CN113637136A - Mixed foaming agent combined polyether and polyurethane hard foam - Google Patents
Mixed foaming agent combined polyether and polyurethane hard foam Download PDFInfo
- Publication number
- CN113637136A CN113637136A CN202110841984.6A CN202110841984A CN113637136A CN 113637136 A CN113637136 A CN 113637136A CN 202110841984 A CN202110841984 A CN 202110841984A CN 113637136 A CN113637136 A CN 113637136A
- Authority
- CN
- China
- Prior art keywords
- parts
- polyester polyol
- catalyst
- polyether
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
-
- 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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- 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
- 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
- C08J9/125—Water, e.g. hydrated salts
-
- 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
- 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
- C08J9/141—Hydrocarbons
-
- 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
- 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
-
- 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
-
- 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
-
- 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
- C08J2203/10—Water or water-releasing compounds
-
- 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
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2203/20—Ternary blends of expanding agents
- C08J2203/202—Ternary blends of expanding agents of physical blowing agents
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a mixed foaming agent combined polyether and polyurethane hard foam, and belongs to the technical field of high polymer materials. The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 30-50 parts of polyester polyol I; 30-40 parts of polyester polyol II; 10-40 parts of polyester polyol III; 10-15 parts of a mixed foaming agent; 2.5-3.5 parts of a catalyst I; 1.5-2.0 parts of a catalyst II; 2.5-3.0 parts of foam stabilizer; 15-30 parts of a flame retardant; the total amount of the polyester polyols I, II and III is 100 parts. Zero DOP, low GWP, low cost and environmental protection; the invention also provides the polyurethane rigid foam prepared from the mixed foaming agent combined polyether, and the polyurethane rigid foam has the advantages of good dimensional stability, excellent mechanical property, low thermal conductivity, lower feeding density, high yield and better cost saving.
Description
Technical Field
The invention relates to a mixed foaming agent combined polyether and polyurethane hard foam, and belongs to the technical field of high polymer materials.
Background
The polyurethane rigid foam is a foam product prepared from polyol and isocyanate under the action of auxiliary agents such as a foaming agent, a catalyst and the like, has excellent thermal insulation performance and better mechanical property, simultaneously has excellent electrical property and chemical resistance, and is widely applied to the thermal insulation fields of refrigerators, freezers, water heaters, cold storage plates, pipeline thermal insulation, refrigerated containers, external wall thermal insulation and the like. The blowing agents currently used in the production of rigid polyurethane foams are mainly HCFC141b, cyclopentane and HFC-365 mfc. Three blowing agents each have disadvantages: when HCFC141B was used, there was a certain ODP (ozone depletion potential) and the Montreal protocol implemented complete industrial phase-out in 2026 for HCFC141 b. When cyclopentane is adopted, the output rate is low, the safety coefficient is low, and the dimensional stability is poor; when HFC-365mfc is used for preparing the foam, although the foam has low heat conductivity coefficient and better heat insulation performance, the safety coefficient is low, the cost is higher, and the cost of the prepared foam is obviously increased. For this reason, there is a need in the art to develop a blowing agent system that is low in cost, low in thermal conductivity, zero in ODP value, relatively high in safety factor, good in dimensional stability, excellent in mechanical properties, and high in squareness.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides the mixed foaming agent combined polyether which can reach zero DOP, low GWP, low cost and environmental protection; the invention also provides the polyurethane rigid foam prepared from the mixed foaming agent combined polyether, and the polyurethane rigid foam has the advantages of good dimensional stability, excellent mechanical property, low thermal conductivity, lower feeding density, high yield and better cost saving.
