CN109400839B - Flame-retardant combined polyether, flame-retardant polyisocyanurate foam and preparation method thereof - Google Patents
Flame-retardant combined polyether, flame-retardant polyisocyanurate foam and preparation method thereof Download PDFInfo
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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
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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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
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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Abstract
The application relates to flame-retardant combined polyether which is prepared from the following raw materials in parts by weight: 15-30 parts of polyether polyol, 50-75 parts of first polyester polyol, 10-20 parts of second polyester polyol, 3.0-5.0 parts of surfactant, 0.5-1.0 part of first catalyst, 1.0-2.0 parts of second catalyst, 1.0-2.0 parts of third catalyst, 25-40 parts of flame retardant, 1.0-1.5 parts of chemical foaming agent, 2.6-3.6 parts of additive and 13-18 parts of physical foaming agent; wherein the sum of the use amounts of the polyether polyol, the first polyester polyol and the second polyester polyol is 100 parts; wherein the first polyester polyol and the second polyester polyol are aromatic polyester polyols with flame retardant structures, and the additive is aliphatic ketone. The application also provides a flame-retardant polyisocyanurate foam and a preparation method thereof, wherein the flame-retardant polyisocyanurate foam is prepared from a first component and a second component, wherein the first component is formed by mixing the raw material components of the flame-retardant combined polyether; the second component is polymethylene polyphenyl polyisocyanate.
Description
Technical Field
The application relates to the technical field of chemical synthesis, in particular to a flame-retardant combined polyether, flame-retardant polyisocyanurate foam derived from the flame-retardant combined polyether and a preparation method of the flame-retardant polyisocyanurate foam.
Background
The polyurethane material is a heat-insulating material with excellent performance, has low heat conductivity coefficient, good weather resistance and better cohesiveness and corrosion resistance than other heat-insulating materials, and is widely popularized in the heat-insulating fields of household appliances, buildings, chemical pipelines and the like in China at present. However, with the improvement of the fire-retardant rating of the heat-insulating material in China, the defect of low fire resistance of the polyurethane material is gradually reflected, and as an organic heat-insulating material, the highest fire resistance of the polyurethane material can only reach the B2 rating, and the polyurethane material is far from the A-level fire resistance of a common inorganic heat-insulating material.
Aiming at the defect that the flame retardant property of a polyurethane material is not high, a polyisocyanurate material is developed, the polyisocyanurate material is a modified material of the polyurethane material, the flame retardant property can reach more than B1 grade by introducing a large number of benzene ring structures, and the polyisocyanurate material can also reach more than A grade by compounding materials such as steel plates, cement fiber cloth and the like. Therefore, the advantages of the polyisocyanurate material are gradually reflected, compared with an inorganic heat-insulating material, the same heat-insulating effect is achieved, only 1/2-1/3 of the thickness of the heat-insulating layer is needed, the construction is simpler and more convenient, the material waste is low, and the polyisocyanurate heat-insulating material is popularized and used in a large scale in a plurality of provinces of China.
The mainstream blowing agents currently used in polyisocyanurate include HCFC-141b, HFC-245fa, HFC-365mfc, pentane, etc. HCFC-141b has been largely banned in the industry because of its greater ozone depletion potential. HFC-245fa and HFC-365mfc have an Ozone Depletion Potential (ODP) of 0 and a Global Warming Potential (GWP) of 820 and 840, respectively, are transition products and also face replacement problems.
In the current mainstream foaming agent with zero ODP value and low GWP value, pentane is flammable and explosive, has high danger and high thermal conductivity, and the prepared foam has poor flame retardant property and large use limitation. Water has a very high thermal conductivity and is used in a large amount compared to other systems using physical blowing agents, and is used only in individual industries. Fourth generation blowing agents such as LBA from HONEWEIRE, or Opteon1100 from Kemu, are currently produced in very small scale and are expensive and not widely available. The boiling point and the solubility of the methyl formate are very close to those of HCFC-141b, the cost is low, and the methyl formate does not contain Volatile Organic Compounds (VOC), so that the methyl formate is an ideal foaming agent substitute at present.
