CN112646163A - Preparation method of cardanol polyether polyol with high pentane intersolubility - Google Patents
Preparation method of cardanol polyether polyol with high pentane intersolubility Download PDFInfo
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- CN112646163A CN112646163A CN202011465499.5A CN202011465499A CN112646163A CN 112646163 A CN112646163 A CN 112646163A CN 202011465499 A CN202011465499 A CN 202011465499A CN 112646163 A CN112646163 A CN 112646163A
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- cardanol
- polyether polyol
- pentane
- miscibility
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 43
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920000570 polyether Polymers 0.000 title claims abstract description 43
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 41
- 229920005862 polyol Polymers 0.000 title claims abstract description 33
- 150000003077 polyols Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 olefin compound Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 3
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 230000005587 bubbling Effects 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004088 foaming agent Substances 0.000 abstract description 8
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- C08G65/2627—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 aromatic or arylaliphatic 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
- 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
-
- 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
Abstract
The invention relates to a preparation method of cardanol polyether polyol with high pentane intersolubility, and belongs to the technical field of modification of polyether polyol. The preparation method of the cardanol polyether polyol with high pentane intersolubility comprises the steps of taking Mannich base and micromolecular alcohol as composite initiators, and reacting with an epoxy olefin compound under the action of an alkaline catalyst to prepare the polyether polyol; the Mannich base is prepared from cardanol, formaldehyde and an alcohol amine compound serving as raw materials through a Mannich reaction. The method has the advantages of simple and easy implementation process and low raw material cost, and the prepared polyether polyol and the cyclopentane foaming agent have good intersolubility and wide industrial utilization value.
Description
Technical Field
The invention relates to a preparation method of cardanol polyether polyol with high pentane intersolubility, and belongs to the technical field of modification of polyether polyol.
Background
According to the provisions of Montreal's book of coordination, HCFC-141b in polyurethane foam industry will be eliminated in the world before 2030 years, the first-stage elimination target of freezing in 2013 and 10% reduction in 2015 in HCFC production industry in China is successfully realized in China at present, and the target of continuously reducing 30% production and consumption of HCFC production industry in the second stage before 2020 is completed. The annual reduction in the production of HCFC-141b and the high cost of other 245fa blowing agents have promoted the replacement of other types of blowing agents such as pentane systems, water and the like and the innovation of new blowing agents.
The substitution and innovation of the foaming agent brings about the formulation innovation of the rigid polyurethane foam combined polyether and also brings about the change and development of the polyether product. The pentane foaming agent is environment-friendly, low in price and easy to obtain, so that the pentane foaming agent is more and more widely applied to countries in Europe and America and China, but the pentane foaming agent has the problems of being basically insoluble with polyester polyol and poor in polyether polyol miscibility, combined polyether is easy to be turbid and even delaminated, foaming use is affected, and the problem that foam strength is reduced due to the fact that oil ether is used in the traditional method to promote the formula system miscibility is solved. Therefore, according to the increasing application and performance requirements of pentane foaming agents in the polyurethane industry, novel polyether is developed to meet the market demand and promote the industry development.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art, and provides a preparation method of cardanol polyether polyol with high pentane intersolubility, which has the advantages of simple and easy-to-implement process and low raw material cost, and the prepared polyether polyol and a cyclopentane foaming agent have good intersolubility and wide industrial utilization value.
The preparation method of the cardanol polyether polyol with high pentane intersolubility comprises the steps of taking Mannich base and micromolecular alcohol as composite initiators, and reacting with an epoxy olefin compound under the action of an alkaline catalyst to prepare the polyether polyol;
the Mannich base is prepared from cardanol, formaldehyde and an alcohol amine compound serving as raw materials through a Mannich reaction.
Preferably, the cardanol is refined-grade cardanol.
Preferably, the alcohol amine compound is one or two of 25-28% by mass of an aqueous ammonia solution, diethanolamine or monoethanolamine.
