700r/min, and then standing for 24 hours to obtain a solution containing magnesium oxide; in the step (1), the weight ratio of the magnesium oxide to the ethyl acetate to the cyclohexane is 2.9:1.6:29;
(2) Adding p-tert-butyl phenol formaldehyde resin into the solution containing magnesium oxide prepared in the step (1), and carrying out reflux reaction on the obtained mixture for 8 hours at 50 ℃ under the stirring condition of the rotation speed of 700r/min to obtain a pre-reaction liquid for the chlorinated rubber adhesive; the weight ratio of the solution containing magnesium oxide prepared in the step (1) in the step (2) to the p-tert-butylphenol formaldehyde resin is 35:31.
comparative example 8
In this example, in order to illustrate the effect of the magnesium oxide-hydrotalcite-sodium phenolate-containing composite on the performance of the pre-reaction solution, compared with example 3, the preparation process in this example does not involve the preparation of the magnesium oxide-hydrotalcite-sodium phenolate-containing composite, but only the hydrotalcite-sodium phenolate composite powder and the magnesium oxide are physically mixed at normal temperature, and other preparation steps and reagent amounts are the same as those in example 3, and the specific test steps are as follows:
steps (1) and (2) of this example are the same as steps (1) and (2) of example 3,
(3) Adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane at room temperature to obtain a solution containing hydrotalcite-sodium phenolate composite and magnesium oxide, wherein the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) in the step (3) to the magnesium oxide to the ethyl acetate to the cyclohexane is 1:2.9:1.6:29;
(4) Adding p-tert-butylphenol formaldehyde resin to the hydrous talc-sodium phenolate compound-magnesium oxide-containing solution obtained in the step (3), and carrying out reflux reaction on the obtained mixture for 8 hours at 50 ℃ under the stirring condition of 700r/min of rotation speed to obtain a pre-reaction liquid for chlorinated rubber adhesive, wherein the weight ratio of the hydrous talc-sodium phenolate compound-magnesium oxide-containing solution prepared in the step (3) to the p-tert-butylphenol formaldehyde resin is 35:31.
comparative example 9
In this example, in order to illustrate the influence of the weight ratio between the hydrotalcite-sodium phenolate complex and the magnesium oxide in the magnesium oxide-hydrotalcite-sodium phenolate complex on the performance of the pre-reaction solution, compared with example 3, the weight ratio between the hydrotalcite-sodium phenolate complex of step (3) and the magnesium oxide in the preparation process of this example is 0.3:2.9, outside the scope of the claims (0.5-1.5): (2-3.8), other preparation steps and the amounts of reagents were the same as in example 3.
Application example 10
In this example, chlorinated rubber adhesives were prepared by using the pre-reaction solutions prepared in example 3 (added in amounts of 5, 25 and 50 parts by weight, respectively, to the chlorinated rubber adhesives) and the pre-reaction solution samples obtained in comparative examples 7 to 9, and the pre-reaction solutions obtained in comparative examples 7 to 9 were used in amounts of 50 parts by weight of the chlorinated rubber adhesives. The chlorinated rubber adhesive formulation in this example is shown in table 1:
TABLE 1 chlorinated rubber Adhesives formulation
The preparation method of the chlorinated rubber adhesive comprises the following steps:
adding a mixed solvent consisting of toluene, 120# solvent oil and ethyl acetate into a glue preparation kettle at room temperature, adding chlorinated rubber and an anti-aging agent into the mixed solvent, stirring and dissolving completely, then adding the pre-reaction liquid, and stirring fully and uniformly to obtain the product.
Effect embodiment:
next, storage stability tests were conducted on the pre-reaction solutions obtained in examples 1 to 5 and comparative examples 6 to 9, respectively. Adhesive force, heat resistance and storage stability tests were performed on each adhesive sample obtained in application example 10. The test methods and test results are shown below.
1. Adhesion test
A sample was prepared from canvas 2.5cm wide by uniformly coating each adhesive obtained in application example 10 on a pair of sample pieces, the coating length was about 15cm, the coating thickness was 0.2mm, and the amount of the adhesive used was 1000-1200g/m 2 Coating in two layers, after the first layer is coated and naturally dried, coating the second layer, and after the coating is dried again until the solvent is basically volatilized, the finger-touch glueWhen the layer has sticky feeling but is not sticky, the two sample sheets are aligned and bonded in a gluing surface mode, a hammer is used for knocking tightly, a sample strip bonded by double-layer canvas is obtained after 24 hours at room temperature, and the peel strength of the sample strip is tested according to the method of GB-2792-81.
2. Heat resistance test
And (3) respectively drying the strips bonded by the double-layer canvas obtained in the bonding force test at 50 ℃ for 120 hours, taking out the strips, and testing the peel strength of the strips according to the method of GB-2792-81.
