阅读说明：本技术 一种吗啉基植物油多元醇制备方法及其应用 (Preparation method and application of morpholinyl vegetable oil polyol ) 是由 黄凤翔 袁波 王海平 于 2019-10-09 设计创作，主要内容包括：本申请实施例提供一种本发明公开了一种吗啉基植物油多元醇制备方法及其应用,(a)在反应釜中有机溶剂,将反应釜内的有机溶剂加热至70-80℃,保温10-20min；先向所述反应釜中加入缓释型催化剂,再向反应釜中加入含吗啉的醇溶液,并搅拌升温至90-110℃,再向所述反应釜中添加环氧基植物油,反应2-5h；(b)将所述反应釜中的混合液引入到分液釜中,冷却至室温,向所述分液釜中加入乙酸乙酯,搅拌均匀,并加热至80-90℃,负压吸附,除去分液釜中的乙酸乙酯,制得吗啉基植物油多元醇。多元醇的羟基值高,粘度小；将制得的吗啉基植物油多元醇用于制备聚氨酯泡沫,其具有优异的力学性能和保温性能。(The embodiment of the application provides a preparation method and application of a morpholinyl vegetable oil polyalcohol, wherein (a) organic solvent is heated to 70-80 ℃ in a reaction kettle, and the temperature is kept for 10-20 min; firstly, adding a slow-release catalyst into the reaction kettle, then adding an alcoholic solution containing morpholine into the reaction kettle, stirring and heating to 90-110 ℃, then adding epoxy vegetable oil into the reaction kettle, and reacting for 2-5 hours; (b) and introducing the mixed solution in the reaction kettle into a liquid separation kettle, cooling to room temperature, adding ethyl acetate into the liquid separation kettle, stirring uniformly, heating to 80-90 ℃, performing negative pressure adsorption, and removing the ethyl acetate in the liquid separation kettle to obtain the morpholinyl vegetable oil polyol. The hydroxyl value of the polyol is high, and the viscosity is low; the prepared morpholinyl vegetable oil polyol is used for preparing polyurethane foam, and has excellent mechanical property and heat preservation property.)

1. A preparation method of morpholinyl vegetable oil polyol is characterized by comprising the following steps: comprises the following steps;

(a) heating the organic solvent in the reaction kettle to 70-80 ℃ in the organic solvent in the reaction kettle, and preserving the heat for 10-20 min; firstly, adding a slow-release catalyst into the reaction kettle, then adding an alcoholic solution containing morpholine into the reaction kettle, stirring and heating to 90-110 ℃, then adding epoxy vegetable oil into the reaction kettle, and reacting for 2-5 hours;

(b) and introducing the mixed solution in the reaction kettle into a liquid separation kettle, cooling to room temperature, adding ethyl acetate into the liquid separation kettle, stirring uniformly, heating to 80-90 ℃, performing negative pressure adsorption, and removing the ethyl acetate in the liquid separation kettle to obtain the morpholinyl vegetable oil polyol.

2. The method for preparing a morpholino vegetable oil polyol as claimed in claim 1, wherein: the organic solvent is C5-C8 fatty alcohol.

3. The method for preparing a morpholino vegetable oil polyol as claimed in claim 2, wherein: the organic solvent is one of amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, 3-dimethyl butanol and 3-methyl amyl alcohol.

4. The method for preparing a morpholino vegetable oil polyol as claimed in claim 1, wherein: the slow-release catalyst comprises a carrier and an active component loaded on the surface of the carrier, wherein the active component is metal halide, and the carrier is a mixture of an alkaline earth metal compound and organic zinc halide.

5. The method for producing a morpholino vegetable oil polyol according to claim 4, wherein: the alkaline earth metal compound is one of magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, barium oxide and calcium oxide.

6. The method for producing a morpholino vegetable oil polyol according to claim 4, wherein: the organic zinc halide is dimethyl zinc, diethyl zinc or diphenyl zinc.

