CN101314638B - Process for preparing polyether polylol for water resource cyclic utilization - Google Patents
Process for preparing polyether polylol for water resource cyclic utilization Download PDFInfo
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- CN101314638B CN101314638B CN2008101235865A CN200810123586A CN101314638B CN 101314638 B CN101314638 B CN 101314638B CN 2008101235865 A CN2008101235865 A CN 2008101235865A CN 200810123586 A CN200810123586 A CN 200810123586A CN 101314638 B CN101314638 B CN 101314638B
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- polyether glycol
- polyether
- waste water
- glycol
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- 229920000570 polyether Polymers 0.000 title claims abstract description 86
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 125000004122 cyclic group Chemical group 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003999 initiator Substances 0.000 claims abstract description 47
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002351 wastewater Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 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 claims description 15
- 229930006000 Sucrose Natural products 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000005720 sucrose Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 10
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 229960004418 trolamine Drugs 0.000 claims description 6
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000011218 segmentation Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- -1 amine compound Chemical class 0.000 abstract description 5
- 229920005862 polyol Polymers 0.000 abstract description 5
- 150000003077 polyols Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000003518 caustics Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Abstract
The invention discloses a method for preparing polyether glycol capable of recycling water resources. The polyether glycol is prepared from the reaction of a co-initiator and oxidized olefin in the presence of an alkaline catalyst. The preparation method comprises the following steps: adding polyether waste water recovered from the polyether production process and polyol or amine compound or mixture thereof into a reactor as the co-initiator; adding the catalyst and the oxidized olefin; and reacting the co-initiator with the oxidized olefin at a certain temperature and under a certain pressure in the presence of the catalyst to obtain the polyether glycol. The method for preparing the polyether glycol can reuse the polyether waste water produced in the prior polyether glycol production process as the material for the production of polyether glycol, thus eliminating the influence of polyether waste water of the polyether production process on the environment, achieving good environment protection effect, and saving water resources.
Description
Technical field
The invention belongs to the preparation method of organic high molecular compound, be a kind of be the method that feedstock production contains multi-hydroxy polyether with olefin oxide, polyol compound or aminated compounds, the preparation method of the polyether glycol of the tangible recycle water resources of specifically a kind of environment protecting.
Background technology
Polyether glycol is the important source material of polyurethanes porous plastics, its preparation method mostly is under certain pressure, temperature and catalyst action, by ethylene glycol, propylene glycol, Diethylene Glycol, glycerol, quadrol, trolamine, tri-isopropanolamine, tolylene diamine etc. and polyvalent alcohol (as sucrose, sorbyl alcohol etc.) is to be total to initiator altogether, makes with the olefin oxide reaction.Used catalyzer mainly is an alkali metal hydroxide in these class methods, and wherein again based on potassium hydroxide, consumption is generally 0.1～1% in olefin oxide.What be used for that the polyether glycol of polyurethane products production will avoid a bit is that Aethoxy Sklerol can not have caustic catalyst to exist.Because caustic alkali is that isocyanate compound forms tripolymer, the strong catalyzer of biuret and allophanate reaction as potassium hydroxide.Any basic salt also is these catalyst for reaction as disodic alkaliine.So will get rid of the trace caustic catalyst for " urethane level " polyether glycol, and, make it slightly subacidity with the neutralizing agent neutralization.Because trace acidic impurity is little to the isocyanate reaction influence.But acidity is excessive, then can suppress the reaction to isocyanic ester again.
Usually the method for removing caustic catalyst in the polyether glycol is: the water that adds thick polyethers weight 2～5% earlier in the thick Aethoxy Sklerol that contains caustic catalyst, add in the phosphoric acid after stirring and caustic catalyst, generate phosphoric acid salt, underpressure distillation removes moisture then, phosphate crystal forms solid, obtains the polyethers finished product after removing impurity such as phosphoric acid salt after filtration.Can produce a large amount of organic polyethers waste water such as small molecule alcohol that contain in the process of removing caustic catalyst.Polyethers discharge of wastewater among this polyether glycol preparation method causes detrimentally affect to environment; And increased the consumption of water, caused the waste of water resources.