However, the biggest problem influencing the use of the methyl formate is that the methyl formate is very easy to hydrolyze in a combined polyether system to generate formic acid and methanol, and the formic acid and an amine catalyst undergo an irreversible chemical reaction, so that the reaction activity of raw materials is slow, the density of products is increased, and the storage time of the system is shortened. Even in a product system, the slow hydrolysis can occur, hydrolysis products formic acid and methanol have a large dissolving effect on a foam product, and the phenomena of foam shrinkage, great reduction of product compressive strength and the like can occur within three months. The problem of hydrolysis of methyl formate and the dissolution effect on foam products is solved, and the problem is the greatest difficulty in application of the methyl formate foaming agent.
For this reason, there is an urgent need in the art to develop a flame retardant conjugate polyether, a flame retardant polyisocyanurate foam and a method for preparing the same, which can effectively inhibit the hydrolysis of methyl formate.
Disclosure of Invention
In the existing methyl formate foaming solution, the problem of methyl formate hydrolysis is generally solved by using a special catalyst and reducing the using amount of methyl formate, but the problem cannot be completely solved in practical application, the storage stability still occurs in about 10 days at most in summer, the deterioration still occurs, the dissolving effect of a foam product still exists, and the use is very limited.
The application aims to provide the flame-retardant combined polyether capable of effectively inhibiting the hydrolysis of methyl formate, so as to solve the problems in the prior art. According to the application, the methyl formate is dissolved in the special additive, so that the hydrolysis condition of the methyl formate is reduced, a good use effect is obtained, the quality guarantee period can be prolonged to more than 90 days, and the special additive can be suitable for production of most customers. At the same time, the dissolution effect in the foamed article is considerably improved, the article remaining substantially without a decrease in properties after standing for up to 1 year. Both of the foregoing problems have been solved well and the late spread of methyl formate blowing agents in polyisocyanurate systems will be much more successful.
It is also an object of the present application to provide a flame retarded polyisocyanurate foam derived from the flame retarded conjugate polyether.
It is also an object of the present application to provide a process for preparing flame-retardant polyisocyanurate foams.
In order to achieve the above object, the present application provides the following technical solutions.
In a first aspect, the present application provides a flame-retardant conjugate polyether, which is prepared from the following raw material components in parts by weight:
wherein the sum of the use amounts of the polyether polyol, the first polyester polyol and the second polyester polyol is 100 parts;
wherein the first polyester polyol and the second polyester polyol are aromatic polyester polyols with a flame retardant structure;
wherein the additive comprises an aliphatic ketone.
In one embodiment of the first aspect, the additive is methyl ethyl ketone.
In one embodiment of the first aspect, the polyether polyol is a halogenated polyether polyol having a functionality of 3, a hydroxyl value of 320 to 340mgKOH/g, and a viscosity of 6000 to 8000mPa · s;
and/or the first polyester polyol is an aromatic polyester polyol with a flame-retardant structure, the functionality of the aromatic polyester polyol is 2-2.5, the hydroxyl value is 280-310 mgKOH/g, and the viscosity is 5000-9000 mPa & s;
and/or the second polyester polyol is an aromatic polyester polyol with a flame-retardant structure, and the second polyester polyol has the functionality of 2.5-3, the hydroxyl value of 390-420 mgKOH/g and the viscosity of 6300-9300 mPa & s.
In one embodiment of the first aspect, the surfactant comprises a foam stabilizer;
and/or, the first catalyst is an amine catalyst;
and/or, the second catalyst is a metal-based catalyst;
and/or, the third catalyst is a trimerization catalyst;
and/or the flame retardant is a chlorine flame retardant and/or a phosphorus flame retardant commonly used for polyurethane;
and/or, the chemical blowing agent is water;
and/or, the physical blowing agent comprises methyl formate.
In one embodiment of the first aspect, the first polyether polyol is polyether polyol Ixol B251, manufactured by suwei fluorochemicals, inc;
and/or the first polyester polyol is polyester polyol PS-3158 of Nanjing Jinling Spodopan chemical company, Inc.;
and/or the second polyester polyol is polyester polyol PS-4027 of Nanjing Jinling Spandel chemical company Limited;
and/or the first catalyst is Polycat 15 produced by air chemical products company;
and/or the second catalyst is Dabco K15 and/or Polycat 46 produced by air chemical products company;
and/or the third catalyst is Dabco TMR-30 produced by air chemical products company;
and/or the foam stabilizer is L-6900 produced by Michigan advanced materials (China) and/or AK-8825 produced by Jiangsu Messide chemical Co., Ltd;
and/or the flame retardant is tri (2-chloropropyl) phosphate and/or diethyl ethylphosphate;
and/or the water comprises deionized water.
In a second aspect, the present application provides a flame-retardant polyisocyanurate foam made of a first component and a second component, wherein the first component is formed by mixing the raw material components of the flame-retardant conjugate polyether according to the first aspect; the second component is polymethylene polyphenyl polyisocyanate.
In one embodiment of the second aspect, the second component is PM200, PM400, manufactured by hattai warfarin polyurethane gmbh; 44V20 from Bayer corporation, and M20S from Pasteur Gregorian corporation.
In one embodiment of the second aspect, the weight ratio of the first component to the second component is 1:1.5 to 1.7.
In one embodiment of the second aspect, the flame retardant polyisocyanurate foam achieves a flame retardant performance of grade B1 when tested according to the national standard GB/T8624 and 2012 classification of building materials and articles of fire performance.
In a third aspect, the present application provides a method for preparing the flame-retardant polyisocyanurate foam according to the second aspect, the method comprising mixing the first component and the second component in a predetermined weight ratio, and obtaining the flame-retardant polyisocyanurate foam after constant-temperature foaming.
In one embodiment of the third aspect, the foaming temperature for the constant temperature foaming is 55 ℃ to 65 ℃.
Compared with the prior art, the method has the advantages that the hydrolysis condition of methyl formate in a polyisocyanurate combined polyether system is solved, the quality guarantee period can be prolonged to more than 90 days, meanwhile, the produced foam product is free of shrinkage, deformation and the like, the flame retardant property reaches B1 level, the popularization of methyl formate in the combined polyether system for household appliances is facilitated, the safety and the physical property of the composite polyether system are superior to those of a pentane system, the comprehensive cost is much lower than that of HFC and HFO foaming agents, the ODP, GWP and VOC values are zero, and the environmental protection property is also optimal in all foaming agents.
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. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.
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, except those 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.
In one embodiment, the present application provides a flame retardant conjugate polyether.
The flame-retardant combined polyether comprises the following components in parts by mass, wherein the total of polyether polyol, first polyester polyol and second polyester polyol is 100 parts:
in one embodiment, the flame retardant conjugate polyether of the present application includes a second polyether polyol. Polyether polyols suitable for the purposes of this application include, but are not limited to, products obtained by polymerizing an epoxide such as ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran in the presence of a polyfunctional initiator. Suitable initiators contain a plurality of active hydrogen atoms, specific examples of which include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, aniline, diphenylmethane diamine, ethylene diamine, cyclohexane dimethanol, resorcinol, bisphenol a, glycerol, trimethylolpropane, 1,2, 6-hexanetriol, pentaerythritol, or combinations thereof.
In one embodiment, the polyether polyol is preferably a halogenated polyether polyol having a functionality of 3, a hydroxyl number of 320 to 340mgKOH/g, a viscosity of 6000 to 8000mPa · s, and is typically the polyether polyol Ixol B251 from Suwei fluorochemical Co. Ixol B251 is a halogenated aliphatic polyether triol whose major component is a mixture of an epichlorohydrin-based polyol (sold under the trademark Ixol B350 by solvay fluor) and a small amount of triethyl phosphate.
In one embodiment, the flame retardant conjugate polyether of the present application further comprises an aromatic polyester polyol having a flame retardant structure. The aromatic polyester polyol refers to a polyester polyol containing a benzene ring, and is generally synthesized from an aromatic dibasic acid (or anhydride, ester) and a diol (and/or polyol) as raw materials. The raw material of the polyester is generally phthalic anhydride or terephthalic acid, and the commonly used diol raw material is diethylene glycol, trihydric alcohol, etc.
In one embodiment, the first polyester polyol is an aromatic polyester polyol with a flame retardant structure, the functionality of the aromatic polyester polyol is 2-2.5, the hydroxyl value is 280-310 mgKOH/g, the viscosity is 5000-9000 mPa · s, and the aromatic polyester polyol is a polyester polyol PS-3158 of Nanjing Jinlingstapane chemical company Limited.
In one embodiment, the second polyester polyol is an aromatic polyester polyol with a flame retardant structure, and has a functionality of 2.5-3, a hydroxyl value of 390-420 mgKOH/g, a viscosity of 6300-9300 mPa · s, and a typical type of PS-4027 polyester polyol from Nanjing Jinlingstapane chemical Limited.
The flame retardant conjugate polyethers of the present application also include surfactants that generally support homogenization of the blowing agent and polyol and regulate the cell structure of the polyisocyanurate foam. The surfactant may comprise any suitable surfactant or mixture of surfactants known in the art.
In one embodiment, the surfactant herein comprises a foam stabilizer. The foam stabilizer is a siloxane foam stabilizer, preferably L-6900 of Mitigo advanced materials (China) Co., Ltd and/or AK-8825 of Jiangsu Messide chemical Co., Ltd.
In one embodiment, the flame retardant conjugate polyether described herein further comprises a catalyst composition. Catalysts are typically used to catalyze the reaction between the isocyanate and the polyol and are not consumed in the reaction. In one embodiment, the flame retardant conjugate polyether of the present application comprises at least a first catalyst, a second catalyst, and a third catalyst. The first catalyst is an amine catalyst commonly used in the field of polyurethane, and is preferably Polycat 15 (manufactured by air chemical products). The second catalyst is a metal catalyst commonly used in polyurethane, and Dabco K15 (manufactured by air chemical products company) and/or Polycat 46 (manufactured by air chemical products company) are preferred in the application. The third catalyst is a trimerization catalyst commonly used in polyurethane, and Dabco TMR-30 (manufactured by air chemical products) is preferred in the present application.
In one embodiment, the flame retardant conjugate polyether of the present application further comprises a flame retardant. The flame retardant is a common chlorine-based flame retardant and/or phosphorus-based flame retardant for polyurethane, preferably tris (2-chloropropyl) phosphate (TCPP) and/or diethyl ethylphosphate (DEEP).
In one embodiment, the flame retardant conjugate polyether of the present application further comprises an additive. The additive may be used as a solvent for dissolving methyl formate and inhibiting hydrolysis of methyl formate. In one embodiment, the additives described herein are aliphatic ketones, including but not limited to butanone, pentanone, neopentanone, cyclohexanone, and the like. In a particularly preferred embodiment, the additive described herein is butanone.
In one embodiment, the flame retardant co-polyether compositions of the present application may optionally further comprise other conventional additives including, but not limited to, chain extenders, chain terminators, processing aids, adhesion promoters, antioxidants, defoamers, water scavengers, molecular sieves, ultraviolet light stabilizers, fillers, thixotropic agents, colorants, inert diluents, or combinations thereof.
The flame retardant conjugate polyethers described herein may also include chemical and physical blowing agents. As used herein, the term "physical blowing agent" refers to a blowing agent that does not chemically react with either the isocyanate or the polyol. The physical blowing agent may be a gas or a liquid. Liquid physical blowing agents typically evaporate to a gas when heated and typically revert to a liquid when cooled. In one embodiment, the physical blowing agent described herein is methyl formate.
As used herein, the term "chemical blowing agent" refers to a blowing agent that chemically reacts with an isocyanate, polyol, or other component and releases a gas for foaming. In one embodiment, the chemical blowing agent described herein comprises water, particularly deionized water.
The application also provides a flame-retardant polyisocyanurate foam, which is synthesized by a series of chemical reactions after a first component and a second component are mixed according to a certain proportion through mechanical stirring. The first component is formed by mixing the raw material components of the flame-retardant combined polyether. The first component is formed by mechanically mixing polyether polyol, polyester polyol, a surfactant, a catalyst, an additive, a foaming agent and the like in a certain proportion; the second component is polymethylene polyphenyl polyisocyanate (PAPI).
The polymethylene polyphenyl polyisocyanate is polymethylene polyphenyl polyisocyanate commonly used in the field of polyurethane, such as PM200 and PM400 produced by Nicotiana Vanhua polyurethane GmbH, 44V20 produced by Bayer, M20S produced by Pasteur GmbH and the like. PM400 from Tantawa polyurethane, Inc. is preferred for this application.
The weight ratio of the first component to the second component is 1: 1.5-1.7.
The present application also provides a method for preparing the flame-retardant polyisocyanurate foam according to the second aspect, which comprises mixing the first component and the second component in a predetermined weight ratio, and foaming at a constant temperature to obtain the flame-retardant polyisocyanurate foam.
Examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. 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.
Examples 1 to 4 and comparative examples 1 to 2
First, the first components of examples 1 to 4 and comparative examples 1 to 2 were prepared according to the ingredients in the following table, and the parts shown in table 1 are parts by mass.
TABLE 1 first set of recipes for examples 1-4 and comparative examples 1-2
Pouring the raw materials except the PAPI into a reaction container according to a specified proportion, and uniformly mixing by using an electric stirrer to prepare a first component; and then regulating the temperature of the first component and the second component to 22 ℃, pouring the first component and the second component into a reaction container according to the corresponding weight proportion, stirring the mixture for 10 to 15 seconds by using an electric stirrer, pouring the uniformly mixed liquid into a mold with the constant temperature of 55 to 65 ℃ and the thickness of 12cm, closing the mold, standing the mold at the constant temperature of 60 ℃ for 25min, and opening the mold to obtain the polyisocyanurate heat-preservation foam.
The materials obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to a performance test, and the results are shown in Table 2 below. Performance test standard:
cream time, gel time, debonding time: visual inspection using a stopwatch;
free bubble density, molded bubble density: density testing of GB/T6343-95 polyurethane foams;
compressive strength: GB/T8813-;
coefficient of thermal conductivity: GB/T10295 and 2008 heat-insulating material steady-state thermal resistance and a heat flow meter method for measuring relevant characteristics;
dimensional stability: GB/T6342-1996 determination of linear dimensions of the foam and the rubber;
flame retardant property: GB/T8624-.
TABLE 2 results of the Performance test of examples 1 to 4 and comparative examples 1 to 2
As can be seen from Table 2, after the flame-retardant combined polyether prepared by the method is placed for 30 days, the reaction time and the free foam density are not greatly changed, the flame-retardant combined polyether can be stored and used for a long time, the volume change rate of the flame-retardant polyisocyanurate foam product prepared by the method is very small after the flame-retardant polyisocyanurate foam product is placed for 180 days at a low temperature, and the long-term performance stability of the product is ensured. Compared with the mainstream cyclopentane foaming system in the current market, the physical properties such as compression strength, thermal conductivity, dimensional stability, flame retardance and the like of the cyclopentane foaming system are better than those of the cyclopentane system, and the cyclopentane foaming system is higher in safety and has large-scale popularization value. The raw materials used in the application are all commercially available raw materials, are wide in source and can be produced in a large scale.
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 (9)
1. The flame-retardant combined polyether is prepared from the following raw materials in parts by weight:
15-30 parts of polyether polyol
50-75 parts of first polyester polyol
10-20 parts of second polyester polyol
3.0 to 5.0 portions of surfactant
0.5 to 1.0 portion of first catalyst
1.0 to 2.0 portions of second catalyst
1.0 to 2.0 portions of third catalyst
25-40 parts of flame retardant
1.0 to 1.5 portions of chemical foaming agent
2.6 to 3.6 portions of additive
13-18 parts of a physical foaming agent;
wherein the sum of the use amounts of the polyether polyol, the first polyester polyol and the second polyester polyol is 100 parts;
wherein the additive is butanone;
wherein the chemical blowing agent is water;
wherein the physical blowing agent comprises methyl formate;
wherein the polyether polyol is a halogenated polyether polyol, the functionality of the halogenated polyether polyol is 3, the hydroxyl value is 320-340 mgKOH/g, and the viscosity is 6000-8000 mPa & s;
wherein the first polyester polyol is polyester polyol PS-3158 of Nanjing Jinling Spodol chemical Co., Ltd;
wherein the second polyester polyol is polyester polyol PS-4027 of Nanjing Jinlingsi Span chemical Co.
2. The flame retardant conjugate polyether of claim 1, wherein the surfactant comprises a foam stabilizer;
the first catalyst is an amine catalyst;
the second catalyst is a metal catalyst;
the third catalyst is a trimerization catalyst;
the flame retardant is a common chlorine flame retardant and/or a common phosphorus flame retardant for polyurethane.
3. The flame retardant conjugate polyether of claim 2, wherein the polyether polyol is polyether polyol Ixol B251 manufactured by suwei fluorochemical ltd;
the first catalyst is Polycat 15 produced by air chemical products company;
the second catalyst is Dabco K15 and/or Polycat 46 produced by air chemical products company;
the third catalyst is Dabco TMR-30 produced by air chemical products company;
the foam stabilizer is L-6900 produced by Michigan high and new materials (China) and/or AK-8825 produced by Jiangsu Meiside chemical Co., Ltd;
the flame retardant is tri (2-chloropropyl) phosphate and/or ethyl diethyl phosphate;
the water includes deionized water.
4. A flame-retardant polyisocyanurate foam made of a first component and a second component, wherein the first component is formed by mixing the raw material components of the flame-retardant conjugate polyether as described in any one of claims 1 to 3; the second component is polymethylene polyphenyl polyisocyanate.
5. The flame-retarded polyisocyanurate foam according to claim 4, wherein said second component is PM200, PM400, produced by Tantawa polyurethane, Inc.; 44V20 from Bayer corporation, and M20S from Pasteur Gregorian corporation.
6. The flame-retarded polyisocyanurate foam according to claim 4, wherein the weight ratio of the first component to the second component is 1: 1.5-1.7.
7. The flame-retardant polyisocyanurate foam according to claim 4, wherein the flame-retardant polyisocyanurate foam has a flame-retardant property of class B1 when tested according to the national standard GB/T8624-2012 fire-retardant property classification for building materials and articles.
8. A process for preparing the flame retarded polyisocyanurate foam of claim 4 comprising mixing the first component and the second component in a predetermined weight ratio and foaming at constant temperature to obtain the flame retarded polyisocyanurate foam.
9. The method for preparing a flame-retardant polyisocyanurate foam according to claim 8, wherein the foaming temperature for the constant-temperature foaming is 55 ℃ to 65 ℃.
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| CN111808264A (en) * | 2020-07-23 | 2020-10-23 | 长虹美菱股份有限公司 | Polyurethane foaming raw material |
| CN113698568A (en) * | 2021-07-20 | 2021-11-26 | 佳化化学科技发展（上海）有限公司 | Combined polyether, polyisocyanurate foam, preparation method and application thereof |
| CN115536801B (en) * | 2022-09-23 | 2023-06-23 | 上海玓墨节能科技有限公司 | Cold-insulation high-flame-retardance spray-type rigid polyurethane foam and preparation method thereof |
| CN117510779A (en) * | 2023-11-30 | 2024-02-06 | 廊坊全振化工开发有限公司 | Combined polyether for polyisocyanurate shell, shell and preparation method |
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| US5336696A (en) * | 1993-12-10 | 1994-08-09 | Nisshinbo Industries, Inc. | Halogen-free blowing agents that include cycloaliphatic hydrocarbons and are suitable for isocyanate-based polymeric foams |
| US6329440B2 (en) * | 1998-05-09 | 2001-12-11 | Basf Aktiengesellschaft | Preparation of polyisocyanate polyaddition products |
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