CN114891172A - Comprehensive utilization method of aromatic diol by-product - Google Patents
Comprehensive utilization method of aromatic diol by-product Download PDFInfo
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- CN114891172A CN114891172A CN202210752501.XA CN202210752501A CN114891172A CN 114891172 A CN114891172 A CN 114891172A CN 202210752501 A CN202210752501 A CN 202210752501A CN 114891172 A CN114891172 A CN 114891172A
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- polyurethane
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- epoxide
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- 239000006227 byproduct Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 40
- -1 aromatic diol Chemical class 0.000 title claims abstract description 18
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 claims abstract description 35
- 239000004814 polyurethane Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 26
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 19
- 150000002924 oxiranes Chemical class 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000000806 elastomer Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004588 polyurethane sealant Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000004382 potting Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 2
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a method for comprehensively utilizing aromatic diol by-products. The method comprises the following steps: adding epoxide into hydroquinone dihydroxyethyl ether or resorcinol dihydroxyethyl ether by-product and catalyst under the protection of nitrogen, reacting for 3 hours at the pressure of less than 1MPa and the temperature of less than 120 ℃, neutralizing until the pH value is 6-7, distilling under reduced pressure at the temperature of 80-120 ℃, and filtering under pressure to obtain amber transparent liquid, thereby completing the comprehensive utilization of aromatic diol by-product. The method takes solid HQEE/HER byproduct as an initiator to carry out ring-opening polymerization with epoxide under the action of a specific catalyst to prepare the liquid hydroxyl-terminated polyurethane curing agent. The liquid hydroxyl-terminated polyurethane curing agent can be used as a bi-component polyurethane material to produce polyurethane plastic tracks, paving materials, waterproof materials and the like. The method can change the by-products into valuables, does not produce harmful waste in the production process, and has good social and economic benefits.
Description
Technical Field
The invention relates to a method for comprehensively utilizing byproducts, in particular to a method for comprehensively utilizing aromatic diol byproducts, and belongs to the technical field of byproduct recycling.
Background
With the increasing scarcity of non-renewable resources/energy sources and the enhancement of safety/environmental protection awareness, under the large background of carbon peak reaching and carbon neutralization, the high-efficiency utilization technology of the resources/energy sources and the green, energy-saving and environment-friendly process are becoming hot points of research of people, and comprehensive utilization is carried out on the basis of substance characteristic analysis, so that the treatment capacity of three wastes can be reduced, the pollution to the environment can be reduced, the utilization rate of the resources can be improved, and multiple purposes can be achieved.
HQEE (hydroquinone dihydroxy ethyl ether) and HER (resorcinol dihydroxy ethyl ether) are non-toxic and pollution-free aromatic diol compounds, and can be used as chain extenders for polyurethane elastomers, raw materials for preparing polyester polyols, and the like. When the HQEE/HER is used as a chain extender of a polyurethane elastomer, HQEE/HER is often used together with MDI-based prepolymer, compared with the MOCA/TDI prepolymer system which is dominant at home at present, MDI is safer to use, the environmental protection performance is more excellent, the HQEE/HER/MDI polyurethane elastomer has better heat resistance, and the HQEE/HER is increasingly widely used.
US4119594a1 describes a process for producing HQEE chain extended thermoset polyurethane elastomers: HQEE, polyether triol, a zinc stearate catalyst and liquefied MDI are mixed (HQEE can be heated and dissolved in polyether firstly), the mixture can keep the storage stability for a certain time at room temperature (zinc stearate shows good catalytic activity only when the temperature is higher than 80 ℃), and the combined material is injected into a mold at 150 ℃, so that the thermosetting polyurethane elastomer with good performance can be prepared.
Concerning the synthesis of HQEE/HER, CN101244989B describes a process for preparing HQEE and HER by using Hydroquinone (HQ) or Resorcinol (RC) as an initiator and sodium carbonate as a catalyst to catalyze the anionic ring-opening polymerization of diphenol and ethylene oxide. US3644534 describes a process for the preparation of HQEE/HER by polymerization of HQ/RC with ethylene oxide in aqueous solution using HQ, RC as starters and sodium hydroxide as catalyst and neutralization with acid. U.S. Pat. No. 5,332,972,3describes a method for preparing HQEE/HER by using triphenylphosphine as a catalyst to catalyze the addition of diphenol and ethylene carbonate at 150-170 ℃. WO91/16292 describes a process for increasing the yield and purity of HER products by post-treatment with 4% sodium hydroxide solution and crystallization after reaction of resorcinol with ethylene carbonate at 130-150 ℃ for 4-6 hours under the catalytic action of potassium carbonate.
