CN108047442B - Rigid foam composite polyether polyol and preparation method thereof - Google Patents
Rigid foam composite polyether polyol and preparation method thereof Download PDFInfo
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- CN108047442B CN108047442B CN201711379331.0A CN201711379331A CN108047442B CN 108047442 B CN108047442 B CN 108047442B CN 201711379331 A CN201711379331 A CN 201711379331A CN 108047442 B CN108047442 B CN 108047442B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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Abstract
The application relates to a preparation method of rigid foam composite polyether polyol, which comprises the steps of gradually introducing an epoxy compound into a polyether polyol mixed initiator and a polyether polyol synthesis catalyst under the conditions that the reaction temperature is 80-135 ℃ and the reaction pressure is not more than 0.4Mpa to perform ring-opening polymerization reaction to obtain the composite polyether polyol; the polyether polyol mixed initiator comprises polyether triol taking glycerol as an initiator and polyether diol taking propylene glycol as an initiator, and the mass ratio of the polyether triol to the polyether diol is (3-6): 1. The rigid foam composite polyether polyol has the advantages of low viscosity, high functionality, high reaction activity and the like, and the rigid foam polyurethane prepared by using the composite polyether polyol as a cross-linking agent has excellent surface property and strength.
Description
Technical Field
The application relates to the technical field of chemical synthesis, is applied to industries such as cross-linking agents, chain extenders and the like, and particularly relates to a preparation method of rigid foam composite polyether polyol.
Background
The polyurethane foam plastic is prepared by polymerizing and foaming polyisocyanate and hydroxyl compound, and the form and the performance of the product can be greatly changed by changing the types and the compositions of the raw materials, so that the flexible to hard polyurethane foam plastic product is obtained. Among them, polyurethane rigid foam plastic has good physical and mechanical properties, acoustic properties and chemical resistance, especially low thermal conductivity, and is widely applied to various heat preservation fields such as household appliances, building boards, pipelines, outer wall spraying and the like.
In the preparation of polyurethane rigid foam plastics, a cross-linking agent is used for generating chemical bonds among linear molecules, so that the linear molecules are mutually connected to form a net structure, and the strength and the elasticity of a polyurethane product are improved; the chain extender is used for reacting with functional groups on a linear polymer chain to expand molecular chains and increase molecular weight, and improves the mechanical property and the technological property of a polyurethane product. Conventional crosslinkers/chain extenders employ synergistic combinations of organic amines such as diethanolamine, triethanolamine and polyols such as ethylene glycol, propylene glycol and the like. The polyurethane rigid foam plastic prepared by the cross-linking agent/chain extender is easy to crack, has poor forming, poor finish, poor mechanical property, poor dimensional stability and the like.
To this end, there is a strong need in the art for a rigid foam syntactic polyether polyol as a cross-linker/chain extender that addresses at least the above-mentioned problems.
Disclosure of Invention
The application aims to overcome the defects of the existing products and technologies and provide the composite polyether polyol capable of serving as a rigid foam cross-linking agent and a chain extender and the preparation method thereof.
The preparation method comprises the steps of gradually introducing an epoxy compound into a polyether polyol mixed initiator and a polyether polyol synthesis catalyst under the conditions that the reaction temperature is 80-135 ℃ and the reaction pressure is not more than 0.4Mpa, so that ring-opening polymerization reaction is carried out on the epoxy compound to prepare the composite polyether polyol; the polyether polyol mixed initiator comprises polyether triol taking glycerol as an initiator and polyether diol taking propylene glycol as an initiator, and the mass ratio of the polyether triol to the polyether diol is (3-6): 1.
In some embodiments, the polyether polyol blend initiator may also include other polyether compositions not limited to polyether diols and polyether triols.
In some embodiments, the polyether polyol synthesis catalyst is potassium hydroxide, and the amount of the polyether polyol synthesis catalyst is 0.2% to 0.25% of the total mass of the polyether polyol mixed initiator and the epoxy compound. In some embodiments, the molecular weight of the glycerol-initiated polyether triol is 450-550, and the molecular weight of the propylene glycol-initiated polyether diol is 350-450.
