CN111363134A - H12MDA polyether ester polyol, preparation method, application and polyurethane rigid foam - Google Patents

H12MDA polyether ester polyol, preparation method, application and polyurethane rigid foam Download PDF

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CN111363134A
CN111363134A CN201811604814.0A CN201811604814A CN111363134A CN 111363134 A CN111363134 A CN 111363134A CN 201811604814 A CN201811604814 A CN 201811604814A CN 111363134 A CN111363134 A CN 111363134A
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mda
parts
polyol
polyether
prepared
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CN111363134B (en
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王诗文
陈文靖
钟仁升
叶俊
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Wanhua Chemical Ningbo Rongwei Polyurethane Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine 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
    • C08G18/28—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
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5033—Polyethers having heteroatoms other than oxygen having nitrogen containing carbocyclic 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
    • C08J9/14—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
    • 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
    • C08J2203/14—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
    • 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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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a method for producing H12MDA polyether ester polyol, a preparation method, application and polyurethane rigid foam, wherein the preparation method comprises the following steps: (1) with H12MDA is used as a raw material, and is subjected to addition reaction with added olefin oxide under the action of an alkaline catalyst to obtain a polymerization product; (2) performing ester exchange reaction on the polymerization product obtained in the step (1) and diglyceride to obtain H12MDA polyetherester polyol; the polyurethane rigid foam is prepared fromContaining H12The raw materials of the combined polyether of MDA, water, catalyst, surfactant, foaming agent and isocyanate are prepared by a high-pressure foaming machine. H of the invention12When the MDA polyether ester polyol is applied to preparing polyurethane rigid foam, the surface defect condition of the polyurethane foam can be effectively improved, and the polyurethane foam has better heat preservation and yellowing resistance.

Description

H12MDA polyether ester polyol, preparation method, application and polyurethane rigid foam
Technical Field
The invention relates to a method for producing H12The polyether ester polyol has the structure and the performance of improving surface defects. The foam is used as the heat insulating material for refrigerator, ice chest and other household appliances.
Background
The development of polyurethane is extremely rapid due to the advantages of polyurethane, and polyether polyol which is an important component of polyurethane is developed, but in the application process, due to some application problems and the technical development and requirements of heat-insulating materials of household appliances such as refrigerators, freezers and the like, urgent needs are provided for various special polyether polyols.
The reaction mechanism of the polyurethane foam in the initial stage is as follows: the amine in the amine catalyst added in the raw materials increases the nucleophilicity of oxygen atoms in water molecules, the activated oxygen attacks carbon in isocyanate, then the activated oxygen is reprotonated to generate carbamic acid, the catalyst is regenerated, the carbamic acid is subjected to decarboxylation reaction to generate carbon dioxide and amine, and the amine is rapidly reacted with other isocyanate groups.
The reaction mechanism is shown in appearance that after the foam is uniformly mixed and injected by a machine, the foam raw material begins to rapidly expand and grow outwards, and carbon dioxide and a foaming agent in the foam raw material are generated and overflow from the raw material. The gas is generated and overflowed, and under the conditions that the compatibility of the foam to the gas is poor and the initial rise is too fast, the foam surface is easy to leave more bubbles, particularly in the interior of a back plate of a refrigerator and the like, and in the continuous rising process of the foam, due to factors such as the blocking of a refrigerator body structure and the like, the foam rolls, the interior is easy to wrap more gas, and the energy consumption performance of products such as the refrigerator and the like is influenced.
Disclosure of Invention
In view of the above problems, the present invention provides a method for producing H12The polyether ester polyol prepared by the method has lipophilic groups, so that the whole polyurethane system can be obviously improved for foaming agents such as cyclopentane and the likeThe solubility of (2) reduces the defects such as surface bubbles which are easily formed after the blowing agent such as cyclopentane is easy to overflow from the system because of its low boiling point. Although the polyether polyol prepared by the method has the basically same effect by using the same substances such as o-toluenediamine and the like, the polyether polyol has obvious side effects, such as the problem of excessive gas wrapping in the foam due to excessively high early-stage reaction speed in the whole polyurethane system, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
h12A method for producing MDA polyetherester polyols, wherein the production method comprises the following steps:
(1) with H12MDA is used as a raw material, and is subjected to addition reaction with added olefin oxide under the action of an alkaline catalyst to obtain a polymerization product;
(2) performing ester exchange reaction on the polymerization product obtained in the step (1) and diglyceride to obtain H12MDA polyetherester polyol.
In the present invention, the reaction processes of the above steps (1) and (2) can be represented as follows:
Figure BDA0001923363080000031
wherein: n is1，n2，n3，n4And n5Each independently is an integer of not less than 0, preferably each independently is an integer of 0 to 3; r1-R9(i.e., R)1、R2、R3、R4、R5、R6、R7、R8And R9) Each independently is H or methyl; x is an integer of 0 to 10.
According to the production method of the present invention, preferably, in the step (1), the H12The molar ratio of MDA to olefin oxide used is from 1:1 to 12, preferably from 1:4 to 10, such as 1:5, 1:6 or 1: 8; the addition reaction temperature is 120 ℃ and 140 ℃, such as 130 ℃, in a closed reaction vessel, the pressure in the vessel is reduced as the reaction proceeds and the oxidation system is consumed, and in the present invention, the pressure is preferably less than or equal to 0.6MPa, such as 0.1-0.6MPa, 0.2MPa or 0.4 MPa.
According to the preparation method of the present invention, preferably, the alkylene oxide is ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, wherein the mass ratio of ethylene oxide to propylene oxide in the mixture of propylene oxide and ethylene oxide is 1:0.5-2.0, such as 1:1 or 1: 1.5.
According to the production method of the present invention, preferably, in the step (1), during the feeding of the oxyalkylene, ethylene oxide and H are first fed12After the MDA reacts until the pressure is not reduced any more, adding an alkaline catalyst and propylene oxide, and continuing to react until the pressure is not reduced any more; in the context of the present invention, "no further pressure drop" is understood to mean that the pressure does not decrease by more than 1% over at least half an hour at constant temperature. It will be appreciated by those skilled in the art that a basic catalyst may be used to catalyze the above addition reaction, and in the present invention, the basic catalyst may be an organic amine, such as dimethylamino, preferably used in an amount of 0.1 to 0.3 wt%, such as 0.2 wt%, based on the mass of the reaction system of step (1).
According to the production method of the present invention, preferably, in the step (2), the H12The molar ratio of MDA to diglyceride is 1:0.1-5, such as 1:0.2, 1:0.5, 1:1, 1:3 or 1:4, preferably 1: 0.1-2; the temperature of the ester exchange reaction is 160-190 ℃, such as 170 or 180 ℃, and the pressure is less than or equal to 0.3MPa, such as 0.1 or 0.2 MPa; preferably, the molecular weight of the diglyceride is 100-.
The invention also provides H prepared according to the preparation method12MDA polyether ester polyol; preferably, said H12The hydroxyl value of MDA polyether ester polyol is 350-480mgKOH/gOne step is preferably 380-440mgKOH/g, such as 400, 410 or 420.
H according to the invention12MDA polyetherester polyol, preferably, the H12The structural general formula of the MDA polyether ester polyol is shown as the following formula (1):
Figure BDA0001923363080000041
formula (1)
Wherein: n is1，n2，n3，n4And n5Each independently is an integer of not less than 0, preferably each independently is an integer of 0 to 3; r1-R9Each independently is H or methyl; x is an integer of 0 to 10.
The invention also provides the above H12The use of MDA polyether ester polyols for producing rigid polyurethane foams. By applying H of the invention12The polyurethane foam prepared from the MDA polyether ester polyol can optimally solve the problems of serious air bubbles on the surface and air wrapping inside the foam of the back panel in the production process of household appliance manufacturers such as refrigerators and the like, and reduces the generation of side effects.
The invention also provides the polyurethane rigid foam, which is prepared by foaming the following components in parts by weight through a foaming machine:
(a) 100 parts of the composition;
(b) 12.5-15 parts of foaming agent, such as 13 or 14 parts;
(c) 140 parts, such as 150 parts, of polyisocyanate;
wherein the composition comprises 91-96 parts of a combination polyether, such as 92 or 94; 1.5-3 parts of surfactant, such as 2 parts; 1.5-3 parts of catalyst, such as 2 parts; 1-3 parts of water, such as 2 parts; the combined polyether is prepared from the H1220-50 parts, such as 25 or 35 parts, preferably 30-40 parts of MDA polyether polyol A, 20-40 parts, such as 25, 30 or 35 parts of polyether polyol B prepared by performing addition reaction on sucrose and glycerol serving as initiators and propylene oxide, and 20-40 parts of polyether polyol C prepared by performing addition reaction on sorbitol serving as an initiator and propylene oxideSuch as 25, 30 or 35 parts, and 5-10 parts, such as 8 parts, of polyether polyol D prepared by the addition reaction of glycerin as an initiator and propylene oxide.
The rigid polyurethane foam according to the present invention is preferably the H12The hydroxyl value of the MDA polyether ester polyol A is 380-440 mgKOH/g; the hydroxyl value of the polyether polyol B is 390-450mgKOH/g, such as 400 or 420; the hydroxyl value of the polyether polyol C is 340-420mgKOH/g, such as 350, 380 or 400; the hydroxyl value of the polyether polyol D is 180-240 mgKOH/g; such as 200 or 220.
The preparation process of the rigid polyurethane foam is well known in the art, and in one embodiment, the rigid polyurethane foam is prepared as follows: uniformly mixing the combined polyether, the surfactant, the catalyst and the distilled water according to the proportion to obtain a composition, uniformly mixing the composition and the foaming agent, and filling the isocyanate and the composition containing the foaming agent into a mould by using a high-pressure foaming machine to prepare the polyurethane rigid foam; preferably, the blowing agent is cyclopentane; the operating conditions of the foaming machine are as follows: the temperature of the feed is 15-22 deg.C, such as 17, 20 or 21 deg.C, and the operating pressure is 100-150bar, such as 120, 130 or 140 bar.
The polyisocyanate may be polymeric MDI (polymethylene polyphenyl polyisocyanate) having an NCO content of 30-32%. Polymeric isocyanates that may be used include PM-200, PM-2010, and PM-400 of Nitidow.
The surfactant used in the present invention may be a silicone surfactant, such as AK8805 and AK8830 from south kyo de mei limited chemical industry, B8525 and B8546 from Evonik Degussa, and the like.
The catalyst used in the invention can be a composite catalyst of a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the foaming catalyst can be pentamethyldiethylenetriamine, triethylene diamine and/or N, N-dimethylcyclohexylamine, the gel catalyst can be dimethylcyclohexylamine and/or hexahydrotriazine, the trimerization catalyst can be potassium acetate, and the dosage ratio of the foaming catalyst, the triethylene diamine and/or the N, N-dimethylcyclohexylamine can be 1:4-6:1.5-2.5, such as 1:5: 2.
Compared with the prior art, the invention has the following advantages:
1) the polyurethane foam prepared by the invention can form a flat surface on the back panel foam of a refrigerator and the like, has few bubble defects, plays an important role in the appearance flatness of products, and solves the practical application problem of household appliance manufacturers.
2) The polyurethane foam prepared by the invention reduces the phenomenon of air entrainment inside the foam in the foam rising and flowing processes, the foam heat insulation performance inside the product becomes uniform, the overall heat insulation performance of the product is improved, the energy consumption is further reduced, and the actual benefit is created for household appliance manufacturers.
3) The polyurethane foam prepared by the invention has good strength test result, high foam size stability, good heat resistance and humidity resistance, and good overall appearance weather resistance of white household appliances such as refrigerators, freezers and the like applying the polyurethane foam system.
4) The polyether ester polyol disclosed by the invention has a cyclic structure, so that the compressive strength and the dimensional stability of the polyurethane foam are improved, and on the other hand, the polyurethane foam applied with the polyether ester polyol also has the characteristic of yellowing resistance in appearance because the initiator does not contain a benzene ring double bond structure.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Embodiments of the present invention are further illustrated by the following examples. The invention is not limited to the examples listed.
The main materials and reagents of the embodiment of the invention are as follows:
polyether ester polyol A: with H12MDA is used as a raw material, and is prepared by addition reaction with olefin oxide and ester exchange reaction with diglyceride, and the hydroxyl value is 380-440 mgKOH/g.
Polyether polyol B: vanwatt chemical R8242 is prepared by the addition reaction of sucrose and glycerol as initiator and propylene oxide, and has a hydroxyl value of 390-450mgKOH/g as a product index.
Polyether polyol C: vanwatt chemical (Ningbo) Wirb R8338 is prepared by addition reaction of sorbitol as an initiator and propylene oxide, and has a hydroxyl value of 340-420mgKOH/g as a product index.
Polyether polyol D: van Hua chemical (Ningbo) Wawei S3007 is prepared by the addition reaction of glycerin as an initiator and propylene oxide, and the hydroxyl value of the product index is 180-240 mgKOH/g.
Polyether polyol a 1: vanwatt chemical (Ningbo) Wircarb R4039 is prepared by the addition reaction of o-toluenediamine serving as an initiator and propylene oxide, and has a hydroxyl value of 360-420mgKOH/g as a product index.
Hereinafter, unless otherwise specified, the reagents used were analytical grade.
Example 1
H12The preparation of MDA polyether ester polyol comprises the following steps:
adding 403g of H12MDA is put into a high-pressure reaction kettle, nitrogen is replaced, 176g of ethylene oxide is put into the high-pressure reaction kettle, the temperature is raised to 130 ℃ for reaction, the pressure is controlled to be less than or equal to 0.6MPa, the ethylene oxide completely reacts after the pressure is not reduced any more, at the moment, 3g of alkaline catalyst dimethylamine is put into the high-pressure reaction kettle, 232g of propylene oxide is put into the high-pressure reaction kettle again, the reaction is continued until the pressure is not reduced any more, namely, the propylene oxide completely reacts, 84g of diglyceride (Annaiji chemical, average molecular weight is 280, the same below) is added into the high-pressure reaction kettle, the temperature is12The hydroxyl value of the MDA polyether ester polyol A product is 380 mgKOH/g.
Example 2
H12The preparation of MDA polyether ester polyol comprises the following steps:
adding 403g of H12MDA is put into a high-pressure reaction kettle, nitrogen is replaced, 264g of ethylene oxide is put into the high-pressure reaction kettle, the temperature is raised to 130 ℃ for reaction, the pressure is controlled to be less than or equal to 0.6MPa, the ethylene oxide completely reacts after the pressure is not reduced any more, at the moment, 3g of alkaline catalyst dimethylamine is put into the high-pressure reaction kettle, 174g of propylene oxide is put into the high-pressure reaction kettle again, the reaction is continued until the pressure is not reduced any more, namely, the propylene oxide completely reacts, 112g of diglyceride is added into the high-pressure reaction kettle, the temperature is raised to 180 ℃12And the hydroxyl value of the MDA polyether ester polyol A product is 353 mgKOH/g.
