CN112375215A - High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic - Google Patents
High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic Download PDFInfo
- Publication number
- CN112375215A CN112375215A CN202011361636.0A CN202011361636A CN112375215A CN 112375215 A CN112375215 A CN 112375215A CN 202011361636 A CN202011361636 A CN 202011361636A CN 112375215 A CN112375215 A CN 112375215A
- Authority
- CN
- China
- Prior art keywords
- polyether
- polyurethane foam
- alpha
- oleophylic
- weight parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/2603—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 oxygen
- C08G65/2606—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 oxygen containing hydroxyl groups
- C08G65/2609—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 oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- 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
- C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides high oleophylic polyether and application thereof in preparation of polyurethane foam plastic, belonging to the field of high polymer materials. The high oleophylic polyether is prepared by ring opening polymerization of polyhydric alcohol and high carbon chain alpha-alkylene oxide under the action of a catalyst. The preparation method of the polyurethane foam comprises the following steps: mixing 100 weight parts of the high oleophylic polyether in the claim 1-3, 0.3-2 weight parts of catalyst, 0.5-15 weight parts of water, 0.5-10 weight parts of foam stabilizer and 0-50 weight parts of physical foaming agent at 20-30 ℃, and stirring uniformly; and adding 10-150 parts by weight of polyisocyanate into the obtained mixture, stirring, foaming and curing to obtain the polyurethane foam plastic. The polyurethane foam plastic prepared by the high oleophylic polyether has high oil absorption efficiency and high oil absorption speed.
Description
Technical Field
The invention provides high oleophylic polyether and application thereof in preparation of polyurethane foam plastic, belonging to the field of high polymer materials.
Background
With the rapid growth of petrochemical industry, a series of accidents such as oil field leakage, oil ship leakage, oil pipeline breakage and the like caused in oil product transportation and water pollution accidents caused by the discharge of waste water and liquid containing oil pollution frequently occur, and the environment on which human beings live is seriously threatened.
The polyurethane foam plastic has the characteristics of large specific surface area, wear resistance, portability, flexibility, acid and alkali corrosion resistance, high strength and the like. The oil absorption material has large specific surface area and rich internal void structure, so that the oil absorption material can be used for absorbing oil stains. However, in the prior art, the polyurethane foam plastic for absorbing oil stains has the disadvantages of complicated preparation steps and high cost, and the oil absorption efficiency and speed can not meet the requirements of practical application.
Disclosure of Invention
The invention aims to provide high oleophylic polyether, and polyurethane foam plastic prepared by adopting the high oleophylic polyether has high oil absorption efficiency and high oil absorption speed.
The invention also aims to provide the application of the high oleophylic polyether in preparing polyurethane foam plastics, and the obtained polyurethane foam plastics have high oil absorption efficiency and high oil absorption speed.
The purpose of the invention is realized by adopting the following technical scheme.
A high oleophylic polyether is prepared by ring opening polymerization of polyhydric alcohol and high carbon chain alpha alkylene oxide under the action of a catalyst; the polyhydric alcohol is one or a mixture of more than two of allyl alcohol, methanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylenediamine, cyclohexanediol and resorcinol; the catalyst is selected from one or a mixture of more than two of potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide, sodium methoxide, potassium methoxide and a bimetallic complex catalyst; the high carbon chain alpha alkylene oxide is selected from alpha alkylene oxides of C4-C30.
In the invention, the high carbon chain alpha alkylene oxide is one or more than two of alpha butylene oxide, alpha hexylene oxide, alpha heptane oxide, alpha octane oxide and alpha sunflower oxide.
In the invention, the reaction temperature is 120-140 ℃, and the reaction time is 2-5 h.
The invention also provides an application of the high oleophylic polyether in preparing polyurethane foam plastics, which comprises the following steps:
(1) mixing 100 weight parts of the high oleophylic polyether in the claim 1-3, 0.3-2 weight parts of catalyst, 0.5-15 weight parts of water, 0.5-10 weight parts of foam stabilizer and 0-50 weight parts of physical foaming agent at 20-30 ℃, and stirring uniformly;
(2) and (2) adding 10-150 parts by weight of polyisocyanate into the mixture obtained in the step (1), stirring, foaming and curing to obtain the polyurethane foam.