Summary of the invention
In order to overcome the waste water pollution problem that exists among the present polyether glycol preparation method, the purpose of this invention is to provide a kind of preparation method of polyether glycol of recycle water resources.The present invention adopts the polyethers waste water that produces among the existing polyether glycol preparation method to produce polyether glycol as one of raw material, has eliminated the environmental pollution that waste water that existing polyether glycol preparation process produces causes, and has saved water resources.
The objective of the invention is to be achieved through the following technical solutions:
After condensation is reclaimed, concentrate standby with removing the polyethers waste water that produces in the caustic catalyst process in the polyether glycol in the prior art.
A kind of preparation method of polyether glycol of recycle water resources is characterized in that it under the amines catalyst effect, is made by common initiator that comprises polyethers waste water and olefin oxide reaction, comprises the steps:
1. the mixture with polyethers waste water and polyvalent alcohol or aminated compounds or polyvalent alcohol and aminated compounds adds in the reactor as being total to initiator; The part by weight of polyvalent alcohol, aminated compounds and polyethers waste water is in the initiator altogether: polyvalent alcohol 0-98%, aminated compounds 0-99%, polyethers waste water 1-8%.Described polyol compound is one or more mixtures in sucrose, sorbyl alcohol, α-Jia Jiputaotanggan, N.F,USP MANNITOL, Diethylene Glycol, glycerol, propylene glycol, ethylene glycol, the tetramethylolmethane; Described aminated compounds is one or more mixtures in quadrol, Monoethanolamine MEA BASF, diethanolamine, trolamine, a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, the tolylene diamine.
2. in above-mentioned reactor, add catalyzer; The weight of catalyzer is for being total to 0.2～10% of initiator.Described catalyzer is one or more mixtures of Monomethylamine, dimethylamine, Trimethylamine 99.For being convenient to use, also catalyst dissolution can be made liquid catalyst in water.
3. add the olefin oxide of 2～6 times of weight of initiator total amount altogether under 90～155 ℃ of temperature in above-mentioned reactor, pressure maintains 0.05～0.6MPa, and it is fully reacted; Olefin oxide can be a kind of in ethylene oxide, the propylene oxide, also can be two kinds shared; If two kinds when shared, the adding mode of olefin oxide can be to mix the back to add, and also can be that different olefin oxide segmentations adds.
4. above-mentioned reaction product outgased, make with extra care, obtain the urethane polyether glycol.The molecular-weight average of polyether glycol is 300～1000.
The prepared polyether glycol of the preparation method of above-mentioned polyether glycol, basic identical with the polyethers quality that common caustic catalyst technology makes.Owing to do not contain alkalimetal ion in the inventive method, therefore do not remove the process of caustic alkali, avoid removing a large amount of waters in the caustic alkali process, and can recycle the polyethers waste water that manufacturing processed such as caustic alkali produces.
When the prepared polyether glycol of the inventive method uses, get 100 parts of polyether glycols, silicone oil 1-4 part, catalyzer 0.3-4 part, whipping agent 0.5-50 part, isocyanic ester 80-350 part, high-speed stirring is mixed post-foaming and is made polyurethane foam product.Catalyzer is an amines catalyst, comprises triethylamine, triethylenediamine, dimethylcyclohexylamine, dimethylethanolamine, trolamine, pentamethyl-diethylenetriamine, can singlely use, and also can several mixing use.Whipping agent is water and low boiling point hydrocarbon, and low boiling point hydrocarbon comprises a trifluorotrichloroethane (HCFC-141b), dichlorotrifluoroethane (HCFC-123), pentamethylene, iso-pentane, can singlely use, and also can several mixing use.