In some embodiments, the epoxy compound is propylene oxide, wherein the mass ratio of the propylene oxide to the polyether polyol mixed starter is (4.2-5.3): 1.
In some embodiments, the method of preparing the rigid foam syntactic polyether polyol is performed according to the following steps:
(1) adding a polyether polyol mixed initiator and a polyether polyol synthesis catalyst into a reaction kettle, mixing, starting stirring under the condition of negative pressure, and heating to 80-90 ℃;
(2) heating is suspended, a first part of epoxy compound is rapidly added into the reaction kettle, and the reaction temperature is controlled to be 80-90 ℃, wherein the first part of epoxy compound accounts for 30-40% of the total amount of the epoxy compound;
(3) adding a second part of epoxy compound in a continuous feeding or batch feeding manner, and carrying out polymerization reaction at the temperature of 90-105 ℃ and under the reaction pressure of not more than 0.4MPa, wherein when batch feeding is adopted, the feeding amount of each batch is 6-10% of the total amount of the second part of epoxy compound;
(4) maintaining the reaction temperature within the range of 100-135 ℃ for curing until the pressure is not changed;
(5) and (4) carrying out refining treatment of neutralization, dehydration and filtration cooling.
In some embodiments, the polyether polyol mixed initiator and the polyether polyol synthesis catalyst are subjected to dehydration and drying treatment before reaction; and after adding the polyether polyol mixed initiator and the polyether polyol synthetic catalyst into a reaction kettle for mixing, introducing inert gas and performing positive-negative pressure alternate displacement for at least two times to ensure the anhydrous and anaerobic reaction conditions of the system. Finally, under the condition of negative pressure, for example-0.1 mPa, starting stirring and heating to 80-90 ℃. In some embodiments, the inert gas may be nitrogen or argon.
In some embodiments, after the temperature of the polyether polyol mixing initiator and polyether polyol synthesis catalyst mixture reaches about 80 ℃, the heating is stopped and a first portion of the epoxy compound is rapidly added to the reaction vessel. The first part of propylene oxide is pre-dripped before feeding, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, when the temperature rises and the pressure drops, the material starts to react, the epoxy compound is continuously fed, and the reaction temperature is controlled to be 80-90 ℃.
In some embodiments, after the temperature reaches 90 ℃, propylene oxide is continuously added, the propylene oxide is slowly fed in the early stage, the temperature is raised by using the reaction heat, and the reaction temperature is controlled to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa.
In some embodiments, the reaction temperature is maintained for maturation until the pressure will not be. In the process, the curing process is divided into two parts: the temperature of the early curing is controlled within the range of 100-115 ℃, and the temperature of the later curing is controlled within the range of 120-135 ℃.
In some embodiments, after the reaction is completed, the product is subjected to a purification treatment such as neutralization, dehydration, temperature reduction and filtration. The neutralization process comprises adding water, preferably soft water, stirring at 80-90 deg.C for 40-80 min, preferably 60min, and continuously adding phosphoric acid, stirring at 80-90 deg.C for 80-100 min, preferably 90 min; the dehydration process comprises adding an adsorbent, stirring for 50-80 minutes, preferably 60 minutes, heating to 110-120 ℃, and dehydrating for 4-8 hours, preferably 6 hours; finally, cooling and filtering, and discharging after the materials are qualified.
In some embodiments, the adsorbent can be a dehydration adsorbent known to those skilled in the art, such as FR-6 and FR-7.
In a second aspect, the present application provides a rigid foam syntactic polyether polyol prepared by a process as described in the first aspect.
On the basis of the common knowledge in the field, the components can be combined randomly to obtain the preferred embodiments of the invention.