In the present invention, the polyisocyanate in step (2) is one or a mixture of two or more of toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated phenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
In the invention, the catalyst is at least one of ethylenediamine, A1, A33, N' -dimethylaniline, triethylenediamine, N-methylmorpholine, triethanolamine, ethanolamine, diethanolamine, ethylenediamine, formic acid, dimethylethanolamine, N-dimethylcyclohexylamine, stannous octoate, dibutyltin dilaurate, zinc isooctanoate, bismuth isooctanoate, tetrabutyl titanate, and tetraisopropyl titanate.
In the invention, the foam homogenizing agent is one or a mixture of more than two of polyether modified organosilicon surfactants, fatty alcohols, silicones, alkylolamides and fatty alcohol-polyoxyethylene ether surfactants; the foam stabilizer is preferably polyether modified silicone surfactant, such as one or mixture of more than two of L580 of Meighur, and DC-5810 and DC-5188 of air chemical products, Inc.
In the invention, the physical foaming agent is one or a mixture of more of dichloromethane, liquid carbon dioxide, n-pentane, cyclopentane, isopentane or petroleum ether.
The invention also provides application of the polyurethane foam in the aspect of oil stain adsorption.
The polyether polyol has high lipophilicity, and can endow polyurethane foam with ultrahigh lipophilicity and openness.
The number average molecular weight of the highly lipophilic polyether prepared in examples 1-3 of the present invention is 200-.
Compared with the prior art, the invention has the following advantages:
(1) the high oleophylic polyether of the invention introduces a great deal of oleophylic high-carbon chain segments, so that the prepared polyurethane foam has higher oil absorption rate, higher oil absorption speed and lower cost; in addition, the opening rate of the polyurethane soft foam material prepared by the invention is more than 98 percent, and the foam holes are uniform.
(2) The polyurethane foam plastic prepared by the method is simple, safe and environment-friendly to operate, and the prepared polyurethane soft foam material is very suitable for a carrier in oil stain treatment.
(3) The polyurethane foam plastic prepared by the method has the density of 5-50 kg/m3And the oil absorption foam with lower density can be prepared, and the cost is saved.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Sources of reagents used in the present invention:
catalyst A33 was an amine catalyst, produced by Meiji corporation, USA, and was a liquid containing 33% (by mass) of triethylenediamine. Catalyst A1 is an amine catalyst, manufactured by Shanghai Deyin chemical Co., Ltd, and is a dipropylene glycol solution of bis (dimethylaminoethyl) ether with a mass percentage of 70%.
EXAMPLE 1 preparation of polyurethane foam 1
Polyurethane foam 1 was prepared as follows:
(1) adding 30.6 g of glycerol and 3.5 g of KOH into a reaction kettle, replacing air by nitrogen, vacuumizing to-0.085 Mpa of vacuum degree, heating to 120 ℃, and preserving heat for 2 hours at 120 ℃; and (3) closing the vacuum pump, starting to dropwise add 969.4 g of alpha epoxy decane, ensuring the temperature of the materials in the kettle to be 125 ℃ during dropwise adding, and reacting for 5 hours at 140 ℃ after dropwise adding is finished. After the reaction is finished, the temperature is reduced to 120 ℃, then the vacuum degree is pumped to-0.085 Mpa, and the temperature is kept for 1h at 120 ℃ and-0.085 Mpa. Cooling to 80 ℃ and discharging to obtain the high oleophylic polyether crude ether. Adding 50 g of water into high oleophylic polyether crude ether at the temperature of 80 ℃, stirring for 1h, adding 6.7 g of phosphoric acid (solid), stirring for 1h, adding 3.0 g of polyether adsorbent (product number 100# of Shandong jujube Yang Yonghua chemical Co., Ltd.), stirring for 1h, heating to 120 ℃, dehydrating for 2 h, press-filtering to remove the polyether adsorbent, and taking the filtrate to obtain the high oleophylic polyether a.