7. The process for preparing a morpholino vegetable oil polyol according to any one of claims 1-6, wherein: the preparation method of the slow-release catalyst comprises the following steps:

(a) preparing a carrier: mixing acetic acid, organic zinc halide, triethylamine and methanol, stirring uniformly, heating to 200 ℃ under 1.1-1.2 atmospheric pressures, reacting for 1-2h, and cooling to room temperature under normal pressure; adding alkaline earth metal hydroxide or alkaline earth metal oxide and methanol, stirring uniformly, and standing for 12-24 h;

(b) loading active components: dissolving the metal halide in an alcohol solution, adding the solution into the reaction system in the step (a), uniformly stirring, and sintering at the temperature of 200-250 ℃ for 1-2h to prepare the catalyst.

8. A preparation method of a morpholinyl vegetable oil polyalcohol catalyst is characterized by comprising the following steps: comprises the following steps;

(a) preparing a carrier: mixing acetic acid, organic zinc halide, triethylamine and methanol, stirring uniformly, heating to 200 ℃ under 1.1-1.2 atmospheric pressures, reacting for 1-2h, and cooling to room temperature under normal pressure; adding alkaline earth metal hydroxide or alkaline earth metal oxide and methanol, stirring uniformly, and standing for 12-24 h;

(b) loading active components: dissolving the metal halide in an alcohol solution, adding the solution into the reaction system in the step (a), uniformly stirring, and sintering at the temperature of 200-250 ℃ for 1-2h to prepare the catalyst.

9. A method for preparing a polyurethane foam, characterized in that: the method comprises the following steps of uniformly mixing 10-20 parts of epoxy resin, 1-5 parts of foam stabilizer, 10-30 parts of foaming agent, 1-2 parts of catalyst, 1-2 parts of water and 100 parts of morpholinyl vegetable oil polyol prepared by the preparation method of claim 1 or 2 to prepare a mixed solution, foaming the mixed solution and isocyanate in a foaming machine, and injecting the foamed mixture into a mold to prepare the polyurethane foam.

10. The method of producing a polyurethane foam according to claim 9, characterized in that: the foaming agent comprises a mixture of carbonic acid, lithium carbonate, sodium carbonate and 1, 1-azo (cyanocyclohexyl completion); the foaming agent comprises carbonic acid, lithium carbonate, sodium carbonate and 1, 1-azo (cyanocyclohexyl) with the mass ratio of 0.5: (1-2): (2-3): (1-3).

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of a morpholinyl vegetable oil polyol.

Background

Vegetable oil polyalcohol can replace petroleum polyalcohol to prepare polyurethane, and is a common chemical raw material. The preparation method of the vegetable oil-based polyol is various, and mainly comprises an alcoholysis method, an ozone oxidation method and an epoxy ring opening method, wherein the epoxy ring opening method is more applied in industry; the ring opening method means that under the action of a catalyst, epoxy group of epoxy vegetable oil and a nucleophilic reagent is subjected to ring opening, and nucleophilic group is combined with-C group to form substituent group, and-H is combined with-O to form hydroxyl. The nucleophilic agent mainly adopts alcohol, alcohol amine and acid.

For preparing polyol by an epoxy ring-opening method, patent CN104945256B discloses a preparation method of vegetable oil polyol, vegetable oil polyol and application thereof, in the patent, firstly, vegetable oil is subjected to epoxidation reaction under the conditions of formic acid and acetic acid/hydrogen peroxide to obtain epoxy group vegetable oil, the epoxy group vegetable oil is subjected to ring-opening reaction under the acidic condition to obtain vegetable oil polyol, the ring-opening reaction is normal pressure or pressurized ring opening, and in the process of the ring-opening reaction, a surfactant containing halogen elements is added; the ring-opening reaction in the patent takes water as a ring-opening agent, the hydroxyl value of the prepared polyol is between 100 and 700mgKOH/g, and the polyol can be used as a raw material for preparing the flexible polyurethane foam. However, in this patent, although water is used as a ring-opening agent, it is practically required to blend a surfactant, which contains halogen and is not environmentally friendly, and this type of surfactant is expensive and is not suitable for industrial production.

