Pre-reaction liquid for chlorinated rubber adhesive and preparation method thereof
阅读说明：本技术 一种氯化橡胶胶粘剂用预反应液及其制备方法 (Pre-reaction liquid for chlorinated rubber adhesive and preparation method thereof ) 是由 李文卓 王丹阳 耿浩浩 于 2021-09-13 设计创作，主要内容包括：本发明提供一种氯化橡胶胶粘剂用预反应液及其制备方法,该预反应液以硝酸镁和硝酸铝制备镁铝水滑石,再制备层嵌型的水滑石-苯酚钠复合物,这种水滑石-苯酚钠复合物先包覆在氧化镁颗粒表面,然后使大分子量的对叔丁基苯酚甲醛树酯能吸附在氧化镁颗粒表面,促使预反应液中的氧化镁颗粒悬浮在溶液中和不易彼此凝聚而形成沉淀,从而防止预反应液产生固液分层现象。本发明制备的预反应液可应用于制备氯化橡胶的胶粘剂,提高胶粘剂的粘着力、耐热性和贮存稳定性,该预反应液制备容易,适于推广应用。(The invention provides a pre-reaction liquid for a chlorinated rubber adhesive and a preparation method thereof, wherein the pre-reaction liquid uses magnesium nitrate and aluminum nitrate to prepare magnesium-aluminum hydrotalcite, and then prepares a layered hydrotalcite-sodium phenolate compound, the hydrotalcite-sodium phenolate compound is firstly coated on the surface of magnesium oxide particles, and then p-tert-butylphenol formaldehyde resin with large molecular weight can be adsorbed on the surface of the magnesium oxide particles, so that the magnesium oxide particles in the pre-reaction liquid are suspended in the solution and are not easy to agglomerate with each other to form precipitates, thereby preventing the pre-reaction liquid from generating a solid-liquid layering phenomenon. The pre-reaction liquid prepared by the invention can be applied to preparing 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.)
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 7.0-10.0 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 the filtrate by using the distilled water for removing the 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) 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.
2. The method of claim 1, wherein the alkali solution in step (1) is 5-25 wt% 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 hydrotalcite-sodium phenolate composite powder prepared in step (2) in step (3), the magnesium oxide, the ethyl acetate and the cyclohexane is (0.5-1.5): (2-3.8): (1.2-2): (20-38).
6. The preparation 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).
7. A pre-reaction liquid for a chlorinated rubber adhesive obtained by the production method according to any one of claims 1 to 6.
8. Use of the pre-reaction solution for a chlorinated rubber adhesive according to claim 7 in a chlorinated rubber adhesive.
The technical field is as follows:
the invention provides a pre-reaction liquid for a chlorinated rubber adhesive and a preparation method of the pre-reaction liquid, belonging to the technical field of 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 a material (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 a remedy after delamination, China adhesive, 2003, 12(2), 38-40). The solid-liquid delamination of the pre-reaction liquid not only reduces the performance of the adhesive product and brings much inconvenience to users, but also causes distrust of the users to manufacturers due to the non-uniformity of the appearance and the white precipitate at the bottom of the barrel, thereby influencing the market sale of the adhesive. The main reason why the solid-liquid separation occurs in the pre-reaction liquid 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 flocculation and precipitation, and finally the solid-liquid separation occurs (document 2: Guoji, phenolic resin for chloroprene adhesive, 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 a 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 the filtrate by using the distilled water for removing the 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) 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:
in the step (1), the alkali liquor adopts 5-25 wt% 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 compound prepared in the step (3) to the p-tert-butylphenol formaldehyde resin in the step (4) 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 [ Mg1-xAlx(OH)2](NO3)xAnd x: 0.17-0.22. The hydrotalcite is on brucite [ Mg (OH)2]On the basis of structure, the oxide is composed of MgO6Mg in unit layers formed by octahedral common edges2+Can be coated with Al within a certain range3+Isomorphous substitution to give positive charge to the laminate with exchangeable NO between layers3 -Balancing with positive charges on the laminate to make the whole structure of the hydrotalcite be electrically neutral. The surface of the magnalium hydrotalcite inorganic laminate is positively charged, metal ions at the edge of the hydrotalcite inorganic laminate are in an unsaturated coordination state, so that the hydrotalcite inorganic laminate has stronger activity, and flat hydroxyl at the edge of the hydrotalcite laminate is easy to provide electrons, thereby being beneficial to attracting other surrounding particles with positive charges (document 3: Zhongying et al, theoretical research on adsorption of azo dye acid orange in hydrotalcite interlayer, Industrial catalysis 2008, 16(10), 180-plus 183). In the hydrotalcite structure, the interaction between nitrate ions and inorganic laminates is weak, so that the nitrate ions between layers can be absorbedWith other ions and molecules, a new lamellar complex is formed, which will have 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 laminate, and the hydrophilic surface of the hydrotalcite inorganic laminate is modified into a hydrophobic surface, so that the hydrotalcite laminate is easily dispersed in a hydrophobic mixed organic solvent formed by ethyl acetate and cyclohexane; otherwise, the unmodified hydrotalcite inorganic laminate with a strong hydrophilic surface in a hydrophobic organic solvent causes polymerization and precipitation among hydrotalcite particles because the properties of the two are completely opposite.