Compared with the prior art, the preparation method has the beneficial effects that (1) the preparation method of the rigid foam composite polyether polyol comprises the following steps: the method is simple, the production period is short, the process operation is simple, the production cost is low, the prepared composite polyether is easy to dissolve in water, the hydroxyl value and the viscosity are adjustable, the stability is good, and different customer requirements can be met. (2) The polyurethane rigid foam plastic produced by using the rigid foam composite polyether polyol prepared by the method as a cross-linking agent/chain extender has strong mechanical property and good dimensional stability.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, insofar as such terms are necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
Crosslinking agent
The cross-linking agent, also called curing agent, hardening agent and curing agent, can convert linear or slightly branched chain type macromolecules into three-dimensional network structure, so as to raise the properties of strength, heat resistance, wear resistance and solvent resistance, etc., and can be used for foamed or unfoamed products. The cross-linking agent is a substance which can play a bridging role between linear molecules, thereby enabling a plurality of linear molecules to be mutually bonded and cross-linked into a net structure, and promoting or regulating the formation of covalent bonds or ionic bonds between polymer molecular chains.
Crosslinking agents are mainly used in high molecular materials (rubbers and thermosetting resins). Because the molecular structure of the high molecular material is like a long line, the high molecular material has low strength when not crosslinked, is easy to break and has no elasticity, the crosslinking agent has the function of generating chemical bonds among linear molecules so as to ensure that the linear molecules are mutually connected to form a net structure, thereby improving the strength and the elasticity of the rubber.
Chain extender
The chain extender, also called chain extender, is a substance that can react with functional groups on the linear polymer chain to extend the molecular chain and increase the molecular weight. Is often used for improving the mechanical property and the processing property of products such as polyurethane, polyester and the like.
The preparation method of the rigid foam composite polyether polyol comprises the steps of introducing propylene oxide gradually into polyether polyol mixed initiator and polyether polyol synthesis catalyst KOH which accounts for 0.2-0.25% of the total mass of the polyether polyol mixed initiator and epoxy compound under the conditions that the reaction temperature is 80-135 ℃ and the reaction pressure is not more than 0.4Mpa to enable the propylene oxide to generate ring-opening polymerization reaction, and obtaining the composite polyether polyol; the polyether polyol mixed initiator comprises polyether triol taking glycerol as an initiator and having a molecular weight of about 500 and polyether diol taking propylene glycol as an initiator and having a molecular weight of about 400, wherein the mass ratio of the polyether triol to the polyether diol is (3-6): 1, and the mass ratio of the propylene oxide to the polyether polyol mixed initiator is (4.2-5.3): 1.
In some embodiments, the polyether polyol blend initiator may also include other polyether compositions not limited to polyether diols and polyether triols.
In some embodiments, the molecular weight of the glycerol-initiated polyether triol is 350-450, and the molecular weight of the propylene glycol-initiated polyether diol is 450-550.
In some embodiments, the method of preparing the rigid foam syntactic polyether polyol is performed according to the following steps:
(1) adding a polyether polyol mixed initiator and a polyether polyol synthesis catalyst into a reaction kettle, mixing, starting stirring under the condition of negative pressure, and heating to 80-90 ℃;
(2) heating is suspended, a first part of epoxy compound is rapidly added into the reaction kettle, and the reaction temperature is controlled to be 80-90 ℃, wherein the first part of epoxy compound accounts for 30-40% of the total amount of the epoxy compound;
(3) adding a second part of epoxy compound in a continuous feeding or batch feeding manner, and carrying out polymerization reaction at the temperature of 90-105 ℃ and under the reaction pressure of not more than 0.4MPa, wherein when batch feeding is adopted, the feeding amount of each batch is 6-10% of the total amount of the propylene oxide;
(4) maintaining the reaction temperature within the range of 100-135 ℃ for curing until the pressure is not changed;
(5) and (4) carrying out refining treatment of neutralization, dehydration and filtration cooling.
In some embodiments, the polyether polyol mixed initiator and the polyether polyol synthesis catalyst are subjected to dehydration and drying treatment before reaction; and after adding the polyether polyol mixed initiator and the polyether polyol synthetic catalyst into a reaction kettle for mixing, introducing inert gas and performing positive-negative pressure alternate displacement for at least two times to ensure the anhydrous and anaerobic reaction conditions of the system. Finally, under the condition of negative pressure, for example-0.1 mPa, starting stirring and heating to 80-90 ℃. In some embodiments, the inert gas may be nitrogen or argon.
