阅读说明：本技术 一种全水发泡用硬泡阻燃聚醚多元醇的制备方法 (Preparation method of hard foam flame-retardant polyether polyol for all-water foaming ) 是由 *** 张宝银 吕兴连 张坤 魏学福 米新强 周小光 付文辉 于 2019-10-21 设计创作，主要内容包括：本发明属于聚氨酯合成技术领域,尤其涉及一种全水发泡用硬泡阻燃聚醚多元醇的制备方法,所述制备方法以蔗糖、低分子量多元醇以及卤代醇、酚醛树脂、油脂为起始剂,以碱金属盐作为催化剂,通入一段环氧丙烷进行反应；反应完毕再通入环氧丙烷环与环氧乙烷的混合物进行混聚反应,粗醚经后处理精制得到成品。工艺过程操作简单,得到的全水发泡用硬泡阻燃聚醚产品,粘度低,与水的相容性好,以此制备的聚氨酯泡沫塑料制品具有较窄的密度分布、较高的强度、良好的尺寸稳定性和粘结强度以及较低的导热系数,具有一定的阻燃效果,特别适合全水发泡保温管道及其它保温领域。(The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a preparation method of hard foam flame-retardant polyether polyol for full water foaming, which takes cane sugar, low molecular weight polyol, halohydrin, phenolic resin and grease as initiators, takes alkali metal salt as a catalyst, and is introduced with a section of propylene oxide for reaction; after the reaction is finished, the mixture of the epoxypropane ring and the ethylene oxide is introduced for mixed polymerization reaction, and the crude ether is refined to obtain the finished product. The preparation method is simple in technological process operation, the obtained rigid foam flame-retardant polyether product for all-water foaming has low viscosity and good compatibility with water, and the polyurethane foam plastic product prepared by the preparation method has narrow density distribution, high strength, good dimensional stability and bonding strength, low heat conductivity coefficient and certain flame-retardant effect, and is particularly suitable for all-water foaming heat-insulating pipelines and other heat-insulating fields.)

1. A preparation method of hard foam flame-retardant polyether polyol for full water foaming is characterized by comprising the following steps:

(1) feeding and pretreating: adding sucrose, halohydrin, low-molecular-weight polyol, phenolic resin and grease into a reaction kettle, then adding an alkali metal salt catalyst, replacing for 3-5 times with nitrogen, then heating to 100-105 ℃, and performing vacuum dehydration until the water content of materials in the kettle is within 0.5% (wt);

(2) polymerization reaction: controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding propylene oxide to 80-90% of the total added mass of the propylene oxide, mixing the residual propylene oxide and ethylene oxide, dropwise adding the mixture of the propylene oxide and the ethylene oxide into a reaction kettle, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and then curing for 1.5-3.5 hours;

(3) and (3) post-treatment: adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the product, namely the hard foam polyether polyol for full-water foaming.

2. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the halogenated alcohol is one or more of tribromoneopentyl alcohol, dibromo neopentyl glycol, bromo neopentyl glycol, phosphorus bromine-containing polyol and polyol-epoxy chlorobutane addition compound.

3. The low molecular weight polyol of claim 1 being one or more of glycerol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol, or triethylene glycol.

4. The method for preparing the hard foam flame-retardant polyether polyol for all-water foaming according to claim 3, wherein the method comprises the following steps: the low molecular weight polyol is diethylene glycol and propylene glycol.

5. The method for preparing the rigid foam flame-retardant polyether polyol for all-water foaming according to claim 4, wherein the rigid foam flame-retardant polyether polyol comprises the following steps: the mass ratio of the diethylene glycol to the propylene glycol is 1:1 to 5.

6. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the alkali metal salt catalyst is potassium hydroxide, and the mass percentage of the catalyst added in the whole reaction system is 2.0-4.0%.

7. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the mass ratio of the sucrose to the halogenated alcohol to the low-molecular-weight polyol to the phenolic resin to the grease is 342: 15-50: 25-90: 20-30: 200 to 300.

8. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the oil is palm oil, and the oil accounts for 14-21% of the whole reaction system by mass.

9. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: in the mixture of propylene oxide and ethylene oxide in the step 2, the mass ratio of propylene oxide to ethylene oxide is 1: 0.2 to 1.

