CN109320679A - High self-adhesion stainless steel freezing cabinet environmentally friendly combined polyether, preparation method and application - Google Patents
High self-adhesion stainless steel freezing cabinet environmentally friendly combined polyether, preparation method and application Download PDFInfo
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- CN109320679A CN109320679A CN201811154673.7A CN201811154673A CN109320679A CN 109320679 A CN109320679 A CN 109320679A CN 201811154673 A CN201811154673 A CN 201811154673A CN 109320679 A CN109320679 A CN 109320679A
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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
-
- 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
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- 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 belongs to polyurethane foam plastics technical fields, and in particular to a kind of high self-adhesion stainless steel freezing cabinet environmentally friendly combined polyether, preparation method and application.The combined polyether is made of the raw material of following parts by weight: I 20~50 parts of polyether polyol；II 20~30 parts of polyether polyol；III 30~50 parts of polyether polyol；10~15 parts of additive；I 0.2~0.6 part of catalyst；1.0~2.0 parts of catalyst II；III 0.5~1.5 parts of catalyst；IV 0.5~1.0 parts of catalyst；5~10 parts of foam stabiliser；2.1~3.1 parts of water；26~36 parts of foaming agent.Preparation method is simple, the foam prepared after being reacted using the combined polyether with thick MDI, compressive strength with higher, preferable dimensional stability, thermal coefficient is low, and the adhesion strength between stainless steel plate is high, foaming properties meet requirement, and there is zero DOP, low GWP, the good feature of environmental-protecting performance.
Description
Technical field
The invention belongs to polyurethane foam plastics technical fields, and in particular to a kind of high self-adhesion stainless steel freezing cabinet ring
Protect combined polyether, preparation method and application.
Background technique
Polyurethane foam plastics is to be helped by polyether polyol, the pure and mild isocyanates of polyester polyols in foaming agent, catalyst etc.
Foamed product obtained under the action of agent has good thermal and insulating performance, mechanical property, chemical resistance, especially
With excellent heat-insulating property, and it is widely used in refrigerator, refrigerator-freezer, water heater, cold storage plate, battenboard, pipe insulation, refrigeration collection
The adiabatic heat-insulations fields such as vanning.Stainless steel freezing cabinet is to keep the temperature one kind very special in cold chain field, such product is for big
The related services such as type hotel, food and drink mechanism.Because it is stainless steel materials using material, decorative effect is played with surface silver color, it is brief
Atmosphere.Traditional domestic refrigerator-freezer, the programs such as shell plate is washed, dried, dusting by pickling, phosphorus, high temperature is dried, by plate
The processing such as the greasy dirt on surface are clean, therefore have good caking property with polyurethane insulation coating.And stainless steel freezes cabinet, stainless steel
Plate surface is without any processing, and surface of stainless steel has the oiliness reagent for the anti-plate adhesion of antirust that processing leaves, oil
Property substance plays the role of defoaming, plays the role of release agent for conventional combination polyethers, therefore, will affect and polyurethane
The cohesive force of foam is easy to disengage foaming layer and stainless steel plate.If stainless steel materials and polyurethane insulation coating disengage, intermediate
Bubble is had, influences the beautiful thermal insulation property for influencing cabinet again in this way.In order to solve this problem, manufacturer is stainless in processing
When steel plate, glue spraying processing can be being carried out with polyurethane insulation coating contact surface, both increase process in this way, effect is also undesirable.If
Glue spray is lacked, and cohesive force improves unobvious；Glue sprays more, will cause cabinet injustice.
In addition, stainless steel freezes cabinet, liner and outer gallbladder are all stainless steel materials, and heat transfer is fast compared to ordinary electrical home appliance,
Therefore there is very high requirement to the thermal insulation property of polyurethane foamed material.Stainless steel freezing cabinet use environment temperature is higher, this
Sample internal temperature is used at subzero 20 DEG C, and nearly 50 DEG C of internal-external temperature difference.It is raw with combined polyether product using common refrigerator-freezer in this way
The polyurethane foam of production, in the condition for being unable to satisfy stainless steel freezing cabinet with stainless steel plate caking property, heat insulating ability.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of environmentally friendly groups of high self-adhesion stainless steel freezing cabinet
Conjunction polyethers, the polyurethane foam generated after reacting with thick MDI compressive strength with higher, preferable dimensional stability are thermally conductive
Coefficient is low, and the adhesion strength between stainless steel plate is high；It is scientific and reasonable, simple present invention simultaneously provides preparation method and application
It is easy.
The environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet of the present invention, by the raw material system of following parts by weight
At:
Wherein:
Polyether polyol I, polyether polyol II and polyether polyol III are 100 parts total；
The polyether polyol I using sucrose, glycerol and diethylene glycol as initiator, with propylene oxide ring-opening polymerisation and
At degree of functionality 4.6-4.9, hydroxyl value 400-430；
The polyether polyol II forms, official using sucrose and diethylene glycol as initiator with propylene oxide ring-opening polymerisation
Energy degree is 5.5-5.8, hydroxyl value 360-400；
The polyether polyol III forms, degree of functionality using sorb alcohol and water as initiator with propylene oxide ring-opening polymerisation
For 3.8-4.2, hydroxyl value 360-400；
The additive, using PET (ethylene glycol terephthalate) plastic bottle of waste and old recycling, after crushed, with
Antimony oxide is that catalyst and soybean oil react obtained under 200 DEG C of hot conditions；
The catalyst I is the catalyst PT303 of Air Prod & Chem of the U.S.；
The catalyst II is the alcoholic solution of 33% triethylenediamine, is commonly called as catalyst A-33；
The catalyst III is dimethyl benzylamine；
The catalyst IV is 2,4,6- tri- (dimethylamino methyl) phenol；
The foaming agent is the mixture of pentamethylene and 1,1,1,4,4,4- hexafluorobutene (1336mzzm).
Preferably, the polyether polyol I is INOVOL R6001C；The polyether polyol II is INOVOL
R5118G；The polyether polyol III is INOVOL R6205, is Shandong Inov New Material Co., Ltd. commercial product.
Preferably, the pentamethylene and 1,1, Isosorbide-5-Nitrae, the mass ratio of 4,4- hexafluorobutenes is 20-70:80-30.
The foam stabiliser is L-6895, and manufacturer is Mai Tu new high-tech material Co., Ltd.
The preparation method of the high environmentally friendly combined polyether of self-adhesion stainless steel freezing cabinet of the present invention, including following step
It is rapid:
Firstly, polyether polyol, additive, foam stabiliser, water and catalyst are uniformly mixed, extra dry white wine is made
Material；By extra dry white wine material, pentamethylene and 1,1, Isosorbide-5-Nitrae, 4,4- hexafluorobutenes mixed by three component static state premixed devices after to get the present invention
Combined polyether.
The application of the high environmentally friendly combined polyether of self-adhesion stainless steel freezing cabinet of the present invention: poly- by weight combining
Ether: thick MDI=1:1.0-1.3, which is uniformly mixed, to be reacted, and polyurethane rigid foam plastic is made.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) present invention uses three kinds of polyethers: polyether polyol I, polyether polyol II and polyether polyol III, advantage exists
The polyurethane foam compressive strength with higher and preferable size generated after the combined polyether of production is reacted with thick MDI is steady
It is qualitative, to meet requirement of the stainless steel freezing cabinet to foam.It uses and is added made from the PET plastic bottle with waste and old recycling
Agent had both improved the adhesion strength between polyurethane foam and stainless steel plate, tensile bond strength >=80kPa with stainless steel plate, again
Improve the compressive strength and dimensional stability of polyurethane foam.
(2) present invention uses high viscosity foam stabiliser L-6895, makes the more uniform exquisiteness of foam cell generated, has
Low thermal coefficient, and improve the cohesive force between polyurethane foam and stainless steel；And pentamethylene and 1,1,1,4,4,4- hexafluoro
The mixture of butylene is as foaming agent, and zero DOP, low GWP, environmental-protecting performance is good, and thick MDI can be made to be formed when reacting with combined polyether
Fine and closely woven uniform closed abscess, also effectively reduces thermal coefficient, improves thermal insulation property.
(3) combined polyether is to carry out at normal temperature, and production energy consumption is low, easy to operate.Life is reacted with thick MDI by combined polyether
It is also to carry out under room temperature, normal pressure that high self-adhesion stainless steel freezing cabinet, which is produced, with environment-protecting polyurethane foamed material, and simple process is waved
Send out low, no three wastes generates, and also carries out the recycling and reusing of waste PET plastics, and stable product quality, producing cost are low.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but does not limit the present invention.
All raw materials used in embodiment are commercially available unless otherwise specified.
Combined polyether in embodiment is prepared with the following method:
Firstly, polyether polyol, additive, foam stabiliser, water and catalyst are uniformly mixed, extra dry white wine is made
Material；By extra dry white wine material, pentamethylene and 1,1, Isosorbide-5-Nitrae, 4,4- hexafluorobutenes are formed uniform steady by three component static state premixed devices after mixing
Fixed liquid is to get combined polyether of the invention.