Patent CN109608333A discloses a high-quality vegetable oil polyol, a preparation method and application thereof, wherein epoxy vegetable oil is prepared by epoxydizing, the epoxy vegetable oil and polyhydroxy compound generate ring-opening reaction, the polyhydroxy group is used as a vegetable oil molecular chain substituent, and the prepared vegetable oil polyol has more flexible molecular chains and can be applied to polyurethane foaming.

Patent CN102212043B discloses a method for preparing a morpholinyl vegetable oil polyol, which takes morpholine and epoxy vegetable oil as raw materials, and performs a ring-opening reaction under the action of zinc chloride to prepare the morpholinyl vegetable oil polyol. The hydroxyl number of the prepared vegetable oil polyalcohol can be determined by the epoxy value of the epoxidized vegetable oil, the vegetable oil polyalcohol has good quality, the used raw materials have rich sources, the cost is low, and the vegetable oil polyalcohol is environment-friendly. However, in the technical scheme of the patent, the number of hydroxyl groups of the prepared vegetable oil polyol is determined by the number of epoxy groups of the vegetable oil, when the vegetable oil polyol with a high hydroxyl value is prepared, the vegetable oil with a high epoxy value is used as a raw material, so that the production cost is increased, and when the epoxy group value on a molecular chain of the vegetable oil is high, the newly generated hydroxyl groups on the molecular chain of the epoxidized vegetable oil are easy to perform ring-opening reaction with an epoxy group generator with the same molecular weight or an adjacent molecular weight in the ring-opening reaction process, so that cross-linking is generated between the molecular chains, the viscosity of a reaction solution is high, and the industrial mass production is not facilitated.

Disclosure of Invention

The invention aims to: the preparation method of the morpholinyl vegetable oil polyol solves the defects in the prior art, the high-hydroxyl-value vegetable oil polyol is prepared by taking the high-epoxy-value epoxy vegetable oil as a raw material for ring-opening reaction, in the preparation process, the molecular chain of the vegetable oil is not easy to aggregate, the viscosity of a reaction solution is low, the reaction process is easy to control, and the morpholinyl vegetable oil polyol can be widely applied to industrial production.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of morpholinyl vegetable oil polyalcohol comprises the following steps;

(a) heating the organic solvent in the reaction kettle to 70-80 ℃ in the organic solvent in the reaction kettle, and preserving the heat for 10-20 min; firstly, adding a slow-release catalyst into the reaction kettle, then adding an alcoholic solution containing morpholine into the reaction kettle, stirring and heating to 90-110 ℃, then adding epoxy vegetable oil into the reaction kettle, and reacting for 2-5 hours;

(b) and introducing the mixed solution in the reaction kettle into a liquid separation kettle, cooling to room temperature, adding ethyl acetate into the liquid separation kettle, stirring uniformly, heating to 80-90 ℃, performing negative pressure adsorption, and removing the ethyl acetate in the liquid separation kettle to obtain the morpholinyl vegetable oil polyol.

The organic solvent is C5-C8 fatty alcohol.

The organic solvent is one of amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, 3-dimethyl butanol and 3-methyl amyl alcohol.

In the invention, fatty alcohol is used as an organic solvent, morpholine is mixed with an alcohol solution, and under the action of a catalyst, epoxy groups on epoxy vegetable oil molecular chains and morpholine are subjected to ring-opening reaction to be used for containing a large amount of alcoholic hydroxyl groups in the solution.

In the preparation method, in the process of ring-opening reaction, alcoholic hydroxyl in the solvent can also be used as a ring-opening agent to perform ring-opening reaction with epoxy groups, so that aliphatic hydrocarbon groups are formed on the molecular chain of the vegetable oil, and the aliphatic hydrocarbon groups have good flexibility, thereby reducing the viscosity of the vegetable oil polyol and improving the fluidity of the vegetable oil polyol.

The slow-release catalyst comprises a carrier and an active component loaded on the surface of the carrier, wherein the active component is metal halide, and the carrier is a mixture of an alkaline earth metal compound and organic zinc halide.

The alkaline earth metal compound is one of magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, barium oxide and calcium oxide.

The organic zinc halide is dimethyl zinc, diethyl zinc or diphenyl zinc.