Technical Field

The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a preparation method of hard foam flame-retardant polyether polyol for full water foaming.

Background

Disclosure of Invention

The invention aims to provide a preparation method of rigid foam flame-retardant polyether polyol for full-water foaming, and the full-water foaming rigid foam polyether product obtained by the method has a hydroxyl value of 310-350 mgKOH, low viscosity and low cost; the foamed product has high compression strength and good dimensional stability; the adhesive force with a heat insulation system is strong; has certain flame retardant effect; the foam has low heat conductivity coefficient and good toughness.

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

a preparation method of hard foam flame-retardant polyether polyol for full water foaming comprises the following steps:

(1) feeding and pretreating: adding sucrose, halohydrin, low-molecular-weight polyol, phenolic resin and grease into a reaction kettle, then adding an alkali metal salt catalyst, replacing for 3-5 times with nitrogen, then heating to 100-105 ℃, and performing vacuum dehydration until the water content of materials in the kettle is within 0.5% (wt);

(2) polymerization reaction: controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding propylene oxide to 80-90% of the total added mass of the propylene oxide, mixing the residual propylene oxide and ethylene oxide, dropwise adding the mixture of the propylene oxide and the ethylene oxide into a reaction kettle, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and then curing for 1.5-3.5 hours;

(3) and (3) post-treatment: and adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the product, namely the hard foam flame-retardant polyether polyol for full-water foaming.

Aiming at the defects of high polyether viscosity, high cost, unstable product quality, poor flame-retardant effect and the like existing in the current market application, a brand-new hard flame-retardant polyether polyol for full-water foaming is prepared by optimizing an initiator formula and simultaneously properly accessing EO (ethylene oxide), and the invention takes sucrose, halohydrin, low-molecular-weight polyol, a small amount of halohydrin, phenolic resin and grease as initiators and takes alkali metal salt as a catalyst and introduces a section of propylene oxide for reaction; after the reaction is finished, the mixture of the epoxypropane ring and the ethylene oxide is introduced for mixed polymerization reaction, the crude ether is refined to obtain a finished product through post-treatment, the prepared polyether polyol has better fluidity and is suitable for full-water foaming, the adhesive force with a pipe wall (wall and other attachments) is enhanced during foaming, and the foamed product has increased toughness, is not easy to tear and is not crisp; the size stability of the manufactured product is better, and the product is not deformed; has certain flame retardant effect; the heat conductivity coefficient is low, and the heat preservation effect is better; because the initiator introduces alcohols containing halogen, the initiator is a reactive flame retardant and is matched with an external additive flame retardant for use, the flame retardant property is greatly improved; the construction process is simple, and the method has wide application prospect.

Preferably, the halohydrin is tribromoneopentyl alcohol, dibromoneopentyl glycol, bromoneopentyl glycol, phosphorus bromine-containing polyol, polyol-chlorobutylene oxide adduct, or the like.

Preferably, the halohydrin is bromoneopentyl glycol.

Preferably, the low molecular weight polyol is one or more of glycerol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol or triethylene glycol.

Preferably, the low molecular weight polyol is diethylene glycol and propylene glycol.

Preferably, the mass ratio of the diethylene glycol to the propylene glycol is 1:1 to 5.

Preferably, the alkali metal salt catalyst is potassium hydroxide, the addition amount of the potassium hydroxide accounts for 2.0-4.0% by mass of the whole reaction system, and the whole reaction system refers to the total addition amount of the composite initiator, the catalyst and the epoxide.

Preferably, the mass ratio of the sucrose, the halogenated alcohol, the low-molecular-weight polyol, the phenolic resin and the oil is 342: 15-50: 25-90: 20-30: 200 to 300.

Preferably, the grease is palm oil, the mass percentage of the grease in the whole reaction system is 14-21%, and the whole reaction system refers to the total added mass of the composite initiator, the catalyst and the epoxide.

Preferably, in the mixture of propylene oxide and ethylene oxide in the step 2, the mass ratio of propylene oxide to ethylene oxide is 1: 0.2 to 1.

