Solid-phase polyurethane composite catalyst and preparation method thereof
阅读说明：本技术 一种固相聚氨酯复合催化剂及其制备方法 (Solid-phase polyurethane composite catalyst and preparation method thereof ) 是由 邱元进 饶长贵 陈国栋 于 2020-07-15 设计创作，主要内容包括：本发明公开了一种固相聚氨酯复合催化剂及其制备方法,属于精细化工技术领域,该制备方法先将在溶剂中溶胀的胺甲基树脂与己二酸单酯溶、溶剂和氨水混合后分离的有机溶剂层反应,再加入硝酸铋、硝酸镓、2,4-二甲基-1-辛酸和杂多酸催化剂反应得到树脂；所得树脂经溶剂清洗、抽干溶剂、干燥后得固相聚氨酯复合催化剂。该制备方法原料处理简单,适于工业化生产,且生产效率较高,通过该制备方法制备得到的固相聚氨酯复合催化剂,用于制备聚氨酯后可以简单过滤的方式滤除出体系,提高了聚氨酯产品的稳定性,在过滤后用溶剂清洗干净,干燥处理后可重复使用,大大降低了聚氨酯生产成本。(The invention discloses a solid-phase polyurethane composite catalyst and a preparation method thereof, belonging to the technical field of fine chemical engineering.A preparation method comprises the steps of firstly mixing amine methyl resin swelled in a solvent with adipic acid monoester solution, the solvent and ammonia water, then reacting the separated organic solvent layer, and then adding bismuth nitrate, gallium nitrate, 2, 4-dimethyl-1-caprylic acid and a heteropoly acid catalyst for reaction to obtain resin; and washing the obtained resin with a solvent, draining the solvent, and drying to obtain the solid-phase polyurethane composite catalyst. The preparation method has the advantages that raw materials are easy to process, the preparation method is suitable for industrial production, the production efficiency is high, the solid-phase polyurethane composite catalyst prepared by the preparation method can be used for filtering out a system in a simple filtering mode after being used for preparing polyurethane, the stability of a polyurethane product is improved, the solid-phase polyurethane composite catalyst is cleaned by a solvent after being filtered, the solid-phase polyurethane composite catalyst can be repeatedly used after being dried, and the production cost of the polyurethane is greatly reduced.)
1. The preparation method of the solid-phase polyurethane composite catalyst is characterized by comprising the following steps of:
step 1, adding a solvent into 1 part of aminomethyl resin by mol parts, and swelling for later use;
step 2, dissolving 1 part of adipic acid monoester in a solvent, adding 2-5 parts of ammonia water, stirring and separating to obtain an upper organic solvent layer;
step 3, mixing the organic solvent layer obtained in the step 2 with the swelled aminomethyl resin obtained in the step 1, heating to 60-88 ℃, keeping the temperature, cooling to 40-50 ℃, and then adjusting the pH to 3-5.5 to obtain a first reaction system;
step 4, adding 0.86-0.89 part of bismuth nitrate, 0.11-0.14 part of gallium nitrate and 1.95-2.05 parts of 2, 4-dimethyl-1-octanoic acid into the first reaction system obtained in the step 3, mixing, adding 0.008-0.015 part of heteropolyacid catalyst, heating to 80-120 ℃, keeping the temperature until the water is completely distilled, and cooling to 30-40 ℃ to obtain resin;
and 5, cleaning the resin obtained in the step 4 by using a solvent, draining the solvent, and placing the resin in a vacuum drying oven until the content of volatile matters is less than 0.1%, thereby obtaining the solid-phase polyurethane composite catalyst.
2. The method for preparing solid phase polyurethane composite catalyst as claimed in claim 1, wherein the amine group content of the aminomethyl resin is 0.5-0.7mmol/g, and the aminomethyl resin has a 200-300 mesh cross-linked polymer microsphere structure.
3. The preparation method of the solid-phase polyurethane composite catalyst according to claim 1, wherein the solvent is one or more of toluene, xylene, butyl acetate, methylcyclohexanone, and tetrahydrofuran.
4. The method for preparing the solid-phase polyurethane composite catalyst according to claim 1, wherein the adipic acid monoester is adipic acid methyl ester and/or adipic acid ethyl ester.
5. The method for preparing the solid-phase polyurethane composite catalyst according to claim 1, wherein the heteropoly acid catalyst is 1mol/L of H4GeW12O40Tetrahydrofuran solution.