HQ/RC reacts with EO to synthesize HQEE/HER, which has the advantage of low cost, but the synthesis conditions need to be controlled to reduce the self-polymerization of EO and the excessive reaction of EO and an initiator, and the HQEE/HER can be used after being purified by post-treatment. In the recrystallization purification process, the crystallization mother liquor is a byproduct of HQEE/HER after the solvent is removed, the main components of the crystallization mother liquor are single side of incomplete reaction of an initiator and EO, HQEE/HER, excessive reactants of the initiator and the EO and the like, and the substances are mixed together, and the whole body is in a solid state and is difficult to separate.
On the basis of the analysis of the composition of the recrystallization by-products, it is considered to continue the reaction with the epoxide. As the number of soft segments in the molecule increases, the by-product can form a liquid hydroxyl terminated polyurethane curing agent. Tests prove that the method has feasibility.
The method for recycling the recrystallization by-products by adopting the environment-friendly method can reduce the burden on the environment, can generate certain economic benefit, and accords with the current trends of environment protection, full utilization of materials and comprehensive utilization.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects of the prior art and provide a method for effectively utilizing byproducts generated by hydroquinone dihydroxyethyl ether (HQEE) and resorcinol dihydroxyethyl ether (HER) to realize secondary utilization of resources.
In order to achieve the purpose, the technical scheme adopted by the invention is to provide a method for comprehensively utilizing aromatic diol byproducts, which comprises the following steps:
adding epoxide into hydroquinone dihydroxyethyl ether or resorcinol dihydroxyethyl ether by-product and catalyst under the protection of nitrogen, reacting for 3 hours at the pressure of less than 1MPa and the temperature of less than 120 ℃, neutralizing until the pH value is 6-7, distilling under reduced pressure at the temperature of 80-120 ℃, and filtering under pressure to obtain amber transparent liquid, thereby completing the comprehensive utilization of aromatic diol by-product.
The method for comprehensively utilizing the aromatic diol by-product is also a method for preparing the liquid polyurethane curing agent, and epoxide and a by-product of hydroquinone dihydroxy ethyl ether (HQEE) or resorcinol dihydroxy ethyl ether (HER) are subjected to anionic ring-opening polymerization reaction under the alkaline condition to generate the liquid aromatic polyurethane curing agent with the end group of hydroxyl.
In one embodiment of the present invention, the hydroquinone dihydroxyethyl ether or resorcinol dihydroxyethyl ether by-product is a solid obtained by reacting hydroquinone or resorcinol with ethylene oxide and recrystallizing to remove the solvent.
In one embodiment of the invention, the mass ratio of by-product to epoxide is from 1:1 to 6: 1; preferably, the mass ratio of by-product to epoxide is from 4:1 to 6: 1.
In a specific embodiment of the invention, the amount of the catalyst is 0.5-1.5% of the mass of the byproduct; the amount of catalyst used is preferably 0.7 to 1.3% by mass of by-product.
In one embodiment of the invention, the reaction temperature is 60-120 ℃ and the pressure is 1 MPa; the preferred reaction temperature is 80-110 ℃.
In one embodiment of the invention, the catalyst is an alkali metal carbonate or hydroxide; preferably the catalyst is a hydroxide; more preferably the catalyst is sodium hydroxide or potassium hydroxide.
In one embodiment of the present invention, the epoxide used is ethylene oxide, propylene oxide, tetrahydrofuran, or a mixture of ethylene oxide, propylene oxide, tetrahydrofuran; preferably, the epoxide is ethylene oxide or propylene oxide.
In one embodiment of the invention, hydrochloric acid, sulfuric acid or phosphoric acid is used for neutralization; hydrochloric acid is preferably used.
The invention also provides a liquid polyurethane curing agent, which is prepared by the method for comprehensively utilizing the aromatic diol by-product.
The invention also provides the application of the liquid polyurethane curing agent, and the liquid polyurethane curing agent is used for preparing polyurethane paving materials, polyurethane waterproof coatings, polyurethane sealant for buildings, polyurethane pouring sealant and polyurethane adhesives.