Step 3 of the invention is to react the hydrotalcite-sodium phenolate compound prepared in step 2 with magnesium oxide (active light magnesium oxide) particles. The active light magnesium oxide has high activity, the surface of the particle is easy to 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 Western-style electronics, 2013). Therefore, electron-donating hydroxyl groups at the edge of a hydrotalcite inorganic laminate 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 smaller molecular chains, so the small-molecular-weight p-tert-butylphenol formaldehyde resin can contact with the hydrotalcite-sodium phenolate compound wrapped outside the magnesium oxide particles firstly, and the small-molecular-weight p-tert-butylphenol formaldehyde resin also contains the same phenol group as that in the hydrotalcite-sodium phenolate compound, and is adsorbed by a hydrotalcite-sodium phenolate compound laminated plate according to the principle of like-polarity attraction, so that the molecular weight loaded by the laminated plate of the hydrotalcite-sodium phenolate compound is overlarge, 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, thereby exposing the active sites on the surface of the magnesium oxide; at the moment, the para-tertiary butyl phenol formaldehyde resin with large molecular weight can replace a hydrotalcite-sodium phenolate compound to act with the surface of magnesium oxide, namely the para-tertiary butyl phenol formaldehyde resin with large molecular weight replaces the hydrotalcite-sodium phenolate compound to be wrapped on the surface of magnesium oxide particles, so that a sufficiently thick adsorption layer of the para-tertiary butyl phenol formaldehyde resin with large molecular weight is formed on the surface of the magnesium oxide particles, the suspension property of the para-tertiary butyl phenol formaldehyde resin with large molecular weight is excellent, and the magnesium oxide particles are suspended in a 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 high molecular weight p-tert-butylphenol formaldehyde resin is adsorbed on the surfaces of the magnesium oxide particles, so that the high molecular weight p-tert-butylphenol formaldehyde resin has good suspension property, the coated magnesium oxide particles can be suspended in the solution, the magnesium oxide particles are separated by the high 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 layering 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. 1, a is a dried sample of the jelly prepared in step (1) of example 3, and b is hydrotalcite-sodium phenolate complex powder prepared in step (2) of example 3 according to the present invention.
Detailed Description
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 island chemical company, and the product model is 150; the p-tert-butylphenol formaldehyde resin is produced by chemical technology Limited in the Shanghai of Jinan, and the product model is 2402; anti-aging agent 264 was from Zhengzhou pani chemical reagent factory; 120# solvent oil from landlocked petrochemical company, Inc.; 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 with carbon dioxide removed 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 for reacting for 2h at 70 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water with carbon dioxide removed, and using the filtered jelly for later use; the alkali liquor in the step (1) adopts 5 wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and water for removing carbon dioxide in the step (1) is 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 the filtrate 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 ℃ and under the stirring condition of the rotating 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 (3) to the p-tert-butylphenol formaldehyde resin in the step (4) 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 with carbon dioxide removed 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, reacting for 7h at the temperature of 80 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water with carbon dioxide removed, and filtering out jelly for later use; the alkali liquor in the step (1) adopts 10 wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and water for removing carbon dioxide 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 at 90 ℃ for 20 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: 0.28: 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) to the magnesium oxide, ethyl acetate and 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 (3) to the p-tert-butylphenol formaldehyde resin in the step (4) 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 with carbon dioxide removed 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 with the carbon dioxide removed, and filtering out jelly for later use; the alkali liquor in the step (1) adopts 15 wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and water for removing carbon dioxide 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 500-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: 0.34: 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 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 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 on an ideal Rigaku D/MAX X-ray diffractometer Tubing pressure 40.0kV, tubing flow 30.0mA), 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 complex prepared in step (2) of example 3. Example 3 the dried sample of the gum 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 with carbon dioxide removed 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, reacting for 12 hours at the temperature of 90 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water with carbon dioxide removed, and using the filtered jelly for later use; the alkali liquor in the step (1) adopts 20 wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and water for removing carbon dioxide in the step (1) is 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 500-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: 0.4: 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) to the magnesium oxide, ethyl acetate and 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 ℃ and 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 with carbon dioxide removed 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, reacting for 18 hours at 120 ℃, filtering the obtained mixture, washing the filtrate to be neutral by using the distilled water with carbon dioxide removed, and filtering out jelly for later use; the alkali liquor in the step (1) adopts 25 wt% of NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and water for removing carbon dioxide 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, then 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 400-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: 0.46: 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 at 70 ℃ under the stirring condition of a rotating speed of 3000r/min for 6 hours, 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) to the magnesium oxide, ethyl acetate and 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 for 10 hours at the temperature of 60 ℃ and 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 reagent amounts 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 with carbon dioxide removed 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 with the carbon dioxide removed, and filtering out jelly for later use; the alkali liquor in the step (1) adopts 15 wt% NaOH solution, and the weight ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and water for removing carbon dioxide in the step (1) is 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 illustrates the effect of hydrotalcite-sodium phenolate complex on the performance of pre-reaction solution, and the preparation process is free of hydrotalcite and sodium phenolate; compared with the example 3, the method does not have the step (1) and the step (2) of the example 3, does not relate to the preparation of the hydrotalcite-sodium phenolate complex, and has the same preparation steps and the same reagent dosage as the 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-butylphenol 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 the temperature of 50 ℃ and under the stirring condition of the rotating 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) to the p-tert-butylphenol formaldehyde resin in the step (2) 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 into the hydrous talcum-sodium phenolate compound and magnesium oxide solution obtained in the step (3), and carrying out reflux reaction on the obtained mixture for 8h at the temperature of 50 ℃ and under the stirring condition of 700r/min of rotating speed to obtain a pre-reaction solution for a chlorinated rubber adhesive, wherein the weight ratio of the hydrous talcum-sodium phenolate compound and magnesium oxide solution prepared in the step (3) to the p-tert-butylphenol formaldehyde resin in the step (4) 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 amounts of reagents were the same as in example 3.