Preferably, the formaldehyde is polyformaldehyde with a polymerization degree of 3-100 or more or a formaldehyde solution with a mass content of 37%.
Preferably, the small molecule alcohol is solid sorbitol or liquid sorbitol at a content of 70 wt%.
Preferably, the basic catalyst is potassium hydroxide, sodium hydroxide or triethylamine.
Preferably, the alkylene oxide compound is one or more of ethylene oxide, propylene oxide or butylene oxide.
Preferably, the mass ratio of the cardanol, formaldehyde and alcohol amine compound is 30-60: 7-27: 9-30.
The preparation method of the cardanol polyether polyol with high pentane intersolubility comprises the following steps:
1) preparation of mannich base: putting cardanol and formaldehyde into a reaction kettle, after leakage testing and replacement by closing the reaction kettle, heating to 70-80 ℃ in a nitrogen atmosphere, starting external circulation and simultaneously pressurizing to jack an alcohol amine compound after the temperature is reached, keeping the temperature of 80 +/-2 ℃ in the reaction kettle in the adding process, controlling the pressure to be 0.1-0.2MPa, and reacting for 2-3 hours after the alcohol amine is added to prepare the non-dehydrated Mannich base;
2) after synthesizing the Mannich base in the step 1), adding the micromolecule alcohol and the alkaline catalyst into the reaction kettle, stirring and heating to 105 ℃ and 110 ℃, and starting bubbling and dehydrating for 2-3 h;
3) after the dehydration in the step 2) is finished, continuously heating and stirring; when the temperature is raised to 115-135 ℃, opening the epoxy olefin compound valve, and slowly dropping the epoxy olefin compound for ring-opening reaction; the weight of the epoxy olefin compound is 30-45% of the weight of the dehydrated initiator, the pressure is 0.35MPa in the dropping process, the temperature is controlled at 135 ℃ at 120 ℃, and after the dropping is finished, the internal pressure reaction is continued for 2-3h within the range of 0.2-0.4 MPa;
4) and 3) cooling to 100 +/-5 ℃ after the internal pressure reaction is finished, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, cooling and discharging after bubbling for 1-2h to obtain the polyether polyol.
Preferably, the dosage of the small molecular alcohol is 5-15% of the mass of the Mannich base synthesized in the step 1), and the basic catalyst is 3-5% of the mass of the Mannich base synthesized in the step 1).
Compared with the prior art, the invention has the following beneficial effects:
(1) the cardanol used in the invention is a green and environment-friendly renewable resource, and the raw materials are cheap, renewable and easily available;
(2) the synthesized polyether product uses cardanol as a main raw material, and the C15 straight chain containing unsaturated double bonds is positioned in the cardanol, so that the cardanol can provide the solubility of a system and hydrocarbon substances, the cardanol and cyclopentane foaming agents have good intersolubility, polar hydroxyl groups after chain extension and other conventional polyether products also have good intersolubility, and the pentane solubility and the stability of the composite material can be effectively increased;
(3) the Mannich base adopts ammonia water as a raw material, so that the cost of the starter stub bar is lower;
(4) the product functionality can be effectively improved and the product foam strength can be improved by compounding the micromolecular alcohol initiator;
(5) the invention has simple and easy-to-implement process and wide industrial utilization value.
Detailed Description
The present invention will be further described with reference to comparative examples and examples.
Example 1
Adding 304.5g of cardanol and 31.5g of paraformaldehyde into a reaction kettle, carrying out leak testing replacement after closing the kettle, heating to 75 +/-5 ℃ under the nitrogen atmosphere, starting external circulation after the temperature is reached, simultaneously pressurizing and jacking 60g of ammonia water and 2g of monoethanolamine mixture, simultaneously keeping the nitrogen atmosphere pressure in the kettle at 0.13 +/-0.02 MPa, and reacting for 2 hours after the alcohol amine is added to prepare the Mannich base.