In some embodiments, after the temperature of the polyether polyol mixing initiator and polyether polyol synthesis catalyst mixture reaches about 80 ℃, the heating is stopped and a first portion of the epoxy compound is rapidly added to the reaction vessel. The first part of propylene oxide is pre-dripped before feeding, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, when the temperature rises and the pressure drops, the material starts to react, the epoxy compound is continuously fed, and the reaction temperature is controlled to be 80-90 ℃.
In some embodiments, after the temperature reaches 90 ℃, propylene oxide is continuously added, the propylene oxide is slowly fed in the early stage, the temperature is raised by using the reaction heat, and the reaction temperature is controlled to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa.
In some embodiments, the reaction temperature is maintained for maturation until the pressure will not be. In the process, the curing process is divided into two parts: the temperature of the early curing is controlled within the range of 100-115 ℃, and the temperature of the later curing is controlled within the range of 120-135 ℃.
In some embodiments, after the reaction is completed, the product is subjected to a purification treatment such as neutralization, dehydration, temperature reduction and filtration. The neutralization process comprises the steps of adding water, preferably soft water, stirring for 40-80 minutes, preferably 60 minutes, at a temperature of 80-90 ℃, continuously adding phosphoric acid (the adding amount is calculated according to the molar ratio of 1: 1 of the phosphoric acid to potassium hydroxide), stirring for 80-100 minutes, preferably 90 minutes, at a temperature of 80-90 ℃, adding an adsorbent, stirring for 50-80 minutes, preferably 60 minutes, heating to 110-120 ℃, dehydrating for 4-8 hours, preferably 6 hours, finally cooling, filtering, discharging after the materials are qualified.
In a preferred embodiment, several polyethers are combined together as a mixed starter to prepare a complex polyether polyol, comprising the steps of:
(1) adding dehydrated and dried polyether triol, polyether diol and catalyst potassium hydroxide accounting for 0.2-0.25% of the total mass of reactants into a reaction container, alternately replacing twice under negative pressure and positive pressure, finally, under the condition of negative pressure, starting stirring and heating to 80-90 ℃, stopping heating after reaching about 80 ℃, and starting to feed propylene oxide.
(2) Pre-dripping propylene oxide before feeding, stopping feeding when the pressure in the reaction kettle reaches positive pressure, observing the reaction condition, leading the temperature to rise, indicating that the materials start to react when the pressure drops, and then continuing to feed propylene oxide, wherein the temperature is controlled to be 80-90 ℃.
(3) And when the temperature reaches 90 ℃, continuously feeding propylene oxide, slowly feeding the propylene oxide at the early stage, raising the temperature by utilizing reaction heat, and controlling the reaction temperature to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa.
(4) Maintaining the reaction temperature for curing until the pressure is not changed, wherein in the process, the early curing temperature is controlled within the range of 100-115 ℃, and the later curing temperature is controlled within the range of 120-135 ℃.
(5) Adding soft water, stirring at 80-90 deg.C for 60min, adding phosphoric acid, and stirring at 80-90 deg.C for 90 min. Adding adsorbents FR-6 and FR-7, stirring for 60min, heating to 110-.
The rigid foam plastic produced by using the rigid foam composite polyether polyol prepared by the method as a cross-linking agent/chain extender has strong mechanical property and good dimensional stability.
Examples
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The raw materials used are as follows:
the initiator is polyether glycol of propylene glycol, the molecular weight is 400, and polyurethane is produced.
The initiator is polyether triol of glycerin, the molecular weight is 500, and polyurethane is produced.
The adsorbents are FR-6 and FR-7 (available from Hubei Zhaoyang chemical Co., Ltd.).
Test and assay methods:
OH value: determined according to DIN 53240.
Viscosity: the dynamic viscosity is generally determined by means of a rotary viscometer in accordance with DIN 53019.