The process can obtain the all-water foaming hard foam polyether polyol product with the hydroxyl value of 310-350 mgKOH/g and the viscosity (25 ℃) of 800-1100 mPa.s, and the prepared product has low viscosity of the prepared combined material, better fluidity, good mold filling property when foaming a foam product, certain flame retardant effect and suitability for the all-water foaming process.

Advantageous effects

Aiming at the defects of high polyether viscosity, high cost, unstable product quality, poor flame retardant effect and the like existing in the application of the all-water foaming hard foam polyether in the current market, the invention prepares a brand-new all-water foaming hard flame retardant polyether polyol by optimizing the formula of an initiator and simultaneously mixing and polymerizing a proper amount of EO (ethylene oxide). The method takes sucrose, low molecular weight polyol, halohydrin, phenolic resin and grease as initiators and alkali metal salt as a catalyst, and a section of propylene oxide is introduced for reaction; after the reaction is finished, the mixture of the epoxypropane ring and the ethylene oxide is introduced for mixed polymerization reaction, and the crude ether is refined to obtain the finished product. The prepared polyether polyol has better fluidity, is suitable for a full-water foaming process, enhances the adhesive force with a pipe wall (attachments such as a wall) during foaming, and increases the toughness of a foamed product, so that the foamed product is not easy to tear and crisp; the size stability of the manufactured product is better, and the product is not deformed; the heat conductivity coefficient is low, and the heat preservation and flame retardant effects are better; because the initiator introduces alcohols containing halogen, the initiator is a reactive flame retardant and is matched with an external additive flame retardant for use, the flame retardant property is greatly improved; the construction process is simple, and the method has wide application prospect. The hydroxyl value of the prepared all-water foaming hard foam polyether polyol product is 310-350 mgKOH/g, and the viscosity (25 ℃) is 800-1100 mPa.s.

The hard foam flame-retardant polyether polyol for full water foaming prepared by the invention has low viscosity, the prepared composite material has low viscosity, and the foam product has good mold filling property when being foamed, and is suitable for the full water foaming process. In the synthesis process of the polyether polyol, the proportion of the epoxide is relatively low, and a certain amount of ethylene oxide (the market price of the ethylene oxide is lower than that of the propylene oxide) is polymerized, so that the raw material cost is reduced; because the halogenated alcohol, the phenolic resin and the grease are introduced into the initiator, the foamed product has a certain flame retardant effect, the compressive strength is improved, and the toughness is good; in the polymerization process, ethylene oxide is mixed and polymerized, the bonding strength of the foam product is improved, the raw material cost is reduced, the hydrophilicity of polyether polyol is improved, and the stability of the polyether composite material is improved.

The preparation method has the advantages of simple operation of the process and high production efficiency; the hard foam flame-retardant polyether product for all-water foaming, which is obtained by the preparation method, has moderate hydroxyl value, low viscosity, low cost and good compatibility with water; the foamed product has high compression strength, good dimensional stability, strong binding power with a heat insulation system, low foam heat conductivity coefficient and good toughness; the polyurethane foam plastic prepared by the method has narrower density distribution, higher strength, good dimensional stability and bonding strength and lower heat conductivity coefficient; has certain flame retardant effect, and is particularly suitable for all-water foaming heat-insulating grinding pipelines and other heat-insulating fields. The product has uniform molecular weight distribution, stable product performance and no delamination under high and low temperature environments; the product has high activity, the foaming and rising speed in winter is not weakened, and the method is suitable for environmental construction all the year round; meanwhile, the cost is lower than that of similar products in the current market, so that the method is favorable for market popularization and application.

Detailed Description

Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.

The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.

Comparative example

Adding 342g of cane sugar, 120g of diethylene glycol, 50g of propylene glycol and 7g of potassium hydroxide into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil pipe) and a pressure sensor, replacing 3 times with nitrogen, heating, starting a vacuum pump to perform vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, maintaining the reaction temperature in the autoclave at 80-110 ℃ by controlling the feeding speed of the propylene oxide and the temperature control device, keeping the pressure in the autoclave at 0.1-0.4 MPa until the propylene oxide is added to 1600g, and curing for 3 hours after the reaction after the feeding is finished. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.

The performance indexes of the synthesized full water foaming hard foam polyether polyol are shown in the table 1.