Application example 10
In this example, the pre-reaction solution prepared in example 3 (added in the amount of 5, 25, 50 parts by weight to the chlorinated rubber adhesive) and the pre-reaction solution samples obtained in comparative examples 7 to 9 were used to prepare the chlorinated rubber adhesive, and the pre-reaction solutions obtained in comparative examples 7 to 9 were used in an amount of 50 parts by weight of the chlorinated rubber adhesive. The chlorinated rubber adhesive formulation in this example is shown in table 1:
TABLE 1 chlorinated rubber adhesive 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 fully and uniformly stirring to obtain the product.
Effect embodiment:
next, storage stability tests were conducted on the pre-reaction liquids 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 following shows the test methods and test results.
1. Adhesion test
Canvas with the width of 2.5cm is taken to be made into sample strips, each adhesive obtained in the application example 10 is respectively and evenly coated on a pair of sample strips, the coating length is about 15cm, the coating thickness is 0.2mm, the adhesive consumption is 1000-2Coating the two layers, namely coating the first layer, naturally drying the first layer, coating the second layer, air-drying the second layer again until the solvent is basically volatilized, aligning and bonding the adhesive surfaces of the two sample pieces when the adhesive surfaces of the finger touch adhesive layer have sticky feeling but are not sticky, tightly knocking the two sample pieces by a hand hammer, obtaining a sample strip bonded with the double-layer canvas after 24 hours at room temperature, and testing the peel strength of the sample strip by referring to the GB-2792-81 method.
2. Heat resistance test
And (3) respectively drying the sample strips bonded by the double-layer canvas obtained in the bonding force test at 50 ℃ for 120h, taking out the sample strips, and testing the peel strength of the sample 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 1 show that no precipitation or delamination occurred in the pre-reaction liquid samples prepared in examples 1-5, indicating that examples 1-5 prepared within the parameters claimed in the claims all gave stable pre-reaction liquids that were not prone to solid-liquid delamination. The samples of comparative examples 6 to 9 all developed 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 strongly 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 long 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 pre-reaction solution of comparative example 8 is prepared without preparing a compound containing magnesium oxide-hydrotalcite-sodium phenolate, the compound is prepared by interaction of electron-donating hydroxyl groups located at the edge of an inorganic layered plate of hydrotalcite in the compound with the surface of active light magnesium oxide particles with positive charges under heating and certain reaction time conditions, the magnesium oxide particles in the compound are coated by the compound, so that the p-tert-butylphenol formaldehyde resin with small molecular weight can first contact the compound coated outside the magnesium oxide particles, and the p-tert-butylphenol formaldehyde resin with small molecular weight also contains the same phenol groups as those in the compound, according to the principle of equal adsorption, the small molecular weight p-tert-butylphenol formaldehyde resin can be absorbed by a hydrotalcite-sodium phenolate composite laminate; 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 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 the 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 2 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 serve to enhance the performance of the chlorinated rubber adhesive. The samples prepared in comparative examples 7-9, although also 50 parts by weight in the chlorinated rubber adhesive, correspond to adhesive properties that are far inferior to those of example 3, which contains the same parts by weight. As for comparative example 7, which contains no hydrotalcite-sodium phenolate complex, the adhesive of this example has 34.9% and 51.2% lower adhesive force and heat resistance than the adhesive of example 3(50 parts by weight), respectively, and the adhesive of comparative example 7 is unstable and easily delaminated, which indicates that the function of the hydrotalcite-sodium phenolate complex in the present invention is very important. As for 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 the adhesive of 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 hydrotalcite-sodium phenolate complex is used in a small amount, the adhesive force and 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 easily delaminated, which shows that the proportional relationship between the amounts of hydrotalcite-sodium phenolate complex and magnesium oxide is also very important in the present invention.
TABLE 1 results of storage stability tests conducted on the pre-reaction liquid samples prepared in examples 1 to 5 and the samples prepared in comparative examples 6 to 9
Table 2 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)