42g of liquid sorbitol is pumped into a reaction kettle in vacuum, 3g of triethylamine catalyst is pumped and added at the same time, the temperature is heated to 105 ℃ by stirring, and nitrogen is bubbled and dehydrated for 3 hours after the temperature is reached.
After dehydration, the temperature is raised to 125 +/-5 ℃, after the temperature is reached, the mixture of ethylene oxide and propylene oxide is dripped, the total mass is 268g, the temperature is kept at 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.1 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.2MPa, the temperature is kept at 128 +/-2 ℃, and the internal pressure reaction is continued for 2 hours until the pressure in the kettle is not reduced any more. And then cooling to 80 ℃, discharging to obtain cardanol polyether polyol A1 with a hydroxyl value of 325mgKOH/g and viscosity of 6100 MPa.s.
Example 2
Adding 304.5g of cardanol and 31.5g of paraformaldehyde into a reaction kettle, after leakage testing and replacement in the reaction kettle, heating to 75 +/-5 ℃ under the nitrogen atmosphere, starting external circulation and simultaneously pressurizing and jacking 105g of diethanolamine mixture, simultaneously keeping the pressure of the nitrogen atmosphere in the kettle at 0.13 +/-0.02 MPa, and reacting for 2-3 hours after the alcohol amine is added to prepare the Mannich base.
And (3) pumping 29.4g of solid sorbitol into a reaction kettle in vacuum, simultaneously pumping and adding 5g of macromolecular aliphatic amine catalyst, stirring and heating to 105 ℃, and carrying out nitrogen bubbling dehydration for 3 hours after the temperature is reached.
After dehydration, the temperature is raised to 125 +/-5 ℃, propylene oxide is dripped after the temperature is reached, the mass is 210g, the temperature is kept at 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.1 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.3MPa, the temperature is kept at 128 +/-2 ℃, the internal pressure reaction is continued for 2.5 hours until the pressure in the kettle is not reduced any more. And then cooling to 80 ℃, discharging to obtain cardanol polyether polyol A2 with a hydroxyl value of 321mgKOH/g and viscosity of 3360 MPa.s.
Example 3
Adding 304.5g of cardanol and 85g of 37% formaldehyde solution into a reaction kettle, after leakage test and replacement in the reaction kettle, heating to 75 +/-5 ℃ under the nitrogen atmosphere, starting external circulation after the temperature is reached, simultaneously pressing and jacking 60g of ammonia water and 2g of diethanolamine mixture, simultaneously keeping the nitrogen atmosphere pressure in the reaction kettle at 0.13 +/-0.02 MPa, and reacting for 3 hours after the alcohol amine is added to prepare the Mannich base.
And (3) taking 42g of liquid sorbitol, vacuum-pumping into a reaction kettle, simultaneously pumping and adding 3g of macromolecular aliphatic amine catalyst, stirring and heating to 105 ℃, and carrying out nitrogen bubbling dehydration for 2 hours after the temperature is reached.
After dehydration, the temperature is raised to 125 +/-5 ℃, after the temperature is reached, the mixture of ethylene oxide and propylene oxide is dripped, the total mass is 268g, the temperature is kept at 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.15 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.25MPa, the temperature is kept at 128 +/-2 ℃, and the internal pressure reaction is continued for 2 hours until the pressure in the kettle is not reduced any more. And then cooling to 80 ℃, discharging to obtain cardanol polyether polyol A3 with a hydroxyl value of 348mgKOH/g and viscosity of 5300 MPa.s.
Example 4
Adding 304.5g of cardanol and 85g of 37% formaldehyde into a reaction kettle, after leakage test and replacement in the reaction kettle, heating to 75 +/-5 ℃ under the nitrogen atmosphere, starting external circulation and simultaneously pressurizing and jacking 105g of diethanolamine mixture at the temperature, simultaneously keeping the pressure of the nitrogen atmosphere in the reaction kettle at 0.13 +/-0.02 MPa, and reacting for 2 hours after the alcohol amine is added to prepare the Mannich base.