(2) 100 parts by weight of high oleophilic polyether a, 4 parts by weight of water, 1.2 parts by weight of foam stabilizer L580 (Meyer corporation, USA), 5 parts by weight of dichloromethane, 0.5 part by weight of catalyst A33 and 0.3 part by weight of stannous octoate (T9, Henry high molecular weight materials Co., Ltd.) were mixed and stirred uniformly at 25 ℃ to obtain mixture A. And (2) continuously adding 50 parts by weight of TDI80 (Cangzhou Daghuakigan Co., Ltd.) and 10 parts by weight of polymethylene polyphenyl polyisocyanate (product number PM200, Vanhua chemical group Co., Ltd.) into the mixture A, stirring at a high speed, pouring the mixture into a prepared mould quickly after the material is slightly whitened, filling the mould with foam, standing for 30min, putting the mixture into a 50 ℃ oven for curing for 1h, cooling and demoulding to obtain the polyurethane foam plastic 1. Wherein one part by weight of TDI80 and highly lipophilic polyether a are equal.
EXAMPLE 2 preparation of polyurethane foam 2
Polyurethane foam 2 was prepared as follows:
(1) adding 27g of trimethylolpropane and 3.2 g of CsOH into a reaction kettle, replacing air with nitrogen, vacuumizing until the vacuum degree is-0.09 Mpa, heating to 120 ℃, and preserving heat for 2 hours at 120 ℃; and (3) closing the vacuum pump, starting to dropwise add 973 g of alpha-epoxyoctane, controlling the temperature of materials in the kettle to be 130 ℃ during dropwise adding, and continuing to react for 4 hours at 130 ℃ after dropwise adding is finished. After the reaction is finished, the temperature is reduced to 120 ℃, then the vacuum degree is pumped to-0.085 Mpa, and the temperature is kept for 1h at 120 ℃ and-0.085 Mpa. Finally, the temperature is reduced to 80 ℃, and the high oleophylic polyether crude ether is obtained after discharging. Adding 50 g of water into high oleophylic polyether crude ether at the temperature of 80 ℃, and stirring for 1 h; adding 6.1 g phosphoric acid (solid) and stirring for 1 h; adding 3.5 g polyether adsorbent (Shandong jujube Yang Yonghua chemical Co., Ltd.), and stirring for 1 h; heating to 120 ℃, dehydrating for 2 h at 120 ℃, performing pressure filtration to remove the polyether adsorbent, and taking the filtrate to obtain the high oleophylic polyether b.
(2) 100 parts by weight of high oleophilic polyether B, 3.5 parts by weight of water, 2 parts by weight of foam stabilizer L580 (Meiji Kogyo Co., Ltd.), 0.5 part by weight of catalyst A1 and 0.2 part by weight of stannous octoate (T9, Henry high molecular weight materials Co., Ltd.) were mixed and stirred at 20 ℃ to obtain mixture B. Adding 24 parts by weight of hexamethylene diisocyanate (rich chemical company, Ltd.) and 24 parts by weight of polymethylene polyphenyl polyisocyanate (product number PM200, Vanhua chemical company, Ltd.) into the mixture B, stirring at a high speed, pouring the mixture into a prepared mold quickly after the material is slightly whitened, filling the mold with foam, standing for 30min, putting the mixture into a 50 ℃ oven for curing for 1h, cooling and demolding to obtain the polyurethane foam 2. One part by weight of hexamethylene diisocyanate and the highly lipophilic polyether b being equal
Example 3
The polyurethane foam 3 is prepared by the following method:
(1) adding 151g of diglycol and 3.0 g of KOH into a reaction kettle, replacing air by nitrogen, vacuumizing to the vacuum degree of-0.085 Mpa, heating to 120 ℃, and preserving heat at 120 ℃ and-0.085 Mpa for 2 hours; turning off the vacuum pump, dropwise adding 849 g of alpha epoxy decane while ensuring the temperature of the materials in the kettle to be 120 ℃, and reacting for 3 hours at 120 ℃ after the dropwise adding is finished. After the reaction is finished, vacuumizing to the vacuum degree of-0.085 Mpa, preserving the heat for 1h at the temperature of 120 ℃ and-0.085 Mpa, cooling to 80 ℃, and discharging to obtain the high oleophylic polyether crude ether. Adding 50 g of water into high oleophylic polyether crude ether at the temperature of 80 ℃, and stirring for 1 h; then 5.8 g phosphoric acid (solid) is added and stirred for 1 h; then adding 4.1 g of polyether adsorbent (Shandong jujube Yang Yonghua chemical Co., Ltd.), and stirring for 1 h; and finally, heating to 120 ℃, dehydrating for 2 h at 120 ℃, performing pressure filtration to remove the polyether adsorbent, and taking the filtrate to obtain the high oleophylic polyether c.
