CN109320679B - Environment-friendly combined polyether for high-self-adhesion stainless steel freezer cabinet, preparation method and application - Google Patents
Environment-friendly combined polyether for high-self-adhesion stainless steel freezer cabinet, preparation method and application 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more 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
- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
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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
- 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
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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
- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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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- 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
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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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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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
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- 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
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention belongs to the technical field of polyurethane foam plastics, and particularly relates to environment-friendly composite polyether for a high-self-adhesion stainless steel freezer cabinet, a preparation method and application. The composite polyether is prepared from the following raw materials in parts by weight: 20-50 parts of polyether polyol I; 20-30 parts of polyether polyol II; 30-50 parts of polyether polyol III; 10-15 parts of an additive; 0.2-0.6 part of catalyst I; 1.0-2.0 parts of a catalyst II; 0.5-1.5 parts of a catalyst III; 0.5-1.0 part of catalyst IV; 5-10 parts of a foam stabilizer; 2.1-3.1 parts of water; 26-36 parts of a foaming agent. The preparation method is simple, and the foam prepared by reacting the composite polyether with crude MDI has the characteristics of high compression strength, good dimensional stability, low thermal conductivity coefficient, high bonding strength with a stainless steel plate, use requirement meeting of foam performance, zero DOP, low GWP and good environmental protection performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane foam plastics, and particularly relates to environment-friendly composite polyether for a high-self-adhesion stainless steel freezer cabinet, a preparation method and application.
Background
The polyurethane foam plastic is a foam product prepared from polyether polyol, polyester polyol and isocyanate under the action of auxiliary agents such as foaming agents, catalysts and the like, has good heat preservation and insulation properties, mechanical properties and chemical resistance, particularly excellent heat insulation properties, and is widely applied to the heat insulation and insulation fields of refrigerators, freezers, water heaters, cold storage plates, sandwich plates, pipeline heat preservation, refrigerated containers and the like. A stainless steel freezing cabinet is a special one in the field of heat preservation cold chains, and the product is used for large hotels, restaurants and other related service organizations. Because the used material is stainless steel plate, the surface is silvery to achieve the decorative effect, thereby simplifying the atmosphere. In a traditional household refrigerator and freezer, a shell plate is subjected to procedures of acid washing, phosphorus washing, drying, powder spraying, high-temperature drying and the like to completely treat oil stains and the like on the surface of the plate, so that the plate has good cohesiveness with a polyurethane heat-insulating layer. In the stainless steel freezing cabinet, the surface of the stainless steel plate is not treated, the surface of the stainless steel plate is provided with an oily agent for rust prevention and plate adhesion prevention, and the oily substance has a defoaming effect on common combined polyether and plays a role of a mold release agent, so that the adhesive force with polyurethane foam can be influenced, and a foaming layer is easily separated from the stainless steel plate. If the stainless steel plate and the polyurethane heat-insulating layer are separated, air bubbles exist in the middle, so that the appearance is influenced, and the heat-insulating performance of the box body is also influenced. In order to solve the problem, when a manufacturer processes the stainless steel plate, glue spraying treatment is carried out on the contact surface of the stainless steel plate and the polyurethane heat-insulating layer, so that working procedures are increased, and the effect is not ideal. If the pectin is sprayed less, the adhesive force is not obviously improved; the box body is uneven due to more glue spraying.
In addition, the inner container and the outer container of the stainless steel freezing cabinet are made of stainless steel materials, and the heat conduction is faster than that of common household appliances, so that the stainless steel freezing cabinet has high requirements on the heat insulation performance of polyurethane foam materials. The stainless steel freezer cabinet has high use environment temperature, so that the internal temperature is 20 ℃ below zero, and the internal and external temperature difference is about 50 ℃. The polyurethane foam produced by using the common combined polyether product for the refrigerator can not meet the conditions of stainless steel freezer cabinets in the aspects of adhesion with stainless steel plates and heat preservation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the environment-friendly combined polyether for the high-self-adhesion stainless steel freezing cabinet, and polyurethane foam generated after the reaction with crude MDI has higher compression strength, better dimensional stability, low thermal conductivity coefficient and high bonding strength with a stainless steel plate; the invention also provides a preparation method and application thereof, and the preparation method is scientific, reasonable, simple and feasible.