3. Storage stability test
The samples were observed for precipitation and delamination within 5 days.
4. The results in Table 2 show that no precipitation or delamination occurred in the pre-reaction liquid samples prepared in examples 1 to 5, indicating that examples 1 to 5 prepared within the parameters as claimed in the claims all gave stable pre-reaction liquids that were not easily separated into solid and liquid phases. The samples of comparative examples 6 to 9 all produced a solid-liquid separation phenomenon, indicating that the samples of comparative examples 6 to 9 had poor storage stability. In the pre-reaction solution of comparative example 6, there are only hydrotalcite and no sodium phenolate, so that no phenol anion is adsorbed on the surface of the hydrotalcite inorganic layer plate, and the hydrophilic surface of the hydrotalcite inorganic layer plate is not modified into a hydrophobic surface, so that the highly hydrophilic hydrotalcite inorganic layer plate in the hydrophobic organic solvent causes polymerization and precipitation between hydrotalcite particles because the two properties are completely opposite; since precipitation and solid-liquid separation occurred immediately after the preparation of the pre-reaction liquid sample of comparative example 6 and the storage property was very unstable, the pre-reaction liquid sample of comparative example 6 was not used in the preparation of the adhesive and the corresponding test procedure of application example 10. The pre-reaction solution of comparative example 7 does not contain hydrotalcite-sodium phenolate complex, so in this embodiment, the small molecular weight of p-tert-butylphenol formaldehyde resin will first interact with magnesium oxide, and the molecular chain length of these low molecular weight resins is not enough to form a sufficiently thick adsorption layer on the surface of magnesium oxide particles, so that the suspended magnesium oxide particles lose stability, and finally solid-liquid stratification occurs. The preparation of the pre-reaction solution of comparative example 8 does not involve the preparation of a compound containing magnesium oxide-hydrotalcite-sodium phenolate, which is formed by interaction of electron-donating hydroxyl groups located at the edge of an inorganic layered plate of hydrotalcite in the compound containing hydrotalcite and surfaces of positively charged active light magnesium oxide particles under heating and a certain reaction time, and the magnesium oxide particles in the compound containing magnesium oxide-hydrotalcite-sodium phenolate are coated by the compound containing hydrotalcite-sodium phenolate, so that the small-molecular-weight p-tert-butylphenol formaldehyde resin can first contact the compound containing hydrotalcite-sodium phenolate coated outside the magnesium oxide particles, and the small-molecular-weight p-tert-butylphenol formaldehyde resin also contains the same phenol groups as those in the compound containing hydrotalcite-sodium phenolate, and can be adsorbed by the layered plate of the compound containing hydrotalcite-sodium phenolate according to the principle of like-adsorption; in contrast, in comparative example 8, the hydrotalcite-sodium phenolate complex was merely physically mixed with magnesium oxide, and no magnesium oxide-hydrotalcite-sodium phenolate complex was produced, i.e., magnesium oxide particles were not coated with hydrotalcite-sodium phenolate complex, and then the small molecular weight p-tert-butylphenol formaldehyde resin having a faster migration rate directly acted on the surface of the magnesium oxide particles, thereby causing a solid-liquid stratification phenomenon. In the preparation of the pre-reaction solution of comparative example 9, the weight ratio of the hydrotalcite-sodium phenolate complex of step (3) to magnesium oxide was 0.3:2.9, outside the scope of the claims (0.5-1.5): (2-3.8), namely the usage amount of the hydrotalcite-sodium phenolate compound is less, the surfaces of the magnesium oxide particles are not completely coated by sufficient hydrotalcite-sodium phenolate compound, so that partial surfaces of the magnesium oxide particles are exposed, and the small-molecular-weight p-tert-butylphenol formaldehyde resin is adsorbed on the exposed surfaces of the magnesium oxide particles.
The results in Table 3 show that in application example 10, the adhesive bond, heat resistance and storage stability increased as the amount of example 3 added to the chlorinated rubber adhesive increased from 5 parts to 50 parts by weight, indicating that the pre-reaction solution prepared in example 3 did indeed function to enhance the performance of the chlorinated rubber adhesive. The samples prepared in comparative examples 7-9, although containing 50 parts by weight of chlorinated rubber adhesive, gave adhesive properties far inferior to those of example 3 containing the same parts by weight. In the case of comparative example 7, which contains no hydrotalcite-sodium phenolate composite, the adhesive of this example has 34.9% and 51.2% lower adhesive strength and heat resistance, respectively, than those of example 3 (50 parts by weight), and the adhesive of comparative example 7 is unstable and easily delaminated, which indicates that the hydrotalcite-sodium phenolate composite is very important in the present invention. In the case of comparative example 8, which does not contain the magnesium oxide-hydrotalcite-sodium phenolate complex, the adhesive of this example has 25.6% and 48.8% lower adhesive force and heat resistance than the adhesive of example 3 (50 parts by weight), respectively, and comparative example 8 is unstable and easily delaminated, which indicates that the formation of the magnesium oxide-hydrotalcite-sodium phenolate complex is very important in the present invention. For comparative example 9, the weight ratio between the hydrotalcite-sodium phenolate complex and the magnesium oxide of this example was 0.3:2.9, outside the scope of the claims (0.5-1.5): (2-3.8), namely the amount of the hydrotalcite-sodium phenolate complex is relatively small, the adhesive force and the heat resistance of the adhesive of this example are respectively 18.6% and 29.3% lower than those of the adhesive of example 3 (50 parts by weight), and the adhesive of comparative example 9 is unstable and easy to delaminate, which shows that the relationship of the amount of the hydrotalcite-sodium phenolate complex and the magnesium oxide is also very important in the present invention.