6. The preparation method of the solid phase polyurethane composite catalyst according to claim 1, which is characterized by comprising the following steps:
step 1, adding a solvent into 1 part of aminomethyl resin by mol parts, and swelling for 0.5-1h for later use;
step 2, dissolving 1 part of adipic acid monoester in a solvent, adding 2-5 parts of ammonia water, stirring for 0.5-1h, separating, and taking an upper organic solvent layer;
step 3, mixing the organic solvent layer obtained in the step 2 with the swelled aminomethyl resin obtained in the step 1, heating to 60-88 ℃, preserving heat for 2-6 hours, cooling to 40-50 ℃, and then adding concentrated nitric acid to adjust the pH value to 3-5.5 to obtain a first reaction system;
step 4, adding 0.86-0.89 part of bismuth nitrate, 0.11-0.14 part of gallium nitrate and 1.95-2.05 parts of 2, 4-dimethyl-1-octanoic acid into the first reaction system obtained in the step 3, mixing, adding 0.008-0.015 part of heteropolyacid catalyst, heating to 80-120 ℃, keeping the temperature for 3-8 hours until the water is completely distilled, and cooling to 30-40 ℃ to obtain resin;
and 5, washing the resin obtained in the step 4 by using a solvent for 3 times, draining the solvent, and placing the resin in a vacuum drying oven at the temperature of 50-80 ℃ for drying for 8-16 hours until the content of volatile matters is less than 0.1%, so as to obtain the solid-phase polyurethane composite catalyst.
7. A solid-phase polyurethane composite catalyst prepared by the method for preparing a solid-phase polyurethane composite catalyst according to any one of claims 1 to 6.
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a solid-phase polyurethane composite catalyst and a preparation method thereof.
Background
Catalysts play a very important role in the preparation of polyurethanes. Ever since, the emphasis of polyurethane catalysts has been on catalytic selectivity, catalytic efficiency, catalyst toxicity and catalyst stability in the system. Wherein, the catalytic selectivity refers to the comparison of the degrees of different reactions promoted by the same catalyst in a reaction system capable of carrying out a plurality of reactions, and the catalytic selectivity for the target compound is always the first choice requirement of the technical personnel.
Common polyurethane catalysts are organotin catalysts and organobismuth catalysts. The organic tin catalyst has high catalytic efficiency and low price, but has poor catalytic selectivity, high toxicity and great harm to the environment and human health. Therefore, although the organotin catalysts are currently playing an important role in the preparation, they have been partially replaced by organobismuth catalysts. The organic bismuth catalyst has the catalytic efficiency which is not as high as that of an organic tin catalyst, but has high catalytic selectivity, low catalytic efficiency for side reactions of NCO, water and other substances, and no toxicity. With the intensive research of the technical personnel on the organic bismuth catalyst, the compound of the organic bismuth and the organic zinc becomes a new star of the polyurethane catalyst, the catalytic selectivity, the catalytic efficiency and the toxicity of the polyurethane catalyst are slightly superior to those of the catalyst which only uses the organic bismuth as an active compound, but the composite catalyst consisting of the organic bismuth and the organic zinc is a liquid substance as the existing organic bismuth catalyst and the organic tin catalyst, and the composite catalyst cannot be removed when being used in the existing polyurethane preparation process. For some systems, such as a moisture-curing hot melt adhesive system, the catalyst may continue to slowly catalyze the chain extension and crosslinking reaction in the system, resulting in the quality degradation of the moisture-curing hot melt adhesive and even the serious consequences of product scrapping and the like. And a few catalysts lose activity after being removed by some special means and cannot be technically used, so that the use cost of the catalysts is high.
U.S. patent publication No. US5561205(A), discloses a process for the preparation of crosslinked polymer-based organotin compounds. The method uses dihydride of diphenyl tin and divinylbenzene for copolymerization to obtain a cross-linked polymer carrier, and then modifies the dihydride of tin to obtain the organotin catalyst immobilized on cross-linked polymer resin. The cross-linked polymer-based organotin can be simply discharged from a reaction system through filtration and can be recycled after simple treatment, but the organotin selectivity is not strong, and meanwhile, the organotin in the catalyst particles obtained by the method cannot be effectively utilized due to the problem of reaction diffusion, so that the overall catalytic efficiency is low. The Chinese patent with the publication number of CN1215731A provides an organotin-containing solid catalyst formed by bonding organotin functionalized silane and a solid inorganic carrier containing surface hydroxyl groups. As the carrier is a solid inorganic carrier, compared with a cross-linked polymer carrier, the carrier has high mechanical strength, good heat resistance and uniform porosity, and can be recycled after simple treatment. However, the application of silane bonded with the solid inorganic carrier is greatly limited by the problems of insufficient solvent resistance, low flexibility of the solid inorganic carrier and the like, and the problem of the catalytic selectivity of organic tin cannot be solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problems to be solved by the invention are as follows: provides a high-catalytic-selectivity solid-phase composite catalyst which can be removed from a polyurethane preparation system and can be recycled.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a solid-phase polyurethane composite catalyst comprises the following steps:
step 1, adding a solvent into 1 part of aminomethyl resin by mol parts, and swelling for later use;
step 2, dissolving 1 part of adipic acid monoester in a solvent, adding 2-5 parts of ammonia water, stirring and separating to obtain an upper organic solvent layer;
step 3, mixing the organic solvent layer obtained in the step 2 with the swelled aminomethyl resin obtained in the step 1, heating to 60-88 ℃, keeping the temperature, cooling to 40-50 ℃, and then adjusting the pH to 3-5.5 to obtain a first reaction system;
step 4, adding 0.86-0.89 part of bismuth nitrate, 0.11-0.14 part of gallium nitrate and 1.95-2.05 parts of 2, 4-dimethyl-1-octanoic acid into the first reaction system obtained in the step 3, mixing, adding 0.008-0.015 part of heteropolyacid catalyst, heating to 80-120 ℃, keeping the temperature until the water is completely distilled, and cooling to 30-40 ℃ to obtain resin;
and 5, cleaning the resin obtained in the step 4 by using a solvent, draining the solvent, and placing the resin in a vacuum drying oven until the content of volatile matters is less than 0.1%, thereby obtaining the solid-phase polyurethane composite catalyst.
The other technical scheme adopted by the invention is as follows: the solid-phase polyurethane composite catalyst is prepared by the preparation method of the phase-polyurethane composite catalyst.
The invention has the beneficial effects that: according to the preparation method of the solid-phase polyurethane composite catalyst, organic bismuth and organic gallium are connected to the surface layer of a cross-linked polymer particle under the chemical bonding action of ester groups, the obtained solid-phase polyurethane composite catalyst takes a bismuth compound and a gallium compound as active centers, and the bismuth and the gallium have synergistic effect, so that the solid-phase polyurethane composite catalyst has high selectivity on NCO/OH and high catalytic efficiency, and the active centers of the solid-phase polyurethane composite catalyst are mainly positioned on the surface of the particle, so that the utilization rate is high; meanwhile, due to the use of 2, 4-dimethyl-1-caprylic acid, the steric hindrance of methyl of a side chain reduces the attack of water or alcohol solvents and the like on ester bonds, and the stability is greatly improved; in the preparation process, the heteropolyacid catalyst which is easily soluble in water and a solvent is used, so that the obtained solid-phase polyurethane composite catalyst has higher efficiency than a conventional liquid acid catalyst, and the subsequent separation is not influenced; the preparation method has the advantages of simple raw material treatment, suitability for industrial production and higher production efficiency;
the solid-phase polyurethane composite catalyst prepared by the preparation method of the solid-phase polyurethane composite catalyst provided by the invention can be filtered out in a simple filtering mode after being used for preparing polyurethane, so that the continuous reaction of the polyurethane catalyst in the storage process of a polyurethane product is avoided, the stability of the polyurethane product is improved, the polyurethane product is cleaned by a solvent after being filtered, and the solid-phase polyurethane composite catalyst can be reused after being dried, so that the production cost is greatly reduced.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The invention provides a preparation method of a solid-phase polyurethane composite catalyst, which comprises the following steps:
step 1, adding a solvent into 1 part of aminomethyl resin by mol parts, and swelling for later use;
step 2, dissolving 1 part of adipic acid monoester in a solvent, adding 2-5 parts of ammonia water, stirring and separating to obtain an upper organic solvent layer;
step 3, mixing the organic solvent layer obtained in the step 2 with the swelled aminomethyl resin obtained in the step 1, heating to 60-88 ℃, keeping the temperature, cooling to 40-50 ℃, and then adjusting the pH to 3-5.5 to obtain a first reaction system;
step 4, adding 0.86-0.89 part of bismuth nitrate, 0.11-0.14 part of gallium nitrate and 1.95-2.05 parts of 2, 4-dimethyl-1-octanoic acid into the first reaction system obtained in the step 3, mixing, adding 0.008-0.015 part of heteropolyacid catalyst, heating to 80-120 ℃, keeping the temperature until the water is completely distilled, and cooling to 30-40 ℃ to obtain resin;
and 5, cleaning the resin obtained in the step 4 by using a solvent, draining the solvent, and placing the resin in a vacuum drying oven until the content of volatile matters is less than 0.1%, thereby obtaining the solid-phase polyurethane composite catalyst.
The invention provides a solid-phase polyurethane composite catalyst prepared by the preparation method of the phase-polyurethane composite catalyst.