(2) 50 parts by weight of a highly lipophilic polyether C, 50 parts by weight of a polyether a (prepared in example 1), 10.0 parts by weight of water, 8.0 parts by weight of a foam stabilizer L580 (Meyer corporation, USA), 0.8 part by weight of a catalyst A33, 0.3 part by weight of a catalyst A1, 0.7 part by weight of stannous octoate (T9, Henry Highur Polymer Co., Ltd.) and 30 parts by weight of methylene chloride were mixed and stirred at 30 ℃ to obtain a mixture C. Adding 123 parts by weight of TDI80 (Cangzhou Daghuangsu Co., Ltd.), stirring at high speed, pouring into a prepared mold after the material turns slightly white, filling the mold with foam, standing for 30min, putting into a 50 ℃ oven for curing for 1h, cooling and demolding to obtain the polyurethane foam plastic 3. One part by weight of TDI80 and highly lipophilic polyether c are equal.
Comparative example 1
Preparation of control polyurethane foam 1: at 25 ℃, 100 parts by weight of polyether polyol ZS-2802 (glycerol is used as an initiator, and the hydroxyl value is 56 mgKOH. g)-1Produced by Jiangsu clock mountain chemical Co., Ltd.), 4 parts by weight of water, 1.2 parts by weight of a foam stabilizer L580, 5 parts by weight of methylene chloride, 0.5 part by weight of a catalyst A33 and 0.3 part by weight of stannous octoate (T9, Henry high molecular weight materials Co., Ltd.) were mixed and stirred uniformly to obtain a mixture D. Adding 50 parts by weight of TDI80 (Cangzhou Daghuangsu Co., Ltd.) into the mixture D, stirring at high speed, pouring the mixture into a prepared mold after the material is slightly white, filling the mold with foam, standing for 30min, putting the mixture into a 50 ℃ oven for curing for 1h, cooling and demolding to obtain the control polyurethane foam 1. Wherein the polyether polyol ZS-2802 is propylene oxide polyether with number average molecular weight of 3000Is prepared by addition polymerization with glycerin as initiator and is purchased from Jiangsu clock mountain chemical industry Co.
Comparative example 2
According to the formulation shown in patent CN 106986978A, the polyether polyol is a mixture of polytetrahydrofuran glycol, polypropylene glycol and polyglycerol. The isocyanate is a mixture of hexamethylene diisocyanate and polymethylene phenyl polyisocyanate, and the mixture ratio of the hexamethylene diisocyanate to the polymethylene phenyl polyisocyanate is as follows in parts by weight: polytetrahydrofuran diol (hydroxyl value 56 mgKOH. g)-1) 50 parts of polypropylene glycol (hydroxyl value is 56 mgKOH g)-1) 20 portions of polyglycerol (hydroxyl value is 60 mgKOH. g)-1) 20 parts of resorcinol dihydroxyethyl ether, 2 parts of methyl silicone oil (L580), 8 parts of ammonium polyphosphate, 5 parts of water, 2 parts of dimethylethanolamine, 2 parts of perfluorotriethylamine, 20 parts of hexamethylene diisocyanate and 20 parts of polymethylene phenyl polyisocyanate. The preparation method comprises the following steps: (1) mixing the components except the hexamethylene diisocyanate and the polymethylene phenyl polyisocyanate, and uniformly stirring; (2) mixing hexamethylene diisocyanate and polymethylene phenyl polyisocyanate, and uniformly stirring; (3) and (3) pouring the material obtained in the step (2) into the material obtained in the step (1), quickly stirring for 5s by using an electric stirrer, and pouring into a mold for foaming molding to obtain the control polyurethane foam plastic 2.
The properties of polyurethane foams 1, 2, 3 (examples 1-3) and comparative polyurethane foams 1, 2 were compared.