The preparation method of the catalyst comprises the following steps:

(a) preparing a carrier: mixing acetic acid, organic zinc halide, triethylamine and methanol, stirring uniformly, heating to 200 ℃ under 1.1-1.2 atmospheric pressures, reacting for 1-2h, and cooling to room temperature under normal pressure; adding alkaline earth metal hydroxide or alkaline earth metal oxide and methanol, stirring uniformly, and standing for 12-24 h;

(b) loading active components: dissolving the metal halide in an alcohol solution, adding the solution into the reaction system in the step (a), uniformly stirring, and sintering at the temperature of 200-250 ℃ for 1-2h to prepare the catalyst.

A preparation method of a morpholinyl vegetable oil polyalcohol catalyst comprises the following steps;

(a) preparing a carrier: mixing acetic acid, organic zinc halide, triethylamine and methanol, stirring uniformly, heating to 200 ℃ under 1.1-1.2 atmospheric pressures, reacting for 1-2h, and cooling to room temperature under normal pressure; adding alkaline earth metal hydroxide or alkaline earth metal oxide and methanol, stirring uniformly, and standing for 12-24 h;

(b) loading active components: dissolving the metal halide in an alcohol solution, adding the solution into the reaction system in the step (a), uniformly stirring, and sintering at the temperature of 200-250 ℃ for 1-2h to prepare the catalyst.

In the application, the active component of the catalyst is loaded on the carrier, and compared with the prior art that the active component of the catalyst is directly dissolved in a reaction system, the recovery efficiency of the catalyst can be improved and the recovery process is simplified by adopting the loaded catalyst; in the application, a mixture of an alkaline earth metal compound and an organic zinc halide is used as a carrier, the metal halide is loaded on the carrier, and then the active component and the carrier form a spatial cross-linking structure and a porous structure through roasting, in the ring-opening reaction process, the active component is gradually released from the carrier into a reaction liquid, the speed of the ring-opening reaction is controlled, so that alcoholic hydroxyl in the solution reacts preferentially to hydroxyl on a vegetable oil molecular chain, and the cross-linking of the molecular chain is reduced.

A preparation method of polyurethane foam comprises the following steps of uniformly mixing 100 parts of morpholinyl vegetable oil polyol, 10-20 parts of epoxy resin, 1-5 parts of foam stabilizer, 10-30 parts of foaming agent, 1-2 parts of catalyst and 1-2 parts of water to prepare a mixed solution, foaming the mixed solution and isocyanate in a foaming machine, and injecting the foamed mixture into a mold to prepare the polyurethane foam.

The foaming agent comprises a mixture of carbonic acid, lithium carbonate, sodium carbonate and 1, 1-azo (cyanocyclohexyl completion); the foaming agent comprises carbonic acid, lithium carbonate, sodium carbonate and 1, 1-azo (cyanocyclohexyl) with the mass ratio of 0.5: (1-2): (2-3): (1-3). Carbonic acid, lithium carbonate and sodium carbonate are used as compounded foaming agents, and the foam generation rate is uniform in the foaming process, so that the aperture of the formed polyurethane foam is uniform, and the heat insulation performance and the mechanical property of the polyurethane foam are improved.

Due to the adoption of the technical scheme, the invention has the beneficial effects that:

according to the invention, a slow-release catalyst is adopted, epoxy group vegetable oil is added into an alcoholic solution of morpholine, and under the action of the catalyst, the added epoxy group and morpholine undergo a ring-opening reaction, so that a ring-opening epoxy group on a vegetable oil molecular chain is subjected to ring opening to generate morpholine and hydroxyl. In the reaction process, a large number of hydroxyl groups exist in the reaction system, the hydroxyl groups in the alcohol solution and the epoxy groups are subjected to ring-opening reaction, the phenomenon that the hydroxyl groups newly generated by plants are subjected to ring-opening reaction again is reduced, and further the cross-linking of the molecular weight in the vegetable oil polyol is effectively reduced, the hydroxyl group content of the vegetable oil polyol is high, the flexibility of the molecular chain is good, and the vegetable oil polyol prepared by the method is applied to the preparation of polyurethane foam, so that the prepared foam has good flexibility and high foaming rate.

Detailed Description