The polyethers waste water that the present invention adopts caustic catalyst to produce and produces in the polyether glycol process is common initiator with low molecular weight polyols and aminated compounds, in the presence of amines catalyst, react under certain pressure, temperature with olefin oxide and to make polyether glycol.Its concrete technology is: polyethers waste water, low molecular weight polyols, aminated compounds, catalyzer etc. are added in the reactor, at 90～155 ℃, pressure-controlling under≤0.6MPa, adds 2～6 times altogether the initiator gross weights olefin oxide together initiator react.Remaining on following for some time of temperature of reaction after olefin oxide adds reacts fully, and operation such as outgas then, make with extra care makes molecular-weight average and be 300～1000 polyether glycol.
Compared with prior art, advantage that the present invention has is: will have the polyethers waste water reclamation utilization in the polyethers production process now, and be used to prepare polyether glycol, and eliminate polyethers waste water in the polyethers production process to the influence of environment; And saved water resources.
The present invention is used to prepare the raw material of polyether glycol with the polyethers waste water in the polyethers production process, helps environmental protection, and the polyether glycol that makes can satisfy the needs of urethane foam in producing, its good product mobility, modest viscosity well.
Embodiment
The present invention is further illustrated below by specific embodiment, but each embodiment all is not to concrete restriction of the present invention.
Embodiment 1
With polyethers waste water 3%, sucrose 65%, Diethylene Glycol 27%, glycerol 5% is as being total to initiator, catalyzer is that dimethylamine (40% aqueous solution) is for being total to 3% of initiator total amount, add together in the reactor, heat up, temperature begins to add the oxidation propylene when reaching 95 ℃, the add-on of propylene oxide is 2 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.5MPa.Keep temperature of reaction 2h to react fully after propylene oxide adds and carry out, the 20min that outgases then obtains the sucrose polyethenoxy ether after the filtration.
Embodiment 2
With polyethers waste water 2%, sorbyl alcohol 60%, propylene glycol 28%, quadrol 10% is as being total to initiator, dimethylamine (40% aqueous solution) is as catalyzer, and the amount of catalyzer adds in the reactor for being total to 8% of initiator total amount, heat up, temperature begins to add the oxidation propylene when reaching 100 ℃, the add-on of propylene oxide is for 4 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 155 ℃, and pressure-controlling is below 0.5MPa.Keep temperature of reaction 1.5h to react fully after propylene oxide adds and carry out, the 3h that outgases then makes the glucitols polyethenoxy ether after the filtration.
Embodiment 3
With polyethers waste water 5%, sucrose 50%, tetramethylolmethane 20%, trolamine 25% is as being total to initiator, Monomethylamine (40% aqueous solution) is as catalyzer, the amount of catalyzer adds in the reactor for being total to 10% of initiator total amount, add propylene oxide earlier, the add-on of propylene oxide is 0.5 times of common initiator gross weight, the temperature-rise period pressure-controlling is below 0.5MPa, and temperature begins to add 3 times propylene oxide of common initiator gross weight when reaching 110 ℃, because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.6MPa.Keep temperature of reaction 2h to react fully after propylene oxide adds and carry out, the 20min that outgases then obtains the sucrose polyethenoxy ether after the filtration.
Embodiment 4
With polyethers waste water 5%, sucrose 60%, diethanolamine 35% is as being total to initiator, and Trimethylamine 99 (30% aqueous solution) is as catalyzer, and the amount of catalyzer adds in the reactor for being total to 6% of initiator total amount, heat up, temperature begins to add the oxidation propylene when reaching 100 ℃, the add-on of propylene oxide is for 3 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.6MPa.Keep temperature of reaction 2h to react fully after propylene oxide adds and carry out, the 20min that outgases then obtains the sucrose polyethenoxy ether after the filtration.
Embodiment 5
With polyethers waste water 1%, quadrol 99% is as being total to initiator, dimethylamine is a catalyzer, the amount of catalyzer adds in the reactor for being total to 0.2% of initiator total amount, add propylene oxide earlier, the add-on of propylene oxide is 0.3 times of common initiator gross weight, the temperature-rise period pressure-controlling is below 0.5MPa, temperature begins to add the oxidation propylene when reaching 90 ℃, the add-on of propylene oxide is 5 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.6MPa.Keep temperature of reaction 2h to react fully after propylene oxide adds and carry out, the 20min that outgases then obtains the ethylenediamines polyethenoxy ether after the filtration.
Embodiment 6
With polyethers waste water 8%, N.F,USP MANNITOL 55%, glycerol 15%, tri-isopropanolamine 12%, tolylene diamine 15% as initiator altogether, Trimethylamine 99 (30% aqueous solution) is a catalyzer, the amount of catalyzer is for being total to 21% of initiator total amount, add in the reactor, heat up, temperature begins to add the oxidation propylene when reaching 100 ℃, the add-on of propylene oxide is 6 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 145 ℃, and pressure-controlling is below 0.5MPa.Keep temperature of reaction 3h to react fully after propylene oxide adds and carry out, the 4h that outgases then makes N.F,USP MANNITOL class polyoxypropylene polyethers after the filtration.
Embodiment 7
With polyethers waste water 2%, sucrose 48%, Diethylene Glycol 50% as initiator altogether, Monomethylamine is a catalyzer, the amount of catalyzer adds in the reactor for being total to 2% of initiator total amount, heat up, temperature begins to add the oxidation propylene when reaching 100 ℃, the add-on of propylene oxide is for 2 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.5MPa.After adding, propylene oxide make reaction pressure return to 1 times the ethylene oxide that adds common initiator gross weight before reinforced during pressure again, still controlled temperature and pressure and in 3h, add.Keep temperature of reaction 1h to react fully after adding and carry out, the 3.5h that outgases then makes sucrose polyoxyethylene polyoxypropylene block polyether after the filtration.
Embodiment 8
With polyethers waste water 3%, sucrose 67%, glycerol 30% as initiator altogether, Trimethylamine 99 is a catalyzer, the amount of catalyzer adds in the reactor for being total to 3% of initiator total amount, heat up, temperature begins to add oxidation alkene when reaching 100 ℃, the add-on of olefin oxide is 4 times of common initiator gross weight, wherein, propylene oxide 80%, ethylene oxide 20%.Because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.5MPa.Keep temperature of reaction 2h to react fully after olefin oxide adds and carry out, the 3h that outgases then makes the sucrose polyethers after the filtration.
Embodiment 9
With polyethers waste water 4%, sucrose 45%, propylene glycol 19%, quadrol 32% as initiator altogether, dimethylamine (40% aqueous solution) is a catalyzer, the amount of catalyzer adds in the reactor for being total to 2% of initiator total amount, heat up, temperature begins to add the oxidation propylene when reaching 100 ℃, the add-on of propylene oxide is for 6 times of common initiator gross weight, because of exothermic heat of reaction, controlled temperature must not surpass 135 ℃, and pressure-controlling is below 0.5MPa.Keep temperature of reaction 1.5h to react fully after propylene oxide adds and carry out, the 3h that outgases then makes the sucrose polyethenoxy ether after the filtration.
Embodiment 10
The application of the polyether glycol that preparation method of the present invention makes, get 80 parts of polyether glycols, 4 parts of silicone oil, 0.3 part of catalyzer, catalyzer is a triethylamine, and 50 parts of whipping agents, whipping agent are a water and a trifluorotrichloroethane (HCFC-141b), 350 parts of isocyanic ester, high-speed stirring mix post-foaming and make polyurethane foam product.
