阅读说明：本技术 曼尼希聚醚多元醇的制备方法 (Preparation method of Mannich polyether polyol ) 是由 程铸洪 史宏艺 宋录武 刘忠杰 高伟伟 孙露霞 于 2019-09-26 设计创作，主要内容包括：本发明属于硬泡聚醚多元醇制备技术领域,具体涉及一种曼尼希聚醚多元醇的制备方法。采用双酚A制备曼尼希碱,曼尼希碱、三聚氰胺甲醛溶液、起始剂、催化剂与环氧烷烃聚合反应生成曼尼希聚醚多元醇。本发明通过曼尼希反应在双酚A苯环的侧链接上含有羟基、氨基的基团,有效提高了官能度,同时在接上侧链基团后双酚A变成液体,更加有利于下一步的聚合反应。本发明合成得到的聚醚多元醇具有一定的自催化活性,与阻燃聚酯、添加型阻燃剂相比,其保存稳定性好。(The invention belongs to the technical field of preparation of hard foam polyether polyol, and particularly relates to a preparation method of Mannich polyether polyol. The Mannich base is prepared from bisphenol A, and the Mannich base, a melamine formaldehyde solution, an initiator, a catalyst and alkylene oxide are subjected to polymerization reaction to generate the Mannich polyether polyol. According to the invention, through the Mannich reaction, the side chain of the bisphenol A benzene ring contains a group of hydroxyl and amino, so that the functionality is effectively improved, and meanwhile, after the side chain group is connected, the bisphenol A becomes liquid, so that the next polymerization reaction is facilitated. The polyether polyol synthesized by the method has certain autocatalysis activity, and has good storage stability compared with flame-retardant polyester and additive flame retardants.)

1. A preparation method of Mannich polyether polyol is characterized in that Mannich base is prepared from bisphenol A, and the Mannich base, melamine formaldehyde solution, initiator, catalyst and alkylene oxide are subjected to polymerization reaction to generate the Mannich polyether polyol.

2. The method of preparing a mannich polyether polyol as set forth in claim 1, wherein the mannich base is prepared by reacting bisphenol a, an aldehyde, an amine and a solvent.

3. The method of claim 2, wherein the aldehyde is formaldehyde or acetaldehyde, the amine is one of ethanolamine, diethanolamine, triethanolamine, dimethylamine or ethylenediamine, and the solvent comprises one or more of methanol, ethanol, glycerol, ethylene glycol or water.

4. The method of preparing a mannich polyether polyol according to claim 2, wherein the molar ratio of bisphenol a, aldehyde and amine is 0.2 to 1: 0.1-4: 0.1-5.

5. The process for preparing a mannich polyether polyol as claimed in claim 2, characterized in that the reaction temperature is from 70 to 110 ℃ and the reaction time is from 1 to 4 hours.

6. The method of preparing a mannich polyether polyol as claimed in claim 1, wherein the melamine formaldehyde solution is prepared by mixing melamine with a formaldehyde solution for reaction.

7. The process of claim 6, wherein the molar ratio of melamine to formaldehyde is 0.5-2:1-8, the reaction temperature is 40-120 ℃, and the reaction time is 0.5-3 hours.

8. The method of preparing mannich polyether polyol according to claim 1, wherein the initiator comprises one or more of propylene glycol, glycerol, water, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, diethanolamine, triethanolamine, sorbitol or sucrose, the catalyst is a basic catalyst, and the alkylene oxide comprises one of propylene oxide, epichlorohydrin or ethylene oxide.

9. The process for preparing Mannich polyether polyols according to claim 1, wherein the Mannich base, the melamine formaldehyde solution, the initiator, the catalyst and the alkylene oxide are added to the reaction mixture in an amount of 100% by mass,

10. the process for preparing a mannich polyether polyol according to claim 1, characterized in that the polymerization temperature is 60 to 140 ℃ and the polymerization time is 2 to 10 hours.

Technical Field

The invention belongs to the technical field of preparation of hard foam polyether polyol, and particularly relates to a preparation method of Mannich polyether polyol.

Background

The Mannich reaction is an organic chemical reaction of a compound containing active hydrogen, aldehyde or ketone and secondary amine or ammonia to generate a beta-amino compound, the reaction can combine a plurality of flame-retardant elements together, a proper compound containing active hydrogen is selected as a main body structure, and the Mannich base generated by the reaction has hydroxyl and certain autocatalysis activity and can further generate a polymerization reaction with alkylene oxide to finally obtain the reactive flame-retardant polyether. Compared with an additive flame retardant, the reactive flame retardant polyether exists in a cross-linked network of the polyurethane foam material in a chemical bond form, so that the migration problem does not exist, and the mechanical property of the material cannot be obviously influenced when the reactive flame retardant polyether is added in a large amount.

With the development of environmental protection trend, the innovation of the foaming agent provides a new development direction for polyether polyol for hard foam. At present, the revolution speed of the foaming agent is increasingly accelerated, F11 and 141b are eliminated, and only two paths of full water and pentane exist in the future for various downstream fields, and the full water polyether has the problems of high viscosity of downstream combined materials, easiness in shrinkage of foams, reduction in size stability, poor adhesion of foamed plastics and base materials and the like, and the application field has certain limitation, so that the full development of polyether polyol applicable to a pentane system is urgent.