In order to achieve the purpose, the invention provides the following technical scheme:
the mixed foaming agent composite polyether is characterized by comprising the following raw materials in parts by weight:
30-50 parts of polyester polyol I;
30-40 parts of polyester polyol II;
10-40 parts of polyester polyol III;
10-15 parts of a mixed foaming agent;
2.5-3.5 parts of a catalyst I;
1.5-2.0 parts of a catalyst II;
2.5-3.0 parts of foam stabilizer;
15-30 parts of a flame retardant;
the total amount of the polyester polyols I, II and III is 100 parts;
the mixed foaming agent is a mixture of water, formic acid and n-pentane, and the mass ratio of the water to the formic acid to the n-pentane is (5-10): (7-12): (80-90);
the polyester polyol I is polyester polyol with the viscosity of 2500-4000mPa & s (detected at 25 ℃) and the hydroxyl value of 225-255mgKOH/g, and polyester 2412 of Nanjing Jinling Spandel chemical company Limited is adopted; or the company Ruinor chemical Co., Ltd PS 2412;
the polyester polyol II is polyester polyol with the viscosity of 10000-30000mPa & s (detected at 25 ℃) and the hydroxyl value of 170-205mgKOH/g, and polyester 1919A of Nanjing Jinling Spandel chemical company Limited is adopted; or the company PS3025 of ryinow chemical ltd;
the polyester polyol III is polyester polyol with the viscosity of 2000-4000mPa & s (detected at 25 ℃) and the hydroxyl value of 280-330mgKOH/g, and polyester 3152 of Nanjing Jinling Spandel chemical company Limited is adopted; or the company Reno chemical company PS 3152; or Nanguang polyester Co.Ltd 3152;
the catalyst I is a tertiary amine catalyst;
the catalyst I adopts any two or a mixture of more than two of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, triethylenediamine, tetramethylalkylenediamine, pentamethyldiethylenetriamine, triethylamine, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine and 2-hydroxy-N, N, N-trimethyl-1-propylamine formate;
the catalyst II is an organic metal salt catalyst;
the catalyst II adopts any one or a mixture of two of potassium isooctanoate, potassium oleate and potassium acetate;
the foam stabilizer has the main functions of increasing the intersolubility of all components of the combined polyether and stabilizing the cell structure, and adopts any one of the foam stabilizers of L-16268, L-6866 and L-16368 of a new material group in a Mianji diagram; or MG687 or B84813 originated from specialty Chemicals (Shanghai) Co., Ltd; or any one of foam stabilizers of AK8805, AK8806, AK8810, AK8811, and AK8818, which are available from Meissn Chemicals Ltd;
the flame retardant is one or a mixture of two of tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, tris (1, 3-dichloroisopropyl) phosphate or dimethyl methyl phosphate.
The rigid polyurethane foam is characterized by comprising a component A and a component B, wherein the component A is prepared by mixing the following components in a ratio of 1: (1.4-1.8), mixing and foaming, wherein the component A is the mixed foaming agent combined polyether, and the component B is isocyanate;
the isocyanate adopts PM200 or PM400 of Wanhua chemistry;
the mixed foaming adopts a high-pressure foaming machine, and the foaming temperature is controlled to be 20-25 ℃.
The invention has the advantages that: the mixed foaming agent composite polyether adopts the mixture of water, n-pentane and formic acidDOP, low GWP, ultra-low cost (the price is 1/6-1/4 of HCFC and HFC series common foaming agents), green and environment-friendly; the foaming agent involved in the invention is prepared by reacting water with isocyanate to generate substituted urea and carbon dioxide and release a large amount of heat; the formic acid reacts with the tertiary amine catalyst to form salt in the initial stage, the salt does not participate in the reaction in the initial stage, the salt releases tertiary amine to catalyze the reaction to be carried out at a high speed along with the violent heat release of the reaction, and meanwhile, the carboxylic acid reacts with isocyanate to generate amide and carbon dioxide and releases certain heat; the heat released by the two promotes the volatilization of the n-pentane, thereby promoting the foaming process of the polyurethane and increasing the foaming ratio. The polyurethane rigid foam has the advantages of good dimensional stability, excellent mechanical property and low thermal conductivity coefficient, and the polyurethane rigid foam has lower feeding density (2-3 kg/m lower than that of HCFC141b system)3) The formula ratio is high, the cost can be better saved, and the low hydroxyl value polyester is selected to ensure that the whole system has higher isocyanate index, thereby being beneficial to improving the strength of foam; the foaming agent adopts n-pentane and formic acid, the molecular weight of the foaming agent is less than that of HCFC141b, HFC-365mfc and the like, and the foaming ratio is better.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight:
241230 parts of Spandex polyester polyol, 30 parts of Spandex polyester polyol, 315240 parts of Spandex polyester polyol, 1.0 part of water, 1.3 parts of formic acid, 12 parts of N-pentane, 0.6 part of pentamethyl diethylene triamine, 0.4 part of N, N-dimethyl cyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.7 parts of potassium isooctanoate, 88051.2 parts of AK, 6871.5 parts of MG6871.5 parts of tris (2-chloropropyl) phosphate and 20 parts of tris (2-chloropropyl) phosphate.