The invention relates to environment-friendly combined polyether for a high-self-adhesion stainless steel freezer cabinet, which is prepared from the following raw materials in parts by weight:
wherein:
the total amount of the polyether polyol I, the polyether polyol II and the polyether polyol III is 100 parts;
the polyether polyol I is prepared by ring-opening polymerization of propylene oxide and sucrose, glycerol and diethylene glycol serving as initiators, and has the functionality of 4.6-4.9 and the hydroxyl value of 400-430-;
the polyether polyol II is prepared by ring-opening polymerization of propylene oxide and sucrose and diethylene glycol as initiators, the functionality is 5.5-5.8, and the hydroxyl value is 360-400;
the polyether polyol III is prepared by taking sorbitol and water as initiators and performing ring-opening polymerization with propylene oxide, the functionality is 3.8-4.2, and the hydroxyl value is 360-400;
the additive is prepared by adopting waste and old recycled PET (polyethylene terephthalate) plastic bottles, crushing the PET plastic bottles, and reacting the crushed PET plastic bottles with soybean oil at a high temperature of 200 ℃ by using antimony trioxide as a catalyst;
the catalyst I is a catalyst PT303 of American air chemical products company;
the catalyst II is an alcoholic solution of 33 percent triethylene diamine and is commonly called as catalyst A-33;
the catalyst III is dimethylbenzylamine;
the catalyst IV is 2,4, 6-tris (dimethylaminomethyl) phenol;
the foaming agent is a mixture of cyclopentane and 1,1,1,4,4, 4-hexafluorobutene (1336 mzzm).
Preferably, the polyether polyol I is INOVOL R6001C; the polyether polyol II is INOVOL R5118G; the polyether polyol III is INOVOL R6205 which is a product sold by New materials of Norway in Shandong, Co.
Preferably, the mass ratio of the cyclopentane to the 1,1,1,4,4, 4-hexafluorobutene is 20-70: 80-30.
The foam stabilizer is L-6895, and the manufacturer is Mitigo high and new materials Co.
The preparation method of the environment-friendly combined polyether for the high-self-adhesion stainless steel freezer cabinet comprises the following steps of:
firstly, polyether polyol, an additive, a foam stabilizer, water and a catalyst are stirred and mixed uniformly to prepare a dry white material; and mixing the dry white material, cyclopentane and 1,1,1,4,4, 4-hexafluorobutene through a three-component static premixer to obtain the composite polyether.
The invention discloses application of environment-friendly combined polyether for a high-self-adhesion stainless steel freezer cabinet, which comprises the following steps: combining polyether according to the weight ratio: crude MDI ═ 1:1.0-1.3, and reacting to obtain the polyurethane rigid foam plastic.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses three polyethers: the polyether polyol I, the polyether polyol II and the polyether polyol III have the advantages that polyurethane foam generated after the produced combined polyether reacts with crude MDI has high compressive strength and good dimensional stability, so that the requirements of stainless steel refrigerated cabinets on the foam are met. The additive prepared from the waste and recovered PET plastic bottles is adopted, so that the bonding strength between the polyurethane foam and the stainless steel plate is improved, the tensile bonding strength between the polyurethane foam and the stainless steel plate is more than or equal to 80kPa, and the compression strength and the dimensional stability of the polyurethane foam are improved.
(2) According to the invention, the high-viscosity foam stabilizer L-6895 is adopted, so that the generated foam pores are more uniform and fine, the thermal conductivity coefficient is low, and the binding force between polyurethane foam and stainless steel is improved; and the mixture of cyclopentane and 1,1,1,4,4, 4-hexafluorobutene is used as a foaming agent, has zero DOP, low GWP and good environmental protection performance, can enable crude MDI to form fine, uniform and closed cells when reacting with combined polyether, also effectively reduces the thermal conductivity coefficient and improves the heat preservation performance.
(3) The combined polyether is carried out at normal temperature, the production energy consumption is low, and the operation is simple. The production of the environment-friendly polyurethane foam material for the high-self-adhesion stainless steel refrigerated cabinet by the reaction of the composite polyether and the crude MDI is also carried out at normal temperature and normal pressure, the process is simple, the volatilization is low, three wastes are not generated, the waste PET plastic is recycled, the product quality is stable, and the production cost is low.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
The conjugate polyether in the examples was prepared as follows:
firstly, polyether polyol, an additive, a foam stabilizer, water and a catalyst are stirred and mixed uniformly to prepare a dry white material; and (2) mixing the dry white material, cyclopentane and 1,1,1,4,4, 4-hexafluorobutene through a three-component static premixer to form uniform and stable liquid, thus obtaining the composite polyether.