The environment-friendly liquid polyurethane curing agent is generally applied to a thermosetting bi-component polyurethane system, most of the bi-component polyurethane resin is a solvent-free combined material, and a cured product of the bi-component polyurethane resin is a non-foam elastomer, and the application fields of the environment-friendly liquid polyurethane curing agent comprise solvent-free polyurethane adhesives, polyurethane paving material (plastic tracks, plastic courts, elastic leisure places, elastic terraces, prefabricated elastic cushions and the like) adhesives or glues, polyurethane waterproof coatings, building polyurethane sealants, electronic component pouring sealants and the like.
In the present invention, it was found by analyzing the components of the by-product of HQEE/HER recrystallization that the major components were 60% to 80% of HQEE (or HER), 15% to 35% of adducts such as 3EO (ethylene oxide)/HQ, 4EO/HQ, etc. (or 3EO/RC, 4EO/RC, etc.), and the remaining 5% were single-side addition products (2 hydroxyl groups, one of which was an alcoholic hydroxyl group and the other was a phenolic hydroxyl group), low molecular weight polyether glycol and other impurities. These are all effectively reactive species containing 2 hydroxyl groups.
Liquefaction of HQEE byproduct
Liquefaction of HER by-products
Possible side reactions of HQEE
Possible side reactions of HER
Possible side reactions that may occur are: 3EO/HQ and 4EO/HQ (3EO/RC and 4EO/RC) continue to react with the epoxide by anionic addition; when water is used as solvent, water is used as initiator to react with epoxide to produce small molecular ether alcohol.
The method of the invention keeps the pH range of 8-13 in the synthesis process by using a catalyst (sodium hydroxide) with stronger alkalinity, so that the HQEE/HER byproduct with the end group as hydroxyl can form negative ions; before the reaction, inert gas (such as nitrogen) is used for replacement, the reaction is ensured to be carried out in an oxygen-free environment, meanwhile, the existence of nitrogen above the reaction liquid is kept in the reaction process, the pressure is controlled to be 1MPa, and the problem that the color of the product is deepened due to a small amount of phenolic hydroxyl contained in the by-product is avoided; by controlling the mass ratio of the by-product to the epoxide to be 4:1-6:1, the hardness and strength of a polyurethane part are prevented from being reduced due to the increase of a flexible chain segment in the curing agent; controlling the feeding of epoxide at the temperature lower than 80 ℃, controlling the reaction temperature at 80-110 ℃, keeping the temperature for 2 hours after the feeding is finished, and adding a specific neutralizing reagent (such as a hydrochloric acid solution with the mass fraction of 30%) into the discharged material to neutralize an alkaline catalyst, and controlling the pH value to be 6-7 to ensure that the neutralization is complete; and (3) after the neutralization is finished, carrying out reduced pressure distillation, removing water in the reaction process, controlling the water content to be lower than 0.1%, and carrying out pressure filtration to remove salts generated by neutralization so as to ensure the complete reaction.
The method provided by the invention can be used for recycling solid byproducts generated in the production process of HQEE/HER and preparing the environment-friendly liquid polyurethane chain extender. The solid HQEE/HER byproduct is used as an initiator to carry out ring-opening polymerization with epoxide under the action of a specific catalyst to prepare the liquid hydroxyl-terminated polyurethane curing agent. The liquid hydroxyl-terminated polyurethane curing agent can be used as a bi-component polyurethane material to produce polyurethane plastic tracks, paving materials, waterproof materials and the like. The method can change the by-products into valuables, does not produce harmful waste in the production process, and has good social and economic benefits.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
Example 1
Before the experiment, the by-product of HQEE/HER was pretreated: heating and melting at 90-110 deg.c and filtering to eliminate non-melting impurity.
Nitrogen gas is filled in a 2.5L high-pressure reaction kettle provided with magnetic stirring, circulating cooling water, a thermometer, a pressure gauge and an overpressure protection device, pressure maintaining replacement is carried out for 3 times, and air in the reaction kettle is ensured to be discharged. Setting the oil bath temperature to be 100 ℃, adding 400g of water and 20g of 30% sodium hydroxide solution, fully stirring, adding 600g of a pretreated HQEE byproduct, performing nitrogen replacement again, introducing 109g of ethylene oxide (the mass of the ethylene oxide can be measured by a mass flow meter) when the temperature of the kettle rises to 65 ℃, controlling the reaction temperature to be not more than 100 ℃, controlling the pressure to be less than 1MPa, maintaining the pressure for 2 hours after the ethylene oxide is added, discharging the feed liquid from a bottom valve of the reaction kettle, transferring the feed liquid to a prepared hydrochloric acid solution containing 15g of 37%, stirring and neutralizing, wherein the pH value of the measured solution is 6.5.