Example 1
76g of dehydrated and dried polyether diol (molecular weight is 400, I am self-produced), wherein the initiator in the polyether diol is propylene glycol, 228g of dehydrated and dried polyether triol (molecular weight is 500, I am self-produced) wherein the initiator in the polyether triol is glycerol are respectively added into a reaction kettle, 3g of potassium hydroxide catalyst is added, negative pressure and positive pressure are alternately replaced for two times, finally, under the condition that the negative pressure is-0.1 MPa, stirring is started, the temperature is raised to 80 ℃ while stirring, heating is suspended, then propylene oxide is rapidly added into the reaction kettle, and the preset amount of the propylene oxide is one third of the total amount of the whole propylene oxide. Pre-dripping is carried out before propylene oxide is fed, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, the temperature rises, when the pressure drops, the material starts to react, propylene oxide is fed continuously, and the temperature is controlled to be 80-90 ℃. And when the temperature reaches 90 ℃, continuously feeding PO, slowly feeding in the early stage, raising the temperature by using reaction heat, and controlling the reaction temperature to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa. Maintaining the reaction temperature for curing until the pressure is not changed, wherein in the process, the early curing temperature is controlled within the range of 100-115 ℃, and the later curing temperature is controlled within the range of 120-135 ℃. Adding soft water, stirring at 80-90 deg.C for 60min, adding phosphoric acid (the amount of phosphoric acid is 1: 1 mol ratio to potassium hydroxide), and stirring at 80-90 deg.C for 90 min. Adding adsorbents FR-6 and FR-7, stirring for 60min, heating to 110-.
Example 2
76g of dehydrated and dried polyether diol (molecular weight is 400, I am self-produced), wherein the initiator in the polyether diol is propylene glycol, 298g of dehydrated and dried polyether triol (molecular weight is 500, I am self-produced), wherein the initiator in the polyether triol is glycerol, are respectively added into a reaction kettle, 4g of potassium hydroxide catalyst is added, negative pressure and positive pressure are alternately replaced for two times, finally, under the condition that the negative pressure is-0.1 MPa, stirring is started, the temperature is raised to 80 ℃ while stirring, heating is suspended, then propylene oxide is rapidly added into the reaction kettle, and the preset amount of the propylene oxide is one third of the total amount of the whole propylene oxide. Pre-dripping is carried out before propylene oxide is fed, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, the temperature rises, when the pressure drops, the material starts to react, propylene oxide is fed continuously, and the temperature is controlled to be 80-90 ℃. And when the temperature reaches 90 ℃, continuously feeding PO, slowly feeding in the early stage, raising the temperature by using reaction heat, and controlling the reaction temperature to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa. Maintaining the reaction temperature for curing until the pressure is not changed, wherein in the process, the early curing temperature is controlled within the range of 100-115 ℃, and the later curing temperature is controlled within the range of 120-135 ℃. Adding soft water, stirring at 80-90 deg.C for 60min, adding phosphoric acid (the amount of phosphoric acid is 1: 1 mol ratio to potassium hydroxide), and stirring at 80-90 deg.C for 90 min. Adding adsorbents FR-6 and FR-7, stirring for 60min, heating to 110-.
Example 3
76g of dehydrated and dried polyether diol (molecular weight is 400, I am self-produced), wherein the initiator in the polyether diol is propylene glycol, 368g of dehydrated and dried polyether triol (molecular weight is 500, I am self-produced), wherein the initiator in the polyether triol is glycerol, are respectively added into a reaction kettle, 5g of potassium hydroxide catalyst is added, negative pressure and positive pressure are alternately replaced for two times, finally, under the condition that the negative pressure is-0.1 MPa, stirring is started, the temperature is raised to 80 ℃ while stirring, heating is suspended, then propylene oxide is rapidly added into the reaction kettle, and the preset amount of the propylene oxide is one third of the total amount of the whole propylene oxide. Pre-dripping is carried out before propylene oxide is fed, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, the temperature rises, when the pressure drops, the material starts to react, propylene oxide is fed continuously, and the temperature is controlled to be 80-90 ℃. And when the temperature reaches 90 ℃, continuously feeding PO, slowly feeding in the early stage, raising the temperature by using reaction heat, and controlling the reaction temperature to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa. Maintaining the reaction temperature for curing until the pressure is not changed, wherein in the process, the early curing temperature is controlled within the range of 100-115 ℃, and the later curing temperature is controlled within the range of 120-135 ℃. Adding soft water, stirring at 80-90 deg.C for 60min, adding phosphoric acid (the amount of phosphoric acid is 1: 1 mol ratio to potassium hydroxide), and stirring at 80-90 deg.C for 90 min. Adding adsorbents FR-6 and FR-7, stirring for 60min, heating to 110-.