The rigid polyurethane foam of this example includes component A comprising the mixed blowing agent and polyether polyol, and component B comprising 198.8 parts of isocyanate.
And uniformly mixing the component A and the component B, and reacting to prepare the polyurethane rigid foam. Specifically, the combined polyether of the combined foaming agent obtained in the embodiment and isocyanate are foamed in a high-pressure foaming machine by adopting a one-step foaming process, and the temperature is controlled to be 20-25 ℃.
Example 2
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: PS-241230 parts, RINOL polyester polyol 302540 parts, RINOL polyester polyol 315230 parts, water 0.95 part, formic acid 1.15 parts, N-pentane 12.5 parts, pentamethyldiethylenetriamine 0.6 part, N, N-dimethylcyclohexylamine 0.4 part, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate 2.2 parts, potassium isooctanoate 1.8 parts, AK 88051.2 parts, M6871.4 parts, and tris (2-chloroethyl) phosphate 20 parts.
The rigid polyurethane foam of this example includes an A component composed of the mixed blowing agent and the polyether composition, and a B component composed of 206.2 parts of isocyanate.
Example 3
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 241240 parts of reyno polyester polyol, 302530 parts of reyno polyester polyol, 315230 parts of reyno polyester polyol, 0.9 part of water, 1.1 parts of formic acid, 13 parts of N-pentane, 0.6 part of pentamethyl diethylene triamine, 0.4 part of N, N-dimethyl cyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium oleate, 88051.0 parts of AK, 162681.6 parts of L, and 20 parts of tris (1, 3-dichloroisopropyl) phosphate.
The rigid polyurethane foam of the embodiment comprises an A component consisting of the mixed foaming agent combined polyether and a B component consisting of 214 parts of isocyanate.
Example 4
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 241240 parts of Spilan polyester polyol, 1919A 40 parts of Spilan polyester polyol, 315220 parts of Nanguang polyester polyol, 0.95 part of water, 1.5 parts of formic acid, 11 parts of N-pentane, 0.65 part of bis (2-dimethylaminoethyl) ether, 0.5 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.75 parts of potassium isooctanoate, L163682.8 parts and 20 parts of tris (1, 3-dichloroisopropyl) phosphate.
The rigid polyurethane foam of the embodiment comprises an A component composed of the mixed foaming agent combined polyether and a B component composed of 226 parts of isocyanate.
Example 5
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 241250 parts of Spilan polyester polyol, 302530 parts of Renao polyester polyol, 315220 parts of Renao polyester polyol, 1.0 part of water, 1.35 parts of formic acid, 12 parts of N-pentane, 0.6 part of bis (2-dimethylaminoethyl) ether, 0.6 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium oleate, 6872.8 parts of MG and 20 parts of tris (1, 3-dichloroisopropyl) phosphate.
The rigid polyurethane foam of the embodiment comprises an A component composed of the mixed foaming agent combined polyether and a B component composed of 241.8 parts of isocyanate.
Example 6
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 241250 parts of Renao polyester polyol, 302540 parts of Renao polyester polyol, 315210 parts of Nanguang polyester polyol, 0.95 part of water, 1.45 parts of formic acid, 11 parts of N-pentane, 0.65 part of bis (2-dimethylaminoethyl) ether, 0.55 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium isooctanoate, 88111.0 parts of AK 88111.0 parts of L-68661.8 parts of dimethyl methyl phosphate and 20 parts of dimethyl methyl phosphate.
The rigid polyurethane foam of this example includes an A component composed of the mixed blowing agent and the polyether composition, and a B component composed of 255 parts of isocyanate.