The application method of combined polyether is as follows:
It is poly- by weight combining with polymeric MDI (referred to as B component material) again with the combined polyether (referred to as component A material)
Ether/thick MDI=1:1.0-1.3 is uniformly mixed and is reacted, that is, prepares polyurethane rigid foam plastic.
The performance test results of the raw material composition and the polyurethane rigid foam plastic of preparation of the combined polyether of embodiment 1-4
It is shown in Table 1.
1 embodiment 1-4 raw material of table composition and test result
The performance test results of the raw material composition and the polyurethane rigid foam plastic of preparation of the combined polyether of embodiment 5-8
It is shown in Table 2.
2 embodiment 5-8 raw material of table composition and test result
The performance test knot of the raw material composition and the polyurethane rigid foam plastic of preparation of the combined polyether of embodiment 9-12
Fruit is shown in Table 3.
3 embodiment 9-12 raw material of table composition and test result
Note:
1, raw material is all calculated based on parts by weight.
2, foam density, dimensional stability, thermal coefficient, tensile bond strength are all measured by national standard.
3, in embodiment 12, because of the bubble that collapses in reaction process, foams are not formed, specific value can not be measured.
Claims (6)
1. a kind of environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet, it is characterised in that: by the raw material of following parts by weight
It is made:
Wherein:
Polyether polyol I, polyether polyol II and polyether polyol III are 100 parts total；
The polyether polyol I forms, official using sucrose, glycerol and diethylene glycol as initiator with propylene oxide ring-opening polymerisation
Energy degree is 4.6-4.9, hydroxyl value 400-430；
The polyether polyol II forms, degree of functionality using sucrose and diethylene glycol as initiator with propylene oxide ring-opening polymerisation
For 5.5-5.8, hydroxyl value 360-400；
The polyether polyol III is formed using sorb alcohol and water as initiator with propylene oxide ring-opening polymerisation, and degree of functionality is
3.8-4.2, hydroxyl value 360-400；
The additive, using the PET plastic bottle of waste and old recycling, after crushed, using antimony oxide as catalyst and soybean
Oil reacts under 200 DEG C of hot conditions to be made；
The catalyst I is catalyst PT303；
The catalyst II is catalyst A-33；
The catalyst III is dimethyl benzylamine；
The catalyst IV is 2,4,6- tri- (dimethylamino methyl) phenol；
The foaming agent is the mixture of pentamethylene and 1,1,1,4,4,4- hexafluorobutene.
2. the environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet according to claim 1, it is characterised in that: described
Polyether polyol I is INOVOL R6001C；The polyether polyol II is INOVOL R5118G；The polyether polyol
III is INOVOL R6205.
3. the environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet according to claim 1, it is characterised in that: described
Pentamethylene and the mass ratio of 1,1,1,4,4,4- hexafluorobutene are 20-70:80-30.
4. the environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet according to claim 1, it is characterised in that: described
Foam stabiliser is L-6895.
5. a kind of preparation method of any environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet of claim 1-4,
It is characterized by comprising following steps:
Firstly, polyether polyol, additive, foam stabiliser, water and catalyst are uniformly mixed, extra dry white wine material is made；It will
Extra dry white wine material, pentamethylene and 1,1, Isosorbide-5-Nitrae, 4,4- hexafluorobutenes pass through after three component static state premixed devices mix to get group of the invention
Close polyethers.
6. a kind of application of any environmentally friendly combined polyether of high self-adhesion stainless steel freezing cabinet of claim 1-4, special
Sign is:
By weight combined polyether: thick MDI=1:1.0-1.3, which is uniformly mixed, to be reacted, and polyurethane rigid foam plastic is made.
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| CN201811154673.7A CN109320679B (en) | 2018-09-30 | 2018-09-30 | Environment-friendly combined polyether for high-self-adhesion stainless steel freezer cabinet, preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708092A (en) * | 2020-12-25 | 2021-04-27 | 山东一诺威新材料有限公司 | Combined polyether for ice cream refrigerator and preparation method and application thereof |
| CN114437662A (en) * | 2021-12-29 | 2022-05-06 | 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708092A (en) * | 2020-12-25 | 2021-04-27 | 山东一诺威新材料有限公司 | Combined polyether for ice cream refrigerator and preparation method and application thereof |
| CN114437662A (en) * | 2021-12-29 | 2022-05-06 | 山东一诺威新材料有限公司 | Industrial environment-friendly polyurethane adhesive 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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| CN109320679B (en) | 2020-12-15 |
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