Embodiment 11
The application of the polyether glycol that a kind of preparation method of the present invention makes, get 100 parts of polyether glycols, 1 part of silicone oil, 4 parts of catalyzer, catalyzer is a dimethylethanolamine, and 0.5 part of whipping agent, whipping agent are water and dichlorotrifluoroethane (HCFC-123), 80 parts of isocyanic ester, high-speed stirring mix post-foaming and make polyurethane foam product.
Embodiment 12
The application of the polyether glycol that a kind of preparation method of the present invention makes, get 120 parts of polyether glycols, 2 parts of silicone oil, 2 parts of catalyzer, catalyzer is the mixture of dimethylethanolamine and trolamine, and 30 parts of whipping agents, whipping agent are the mixture of water, pentamethylene and iso-pentane, 200 parts of isocyanic ester, high-speed stirring mix post-foaming and make polyurethane foam product.
Claims (4)
1. the preparation method of the polyether glycol of a recycle water resources is characterized in that it under the amines catalyst effect, utilizes the common initiator and the olefin oxide reaction that comprise polyethers waste water to make, and comprises the steps:
1. the mixture with polyethers waste water and polyvalent alcohol or aminated compounds or polyvalent alcohol and aminated compounds adds in the reactor as being total to initiator; The part by weight of polyvalent alcohol, aminated compounds and polyethers waste water is in the initiator altogether: polyvalent alcohol 0-98%, aminated compounds 0-99%, polyethers waste water 1-8%;
2. add catalyzer in above-mentioned reactor, the amount of the catalyzer of adding is for being total to 0.2～10% of initiator weight;
3. add the olefin oxide of 2～6 times of weight of initiator total amount altogether under 90～155 ℃ of temperature in above-mentioned reactor, pressure maintains 0.05～0.6MPa, and it is fully reacted;
4. above-mentioned reaction product is outgased, filters, obtain polyether glycol.
2. the preparation method of the polyether glycol of recycle water resources according to claim 1, it is characterized in that: step 1. in, described polyvalent alcohol is one or more mixtures in sucrose, sorbyl alcohol, α-Jia Jiputaotanggan, N.F,USP MANNITOL, Diethylene Glycol, glycerol, propylene glycol, ethylene glycol, the tetramethylolmethane; Described aminated compounds is one or more mixtures in quadrol, Monoethanolamine MEA BASF, diethanolamine, trolamine, a Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine, the tolylene diamine.
3. the preparation method of the polyether glycol of recycle water resources according to claim 1 is characterized in that: step 2. in, described catalyzer is one or more mixtures in Monomethylamine, dimethylamine, the Trimethylamine 99.
4. the preparation method of the polyether glycol of recycle water resources according to claim 1 is characterized in that: step 3. in, olefin oxide is one or both mixtures in ethylene oxide or the propylene oxide; When being two kinds of mixtures, the adding mode of olefin oxide is to mix back adding or different olefin oxide segmentation addings.
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| WO2006047436A1 (en) * | 2004-10-26 | 2006-05-04 | Dow Global Technologies, Inc. | Improved method for alkoxylating active hydrogen containing compounds and the alkoxylated compounds made therefrom |
| CN1887929A (en) * | 2006-07-24 | 2007-01-03 | 句容市宁武化工有限公司 | Prepn of polyether polyol for polyurethane foam and application of the product |
| CN101173039A (en) * | 2007-09-29 | 2008-05-07 | 句容市宁武化工有限公司 | Process for preparing polyether polylol and application of prepared product |
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| WO2006047436A1 (en) * | 2004-10-26 | 2006-05-04 | Dow Global Technologies, Inc. | Improved method for alkoxylating active hydrogen containing compounds and the alkoxylated compounds made therefrom |
| CN1887929A (en) * | 2006-07-24 | 2007-01-03 | 句容市宁武化工有限公司 | Prepn of polyether polyol for polyurethane foam and application of the product |
| CN101173039A (en) * | 2007-09-29 | 2008-05-07 | 句容市宁武化工有限公司 | Process for preparing polyether polylol and application of prepared product |
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