The core density, the oxygen index, the thermal conductivity, the compressive strength, the drawing strength and the high and low temperature dimensional change rate of the foam are respectively determined according to national standards GB/T6343-. The following table compares the performance parameters of the rigid polyurethane foams obtained in examples 1 to 6 with those of the prior art:
as can be seen from the above examples and comparative tables, compared with the prior art (adopting HCFC141B/HFC245fa/HFC365 mfc/cyclopentane, etc.), the mixed foaming agent system of the invention has the advantages of lower foam preparation cost, larger foaming ratio, lower thermal conductivity, better heat preservation effect, better dimensional stability and excellent mechanical property.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The mixed foaming agent composite polyether is characterized by comprising the following raw materials in parts by weight:
30-50 parts of polyester polyol I;
30-40 parts of polyester polyol II;
10-40 parts of polyester polyol III;
10-15 parts of a mixed foaming agent;
2.5-3.5 parts of a catalyst I;
1.5-2.0 parts of a catalyst II;
2.5-3.0 parts of foam stabilizer;
15-30 parts of a flame retardant;
the total amount of the polyester polyols I, II and III is 100 parts.
2. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that the mixed blowing agent is a mixture of water, formic acid and n-pentane, the mass ratio of the three being (5-10): (7-12): (80-90).
3. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that
The polyester polyol I is polyester polyol with the viscosity of 2500-;
the polyester polyol II is polyester polyol with the viscosity of 10000-30000mPa & s and the hydroxyl value of 170-205 mgKOH/g;
the polyester polyol III is the polyester polyol with the viscosity of 2000-4000mPa & s and the hydroxyl value of 280-330 mgKOH/g.
4. A mixed blowing agent conjugate polyether as claimed in claim 3, characterized in that
The polyester polyol I adopts polyester 2412 of Nanjing Jinling Span chemical Limited company; or the company Ruinor chemical Co., Ltd PS 2412;
the polyester polyol II adopts polyester 1919A of Nanjing Jinling Span chemical Limited company; or the company PS3025 of ryinow chemical ltd;
the polyester polyol III adopts polyester 3152 of Nanjing Jinling Span chemical Limited; or the company Reno chemical company PS 3152; or Nanguang polyester Inc. 3152.
5. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that the catalyst I is a tertiary amine catalyst; the catalyst II is an organic metal salt catalyst.
6. A mixed blowing agent polyether polyol according to claim 5 wherein said catalyst I is a mixture of any two or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, triethylenediamine, tetramethylalkylenediamine, pentamethyldiethylenetriamine, triethylamine, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate;
the catalyst II adopts any one or a mixture of two of potassium isooctanoate, potassium oleate and potassium acetate.
7. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that
The foam stabilizer is any one of L-16268, L-6866 and L-16368 of Mianji advanced materials group; or MG687 or B84813 originated from specialty Chemicals (Shanghai) Co., Ltd; or any one of AK8805, AK8806, AK8810, AK8811, and AK8818, which are available from Meissn Chemicals Ltd.
8. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that
The flame retardant is one or a mixture of two of tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, tris (1, 3-dichloroisopropyl) phosphate or dimethyl methyl phosphate.
9. Rigid polyurethane foam produced using the mixed blowing agent-polyether polyol composition according to any one of claims 1 to 8, characterized by comprising a component A and a component B, which are prepared by mixing the components in a ratio of 1: (1.4-1.8), wherein the component A is the mixed foaming agent conjugate polyether as described in any one of claims 1-8, and the component B is isocyanate.