And (3) carrying out reduced pressure distillation on the neutralized solution at the temperature of 80-120 ℃, removing water and micromolecule ether alcohol generated in the reaction process, and carrying out pressure filtration to remove salts generated in the neutralization process, so that the reaction is finished, and obtaining the amber transparent liquid.
The viscosity of the solution was measured to be 130 mPas (50 ℃ C.), and the hydroxyl value was 460 mgKOH/g.
Example 2
The experimental procedure is as in example 1, adding 400g of water, 21g of 30% sodium hydroxide solution, 600g of HER byproduct and 133g of propylene oxide (the mass of propylene oxide can be measured by a mass flow meter), controlling the reaction temperature not to exceed 110 ℃ and the pressure to be less than 1MPa, maintaining the pressure for 2 hours, discharging from a bottom valve of a reaction kettle, transferring to a hydrochloric acid solution containing 16g of 37% prepared in advance, stirring and neutralizing, and then measuring the pH value of the solution to be 7.
And (3) carrying out reduced pressure distillation on the neutralized solution at the temperature of 80-120 ℃, removing water and micromolecule ether alcohol generated in the reaction process, and carrying out pressure filtration to remove salts generated in the neutralization process, so that the reaction is finished, and obtaining the amber transparent liquid.
The solution was found to have a viscosity of 143 mPas (50 ℃ C.), and a hydroxyl value of 454 mgKOH/g.
Table 1 shows the tests carried out according to example 1, essentially identical to example 1, with the differences in the experimental parameters referred to in table 1.
TABLE 1 exploitation and utilization of aromatic diol by-product
| Liquid curing agent numbering | Curing agent A | Curing agent B |
| Initiator | By-product of HQEE 600g | HER byproduct 600g |
| Epoxide compound | Ethylene oxide 109g | Propylene oxide 133g |
| Catalyst and process for preparing same | 30% sodium hydroxide solution 20g | 21g of 30% sodium hydroxide solution |
| Synthesis temperature/. degree.C | 65-100 | 65-110 |
| Synthetic pressure/MPa | <1 | <1 |
| viscosity/mPa. multidot.s (50 ℃ C.) | 130 | 143 |
| Hydroxyl value/mgKOH/g | 460 | 454 |
| Appearance of the product | Amber transparent liquid | Amber transparent liquid |
Example 3
After vacuum defoaming TDI-PTMEG type prepolymer with NCO content of 2.9% at 80 ℃ for 1 hour, 100g of prepolymer, 8g of liquid polyurethane curing agent (chain extension coefficient of 0.95) synthesized in example 1 and 0.08g of AUCAT-T62 catalyst are fully stirred, mixed and vacuum defoamed, poured into a mold with the mold temperature of 120 ℃ for curing for 1.5 hours, cured for 16 hours at 100 ℃ for two times, placed for one week, and then the physical properties of the elastomer are measured, wherein the hardness is 52A, the tensile strength is 8.5MPa, and the elongation at break is 667%
Example 4
After vacuum defoaming TDI-PTMEG type prepolymer with NCO content of 2.9% at 80 ℃ for 1 hour, 100g of prepolymer, 8.1g of liquid polyurethane curing agent (chain extension coefficient is 0.95) synthesized in example 2 and 0.08g of AUCAT-F2 catalyst are fully stirred, mixed and vacuum defoamed, poured into a mold with the mold temperature of 120 ℃ for curing for 1.5 hours, cured for 16 hours at 100 ℃ for two times, and placed for one week to measure the physical properties of the elastomer, wherein the hardness is 58A, the tensile strength is 8.8MPa and the elongation at break is 650%.
The curing agents A and B of Table 1 were tested with reference to example 3, and the results are shown in Table 2.
