CN114085371A - Polyether polyol containing benzamide group, polyurethane foam and preparation method of polyether polyol - Google Patents
Polyether polyol containing benzamide group, polyurethane foam and preparation method of polyether polyol Download PDFInfo
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- 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
- C08G65/2633—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 the other compounds containing amide groups
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- 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
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- 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
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5039—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- 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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Abstract
Disclosed are a polyether polyol containing a benzamide group, a preparation method and use thereof, a polyol composition for preparing a polyurethane foam, a use thereof, a polyurethane foam and a preparation method thereof. The polyether polyol prepared from the polyether polyol containing the benzamide group has more excellent performance.
Description
Technical Field
The present application relates to a polyether polyol containing a benzamide group, a preparation method and use thereof, and a method for preparing a polyurethane foam using the polyether polyol containing a benzamide group.
Background
Polyether polyols are widely used for preparing polyurethane rigid foam materials, and can be used as heat insulation materials in products such as refrigerators, freezer cabinets, cold storages and the like.
The currently commonly used polyether polyol is o-toluenediamine polyether polyol, because the steric hindrance is larger after the alkylene oxide is grafted on the ortho-position amino group of the o-toluenediamine polyether polyol, hydrogen on the amino group cannot completely participate in the reaction to become polyether continuous segments, and the existence of the hydrogen on the amino group causes that the viscosity is increased too fast and the cell tropism is deviated in the polyurethane foam growth process, thereby causing poor foam strength, poor fluidity, surface curing and poor surface bubble.
In addition, because o-tolylenediamine is a byproduct in the production process of TDI, the raw material source is limited, and the price thereof has been increasing all the way in recent years, resulting in an excessively high cost of polyether polyol prepared therefrom. Therefore, it is imperative to develop alternatives. The structure of the benzamide polyether, particularly the structure of the o-benzamide polyether is close to that of o-toluenediamine, so that the benzamide polyether is expected to be developed as a substitute.
Disclosure of Invention
The invention aims to provide a novel preparation method of polyether polyol containing benzamide groups, aiming at the defects in the prior art, the polyether polyol containing benzamide groups prepared by the method can be used for replacing the traditional o-toluenediamine polyether, and the prepared polyurethane foam has more excellent performance, low raw material cost and more obvious competitive advantage.
One or more embodiments of the present application provide a benzamide group-containing polyether polyol having the following structure:
wherein
n, m, l, q are each independently 0, 1, 2, 3, 4, 5 or 6;
r is H, -CH3or-CH2-CH3。
In one or more embodiments, the benzamido-containing polyether polyol has an average molecular weight of 350-.
One or more embodiments of the present application provide a method of preparing a polyether polyol, comprising:
(1) uniformly mixing dimethyl phthalate, a catalyst and an amino alcohol compound, and distilling at 70-130 ℃ (such as 80, 90, 100, 110 and 120 ℃) under reduced pressure for 1-4 hours to remove methanol generated in the system;
(2) adding alkylene oxide at 80-150 deg.C (such as 80, 90, 100, 110, 120, 130, 140 deg.C) and 0.05-0.5MPa (such as 0.1, 0.2, 0.3, 0.4MPa) to react for 1-4 hr (such as 1, 2, 3, 4 hr) to obtain polyether polyol containing benzamide group;
(3) optionally, removing unreacted alkylene oxide to obtain the polyether polyol containing benzamide groups.
In one or more embodiments, the amino alcohol compound is a primary or secondary amine alcohol.
In one or more embodiments, the primary or secondary amine alcohol is one or more of monoethanolamine, diethanolamine, diisopropanolamine, monoisopropanolamine.
In one or more embodiments, the primary or secondary amine alcohol is diethanolamine or diisopropanolamine.
In one or more embodiments, the dimethyl phthalate is dimethyl phthalate, dimethyl isophthalate, or dimethyl terephthalate.
In one or more embodiments, the dimethyl phthalate is dimethyl phthalate.