Example 4
76g of dehydrated and dried polyether diol (molecular weight is 400, I am self-produced), wherein the initiator in the polyether diol is propylene glycol, 438g of dehydrated and dried polyether triol (molecular weight is 500, I am self-produced), wherein the initiator in the polyether triol is glycerol, are respectively added into a reaction kettle, 6g of potassium hydroxide catalyst is added, negative pressure and positive pressure are alternately replaced for two times, finally, under the condition that the negative pressure is-0.1 MPa, stirring is started, the temperature is raised to 80 ℃ while stirring, heating is suspended, then propylene oxide is rapidly added into the reaction kettle, and the preset amount of the propylene oxide is one third of the total amount of the whole propylene oxide. Pre-dripping is carried out before propylene oxide is fed, feeding is suspended when the pressure in the reaction kettle reaches positive pressure, the reaction condition is observed, the temperature rises, when the pressure drops, the material starts to react, propylene oxide is fed continuously, and the temperature is controlled to be 80-90 ℃. And when the temperature reaches 90 ℃, continuously feeding PO, slowly feeding in the early stage, raising the temperature by using reaction heat, and controlling the reaction temperature to be 90-105 ℃. The propylene oxide feed was then for about 5 hours. And starting the external circulating pump after the feeding is finished. The temperature is raised by the reaction heat of the materials as much as possible, and heating is not needed, so that local overheating is prevented, and the color depth is prevented. In the reaction process of the materials, the pressure is not more than 0.4 MPa. Maintaining the reaction temperature for curing until the pressure is not changed, wherein in the process, the early curing temperature is controlled within the range of 100-115 ℃, and the later curing temperature is controlled within the range of 120-135 ℃. Adding soft water, stirring at 80-90 deg.C for 60min, adding phosphoric acid (the amount of phosphoric acid is 1: 1 mol ratio to potassium hydroxide), and stirring at 80-90 deg.C for 90 min. Adding adsorbents FR-6 and FR-7, stirring for 60min, heating to 110-.
The test results are collated in Table 1:
TABLE 1 formulation and Properties of the composite polyether polyol of the examples
| Detecting items | Example 1 | Example 2 | Example 3 | Example 3 |
| Polyether glycol (g) | 76 | 76 | 76 | 76 |
| Polyether triol (g) | 228 | 298 | 368 | 438 |
| Hydroxyl value (mgKOH/g) | 324.7 | 331.8 | 338.9 | 346.7 |
| Viscosity (mPa. s) | 213.8 | 223.6 | 242.5 | 246.2 |
The prepared composite polyether polyol has a hydroxyl value ranging from 300-360mgKOH/g and a viscosity ranging from 200-260 mPa.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (8)
1. A preparation method of rigid foam composite polyether polyol is characterized by comprising the following steps: gradually introducing an epoxy compound into a polyether polyol mixed initiator and a polyether polyol synthesis catalyst under the conditions that the reaction temperature is 80-135 ℃ and the reaction pressure is not more than 0.4Mpa, and carrying out ring-opening polymerization reaction on the epoxy compound to obtain the composite polyether polyol; the polyether polyol mixed initiator comprises polyether triol taking glycerol as an initiator and polyether diol taking propylene glycol as an initiator, wherein the molecular weight of the polyether triol taking glycerol as the initiator is 450-550, and the molecular weight of the polyether diol taking propylene glycol as the initiator is 350-450; the mass ratio of the polyether triol to the polyether diol is (3-6) to 1; the epoxy compound is propylene oxide, and the mass ratio of the propylene oxide to the polyether polyol mixed initiator is (4.2-5.3): 1.