TABLE 2 use of liquid curing agents
| Elastomer numbering | 1 | 2 |
| Prepolymer/g | TDI-PTMEG type/100 g | TDI-PTMEG type/100 g |
| NCO％ | 2.9 | 2.9 |
| Curing agent/g | Curing agent A/8g | Curing agent B/8.1g |
| Chain extension coefficient | 0.95 | 0.95 |
| Catalyst/g | AUCAT-T62/0.08g | AUCAT-F2/0.08g |
| Curing conditions/° C/h | 120/1.5 | 120/1.5 |
| Post-maturation conditions/° C/h | 100/16 | 100/16 |
| hardness/A | 52 | 58 |
| Tensile strength/MPa | 8.5 | 8.8 |
| Elongation at break/% | 667 | 650 |
Comparative example 1
The procedure is as described in example 1, except that the amount of ethylene oxide added is 200 g. The solution was found to have a viscosity of 103 mPas (50 ℃ C.), and a hydroxyl value of 403 mgKOH/g.
Meanwhile, the experiment of example 3 was performed with the material of this comparative example, the same chain extension coefficient was ensured, and the physical properties of the elastomer were measured after standing for one week, with a hardness of 41A, a tensile strength of 5.6MPa, and an elongation at break of 740%.
Comparative example 2
The procedure of example 2 was followed except that propylene oxide was added in an amount of 220 g. The solution was found to have a viscosity of 122 mPas (50 ℃ C.), and a hydroxyl value of 400 mgKOH/g.
Meanwhile, the experiment of example 4 was performed with the material of this comparative example, the same chain extension coefficient was ensured, and the physical properties of the elastomer were measured after standing for one week, with a hardness of 48A, a tensile strength of 5.7MPa, and an elongation at break of 730%.
From the above examples, it can be seen that a liquid aromatic diol can be synthesized by using a byproduct generated in the synthesis process of aromatic diol HQEE/HER as an initiator and reacting with an epoxide under a certain condition, and when the liquid aromatic diol is used as a chain extender of a polyurethane elastomer, the elastomer has medium hardness and good tensile property, and can meet the requirements of specific occasions such as polyurethane paving materials, waterproof coatings, sealants, pouring sealants, adhesives and the like on the physical properties of workpieces, so that the green and safe development and utilization of the aromatic diol HQEE/HER byproduct are realized.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for the integrated utilization of an aromatic diol by-product, the method comprising the steps of:
adding epoxide into hydroquinone dihydroxyethyl ether or resorcinol dihydroxyethyl ether byproduct and catalyst under the protection of nitrogen, controlling the pressure to be less than 1MPa and the temperature to be less than 120 ℃, reacting for 3 hours, neutralizing until the pH value is 6-7, carrying out reduced pressure distillation at the temperature of 80-120 ℃ and the vacuum degree of 0.07-0.09MPa, and carrying out micro-positive pressure filtration to obtain amber transparent liquid, thereby completing the comprehensive utilization of aromatic diol byproduct.
2. The process of claim 1 wherein the hydroquinone dihydroxyethyl ether or resorcinol dihydroxyethyl ether by-product is a solid after recrystallization to remove the solvent after reaction of hydroquinone or resorcinol with ethylene oxide.
3. The process of claim 1, wherein the mass ratio of the by-product to epoxide is from 1:1 to 6: 1; preferably, the mass ratio of the by-product to epoxide is from 4:1 to 6: 1.
4. The method of claim 1, wherein the catalyst is used in an amount of 0.5% to 1.5% by mass of the by-product; preferably, the amount of the catalyst used is 0.7 to 1.3% by mass of the by-product.
5. The process according to claim 1, wherein the reaction is carried out at a temperature of 60-120 ℃ and a pressure of 1 MPa;
preferably, the temperature of the reaction is 80-110 ℃.
6. The process of claim 1, wherein the catalyst is an alkali metal carbonate or hydroxide; preferably, the catalyst is a hydroxide; more preferably, the catalyst is sodium hydroxide or potassium hydroxide.
7. The process of claim 1, wherein the epoxide is ethylene oxide, propylene oxide, tetrahydrofuran, or a mixture; preferably, the epoxide is ethylene oxide or propylene oxide.
8. The process according to claim 1, wherein the neutralization is carried out with hydrochloric acid, sulfuric acid or phosphoric acid; preferably, hydrochloric acid is used for the neutralization.
9. A liquid polyurethane curing agent which is easy to use and can impart excellent flexibility to an elastomer, the liquid polyurethane curing agent being prepared by the method of comprehensively utilizing the aromatic diol by-product according to any one of claims 1 to 8.
10. The use of the liquid polyurethane curing agent according to claim 9 for preparing polyurethane paving materials, polyurethane waterproof coatings, polyurethane sealants for buildings, polyurethane potting adhesives, and polyurethane adhesives.
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