In one or more embodiments, the catalyst is selected from CH3ONa、CH3OK, KOH, NaOH and CsOH.
In one or more embodiments, the catalyst is CH3OK or KOH.
In one or more embodiments, the alkylene oxide is one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin.
In one or more embodiments, the alkylene oxide is propylene oxide or ethylene oxide.
In one or more embodiments, the molar ratio of dimethyl phthalate to amino alcohol compound is 1:2 to 12 (e.g., 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or 1: 11).
In one or more embodiments, the molar ratio of dimethyl phthalate to amino alcohol compound is 1:2 to 8.
In one or more embodiments, the catalyst comprises from 0.1% to 1.5% (e.g., 0.5% or 1%) of the total weight of the dimethyl phthalate and amino alcohol compounds.
In one or more embodiments, the catalyst comprises 0.5 to 1.0% (e.g., 0.75%) of the total weight of the dimethyl phthalate and amino alcohol compounds.
One or more embodiments herein provide a polyol composition for making a polyurethane foam comprising 10-90 wt% (e.g., 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 wt%) of a polyether polyol containing a benzamide group, 10-90 wt% (e.g., 10, 20, 30, 40, 50, 60, 70, 80, or 90 wt%) of one or more of the other polyether polyols.
In one or more embodiments, the polyol composition includes 20 to 60 wt% of the polyether polyol containing a benzamido group and 40 to 80 wt% of one or more of the other polyether polyols.
In one or more embodiments, the other polyether polyol is a mixture of one or more of an oil ether, a sucrose-initiated polyether polyol, a propylene glycol or glycerol-initiated polyether polyol.
In one or more embodiments, the polyol composition includes 20 to 60 wt% of the polyether polyol containing a benzamido group, 5 to 40 wt% (e.g., 10, 20, or 30 wt%) of the oil ether, 15 to 40 wt% (e.g., 10, 20, or 30 wt%) of the polyether polyol with sucrose as a starter, and 0 to 20 wt% (e.g., 10, 15, 20 wt%) of the polyether polyol with propylene glycol or glycerin as a starter.
In one or more embodiments, the polyol composition includes 20 to 40 weight percent (e.g., 10, 20, or 30 weight percent) of the polyether polyol containing a benzamido group.
In one or more embodiments, the oil ethers are prepared by the addition reaction of vegetable, animal and recovered oils with small molecule polyols (e.g., sucrose) as initiators and alkylene oxides, and have a hydroxyl value of 350-500mgKOH/g (e.g., 400, 450mgKOH/g) and a functionality of 3.5 to 5.0 (e.g., 4 or 4.5).
In one or more embodiments, the sucrose-initiated polyether polyol is prepared by the addition reaction of sucrose and glycerol as starting materials with propylene oxide, and has a hydroxyl value of 350-450mgKOH/g (e.g., 400, 450mgKOH/g) and a functionality of 5.0-6.5 (e.g., 5 or 6).
In one or more embodiments, the polyether polyol using propylene glycol or glycerol as an initiator is prepared by an addition reaction of glycerol or propylene glycol as an initiator and propylene oxide or ethylene oxide, and has a hydroxyl value of 300-500mgKOH/g and a functionality of 2.0-3.0.
One or more embodiments of the present application provide a method of preparing a polyurethane foam, comprising the steps of:
1) forming a mixture comprising: the above polyol composition, at least one blowing agent, at least one polyisocyanate, at least one catalyst, at least one surfactant;
2) the mixture is reacted to expand and cure to form a polyurethane foam.
In one or more embodiments, the polyurethane foam is a rigid polyurethane foam.
In one or more embodiments, the polyisocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate).
In one or more embodiments, the polymeric MDI is 30 to 32% polymeric MDI.
In one or more embodiments, the polyisocyanate is one or more of polymeric MDI wanhua PM-200, polymeric MDI wanhua PM-2010, polymeric MDI wanhua PM-400.