Table 2 results of storage stability tests on the pre-reaction liquid samples prepared in examples 1 to 5 and the samples prepared in comparative examples 6 to 9
Table 3 results of adhesion, heat resistance and storage stability tests on chlorinated rubber adhesives prepared from samples prepared in application example 10 by different parts by weight of example 3 and comparative examples 7 to 9 (50 parts by weight in adhesive)
Claims (5)
1. A method for preparing pre-reaction liquid for adhesive containing hydrotalcite compound comprises the following steps:
(1) Mixing and stirring aluminum nitrate nonahydrate, magnesium nitrate hexahydrate and distilled water for removing carbon dioxide at room temperature, adjusting the pH of the obtained mixed solution to 7.0-10.0 by using alkali liquor under the stirring condition of the rotating speed of 100-1000r/min, then reacting for 0.5-3h under the protection of nitrogen and the stirring condition of the rotating speed of 500-1500r/min, placing the obtained mixture in a closed reaction kettle, reacting for 2-24h at 70-120 ℃, filtering the obtained mixture, washing the filtrate by using distilled water for removing carbon dioxide until the filtrate is neutral, and reserving the filtered jelly for later use;
(2) Mixing the jelly obtained in the step 1, sodium phenolate and distilled water with carbon dioxide removed at room temperature, then reacting for 10-48h under the protection of nitrogen and stirring at the rotating speed of 200-1200r/min, filtering the obtained product, washing with distilled water with carbon dioxide removed until the filtrate is neutral, drying the filtered precipitate at 80-115 ℃ for 10-48h, and grinding the dried solid into (300-500) mesh white hydrotalcite-sodium phenolate composite powder for later use;
(3) The solution containing hydrotalcite complex is prepared by the following preparation method: adding the hydrotalcite-sodium phenolate composite powder prepared in the step (2) and magnesium oxide into a mixed solvent of ethyl acetate and cyclohexane, carrying out reflux reaction on the obtained mixture at 45-70 ℃ under the stirring condition of the rotating speed of 200-3000r/min for 3-6h, and then standing for 12-36h to obtain a solution containing the magnesium oxide-hydrotalcite-sodium phenolate composite, wherein the weight ratio of the hydrotalcite-sodium phenolate composite powder prepared in the step (2) to the magnesium oxide, the ethyl acetate and the cyclohexane is (0.75-1.5): (2.4-3.8): (1.4-2): (25-38);
(4) Adding p-tert-butylphenol-formaldehyde resin into the solution containing the magnesium oxide-hydrotalcite-sodium phenolate compound prepared in the step (3), and carrying out reflux reaction on the obtained mixture for 6-10h at the temperature of 25-60 ℃ under the stirring condition of the rotating speed of 200-1200r/min to obtain the pre-reaction liquid for the chlorinated rubber adhesive.
2. The preparation method according to claim 1, wherein the alkali solution in step (1) is 5-25wt% NaOH solution.
3. The preparation method according to claim 1, wherein the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and carbon dioxide-removed water in step (1) is (1-1.06): (0.32-0.43): (15-30).
4. The preparation method of claim 1, wherein the weight ratio of the jelly obtained in the step (2) in the step 1 to the sodium phenolate to the distilled water from which carbon dioxide is removed is 1: (0.22-0.46): (5-14).
5. The method according to claim 1, wherein the weight ratio of the solution containing the magnesium oxide-hydrotalcite-sodium phenolate complex prepared in step (3) to the p-tert-butylphenol formaldehyde resin in step (4) is (24-46): (22-40).
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| MX2007003775A (en) * | 2007-03-29 | 2008-10-28 | Mexicano Inst Petrol | Process for preparing multimetallic anionic clays and products thereof. |
| CN101418197A (en) * | 2008-12-01 | 2009-04-29 | 广东三和化工科技有限公司 | Environmental protection chloroprene rubber adhesive agent and production method thereof |
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