2. The method of claim 1, wherein: the polyether polyol synthesis catalyst is potassium hydroxide, and the dosage of the polyether polyol synthesis catalyst accounts for 0.2-0.25% of the total mass of the polyether polyol mixed initiator and the epoxy compound.
3. A process according to any one of claims 1 to 2, wherein the process is carried out according to the following steps:
adding the polyether polyol mixed initiator and the polyether polyol synthesis catalyst into a reaction kettle, mixing, starting stirring under the condition of negative pressure, and heating to 80-90 ℃;
quickly adding a first part of the epoxy compound into the reaction kettle, and controlling the reaction temperature to be 80-90 ℃, wherein the first part of the epoxy compound accounts for 30-40% of the total amount of the epoxy compound;
adding a second part of the epoxy compound in a continuous feeding mode or a batch feeding mode, and carrying out polymerization reaction at the temperature of 90-105 ℃ and the reaction pressure of not more than 0.4MPa, wherein when batch feeding is adopted, the feeding amount of each batch is 6-10% of the total amount of the second part of the epoxy compound;
maintaining the reaction temperature within the range of 100-135 ℃ for curing until the pressure is not changed any more; and
and (4) carrying out refining treatment comprising the steps of neutralization, dehydration, filtration and cooling.
4. The method of claim 3, wherein: the polyether polyol mixed initiator and the polyether polyol synthetic catalyst need to be dehydrated and dried before reaction; and/or after the reaction kettle is added, introducing inert gas and alternately replacing at least two times by positive pressure and negative pressure to ensure the anhydrous and anaerobic reaction conditions of the system.
5. The method of claim 3, wherein: the first portion of propylene oxide was pre-dripped prior to feeding and resumed as the temperature increased and the pressure decreased.
6. The method of claim 3, wherein: the curing process is divided into two parts, wherein the temperature of the early curing is controlled within the range of 100-115 ℃, and the temperature of the later curing is controlled within the range of 120-135 ℃.
7. The method of claim 3, wherein: the neutralization treatment comprises the steps of adding water, stirring for 40-80 minutes at the temperature of 80-90 ℃, and continuously adding phosphoric acid, stirring for 80-100 minutes at the temperature of 80-90 ℃; and/or, the dehydration comprises adding an adsorbent, stirring for 50-80 minutes, heating to 110-120 ℃, and dehydrating for 4-8 hours.
8. A rigid foam syntactic polyether polyol prepared by the process of any one of claims 1-7.
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| CN109485843B (en) * | 2018-09-11 | 2021-03-09 | 万华化学（宁波）容威聚氨酯有限公司 | Amino polyether polyol and preparation method thereof, and polyurethane rigid foam and preparation method thereof |
| CN109266295A (en) * | 2018-09-28 | 2019-01-25 | 淮南宏阳工贸有限责任公司 | A kind of polymer moisture-proof sealing agent |
| CN109485844A (en) * | 2018-11-27 | 2019-03-19 | 山东蓝星东大有限公司 | The preparation method of high activity high molecular polyether polyol polyalcohol |
| CN109762158A (en) * | 2018-12-14 | 2019-05-17 | 上海东大化学有限公司 | A kind of polyether polyol and preparation method thereof |
| CN110423339A (en) * | 2019-08-26 | 2019-11-08 | 上海东大化学有限公司 | A kind of water soluble polyether polyols, polyurethane foam and preparation method thereof |
| CN115141342B (en) * | 2022-05-24 | 2023-08-04 | 佳化化学科技发展（上海）有限公司 | Polyether composition for polyurethane rigid foam, and preparation method and application thereof |
| CN115991866A (en) * | 2022-11-30 | 2023-04-21 | 惠州市红墙化学有限公司 | Preparation method of polyether for polyurethane semi-rigid foam |
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| CN106832248A (en) * | 2017-01-23 | 2017-06-13 | 山东诺威新材料有限公司 | The preparation method of fast demoulding rigid-foam polyether polyol |
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| CN106832248A (en) * | 2017-01-23 | 2017-06-13 | 山东诺威新材料有限公司 | The preparation method of fast demoulding rigid-foam polyether polyol |
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