And (3) oil absorption rate determination: firstly, placing each foamed plastic with the size of 100mm multiplied by 50mm in a vacuum drying oven with the temperature of 100 ℃ for drying for 6 h, accurately weighing the mass of the foamed plastic by an electronic balance, respectively adding 200g of gasoline, 200g of engine oil, 200g of carbon tetrachloride and 200g of toluene in different beakers, putting each foamed plastic into the beakers, adsorbing for 30min, taking out, placing on a filter screen, standing for 5min, weighing, calculating the oil absorption capacity of the foamed plastic, and calculating the oil absorption rate of the obtained foamed plastic according to the following formula: oil absorption capacity = (foam mass after oil absorption-foam mass before oil absorption)/foam mass before oil absorption.
TABLE 1 comparison of oil absorption Properties of polyurethane foams
| Numbering | Polyurethane foam 1 | Polyurethane foam 2 | Polyurethane foam 3 | Comparative polyurethane foam 1 | Comparative polyurethane foam 2 |
| Foam Density (kg/m)3） | 22 | 31 | 8 | 30 | 20 |
| Foam open-cell content (%) | 97.6 | 98.5 | 98.6 | 74.3 | 84.1 |
| Gasoline adsorption rate (g/g) | 75 | 81 | 69 | 36 | 48 |
| Adsorption rate of engine oil (g/g) | 59 | 68 | 61 | 10 | 13 |
| Carbon tetrachloride adsorption Rate (g/g) | 93 | 96 | 91 | 58 | 82 |
| Toluene adsorption Rate (g/g) | 87 | 92 | 83 | 45 | 66 |
The oil absorption of each foam is shown in Table 1.
After the oily substances are recovered by extrusion, the foams are subjected to a recycling test after being washed and dried by ethanol, and after the test is repeated for 100 times, the oil absorption performance of each foam is continuously measured, and the results are shown in table 2.
TABLE 2 comparison of oil absorption Properties of the foams after repeated use
| Numbering | Polyurethane foam 1 | Polyurethane foam 2 | Polyurethane foam 3 | Comparative polyurethane foam 1 | Comparative polyurethane foam 2 |
| Gasoline adsorption rate (g/g) | 72 | 79 | 68 | 25 | 36 |
| Adsorption rate of engine oil (g/g) | 59 | 68 | 58 | 5 | 8 |
| Carbon tetrachloride adsorption Rate (g/g) | 90 | 94 | 88 | 49 | 71 |
| Toluene adsorption Rate (g/g) | 86 | 90 | 80 | 37 | 52 |
From Table 2, it can be seen that the flexible polyurethane foam obtained by the method of the present invention has less oil absorption attenuation after repeated use, still has high oil absorption, and can be repeatedly used.
And (3) measuring the oil absorption rate of the water surface: firstly, placing each foam plastic with the size of 100mm multiplied by 50mm in a vacuum drying box with the temperature of 100 ℃ for drying for 6 h, accurately weighing the mass of each foam plastic by an electronic balance, respectively adding 100g of gasoline, 100g of engine oil and 100g of toluene in different beakers, then adding 1000g of water into each beaker for mixing, clamping each foam plastic close to oil substances on the water surface by using tweezers, taking out each foam plastic after 10min of oil substance adsorption, placing on a filter screen for standing for 5min, weighing, calculating the oil absorption capacity of each foam plastic, and calculating the oil absorption rate of each obtained foam plastic according to the following formula: oil absorption capacity = (foam mass after oil absorption-foam mass before oil absorption)/foam mass before oil absorption.
TABLE 3 comparison of oil absorption Properties of the foams
| Numbering | Polyurethane foam 1 | Polyurethane foam 2 | Polyurethane foam 3 | Control polyurethaneFoamed plastics 1 | Comparative polyurethane foam 2 |
| Gasoline adsorption rate (g/g) | 70 | 75 | 62 | 22 | 30 |
| Adsorption rate of engine oil (g/g) | 55 | 62 | 55 | 4 | 7 |
| Toluene adsorption Rate (g/g) | 80 | 85 | 77 | 30 | 45 |
From Table 3, it can be seen that the polyurethane foam obtained by the method of the present invention has excellent effects on the adsorption of oil stains on water surface, and has a high oil absorption rate and can absorb a large amount of oil stains on water surface in a short time as compared with the control polyurethane foam 1 and the control polyurethane foam 2.