10. The rigid polyurethane foam according to claim 9, wherein the mixing and foaming are performed by a high pressure foaming machine at a foaming temperature of 20 to 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110841984.6A CN113637136B (en) | 2021-07-26 | 2021-07-26 | Mixed foaming agent combined polyether and polyurethane hard foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110841984.6A CN113637136B (en) | 2021-07-26 | 2021-07-26 | Mixed foaming agent combined polyether and polyurethane hard foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113637136A true CN113637136A (en) | 2021-11-12 |
| CN113637136B CN113637136B (en) | 2023-01-31 |
Family
ID=78418414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110841984.6A Active CN113637136B (en) | 2021-07-26 | 2021-07-26 | Mixed foaming agent combined polyether and polyurethane hard foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113637136B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116410434A (en) * | 2023-02-27 | 2023-07-11 | 廊坊华宇创新科技有限公司 | Polyurethane rigid foam combined polyester, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578312A (en) * | 2007-01-09 | 2009-11-11 | 巴斯夫欧洲公司 | Water-blown rigid foams for the insulation of liquefied natural gas tanks |
| CN102300892A (en) * | 2009-01-30 | 2011-12-28 | 因温斯特技术公司 | Aromatic polyesterpolyols, isocyanuratemodified polyurethane foams, and methods of making them |
| CN104530357A (en) * | 2014-10-31 | 2015-04-22 | 扬中市天正合成材料研究中心 | Environmental-friendly high-flame retardancy composite material for stand column board of vehicle interior and preparation method of composite material |
| CN109749613A (en) * | 2018-12-20 | 2019-05-14 | 上海东大聚氨酯有限公司 | A kind of environmentally friendly spraying combined polyether, polyurethane foam and its feedstock composition and preparation method |
| CN111808264A (en) * | 2020-07-23 | 2020-10-23 | 长虹美菱股份有限公司 | Polyurethane foaming raw material |
-
2021
- 2021-07-26 CN CN202110841984.6A patent/CN113637136B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578312A (en) * | 2007-01-09 | 2009-11-11 | 巴斯夫欧洲公司 | Water-blown rigid foams for the insulation of liquefied natural gas tanks |
| CN102300892A (en) * | 2009-01-30 | 2011-12-28 | 因温斯特技术公司 | Aromatic polyesterpolyols, isocyanuratemodified polyurethane foams, and methods of making them |
| CN104530357A (en) * | 2014-10-31 | 2015-04-22 | 扬中市天正合成材料研究中心 | Environmental-friendly high-flame retardancy composite material for stand column board of vehicle interior and preparation method of composite material |
| CN109749613A (en) * | 2018-12-20 | 2019-05-14 | 上海东大聚氨酯有限公司 | A kind of environmentally friendly spraying combined polyether, polyurethane foam and its feedstock composition and preparation method |
| CN111808264A (en) * | 2020-07-23 | 2020-10-23 | 长虹美菱股份有限公司 | Polyurethane foaming raw material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116410434A (en) * | 2023-02-27 | 2023-07-11 | 廊坊华宇创新科技有限公司 | Polyurethane rigid foam combined polyester, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113637136B (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102079803B (en) | Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition | |
| CN102030977B (en) | Conjugate polyether, polyurethane raw material composition, polyurethane foams and applications thereof | |
| EP3115401B1 (en) | Low-thermal conductivity rigid polyurethane foam with c-pentane as main foaming agent and manufacturing method and applications thereof | |
| CN111647191B (en) | Low-conductivity foaming agent composition, polyurethane rigid foam and preparation method thereof | |
| CN102229697B (en) | Solar polyurethane thermal insulation material | |
| JPH08509512A (en) | Method for producing rigid polyurethane foam | |
| CN106750093A (en) | A kind of refrigerator for the polyurethane foam system of refrigerator and based on it | |
| CN110628073A (en) | Formula and preparation method of polyurethane rigid foam | |
| CN102911341B (en) | Formula and process of fire retardance modified polyurethane insulation board | |
| CN103709727A (en) | PIR (polyisocyanurate) high-flame-retardancy heat-insulating material for deep refrigeration and preparation method thereof | |
| CN108192127A (en) | Composite environment-friendly type polyurethane heated board combination material | |
| CN101125910A (en) | Hard polyurethane foam plastic and producing method thereof | |
| CN102558481B (en) | Environment-friendly combination material used for heat preservation of boards and preparation method thereof | |
| CN113637136B (en) | Mixed foaming agent combined polyether and polyurethane hard foam | |
| CN115304733B (en) | Ultralow-temperature hard polyurethane foam and preparation method thereof | |
| CN106188615A (en) | Triple combination foaming agent, hard polyurethane foam and manufacture method thereof | |
| CN106188606A (en) | Combined foaming agent, hard polyurethane foam and manufacture method thereof | |
| CN113563555A (en) | Polyurethane foaming material and foaming process thereof | |
| CN113754850A (en) | Polyurethane foam and preparation method and application thereof | |
| CN112175158B (en) | Refrigerator, hard polyurethane foam and preparation method of hard polyurethane foam | |
| JP2000191742A (en) | Polyurethane foam for ultralow temperature cold insulation and its production | |
| CN101948563B (en) | Pentane type composite polyether and composition containing same, rigid polyurethane rigid foam and application thereof | |
| CN106700119A (en) | Foaming agent composition and polyurethane hard foam | |
| CN106167541B (en) | Continous way produces PIR bulk bubble combined polyether and its preparation method and application | |
| CN103739808A (en) | Polyurethane thermal-insulation material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |