阅读说明：本技术 磷腈催化体系聚醚多元醇的低气味精制方法 (Low-odor refining method of phosphonitrile catalytic system polyether polyol ) 是由 李晓芳 *** 孙兆任 李剑锋 王文涛 于 2019-09-27 设计创作，主要内容包括：本发明涉及聚醚多元醇技术领域,具体涉及一种磷腈催化体系聚醚多元醇的低气味精制方法。所述的磷腈催化体系聚醚多元醇的低气味精制方法,步骤如下：(1)将粗聚醚多元醇投入到精制反应釜中,加水搅拌；(2)加入中和剂中和,然后加入吸附剂吸附；(3)负压脱水,加入离子交换树脂进行吸附交换；(4)加入抗氧剂,过滤得到精制聚醚多元醇。本发明的磷腈催化体系聚醚多元醇的低气味精制方法,方法简单、高效,可以使用常用的中和-吸附设备进行生产,无需设备改造,能有效降低聚醚多元醇的气味,同时最大程度的除去聚醚多元醇中残留的催化剂,精制后的聚醚多元醇挥发性有机物少,气味低。(The invention relates to the technical field of polyether polyol, and particularly relates to a low-odor refining method of phosphazene catalytic system polyether polyol. The low-odor refining method of the phosphazene catalytic system polyether polyol comprises the following steps: (1) putting the crude polyether glycol into a refining reaction kettle, adding water and stirring; (2) adding a neutralizing agent for neutralization, and then adding an adsorbent for adsorption; (3) dehydrating under negative pressure, and adding ion exchange resin for adsorption exchange; (4) adding an antioxidant, and filtering to obtain the refined polyether polyol. The method for refining the polyether polyol with the phosphazene catalytic system is simple and efficient, can be used for producing by using common neutralization-adsorption equipment without equipment transformation, can effectively reduce the odor of the polyether polyol, can remove the residual catalyst in the polyether polyol to the maximum extent, and has less volatile organic compounds and low odor of the refined polyether polyol.)

1. A low-odor refining method of phosphonitrile catalytic system polyether polyol is characterized by comprising the following steps:

(1) Putting the crude polyether glycol into a refining reaction kettle, adding water and stirring;

(2) Adding a neutralizing agent for neutralization, and then adding an adsorbent for adsorption;

(3) Dehydrating under negative pressure, and adding ion exchange resin for adsorption exchange;

(4) Adding an antioxidant, and filtering to obtain refined polyether polyol;

The crude polyether polyol is polyether polyol synthesized by catalysis of a phosphazene catalyst, the functionality is 2-6, the weight-average molecular weight is 300-15000, and the content of the catalyst is 1.5 per thousand;

the ion exchange resin is macroporous cation exchange resin, and is required to be pretreated before use: soaking ion exchange resin in water to swell, soaking with 4-5 wt% dilute hydrochloric acid, soaking with 2-4 wt% sodium hydroxide solution, and washing with water to neutrality.

2. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (1), the adding amount of water is 5-9% of the mass of the crude polyether polyol.

3. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (2), the neutralizer is inorganic acid or organic acid; the adding amount is 0.43-0.47 per mill of the crude polyether polyol; the neutralization conditions were: the temperature is 80-85 deg.C, and the time is 40-80 min.

4. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (2), the adsorbent is one or two of magnesium silicate and aluminum silicate, and the adding amount is 0.05-0.2% of the mass of the crude polyether polyol.

5. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (2), the adsorption conditions are as follows: the temperature is 80-100 deg.C, and the time is 30-120 min.

6. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (3), the negative pressure dehydration conditions are as follows: the temperature is 100-.

7. a method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (3), the adding amount of the cation exchange resin is 0.4-1% of the mass of the crude polyether polyol.

8. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (3), the adsorption exchange conditions are as follows: the temperature is 100 ℃ and 120 ℃, and the time is 1-3 h.

9. A method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: in the step (4), the antioxidant is an antioxidant 1076; the addition amount of the antioxidant is 0.08-0.12 percent of the mass of the crude polyether polyol.

10. a method for the purification of polyether polyols having phosphazene catalyst system according to claim 1, characterized in that: treating the residue filtered in the step (4): and (3) putting the residues into an exchange column, washing the residues from bottom to top by using water, soaking the residues in 3-10 wt% hydrochloric acid or 1-4 wt% sulfuric acid solution, and washing the residues to be neutral by using desalted water to obtain the recovered ion exchange resin.

Technical Field

the invention relates to the technical field of polyether polyol, and particularly relates to a low-odor refining method of phosphazene catalytic system polyether polyol.

Background

polyether polyol is one of the main raw materials for producing polyurethane material, and is a polymer with a main chain containing ether bonds and a terminal group or a side group containing two or more hydroxyl groups. In general, polyether polyols are prepared by ring-opening polymerization of low molecular weight polyols, polyamines or active hydrogen-containing compounds as initiators with alkylene oxides under the action of catalysts. The crude polyether synthesized by the alkali metal or phosphazene catalyst process usually needs to be refined to remove the residual catalyst in the product, and simultaneously improve the color and smell of the polyether to a certain extent.

The catalytic activity of the phosphazene catalyst is 450 times that of a KOH catalyst, the reaction process activity is high and balanced, the side reaction products are few, and the phosphazene catalyst is particularly obvious in the process of catalyzing high molecular weight polyether; compared with DMC catalyst, it has the advantages of using small molecule as initiator, directly using EO to cap without removing catalyst, and the capping rate can reach more than 85%. At present, the catalyst is industrially produced and applied only in Japan abroad, and the research on the PPG catalyst as the PPG catalyst is deficient in China, so that the catalyst has important significance on the research on the catalysis and post-treatment processes.

The main odor sources of polyether polyol are two parts, one part is a byproduct generated in the polymerization process, the other part is derived from micromolecular alcohol, aldehyde and ketone impurities in raw materials, the current mainstream refining process is to add acid and water for neutralization, add an adsorbent for adsorption, dehydrate and filter, although the odor can be reduced to a certain degree, the odor still has larger odor residues. With the rapid development of the times, the environmental awareness of the public is gradually improved, the environmental requirements on products are gradually improved, a plurality of policies and standards are successively established in China, and the control of downstream manufacturers on the odor and the content of organic volatile matters of polyurethane foam products is more strict, which represents the problem that the improvement of a polyether refining process, the reduction of the content of harmful substances and the reduction of the odor of polyether are urgently needed to be solved by polyether manufacturers.

The ion exchange resin is a polymer prepared by polymerizing styrene and divinylbenzene and sulfonating by sulfuric acid, generally presents porous or granular shapes, and can exchange certain active ions with certain ions in a solution, namely, a replacement reaction is carried out to remove soluble ions in the solution. The ion exchange resin, especially cation exchange resin, has the advantages of high treating capacity, capacity of eliminating different kinds of ion, easy adsorption and exchange of organic macromolecular matter, decolorizing effect, repeated regeneration and use, long service life and low running cost.

Patent CN2017111651230 discloses a process and a device for refining polyether containing alkali metal by using cationic resin, wherein the refining process is to dilute polyether containing alkali metal by using an inert solvent; mixing cationic resin and polyether for reaction; removing the inert solvent in the mixed solution; the device comprises a solvent storage tank, a polyether crude product tank, an ion resin exchanger, a filter, a heat exchange reboiler, a distillation tower and a polyether finished product tank which are sequentially connected. The cation exchange resin used in the patent is strong acid type cation resin, and is easy to generate side reaction with polyether glycol to generate aldehyde substances; the process is mainly used for refining the polyether containing alkali metal, and an original device is required to be modified when the process is used, so that the cost is high, and the application range is limited.

Patent CN2018114660541 discloses a refining method and a composition of polyether polyol with low VOC, which uses a composition comprising cation exchange resin and an adsorbent to treat polyether polyol to prepare high-quality polyether polyol with total amount of Na and K less than 5ppm and aldehyde content less than 5 ppm. The polyether polyol is treated by adopting a combination of strong acid type cation exchange resin and aldehyde adsorption resin containing amino, and the polyether polyol applicable to the refining method is an alkali metal catalytic system.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a low-odor refining method of polyether polyol of a phosphazene catalytic system, which is simple and efficient, can be used for production by using common neutralization-adsorption equipment, does not need equipment transformation, can effectively reduce the odor of polyether polyol, can remove residual catalyst in the polyether polyol to the maximum extent, and has less volatile organic compounds and low odor of the refined polyether polyol.