Example 3
H12The preparation of MDA polyether ester polyol comprises the following steps:
adding 403g of H12MDA is put into a high-pressure reaction kettle, nitrogen is replaced, 132g of ethylene oxide is put into the high-pressure reaction kettle, the temperature is raised to 130 ℃ for reaction, the pressure is controlled to be less than or equal to 0.6MPa, the ethylene oxide completely reacts after the pressure is not reduced any more, at the moment, 3g of alkaline catalyst dimethylamine is put into the high-pressure reaction kettle, 232g of propylene oxide is put into the high-pressure reaction kettle again, the reaction is continued until the pressure is not reduced any more, namely, the propylene oxide completely reacts, 56g of diglyceride is added, the temperature is raised to 180 ℃, the pressure is controlled to be12MDA polyether ester polyol A, the hydroxyl value of the product is 410 mgKOH/g.
Example 4
H12The preparation of MDA polyether ester polyol comprises the following steps:
adding 403g of H12MDA is put into a high-pressure reaction kettle, nitrogen is replaced, 88g of ethylene oxide is put into the high-pressure reaction kettle, the temperature is raised to 130 ℃ for reaction, the pressure is controlled to be less than or equal to 0.6MPa, the ethylene oxide completely reacts after the pressure is not reduced any more, at the moment, 3g of alkaline catalyst dimethylamine is put into the high-pressure reaction kettle, 116g of propylene oxide is put into the high-pressure reaction kettle again, the reaction is continued until the pressure is not reduced any more, namely, the propylene oxide completely reacts, 280g of diglyceride is added, the temperature is raised to 180 ℃, the pressure is controlled to be less12The hydroxyl value of the MDA polyether ester polyol A product is 380 mgKOH/g.
Example 5
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.7 parts of combined polyether, 2.5 parts of surfactant, 2.6 parts of composite catalyst and 2.2 parts of distilled water) to cyclopentane (CP, Meilong company, the same below) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h1247.7 parts of MDA polyetherester polyol A (prepared in example 1): 20 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 20 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: and (3) potassium acetate is 1:5:2 (mass ratio).
The preparation method of the polyurethane hard foam comprises the following steps:
1) weighing the raw materials according to the proportion, putting the combined polyether, the surfactant, the composite catalyst, the water and the foaming agent into a container, and fully mixing to obtain a composition mixture;
2) and mixing the obtained mixture with polyisocyanate, foaming under high pressure, wherein the material temperature is 19 ℃, the pressure is 130bar (gauge pressure), the filling coefficient of the reaction mixture in a mould is 1.15, and the demoulding time is 250s, so that the polyurethane hard foam is prepared.
Example 6
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.8 parts of combined polyether, 2.5 parts of surfactant, 2.5 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h1247.8 parts of MDA polyetherester polyol a (prepared in example 2): 20 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 20 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: potassium acetate 1:4.9:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Example 7
Applications H12Polyurethane rigid foam of MDA polyether ester polyol system and raw materialConsists of the following components:
the mass ratio of the composition (92.6 parts of combined polyether, 2.5 parts of surfactant, 2.7 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h1247.6 parts of MDA polyetherester polyol (prepared in example 3 a): 20 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 20 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: potassium acetate 1:5.2:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Example 8
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.5 parts of combined polyether, 2.5 parts of surfactant, 2.8 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h1247.5 parts of MDA polyetherester polyol a (prepared in example 4): 20 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 20 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: potassium acetate 1:5.4:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Example 9
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.5 parts of combined polyether, 2.5 parts of surfactant, 2.8 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h12MDA polyetherester polyol a (prepared in example 1) 37.5 parts: 30 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 20 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: potassium acetate 1:5.4:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Example 10
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.3 parts of combined polyether, 2.5 parts of surfactant, 3 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h12MDA polyetherester polyol a (prepared in example 1) 27.3 parts: 40 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 20 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: and (3) potassium acetate is 1:5.8:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Example 11
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.3 parts of combined polyether, 2.5 parts of surfactant, 3 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h12MDA polyetherester polyol a (prepared in example 1) 27.3 parts: 33 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 25 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 7 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: and (3) potassium acetate is 1:5.8:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Example 12
Applications H12The polyurethane rigid foam of the MDA polyether ester polyol system comprises the following raw materials:
the mass ratio of the composition (92.3 parts of combined polyether, 2.5 parts of surfactant, 3 parts of composite catalyst and 2.2 parts of distilled water) to Cyclopentane (CP) and polyisocyanate (polymeric MDI Wanhua PM-200) is 100:12.5: 140.6.
Combined polyether (in parts by weight): h12MDA polyetherester polyol a (prepared in example 1) 27.3 parts: 25 parts of sucrose and glycerol polyether polyol B (with a hydroxyl value of 424mgKOH/g), 35 parts of sorbitol polyether polyol C (with a hydroxyl value of 362mgKOH/g) and 5 parts of glycerol polyether polyol D (with a hydroxyl value of 202 mgKOH/g);
surfactant (b): and 85462.5 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is potassium acetate, and the weight ratio of pentamethyl diethylenetriamine: dimethyl cyclohexylamine: and (3) potassium acetate is 1:5.8:2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 5.
Table 1: examples 5 to 12 raw Material compositions (parts by weight) and Performance parameters of polyurethane rigid foams
Figure BDA0001923363080000131
Figure BDA0001923363080000141
Note: the foam density, compressive strength and thermal conductivity are all determined according to national standards:
foam core density test according to standard: GB/T6343-2009;
foam thermal conductivity test according to standard: GB/T10295-;
foam compression strength test according to the standard: GB/T8813-;
comparative example 1
The difference from example 5 is that H12The MDA polyetherester polyol A was replaced with the same parts by weight of polyether polyol A1 (hydroxyl value 381mgKOH/g), and the other conditions were the same as in example 5.
Comparative example 2
The difference from example 5 is that the conjugate polyether does not comprise H12The total weight of the MDA polyether polyol A and the combined polyether is not changed, and the weight ratio of the sucrose and glycerol polyether polyol B to the sorbitol polyether polyol C and the glycerol polyether polyol D is not changed. The other conditions were the same as in example 5.
The properties of the rigid polyurethane foams prepared in comparative examples 1 and 2 are shown in Table 2:
Figure BDA0001923363080000142
Figure BDA0001923363080000151

Claims (11)

1. h12The preparation method of the MDA polyether ester polyol is characterized by comprising the following steps:
(1) with H12MDA is used as a raw material, and is subjected to addition reaction with added olefin oxide under the action of an alkaline catalyst to obtain a polymerization product;
(2) performing ester exchange reaction on the polymerization product obtained in the step (1) and diglyceride to obtain H12MDA polyetherester polyol;
preferably, the reaction process of the step (1) and the step (2) is as follows:
Figure FDA0001923363070000011
wherein: n is1，n2，n3，n4And n5Each independently is an integer of not less than 0, preferably each independently is an integer of 0 to 3; r1-R9Each independently is H or methyl; x is an integer of 0 to 10.
2. The method according to claim 1, wherein in the step (1), the H is12The molar ratio of MDA to olefin oxide is 1:1-12, preferably 1: 4-10; the addition reaction conditions are as follows: the temperature is 120 ℃ and 140 ℃, and the pressure is less than or equal to 0.6 MPa.
3. The method according to claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, and the mass ratio of ethylene oxide to propylene oxide in the mixture of propylene oxide and ethylene oxide is 1: 0.5-2.0.
4. The production method according to claim 1, wherein in the step (1), during the feeding of the olefin oxide,first ethylene oxide and H are added12After the MDA reacts until the pressure is not reduced any more, adding an alkaline catalyst and propylene oxide, and continuing to react until the pressure is not reduced any more; preferably, the alkaline catalyst is organic amine, and the amount of the organic amine is 0.1-0.3 wt% of the mass of the reaction system in the step (1).
5. The method according to claim 1, wherein in the step (2), the H is12The molar ratio of the MDA to the diglyceride is 1:0.1-5, preferably 1: 0.1-2; the temperature of the ester exchange reaction is 160-190 ℃, and the pressure is less than or equal to 0.3 MPa; preferably, the molecular weight of the diglyceride is 100-500.
6. H produced by the production method according to any one of claims 1 to 512MDA polyetherester polyol; preferably, said H12The hydroxyl value of MDA polyetherester polyol is 350-.
7. H according to claim 612MDA polyether ester polyol, characterized in that H12The structural general formula of the MDA polyether ester polyol is shown as the following formula (1):
Figure FDA0001923363070000021
wherein: n is1，n2，n3，n4And n5Each independently is an integer of not less than 0, preferably each independently is an integer of 0 to 3; r1-R9Each independently is H or methyl; x is an integer of 0 to 10.
8. H according to claim 6 or 712The use of MDA polyether ester polyols for producing rigid polyurethane foams.
9. The rigid polyurethane foam is prepared by foaming the following components in parts by weight through a foaming machine:
(a) 100 parts of the composition;
(b) 12.5-15 parts of a foaming agent;
(c) 140 portions of polyisocyanate;
wherein the composition comprises 91-96 parts of combined polyether; 1.5-3 parts of a surfactant; 1.5-3 parts of a catalyst; 1-3 parts of water; the combined polyether is prepared from the H as claimed in claim 6 or 71220-50 parts of MDA polyether ester polyol A, preferably 30-40 parts of polyether polyol B prepared by carrying out addition reaction on sucrose and glycerol serving as initiators and propylene oxide, 20-40 parts of polyether polyol C prepared by carrying out addition reaction on sorbitol serving as an initiator and propylene oxide, and 5-10 parts of polyether polyol D prepared by carrying out addition reaction on glycerol serving as an initiator and propylene oxide.
10. The rigid polyurethane foam according to claim 9, wherein: said H12The hydroxyl value of the MDA polyether ester polyol A is 380-440mgKOH/g, the hydroxyl value of the polyether polyol B is 390-450mgKOH/g, the hydroxyl value of the polyether polyol C is 340-420mgKOH/g, and the hydroxyl value of the polyether polyol D is 180-240 mgKOH/g.
11. The rigid polyurethane foam according to claim 9 or 10, wherein the rigid polyurethane foam is prepared by the following method: uniformly mixing the combined polyether, the surfactant, the catalyst and the distilled water according to the proportion to obtain a composition, uniformly mixing the composition and the foaming agent, and filling the isocyanate and the composition containing the foaming agent into a mould by using a high-pressure foaming machine to prepare the rigid polyurethane foam; preferably, the blowing agent is cyclopentane; the operating conditions of the foaming machine are as follows: the material temperature is 15-22 ℃, and the operation pressure is 100-150 bar.
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CN112210072A (en) * 2020-09-17 2021-01-12 万华化学（宁波）容威聚氨酯有限公司 2, 3-diphenylsuccinic acid polyester polyol, low-conductivity and high-flame-retardant polyurethane foam and preparation method thereof
CN113563555A (en) * 2021-08-17 2021-10-29 长虹美菱股份有限公司 Polyurethane foaming material and foaming process thereof
CN116854900A (en) * 2022-03-28 2023-10-10 万华化学（宁波）容威聚氨酯有限公司 Tetraazapassion starting polyether polyol and preparation method thereof, and polyurethane rigid foam and preparation method thereof

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CN111072893A (en) * 2019-12-06 2020-04-28 长虹美菱股份有限公司 Freezer foaming layer
CN112210072A (en) * 2020-09-17 2021-01-12 万华化学（宁波）容威聚氨酯有限公司 2, 3-diphenylsuccinic acid polyester polyol, low-conductivity and high-flame-retardant polyurethane foam and preparation method thereof
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