And (3) pumping 29.4g of solid sorbitol into a reaction kettle in vacuum, simultaneously pumping 4g of macromolecular aliphatic amine catalyst, stirring and heating to 105 ℃, and carrying out nitrogen bubbling dehydration for 2 hours after the temperature is reached.
After dehydration, the temperature is raised to 125 +/-5 ℃, propylene oxide is dripped after the temperature is reached, the mass is 268g, the temperature is kept at 125 +/-5 ℃ in the dripping process, and the pressure in the kettle is controlled to be 0.1 MPa. After the dropwise addition, nitrogen is filled to pressurize to 0.2MPa, the temperature is kept at 128 +/-2 ℃, the internal pressure reaction is continued for 2.5 hours until the pressure in the kettle is not reduced any more. And then cooling to 80 ℃, and discharging to obtain cardanol polyether polyol A4 with a hydroxyl value of 345mgKOH/g and viscosity of 3200 MPa.s.
Comparative example 1
Adding 275g of cane sugar, 60g of diethylene glycol, 40g of glycerol, 139g of palm oil and 1.2g of aliphatic amine catalyst into a reaction kettle, after leakage test and replacement of the reaction kettle, heating to 105 ℃ under negative pressure, dropping 855g of propylene oxide after the temperature is reached, simultaneously keeping the pressure of nitrogen atmosphere in the kettle at 0.13 +/-0.02 MPa, after the propylene oxide is dropped, keeping the temperature for reaction for 3 hours until the pressure in the kettle is not reduced, bubbling for demonomerization for 2 hours, cooling to 80 ℃, discharging to obtain the oleoylether B1 with the oil content of 10%, the hydroxyl value of 355mgKOH/g and the viscosity of 5500 MPa.s.
Comparative example 2
342g of cane sugar, 152g of diethylene glycol, 346g of palm oil and 1.07g of aliphatic amine catalyst are added into a reaction kettle, after leakage test and replacement are carried out in the reaction kettle, the temperature is increased to 105 ℃ under negative pressure, 843g of propylene oxide is dripped into the reaction kettle after the temperature is reached, meanwhile, the pressure of the nitrogen atmosphere in the reaction kettle is kept at 0.13 +/-0.02 MPa, the temperature is kept for reaction for 3 hours after the propylene oxide is dripped into the reaction kettle until the pressure in the reaction kettle is not reduced, the temperature is reduced to 80 ℃ after bubbling and monomer removal is carried out for 2 hours, and the oil ether B2 with the oil content of 20 percent is obtained by discharging, the.
The following table compares the example to comparative example indices:
TABLE 1 indices of products prepared in examples and comparative examples
| Distinguishing | Hydroxyl value (mgKOH/g) | Viscosity (MPa.s) | Pentane solubility (100 parts) |
| Example 1 | 325 | 6100 | Mutual solubility in any proportion |
| Example 2 | 321 | 3360 | Mutual solubility in any proportion |
| Example 3 | 348 | 5300 | Mutual solubility in any proportion |
| Example 4 | 345 | 3200 | Mutual solubility in any proportion |
| Comparative example 1 | 355 | 5500 | 43 |
| Comparative example 2 | 360 | 3100 | 46 |
The pentane solubilities of comparative examples 1 and 2 were compared with those of the examples, and the following pentane solubilities were based on 100 parts of polyether. The example polyethers were used to test the solubility of cyclopentane by replacing different parts of the comparative polyether.
Table 2 examples 1, 3 replace respectively the pentane solubility contrast of comparative example 1
| Number of substitution | 0 | 10 | 20 | 30 | 40 |
| Example 1 | 43 | 44.8 | 49.6 | 53.8 | 66 |
| Example 3 | 43 | 48.2 | 53.3 | 57.9 | 70.9 |
Table 3 examples 2, 4 replace respectively the pentane solubility of comparative example 2
| Number of substitution | 0 | 10 | 20 | 30 | 40 |
| Example 2 | 46 | 50.4 | 51.9 | 57.9 | 63.9 |
| Example 4 | 46 | 52 | 54.4 | 59.6 | 65.8 |
As can be seen from tables 1, 2 and 3, the prepared novel cardanol polyether polyol not only has good pentane intersolubility, but also can improve the pentane intersolubility of products when being compounded with different oil-containing polyethers.