the invention relates to a low-odor refining method of phosphazene catalytic system polyether polyol, which comprises the following steps:

(1) Putting the crude polyether glycol into a refining reaction kettle, adding water and stirring;

(2) Adding a neutralizing agent for neutralization, and then adding an adsorbent for adsorption;

(3) Dehydrating under negative pressure, and adding ion exchange resin for adsorption exchange;

(4) adding an antioxidant, and filtering to obtain refined polyether polyol;

The crude polyether polyol is polyether polyol synthesized by catalysis of a phosphazene catalyst, the functionality is 2-6, the weight-average molecular weight is 300-15000, and the content of the catalyst is 1.5 per thousand;

The ion exchange resin is macroporous cation exchange resin, and is required to be pretreated before use: soaking ion exchange resin in water to swell, soaking with 4-5 wt% dilute hydrochloric acid, soaking with 2-4 wt% sodium hydroxide solution, and washing with water to neutrality.

Preferably, the weight average molecular weight of the crude polyether polyol is 5000-12000.

Preferably, the ion exchange resin is macroporous cation exchange resin D001, produced by Hibei Huarui Lanxing chemical building materials Co. The newly purchased ion exchange resin needs to be pretreated before use: the ion exchange resin is first expanded with water, then the inorganic impurities (mainly iron compounds) are removed with 4-5 wt% dilute hydrochloric acid, the organic impurities are removed with 2-4 wt% sodium hydroxide solution, and finally the solution is washed with water to pH 6-8.

In step (1), the amount of water added is 5-9%, preferably 6-8% by mass of the crude polyether polyol.

Before adding water, the temperature of the crude polyether polyol is increased to 80-90 ℃, and the crude polyether polyol is stirred for 30-60min after adding water.

In the step (2), the neutralizer is inorganic acid or organic acid; the neutralization conditions were: the temperature is 80-85 ℃, the time is 40-80min, and the adding amount is 0.43-0.47 per mill of the mass of the crude polyether polyol.

Preferably, the neutralizing agent is one or more of phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid.

in the step (2), the adsorbent is one or two of magnesium silicate and aluminum silicate, and the adding amount is 0.05-0.2% of the mass of the crude polyether polyol.

In the step (2), the adsorption conditions are as follows: the temperature is 80-100 deg.C, and the time is 30-120 min.

In the step (3), the negative pressure dehydration conditions are as follows: the temperature is 100-.

In the step (3), the cation exchange resin is added in an amount of 0.4 to 1%, preferably 0.5 to 0.8% by mass based on the crude polyether polyol.

In the step (3), the adsorption exchange conditions are as follows: the temperature is 100 ℃ and 120 ℃, and the time is 1-3 h.

in the step (4), the antioxidant is an antioxidant 1076; the addition amount of the antioxidant is 0.08-0.12 percent of the mass of the crude polyether polyol.

Treating the residue filtered in the step (4): and (3) placing the residues into an exchange column, strongly washing the residues from bottom to top by using water for a short time, soaking or washing the residues by using 3-10 wt% hydrochloric acid or 1-4 wt% sulfuric acid solution, and washing the residues to be neutral by using desalted water to obtain the recovered ion exchange resin, wherein the ion exchange resin can be repeatedly used.

Compared with the prior art, the invention has the following beneficial effects:

(1) According to the low-odor refining method of the phosphazene catalytic system polyether polyol, the special refining agent is selected, the refining post-treatment process is changed, and the ion exchange resin with good exchange adsorption effect is applied to the refining of the polyether polyol, so that the odor of the polyether polyol can be effectively reduced, the residual catalyst in the polyether polyol is removed to the greatest extent, and the refined polyether polyol has few volatile organic compounds and low odor;

(2) The conventional neutralizing agent is adopted to neutralize polyether polyol, the ion exchange resin mainly plays a role in displacing and adsorbing small molecular side reaction substances and catalyst residues, and compared with the strong acid type ion exchange resin, the process stability is good, and side reactions are avoided;

(3) The refining method can use common neutralization-adsorption equipment for production, does not need equipment transformation, simultaneously uses the ion exchange resin which is cheap and easy to obtain, can realize cyclic utilization, and is economical, environment-friendly and small in cost increment.

Detailed Description

The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.