The application method of the combined polyether comprises the following steps:
the composite polyether (named as component A) is mixed with polymeric MDI (named as component B) according to the weight ratio of 1:1.0-1.3 to react evenly, thus preparing the polyurethane rigid foam plastic.
The raw material compositions of the conjugate polyethers of examples 1 to 4 and the results of the performance test of the prepared rigid polyurethane foam are shown in Table 1.
Table 1 examples 1-4 raw material compositions and test results
The raw material compositions of the conjugate polyethers of examples 5 to 8 and the results of the performance test of the polyurethane rigid foams prepared are shown in Table 2.
Table 2 examples 5-8 raw material compositions and test results
The raw material compositions of the conjugate polyethers of examples 9 to 12 and the results of the performance tests of the rigid polyurethane foams prepared are shown in Table 3.
Table 3 examples 9-12 raw material compositions and test results
Note:
1. the raw materials are calculated according to the parts by weight.
2. The foam density, dimensional stability, thermal conductivity and tensile bond strength were determined according to national standards.
3. In example 12, no foam was formed due to collapse during the reaction, and no specific value could be measured.
Claims (6)
1. The utility model provides a high self-adhesion stainless steel is environmental protection combined polyether for freezer cabinet which characterized in that: the feed is prepared from the following raw materials in parts by weight:
wherein:
the total amount of the polyether polyol I, the polyether polyol II and the polyether polyol III is 100 parts;
the polyether polyol I is INOVOL R6001C, the functionality is 4.6-4.9, and the hydroxyl value is 400-430;
the polyether polyol II is prepared by ring-opening polymerization of propylene oxide and sucrose and diethylene glycol as initiators, the functionality is 5.5-5.8, and the hydroxyl value is 360-400;
the polyether polyol III is prepared by taking sorbitol and water as initiators and performing ring-opening polymerization with propylene oxide, the functionality is 3.8-4.2, and the hydroxyl value is 360-400;
the additive is prepared by adopting waste and old recycled PET plastic bottles, crushing the PET plastic bottles, and reacting the crushed PET plastic bottles with soybean oil at a high temperature of 200 ℃ by using antimony trioxide as a catalyst;
the catalyst I is a catalyst PT 303;
the catalyst II is a catalyst A-33;
the catalyst III is dimethylbenzylamine;
the catalyst IV is 2,4, 6-tris (dimethylaminomethyl) phenol;
the foaming agent is a mixture of cyclopentane and 1,1,1,4,4, 4-hexafluorobutene.
2. The environment-friendly composite polyether for the high self-adhesion stainless steel freezer cabinet as claimed in claim 1, wherein: the polyether polyol II is INOVOL R5118G; the polyether polyol III is INOVOL R6205.
3. The environment-friendly composite polyether for the high self-adhesion stainless steel freezer cabinet as claimed in claim 1, wherein: the mass ratio of the cyclopentane to the 1,1,1,4,4, 4-hexafluorobutene is 20-70: 80-30.
4. The environment-friendly composite polyether for the high self-adhesion stainless steel freezer cabinet as claimed in claim 1, wherein: the foam stabilizer is L-6895.
5. The preparation method of the environment-friendly composite polyether for the high self-adhesion stainless steel freezer cabinet as claimed in any one of claims 1-4, is characterized in that: the method comprises the following steps:
firstly, polyether polyol, an additive, a foam stabilizer, water and a catalyst are stirred and mixed uniformly to prepare a dry white material; and (3) mixing the dry white material, cyclopentane and 1,1,1,4,4, 4-hexafluorobutene through a three-component static premixer to obtain the composite polyether.
6. The use of the environmentally friendly composite polyether for high self-adhesion stainless steel freezer cabinets of any one of claims 1-4, wherein the environmentally friendly composite polyether comprises the following components:
combining polyether according to the weight ratio: crude MDI ═ 1:1.0-1.3, and reacting to obtain the polyurethane rigid foam plastic.
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| CN112708092B (en) * | 2020-12-25 | 2022-09-06 | 山东一诺威新材料有限公司 | Combined polyether for ice cream freezer and preparation method and application thereof |
| CN114437662B (en) * | 2021-12-29 | 2023-12-12 | 山东一诺威新材料有限公司 | Industrial environment-friendly polyurethane adhesive and preparation method and application thereof |
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