Disclosure of Invention

The invention aims to provide a preparation method of Mannich polyether polyol, which can be applied to the field of flame retardance and has excellent pentane intersolubility, certain autocatalysis activity and good storage stability.

The preparation method of the Mannich polyether polyol comprises the steps of preparing the Mannich base by using bisphenol A, and carrying out polymerization reaction on the Mannich base, a melamine formaldehyde solution, an initiator, a catalyst and alkylene oxide to generate the Mannich polyether polyol.

The Mannich base prepared from bisphenol A is prepared by reacting bisphenol A, aldehyde, amine and a solvent.

The aldehyde is formaldehyde or acetaldehyde, the amine is one of ethanolamine, diethanolamine, triethanolamine, dimethylamine or ethylenediamine, and the solvent is one or more of polar solvents such as methanol, ethanol, glycerol, ethylene glycol or water.

The molar ratio of bisphenol A, aldehyde and amine is 0.2-1: 0.1-4: 0.1-5.

The reaction temperature is 70-110 ℃, and the reaction time is 1-4 h.

The preparation method of the melamine formaldehyde solution is to mix and react melamine and formaldehyde solution to obtain the melamine formaldehyde solution.

The mol ratio of the melamine to the formaldehyde is 0.5-2:1-8, the reaction temperature is 40-120 ℃, and the reaction time is 0.5-3 h.

The initiator comprises one or more of propylene glycol, glycerol, water, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, diethanolamine, triethanolamine, sorbitol or sucrose, the catalyst is an alkaline catalyst, and the alkylene oxide comprises one of propylene oxide, epichlorohydrin or ethylene oxide.

Based on the total mass of the Mannich base, the melamine formaldehyde solution, the initiator, the catalyst and the alkylene oxide being 100 percent,

the polymerization temperature is 60-140 ℃, and the polymerization time is 2-10 h.

The preparation method of the Mannich polyether polyol specifically comprises the following steps:

(1) stirring bisphenol A, aldehyde, amine and a solvent in a certain proportion by a one-step method under a certain condition for reacting for a period of time, removing and recovering the solvent to obtain Mannich base;

(2) mixing melamine and formaldehyde solution according to a certain proportion, reacting for a certain time to obtain melamine formaldehyde solution, compounding an initiator with a certain mass and the Mannich base synthesized in the step (1), and removing water after mixing the melamine formaldehyde solution, the initiator and the Mannich base;

(3) according to the hydroxyl value set by the product, a small amount of catalyst can be added into the mixed solution, and the mixed solution and alkylene oxide are subjected to polymerization reaction under certain conditions to generate the Mannich polyether polyol.

The selection of the solvent in the reaction process in the step (1) plays a crucial role in the synthesis process of the Mannich base, and not only influences the yield of the Mannich base, but also has certain influence on the molecular structure of the synthesized Mannich base.

In the step (1), the stirring speed is 10-25r/min, wherein the aldehyde substances need to be added dropwise, in batches or directly and completely.

In the step (2), the influence of the addition of different initiators on the polyether indexes is different, and polyether polyols with different range indexes can be synthesized according to the requirement.

The catalyst in step (3) includes, but is not limited to, KOH, N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, a solid amine, N-ethylmorpholine, NMM, N, N '-diethylpiperazine, triethanolamine, DMEA, pyridine, N, N' -dimethylpyridine, and the like.

The Mannich base is obtained by reacting bisphenol A with aldehyde and amine in a one-step method under certain conditions; the melamine and formaldehyde solution are mixed and reacted according to a certain proportion, and are uniformly mixed with the Mannich base according to a certain proportion, a certain amount of rigid foam polyether polyol conventional initiator is compounded to improve the flexibility and viscosity index of foam, and the rigid foam polyether polyol conventional initiator and alkylene oxide are subjected to polymerization reaction to finally obtain polyether polyols with different indexes.

The invention has the following beneficial effects:

the invention provides a method for synthesizing Mannich polyether polyol by adopting bisphenol A, wherein a group containing hydroxyl and amino is linked on the side chain of a bisphenol A benzene ring through Mannich reaction, so that the functionality is effectively improved, and meanwhile, after the side chain group is connected, the bisphenol A becomes liquid, so that the next polymerization reaction is more facilitated; after the melamine formaldehyde solution is compounded, the reactivity of the melamine formaldehyde solution with the alkylene oxide is improved, and the special nitrogen-containing heterocyclic ring structure of the melamine can bring good flame retardant property; the addition of the conventional initiator can effectively increase the flexibility of the polyether, plays a role in adjusting the polyether index, is more suitable for downstream application of the polyether, and solves the problems of brittleness, easy shrinkage and the like of foam caused by the addition of melamine. The polyether polyol synthesized by the method has certain autocatalysis activity, and has good storage stability compared with flame-retardant polyester and additive flame retardants. The polyurethane foam plastic prepared by the polyether polyol has good flame retardant effect, excellent pentane intersolubility, low foam size change rate and higher strength than common polyether.

Detailed Description

The present invention is further described below with reference to examples.