Claims (9)
1. A high oleophylic polyether is characterized in that the polyether is prepared by ring opening polymerization of polyhydric alcohol and high carbon chain alpha-alkylene oxide under the action of a catalyst; the polyhydric alcohol is one or a mixture of more than two of allyl alcohol, methanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylenediamine, cyclohexanediol and resorcinol; the catalyst is selected from one or a mixture of more than two of potassium hydroxide, sodium hydroxide, barium hydroxide, cesium hydroxide, sodium methoxide, potassium methoxide and a bimetallic complex catalyst; the high carbon chain alpha alkylene oxide is selected from alpha alkylene oxides of C4-C30.
2. The highly lipophilic polyether according to claim 1, wherein the high carbon chain alpha alkylene oxide is one or more of alpha butylene oxide, alpha hexylene oxide, alpha heptane oxide, alpha octane oxide, and alpha sunflower oxide.
3. Highly lipophilic polyether according to one of claims 1-2, characterized in that: the reaction temperature is 120-140 ℃, and the reaction time is 2-5 h.
4. Use of the high oleophilic polyether of claims 1-3 in the preparation of a polyurethane foam, characterized in that it comprises the steps of:
(1) mixing 100 weight parts of the high oleophylic polyether in the claim 1-3, 0.3-2 weight parts of catalyst, 0.5-15 weight parts of water, 0.5-10 weight parts of foam stabilizer and 0-50 weight parts of physical foaming agent at 20-30 ℃, and stirring uniformly;
(2) and (2) adding 10-150 parts by weight of polyisocyanate into the mixture obtained in the step (1), stirring, foaming and curing to obtain the polyurethane foam.
5. The use according to claim 4, wherein the polyisocyanate in step (2) is one or a mixture of two or more of toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated phenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
6. The use according to claim 5, wherein the catalyst is at least one of ethylenediamine, A1, A33, N' -dimethylaniline, triethylenediamine, N-methylmorpholine, triethanolamine, ethanolamine, diethanolamine, ethylenediamine, formic acid, dimethylethanolamine, N-dimethylcyclohexylamine, stannous octoate, dibutyltin dilaurate, zinc isooctanoate, bismuth isooctanoate, tetrabutyltitanate, tetraisopropyl titanate.
7. The application of claim 6, wherein the foam stabilizer is one or a mixture of more than two of polyether modified organosilicon surfactants, fatty alcohols, silicones, alkylolamides and fatty alcohol-polyoxyethylene ether surfactants; the foam stabilizer is preferably polyether modified silicone surfactant, such as one or mixture of more than two of L580 of Meighur, and DC-5810 and DC-5188 of air chemical products, Inc.
8. The use according to claim 7, wherein the physical blowing agent is one or more of dichloromethane, liquid carbon dioxide, n-pentane, cyclopentane, isopentane or petroleum ether.