Claims (10)
1. A preparation method of cardanol polyether polyol with high pentane intersolubility is characterized by comprising the following steps: mannich base and micromolecular alcohol are used as composite initiator to react with epoxy olefin compound under the action of alkaline catalyst to prepare polyether polyol;
the Mannich base is prepared from cardanol, formaldehyde and an alcohol amine compound serving as raw materials through a Mannich reaction.
2. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the cardanol is refined cardanol; the alcohol amine compound is one or two of ammonia water solution with the mass content of 25-28%, diethanolamine or monoethanolamine.
3. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the formaldehyde is polyformaldehyde with polymerization degree of 3-100 or above or formaldehyde solution with mass content of 37%.
4. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the small molecular alcohol is solid sorbitol or liquid sorbitol with the content of 70 wt%.
5. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the basic catalyst is potassium hydroxide, sodium hydroxide or triethylamine.
6. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the epoxy olefin compound is one or more of ethylene oxide, propylene oxide or butylene oxide.
7. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the mass ratio of the cardanol, formaldehyde and alcohol amine compound is 30-60: 7-27: 9-30.
8. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 1, wherein: the method comprises the following steps:
1) preparation of mannich base: putting cardanol and formaldehyde into a reaction kettle, after leakage testing and replacement in the reaction kettle, heating to 70-80 ℃ in a nitrogen atmosphere, pressurizing to push an alcohol amine compound, and reacting for 2-3 hours after the alcohol amine is added to obtain the non-dehydrated Mannich base;
2) after synthesizing the Mannich base in the step 1), adding the micromolecule alcohol and the alkaline catalyst into the reaction kettle, stirring and heating to 105 ℃ and 110 ℃, and starting bubbling and dehydrating for 2-3 h;
3) after the dehydration in the step 2) is finished, continuously heating and stirring; when the temperature is raised to 115-135 ℃, opening the epoxy olefin compound valve, and slowly dropping the epoxy olefin compound for ring-opening reaction; the weight of the epoxy olefin compound is 30-45% of the weight of the dehydrated initiator, the pressure is 0.35MPa in the dropping process, the temperature is controlled at 135 ℃ at 120 ℃, and after the dropping is finished, the internal pressure reaction is continued for 2-3h within the range of 0.2-0.4 MPa;
4) and 3) cooling to 100 +/-5 ℃ after the internal pressure reaction is finished, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, cooling and discharging after bubbling for 1-2h to obtain the polyether polyol.
9. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 8, wherein: before the alcohol amine compound is pushed in, the external circulation is started, and the temperature of 80 plus or minus 2 ℃ in the kettle is kept and the pressure is controlled to be 0.1-0.2MPa in the adding process of the alcohol amine compound.
10. The method for preparing the high pentane miscibility cardanol polyether polyol according to claim 8, wherein: the dosage of the micromolecular alcohol is 5-15% of the mass of the Mannich base synthesized in the step 1), and the amount of the basic catalyst is 3-5 per mill of the mass of the Mannich base synthesized in the step 1).
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| CN103145955A (en) * | 2013-02-04 | 2013-06-12 | 广东工业大学 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
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| CN110591071A (en) * | 2019-09-26 | 2019-12-20 | 山东一诺威新材料有限公司 | Preparation method of Mannich polyether polyol |
| CN110938202A (en) * | 2019-12-18 | 2020-03-31 | 山东一诺威新材料有限公司 | Preparation method of Mannich flame-retardant polyether polyol |
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| CN103145955A (en) * | 2013-02-04 | 2013-06-12 | 广东工业大学 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
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