In one or more embodiments, the blowing agent is one or more of cyclopentane, HFC-134a, and LBA blowing agents.
In one or more embodiments, the blowing agent is a mixture of cyclopentane and AFC-134 a.
In one or more embodiments, the catalyst is at least one of an organometallic catalyst and an amine catalyst.
In one or more embodiments, the catalyst is at least one of triethylenediamine, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N-methylpyrrolidone, and potassium acetate.
In one or more embodiments, the surfactant is at least one of an alkali metal salt of a fatty acid, an amine salt of a fatty acid, castor oil, ricinoleic acid, a silicone polymer.
In one or more embodiments, the surfactant is a siloxane polymer.
In one or more embodiments, the polyisocyanate is used in an amount of 1.1 to 1.4 (e.g., 1.2 or 1.3) based on the equivalent weight of the polyol composition.
In one or more embodiments, the blowing agent, catalyst, and surfactant are used in an amount of 12 to 25 parts by weight (e.g., 15 or 20 parts by weight), 2 to 4 parts by weight (e.g., 3 parts by weight), and 2 to 6 parts by weight (e.g., 3, 4, 5 parts by weight), respectively, in that order, based on 100 parts by weight of the polyol composition.
One or more embodiments of the present application provide for the use of the benzamido-containing polyether polyol of the present application or the polyol composition of the present application in the preparation of a polyurethane foam.
One or more embodiments of the present application provide polyurethane foams made by the polyurethane foam making methods of the present application.
Detailed Description
In order that the technical features and contents of the present application can be understood in detail, embodiments of the present application will be described in more detail below. While preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the following embodiments.
In one or more embodiments, the structural formula of the polyether polyol containing a benzamido group is as follows:
wherein
n, m, l and q are integers of 0-6;
r is H, -CH3or-CH2-CH3。
In one or more embodiments, the preparation of the polyether polyol containing a benzamido group includes: uniformly mixing dimethyl phthalate, a catalyst and an amino alcohol compound in a reaction kettle, and controlling the temperature to be 70-130 ℃ to remove generated methanol through reduced pressure distillation to obtain polyether polyol containing benzamide groups; under certain conditions, a certain amount of alkylene oxide is continuously added to obtain the polyether polyol containing the benzamide group with the required molecular weight.
In one or more embodiments, the amino alcohols include primary and secondary amine alcohols, for example, one or more of monoethanolamine, diethanolamine, diisopropanolamine, monoisopropanolamine.
In one or more embodiments, the dimethyl phthalate is dimethyl phthalate, dimethyl isophthalate, or dimethyl terephthalate.
In one or more embodiments, the molar ratio of dimethyl phthalate to amino compound is from 1:2 to 12, such as from 1:2 to 8.
In one or more embodiments, the catalyst is CH3ONa、CH3OK, KOH, NaOH or CsOH.
In one or more embodiments, the epoxy compound is ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin.
The preparation method of the polyether polyol containing the benzamido comprises the following steps:
(1) adding dimethyl phthalate, a catalyst and amino alcohol into a reaction kettle, carrying out nitrogen replacement and punching leakage test, then carrying out vacuum degassing for 1-4 hours at the temperature of 70-130 ℃, and recovering the generated methanol;
(2) when the temperature in the reaction device is 80-150 ℃, continuously adding the epoxy compound and reacting, and controlling the pressure of the reaction device to be 0.05-0.5MPa in the whole process;
(3) and (3) after the epoxy compound feeding is finished, continuously reacting for 1-4 hours, and removing unreacted epoxy compound in vacuum to obtain the acylamino-containing polyol.
In one or more embodiments, the amide group-containing polyol prepared has an average molecular weight of 350-1000 and an average functionality of 3.0 to 4.0.
In one or more embodiments, the polyether polyol containing a benzamide group may be used to prepare a rigid polyurethane foam.
In one or more embodiments, the polyol composition used to prepare the polyurethane foam comprises 10 to 90 wt% or more of the aniline group-containing polyether polyol as described above, 10 to 90 wt% of one or more of the other polyether polyols, for example 20 to 60 wt% of the benzamide group-containing polyether polyol as described above, 40 to 80 wt% of one or more of the other polyether polyols.
In one or more embodiments, the other polyether polyol is a mixture of one or more of an oil ether, a sucrose-initiated polyether polyol, a propylene glycol or glycerol-initiated polyether polyol.
In one or more embodiments, the oil ether can be prepared by the addition reaction of vegetable oil, animal oil and recovered oil with other small molecular weight polyols such as sucrose and the like serving as initiators and alkylene oxide, and has the content of 10-30%, the hydroxyl value of 350-500mgKOH/g and the functionality of 3.5-5.0.
In one or more embodiments, the sucrose-initiated polyether polyol is prepared by performing an addition reaction between sucrose and glycerol as initial raw materials and propylene oxide, and has a hydroxyl value of 350 to 450mgKOH/g and a functionality of 5.0 to 6.5.
In one or more embodiments, the polyether polyol using propylene glycol or glycerol as an initiator is prepared by an addition reaction of glycerol or propylene glycol as an initiator and propylene oxide or ethylene oxide, and has a hydroxyl value of 300-500mgKOH/g and a functionality of 2.0-3.0.
In one or more embodiments, in the polyol composition, the benzamide group-containing polyether polyol is 20 to 60 wt%, the sucrose-initiated polyether polyol is 15 to 40 wt%, the propylene glycol or glycerin-initiated polyether polyol is 0 to 20 wt%, and the oleyl ether is 5 to 40 wt%.
In one or more embodiments, the mass percentage of the polyether polyol containing benzamide groups in the polyol composition is 20 to 40%.
A method of making a polyurethane foam comprising the steps of:
1) forming a mixture comprising: the polyol composition of the present application, at least one blowing agent, at least one polyisocyanate, at least one catalyst, at least one surfactant;
2) the mixture is subjected to conditions which allow the mixture to react, expand and cure to form a rigid polyurethane foam.
In one or more embodiments, the polyisocyanate is used in an amount of 1.1 to 1.4 equivalents based on the polyol composition.
In one or more embodiments, the blowing agent, catalyst, and surfactant are used in an amount of 12 to 25 parts, 2 to 4 parts, and 2 to 6 parts, respectively, in that order, based on 100 parts by weight of the polyol composition.
In one or more embodiments, the polyisocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate).
In one or more embodiments, the polyisocyanate is NCO.
In one or more embodiments, the polyisocyanate is polymeric MDI in an amount of 30 to 32%.
In one or more embodiments, the polyisocyanate is one or more of polymeric MDI wanhua PM-200, polymeric MDI wanhua PM-2010, and polymeric MDI wanhua PM-400.
In one or more embodiments, the blowing agent is one or more of cyclopentane, HFC-134a, and LBA blowing agents.
In one or more embodiments, the blowing agent is a mixture of cyclopentane and AFC-134 a.
In one or more embodiments, the catalyst is at least one of an organometallic catalyst and an amine catalyst, preferably at least one of triethylenediamine, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N-methylpyrrolidone, and potassium acetate.
In one or more embodiments, the surfactant is at least one of an alkali metal salt of a fatty acid, an amine salt of a fatty acid, castor oil, ricinoleic acid, a silicone polymer.
In one or more embodiments, the surfactant is a siloxane polymer.
In one or more embodiments, the process for preparing a benzamide group-containing polyol is as follows: dimethyl phthalate, a catalyst and an amino alcohol compound are uniformly mixed in a reaction kettle, the temperature is controlled to be 70-130 ℃, the generated micromolecules are removed by reduced pressure distillation, the polyalcohol containing the benzamido is obtained, and a certain amount of alkylene oxide is added under the condition of not additionally adding the catalyst to obtain the polyalcohol containing the benzamido with the required hydroxyl value. The polyatomic alcohol containing the benzamido contains benzene rings and amido bonds, and has higher strength and lower K value compared with other polyether polyatomic alcohol.
One or more technical scheme's of this application beneficial effect lies in:
1) the structure of the benzamido polyether polyol contains benzene rings and amide groups, and meanwhile, no amino hydrogen exists, so that the catalytic activity is relatively weak, and due to the special structure, the polyurethane foam prepared from the benzamido polyether polyol has lower density, higher strength and lower K value;
2) through the special initial structure and the production process, the time consumption of the existing process on engineering is saved, the production efficiency is improved, meanwhile, the engineering cost and the raw material cost are greatly reduced, and the competitiveness of the product is improved.
Examples
The following examples and comparative examples source of the main materials and reagents:
low-functional polyether polyols with glycerol or propylene glycol as starter: the glycerol polyether polyol is prepared by the addition reaction of glycerol serving as an initiator and propylene oxide, and has a hydroxyl value of 180-240mgKOH/g and a functionality of 2.0-2.7;
oil ether: sucrose, diethylene glycol and palm oil are used as initiators to carry out addition reaction with propylene oxide, the hydroxyl value is 380-420mgKOH/g, and the functionality is 3.5-4.5;
sucrose-based polyether polyol (polyether polyol with sucrose as initiator): the polyether polyol taking sucrose and glycerol as initiators is prepared by the addition reaction of the sucrose and the glycerol as initiators and propylene oxide, and has a hydroxyl value of 380-440mgKOH/g and a functionality of 5.0-6.0.
OTDA polyether polyol: OTDA is used as an initiator, the hydroxyl value is 380mgKOH/g, and the functionality is 3.6.
Polyisocyanate:
purchased from warfarin chemistry;
surfactant (b): silicone oil B8525, from Mylar;
foaming agent: CP 10 parts, HFC-134a 5 parts, purchased from China neutralization.
Composite catalyst: the mixture of pentamethyldiethylenetriamine, potassium acetate and N-methylpyrrolidone in a mass ratio of 1:2: 4; purchased from air chemical industry.
The test method comprises the following steps:
(1) method for testing each index of polyether polyol
Determination of the hydroxyl number of the polyether polyols according to the standard: GB/T12008.3-2009 (GB/T12008.3-2009),
the viscosity of the polyether polyol is measured according to the standard; GB/T10008.7-2010.
(2) Method for testing properties of rigid polyurethane foam
The foam core density was tested according to the standard: GB/T6343-2009,
the foam thermal conductivity was tested according to the standard: GB/T10295-,
the foam compression strength was tested according to the standard: GB/T8813-.
Example 1
The preparation method of the polyether polyol containing the benzamide group comprises the following steps:
(1) adding 500g of dimethyl phthalate, 541g of diethanolamine and 3.5g of potassium methoxide into a stainless steel reaction kettle, replacing three times by nitrogen, punching and leakage testing, starting a vacuum pump to remove methanol generated in the kettle in vacuum when the pressure test is qualified, and condensing and recycling the generated methanol. When the temperature of the reaction kettle is raised to 100 ℃, the temperature is kept for continuously removing methanol in vacuum for 1.5 h;
(2) setting the reaction temperature in a stainless steel reaction kettle to be 115 +/-2 ℃, starting boosting the pressure in the reaction kettle from-0.1 MPa, controlling the pressure in the reaction kettle to be less than or equal to 0.35MPa, adding propylene oxide according to the flow rate of 300g/h, and reacting until 745g of propylene oxide is added into the reaction kettle in total;
(3) and (3) after the propylene oxide feeding is finished, continuing to react for 2h, then carrying out vacuum degassing for 30min at 100 ℃, and neutralizing and removing potassium ions in the system by using phosphoric acid after degassing to obtain the polyether polyol I containing the benzamide. The product had a hydroxyl value of 385mgKOH/g, a viscosity at 25 ℃ of 38475 mPas and a functionality of 4.
Example 2
The preparation method of the polyether polyol containing the benzamide group comprises the following steps:
(1) adding 500g of dimethyl phthalate, 595g of diethanolamine and 3.8g of potassium methoxide into a stainless steel reaction kettle, replacing three times by nitrogen, punching and leakage testing, starting a vacuum pump to remove methanol generated in the kettle in vacuum when the reaction kettle begins to heat up after pressure testing is qualified, and condensing and recovering the generated methanol. When the temperature of the reaction kettle is raised to 120 ℃, the temperature is kept for continuously removing methanol in vacuum for 1.0 h;
(2) setting the reaction temperature in a stainless steel reaction kettle to be 115 +/-2 ℃, starting boosting the pressure in the reaction kettle from-0.1 MPa, controlling the pressure in the reaction kettle to be less than or equal to 0.35MPa, adding propylene oxide according to the flow rate of 400g/h, and reacting until 809g of propylene oxide is added into the reaction kettle;
(3) and (3) after the propylene oxide feeding is finished, continuing to react for 1.8h, then carrying out vacuum degassing for 30min at 100 ℃, and neutralizing and removing potassium ions in the system by using phosphoric acid after degassing to obtain the polyether polyol II containing the benzamide group. The product had a hydroxyl value of 383mgKOH/g, a viscosity of 24996 mPas at 25 ℃ and a functionality of 3.8.
Example 3
The preparation method of the polyether polyol containing the benzamide group comprises the following steps:
(1) adding 500g of dimethyl phthalate, 685g of diisopropanolamine and 4.6g of potassium hydroxide into a stainless steel reaction kettle, replacing three times by nitrogen, punching and testing leakage, starting a vacuum pump to remove methanol generated in the kettle in vacuum when the reaction kettle begins to heat after the pressure test is qualified, and condensing and recovering the generated methanol. When the temperature of the reaction kettle is increased to 90 ℃, the temperature is kept for continuously removing methanol in vacuum for 3.2 hours;
(2) setting the reaction temperature in a stainless steel reaction kettle to be 130 +/-2 ℃, starting boosting the pressure in the reaction kettle from-0.1 MPa, controlling the pressure of the reaction kettle to be less than or equal to 0.35MPa, adding propylene oxide according to the flow rate of 220g/h, and reacting until 565g of propylene oxide is added into the reaction kettle in total;
(3) and (3) after the propylene oxide feeding is finished, continuing to react for 2h, then carrying out vacuum degassing for 30min at 100 ℃, and neutralizing by using phosphoric acid to remove potassium ions in the system after degassing to obtain the benzamido polyether polyol III. The product had a hydroxyl value of 383mgKOH/g, a viscosity of 29436 mPas at 25 ℃ and a functionality of 4.
Example 4
The preparation method of the polyether polyol containing the benzamide group comprises the following steps:
(1) adding 500g of dimethyl phthalate, 685g of diisopropanolamine and 4.2g of potassium hydroxide into a stainless steel reaction kettle, replacing three times by nitrogen, punching and testing leakage, starting a vacuum pump to remove methanol generated in the kettle in vacuum when the reaction kettle begins to heat after the pressure test is qualified, and condensing and recovering the generated methanol. When the temperature of the reaction kettle is increased to 120 ℃, the temperature is kept for continuous vacuum methanol removal for 2.0 h;
(2) setting the reaction temperature in a stainless steel reaction kettle to be 120 +/-5 ℃, starting boosting the pressure in the reaction kettle from-0.1 MPa, controlling the pressure in the reaction kettle to be less than or equal to 0.35MPa, and simultaneously adding propylene oxide and ethylene oxide according to the flow rates of 200g/h and 100g/h respectively and reacting until 395g of propylene oxide and 170g of ethylene oxide are added into the reaction kettle;
(3) and (3) after the feeding of the propylene oxide and the ethylene oxide is finished, continuing to react for 2h, then carrying out vacuum degassing for 30min at the temperature of 100 ℃, and neutralizing and removing potassium ions in the system by using phosphoric acid after degassing to obtain the benzamido polyether polyol IV. The product had a hydroxyl number of 379mgKOH/g, a viscosity of 24359mPa · s at 25 ℃ and a functionality of 4.
Examples 5 to 9
Examples 5 to 9 are examples of rigid polyurethane foams. Rigid polyurethane foams of examples 5 to 9 were produced using the formulations shown in Table 1 below, wherein the formulations of the examples further contained a polyisocyanate (not shown in Table 1) in an amount of 1.2 times the equivalent weight based on the polyol. Rigid polyurethane foams of examples 5-9 were prepared as follows: polyether polyol, a surfactant and a catalyst are uniformly mixed and cooled to below 10 ℃ to obtain combined polyether; and cooling the foaming agent to below 15 ℃, adding the foaming agent into the combined polyether, mixing the foaming agent with isocyanate after uniform mixing, foaming at the material temperature of 17-21 ℃ under the pressure of 100-150 bar (gauge pressure), wherein the filling coefficient of the reaction mixture in a mould is 1.1-1.5, and the demoulding time is less than or equal to 150S, so that the polyurethane rigid foam is prepared.
TABLE 1
| Component/part by weight | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 9 |
| Benzamidopolyether polyols I | 30 | ||||
| Benzamidopolyether polyol II | 30 | ||||
| Benzamidopolyether polyol III | 30 | ||||
| Benzamido polyether polyol IV | 30 | ||||
| OTDA-based polyether polyols | 30 | ||||
| Sucrose-based polyether polyol | 25 | 25 | 25 | 25 | 25 |
| Vegetable oil polyether polyols | 40 | 40 | 40 | 40 | 40 |
| Low-functional polyether polyols | 5 | 5 | 5 | 5 | 5 |
| Surface active agent | 3.2 | 3.2 | 3.2 | 3.2 | 3.2 |
| Composite catalyst | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 |
| Foaming agent | 15 | 15 | 15 | 15 | 15 |
The properties of the rigid polyurethane foams were tested according to the test methods described above and the results are shown in Table 2.
TABLE 2
As can be seen from the results of the performance tests in Table 2, the polyurethane foams obtained in the examples have better compressive strength, lower thermal conductivity and better surface than the comparative products under similar foam core density conditions.
It will be understood by those skilled in the art that various modifications and changes may be made to the present invention without departing from the spirit and scope of the invention. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A benzamide group-containing polyether polyol having the structure:
wherein
n, m, l, q are each independently 0, 1, 2, 3, 4, 5 or 6;
r is H, -CH3or-CH2-CH3；
Preferably, the polyether polyol containing benzamido groups has an average molecular weight of 350-1000 and an average functionality of 3-4.
2. A process for preparing the polyether polyol of claim 1, comprising:
(1) uniformly mixing dimethyl phthalate, a catalyst and an amino alcohol compound, and carrying out reduced pressure distillation at 70-130 ℃ for 1-4 hours to remove methanol generated in the system;
(2) at the temperature of 80-150 ℃ and the pressure of 0.05-0.5MPa, adding alkylene oxide to react for 1-4 hours to obtain polyether polyol containing benzamide groups;
(3) optionally, removing unreacted alkylene oxide to obtain the polyether polyol containing benzamide groups.
3. The production method according to claim 2, wherein the amino alcohol compound is a primary or secondary amine alcohol; preferably, the primary or secondary amine alcohol is one or more of monoethanolamine, diethanolamine, diisopropanolamine, monoisopropanolamine, preferably diethanolamine or diisopropanolamine;
the dimethyl phthalate is dimethyl phthalate, dimethyl isophthalate or dimethyl terephthalate, preferably dimethyl phthalate;
the catalyst is selected from CH3ONa、CH3OK, KOH, NaOH, CsOH, preferably CH3OK or KOH;
the alkylene oxide is one or more of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin, and is preferably propylene oxide or ethylene oxide.
4. The preparation method according to claim 2, wherein the molar ratio of dimethyl phthalate to amino alcohol compound is 1:2-12, preferably 1: 2-8; preferably, the catalyst is 0.1-1.5%, preferably 0.5-1.0% of the total weight of the dimethyl phthalate and the aminoalcohol compound.
5. A polyol composition for preparing a polyurethane foam, the polyol composition comprising 10-90 wt% of the benzamido-containing polyether polyol of claim 1, 10-90 wt% of one or more of other polyether polyols; preferably 20-60 wt% of the benzamido-containing polyether polyol of claim 1, 40-80 wt% of one or more of the other polyether polyols.
6. The polyol composition of claim 5, wherein the other polyether polyol is a mixture of one or more of an oil ether, a sucrose-initiated polyether polyol, a propylene glycol or glycerol-initiated polyether polyol;
preferably, the polyol composition comprises 20-60 wt% of the benzamido-containing polyether polyol of claim 1, 5-40 wt%, preferably 10-30 wt% of the oil ether, 15-40 wt% of the polyether polyol with sucrose as starter, and 0-20 wt% of the polyether polyol with propylene glycol or glycerol as starter;
more preferably, the polyol composition comprises 20-40 wt% of the benzamido-containing polyether polyol of claim 1;
preferably, the oil ether is prepared by the addition reaction of vegetable oil, animal oil and recovered oil with small molecular polyol such as sucrose as an initiator and alkylene oxide, the hydroxyl value is 350-500mgKOH/g, and the functionality is 3.5-5.0;
preferably, the polyether polyol taking sucrose as an initiator is prepared by taking sucrose and glycerol as initial raw materials and carrying out addition reaction with propylene oxide, wherein the hydroxyl value is 350-450mgKOH/g, and the functionality is 5.0-6.5;
preferably, the polyether polyol taking propylene glycol or glycerol as an initiator is prepared by the addition reaction of glycerol or propylene glycol as an initiator and propylene oxide or ethylene oxide, and has a hydroxyl value of 300-500mgKOH/g and a functionality of 2.0-3.0.
7. A method of preparing a polyurethane foam comprising the steps of:
1) forming a mixture comprising: the polyol composition of claim 5 or 6, at least one blowing agent, at least one polyisocyanate, at least one catalyst, at least one surfactant;
2) reacting the mixture to expand and cure to form a polyurethane foam; preferably, the polyurethane foam is a rigid polyurethane foam;
preferably, the polyisocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate), more preferably polymeric MDI with a content of 30-32%; more preferably, the polyisocyanate is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010 and polymeric MDI Wanhua PM-400;
preferably, the blowing agent is one or more of cyclopentane, HFC-134a and LBA blowing agents; more preferably, the blowing agent is a mixture of cyclopentane and AFC-134 a;
preferably, the catalyst is at least one of an organometallic catalyst and an amine catalyst, more preferably at least one of triethylene diamine, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N-methylpyrrolidone, and potassium acetate;
preferably, the surfactant is at least one of an alkali metal salt of a fatty acid, an amine salt of a fatty acid, castor oil, ricinoleic acid, a silicone polymer, preferably a silicone polymer.
8. A production method according to claim 7, wherein the polyisocyanate is used in an amount of 1.1 to 1.4; preferably, the blowing agent, the catalyst and the surfactant are used in an amount of 12 to 25 parts by weight, 2 to 4 parts by weight and 2 to 6 parts by weight, respectively, in this order, based on 100 parts by weight of the polyol composition.
9. Use of a benzamide group-containing polyether polyol of claim 1 or a polyol composition of claim 5 or 6 in the preparation of a polyurethane foam.
10. A polyurethane foam obtained by the production method according to claim 7 or 8.
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