9. Use of the polyurethane foam according to claim 4 for oil stain absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361636.0A CN112375215A (en) | 2020-11-27 | 2020-11-27 | High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361636.0A CN112375215A (en) | 2020-11-27 | 2020-11-27 | High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112375215A true CN112375215A (en) | 2021-02-19 |
Family
ID=74588560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011361636.0A Pending CN112375215A (en) | 2020-11-27 | 2020-11-27 | High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112375215A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961304A (en) * | 2021-03-11 | 2021-06-15 | 江苏钟山化工有限公司 | Method for preparing polyurethane foam capable of rapidly settling in water |
| CN113980237A (en) * | 2021-10-22 | 2022-01-28 | 东莞市米儿塑胶原料有限公司 | Preparation method of reusable TPU (thermoplastic polyurethane) oil stain removing cloth |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101341112A (en) * | 2005-12-22 | 2009-01-07 | 拜尔材料科学有限公司 | Base-catalyzed alkoxylation in the presence of non-linear polyoxyethylene-containing compounds |
| CN101341189A (en) * | 2005-12-22 | 2009-01-07 | 拜尔材料科学有限公司 | Long chain polyether polyols |
| CN108976775A (en) * | 2018-07-05 | 2018-12-11 | 江苏钟山化工有限公司 | The preparation method and applications for the flexible polyurethane foam material that can be settled in water |
-
2020
- 2020-11-27 CN CN202011361636.0A patent/CN112375215A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101341112A (en) * | 2005-12-22 | 2009-01-07 | 拜尔材料科学有限公司 | Base-catalyzed alkoxylation in the presence of non-linear polyoxyethylene-containing compounds |
| CN101341189A (en) * | 2005-12-22 | 2009-01-07 | 拜尔材料科学有限公司 | Long chain polyether polyols |
| CN108976775A (en) * | 2018-07-05 | 2018-12-11 | 江苏钟山化工有限公司 | The preparation method and applications for the flexible polyurethane foam material that can be settled in water |
Non-Patent Citations (1)
| Title |
|---|
| 丁浩: "《塑料工业实用手册》", 31 August 2000, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961304A (en) * | 2021-03-11 | 2021-06-15 | 江苏钟山化工有限公司 | Method for preparing polyurethane foam capable of rapidly settling in water |
| CN113980237A (en) * | 2021-10-22 | 2022-01-28 | 东莞市米儿塑胶原料有限公司 | Preparation method of reusable TPU (thermoplastic polyurethane) oil stain removing cloth |
| CN113980237B (en) * | 2021-10-22 | 2023-01-17 | 东莞市米儿塑胶原料有限公司 | Preparation method of reusable TPU (thermoplastic polyurethane) oil stain removing cloth |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3605848A (en) | Microcellular urethane elastomers of relatively low density | |
| US9035105B2 (en) | Process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams | |
| CN1320016C (en) | Agent for reducing force-to-crush of high-support flexible foams | |
| JP6038775B2 (en) | Polyols suitable for the production of thermoformed foam with renewable resource content | |
| CN112375215A (en) | High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic | |
| CA3003315C (en) | Polyetheresters and their use in rigid polyurethane foams | |
| CN1404503A (en) | Rigid polyurethane foams | |
| KR20130115271A (en) | Process for making low density high resiliency flexible polyurethane foam | |
| JP5824043B2 (en) | Improved polyurethane sealing foam compositions plasticized with fatty acid esters | |
| CN103314031A (en) | Polyetherester polyols | |
| RU2551428C2 (en) | Method of obtaining leather layer basing on plastic, elastic, thermoreactive phase-separated polyurethane material | |
| JP2011208059A (en) | Semi-rigid polyurethane foam used for instrument panel for vehicle and method of manufacturing the same | |
| EP2039711A1 (en) | Storage-stable polyol blends containing N-pentane | |
| US20140329985A1 (en) | Method for producing polyether ester polyols | |
| ES266467A1 (en) | Method of making a polyetherurethane using an aromatic tin catalyst | |
| KR20150128977A (en) | Base-catalyzed, long chain, active polyethers from short chain dmc-catalyzed starters | |
| EP4056615A1 (en) | Novel in-situ formed polyols, a process for their preparation, foams prepared from these in-situ formed polyols and a process for their preparation | |
| JP5763674B2 (en) | Method for producing low density polyurethane foam for sound absorption and vibration absorption | |
| CN114057981B (en) | Polyurethane rigid foam and combined polyether used by same | |
| CN112961304B (en) | Method for preparing polyurethane foam capable of rapidly settling in water | |
| CN109988279B (en) | Molecular chain soft segment flame-retardant polyurethane foam | |
| CN109880058B (en) | Preparation method of molecular chain soft segment flame-retardant polyurethane foam | |
| JPS5947222A (en) | Production of polyurethane elastomer | |
| JPS6346768B2 (en) | ||
| US11718705B2 (en) | In-situ formed polyether polyols, a process for their preparation, and a process for the preparation of polyurethane foams |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220316 Address after: No.158, Fenghua Road, Jiangbei new district, Nanjing City, Jiangsu Province, 210047 Applicant after: Jiangsu Zhongshan new material Co.,Ltd. Address before: No.158, Fenghua Road, Jiangbei new district, Nanjing City, Jiangsu Province, 210047 Applicant before: JIANGSU ZHONGSHAN CHEMICAL Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210219 |