From the above description, the beneficial effects of the present invention are: according to the preparation method of the solid-phase polyurethane composite catalyst, organic bismuth and organic gallium are connected to the surface layer of the cross-linked polymer particles under the chemical bonding action of ester groups, so that the active center of the solid-phase polyurethane composite catalyst is mainly positioned on the surface of the particles, and the utilization rate is high; the solid-phase polyurethane composite catalyst has the advantages that the bismuth compound and the gallium compound are used as active centers, the bismuth and the gallium have synergistic effect, the selectivity to NCO/OH is high, the catalytic efficiency is high, specifically, in the preparation process, the organic bismuth catalyst is firstly combined with polyhydric alcohol to form an organic bismuth alcoholate with high activity, and then the organic bismuth alcoholate reacts with isocyanate groups, and as the electrons of the outer layer of the organic bismuth are 6S26P3Wherein the P orbital is occupied by electrons in the same three directions to form a metastable structure, and the outer layer electron 4S of gallium in organic gallium24P1The P track only has 1 electron, the problem of low activity of organic bismuth can be solved by adding organic gallium, and the two are matched with each other to form a synergistic effect, so that the effects of high catalytic efficiency and controllable reaction are achieved;
due to the use of the 2, 4-dimethyl-1-caprylic acid in the preparation method and the steric hindrance of the methyl of the side chain, the attack of water or alcohol solvent and the like on ester bonds is reduced, and the molecular chain length of the 2, 4-dimethyl-1-caprylic acid is moderate, so that the problems that the steric hindrance is too high, the generation rate of organic metal alcoholate is reduced, the activity of the organic metal alcoholate is too high, and the reaction is difficult to control can not occur, and the stability of the obtained solid-phase polyurethane composite catalyst is greatly improved; in the preparation process, the heteropolyacid catalyst which is easily soluble in water and a solvent is used, so that the obtained solid-phase polyurethane composite catalyst has higher efficiency than a conventional liquid acid catalyst, and the subsequent separation is not influenced; the preparation method has the advantages of simple raw material treatment, suitability for industrial production and higher production efficiency.
The solid-phase polyurethane composite catalyst prepared by the preparation method of the solid-phase polyurethane composite catalyst provided by the invention can be filtered out in a simple filtering mode after being used for preparing polyurethane, so that the continuous reaction of the polyurethane catalyst in the storage process of a polyurethane product is avoided, the stability of the polyurethane product is improved, the polyurethane product is cleaned by a solvent after being filtered, and the solid-phase polyurethane composite catalyst can be reused after being dried, so that the production cost is greatly reduced.
Furthermore, the amino content of the aminomethyl resin is 0.5-0.7mmol/g, the aminomethyl resin is a cross-linked polymer microsphere structure of 200-300 meshes, the surface layer of the cross-linked polymer microsphere is provided with aminomethyl functional groups, and the interior of the cross-linked polymer microsphere is a polystyrene cross-linked structure.
The amine methyl resin is used as a framework compound and is chemically bonded with a catalyst, so that active groups of the catalyst can be fixed, the catalyst can be conveniently removed by a filtering method in the later period, the problems of insufficient functional group coverage, excessive catalyst consumption, excessive solvent swelling and reactant dilution concentration and waste caused by insufficient utilization rate of partial functional groups in the resin can be avoided by selecting the amine methyl resin with the amino group content of 0.5-0.7 mmol/g.
Further, the solvent is one or more of toluene, xylene, butyl acetate, methylcyclohexanone and tetrahydrofuran.
Further, the adipic acid monoester is adipic acid methyl ester and/or adipic acid ethyl ester.
Further, the heteropoly acid catalyst is 1mol/L H4GeW12O40Tetrahydrofuran solution.
Further, the preparation method of the solid-phase polyurethane composite catalyst specifically comprises the following steps:
step 1, adding a solvent into 1 part of aminomethyl resin by mol parts, and swelling for 0.5-1h for later use;
step 2, dissolving 1 part of adipic acid monoester in a solvent, adding 2-5 parts of ammonia water, stirring for 0.5-1h, separating, and taking an upper organic solvent layer;
step 3, mixing the organic solvent layer obtained in the step 2 with the swelled aminomethyl resin obtained in the step 1, heating to 60-88 ℃, preserving heat for 2-6 hours, cooling to 40-50 ℃, and then adding concentrated nitric acid to adjust the pH value to 3-5.5 to obtain a first reaction system;
step 4, adding 0.86-0.89 part of bismuth nitrate, 0.11-0.14 part of gallium nitrate and 1.95-2.05 parts of 2, 4-dimethyl-1-octanoic acid into the first reaction system obtained in the step 3, mixing, adding 0.008-0.015 part of heteropolyacid catalyst, heating to 80-120 ℃, keeping the temperature for 3-8 hours until the water is completely distilled, and cooling to 30-40 ℃ to obtain resin;
and 5, washing the resin obtained in the step 4 by using a solvent for 3 times, draining the solvent, and placing the resin in a vacuum drying oven at the temperature of 50-80 ℃ for drying for 8-16 hours until the content of volatile matters is less than 0.1%, so as to obtain the solid-phase polyurethane composite catalyst.