CN109206607A - A kind of synthetic method and its application of organic amine polyethers - Google Patents
A kind of synthetic method and its application of organic amine polyethers Download PDFInfo
- Publication number
- CN109206607A CN109206607A CN201810946984.0A CN201810946984A CN109206607A CN 109206607 A CN109206607 A CN 109206607A CN 201810946984 A CN201810946984 A CN 201810946984A CN 109206607 A CN109206607 A CN 109206607A
- Authority
- CN
- China
- Prior art keywords
- polyethers
- triethanolamine
- molecular weight
- added
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 188
- 238000010189 synthetic method Methods 0.000 title claims abstract description 19
- 150000001412 amines Chemical class 0.000 title claims abstract description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000047 product Substances 0.000 claims abstract description 67
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 25
- 239000012043 crude product Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000013517 stratification Methods 0.000 claims abstract description 15
- 239000010687 lubricating oil Substances 0.000 claims abstract description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 108
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 56
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 28
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000391 magnesium silicate Substances 0.000 claims description 24
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 24
- 235000019792 magnesium silicate Nutrition 0.000 claims description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- 239000003463 adsorbent Substances 0.000 claims description 18
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000314 lubricant Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 239000004721 Polyphenylene oxide Substances 0.000 description 27
- 238000010792 warming Methods 0.000 description 27
- 238000004321 preservation Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006073 displacement reaction Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 230000018044 dehydration Effects 0.000 description 20
- 238000006297 dehydration reaction Methods 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 239000000126 substance Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000002199 base oil Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 206010067171 Regurgitation Diseases 0.000 description 10
- 238000003379 elimination reaction Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 9
- 238000007664 blowing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- -1 propoxyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009849 vacuum degassing 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
- 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
- C08G65/2624—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 aliphatic 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
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
- C10M107/44—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
- C10M2217/065—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound used as base material
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to lubricating oil fields, and in particular to a kind of synthetic method and its application of organic amine polyethers.A kind of synthetic method of organic amine polyethers of the present invention, include: (1) using the mixture of one or more of triethanolamine, diethanol amine, monoethanolamine as initiator, propylene oxide is added or propylene oxide reacts synthesis low molecular weight triethanolamine class polyethers with the mixture of ethylene oxide；(2) polypropylene glycol is added in the low molecular weight triethanolamine class polyethers that step (1) obtains, catalyst two is added, propylene oxide is added or propylene oxide is reacted with the mixture of ethylene oxide, obtains triethanolamine class polyethers crude product；(3) the unreacted epoxy monomer of triethanolamine class polyethers crude product vacuum removal for obtaining step (2), then deionized water is added and stirs stratification, it is added in the polyethers layer separated in neutralizer and adsorbs, be dehydrated and be obtained by filtration triethanolamine polyethers finished product.The triethanolamine polyethers that the present invention obtains can be used as lubricant.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular to a kind of synthetic method and its application of organic amine polyethers.
Background technique
Lube base oil can be divided into mineral oil and synthetic oil.Mineral oil base oil is refined by crude oil, has cost
Low advantage, lube base oil Minerals base oil occupy 80% or more market.But mineral base oil also has its fatal to lack
Fall into: thermal oxidation stability is poor, thermal decomposition temperature is relatively low, resistance to low temperature is poor, viscosity index (VI) is low etc., these aspects can not show a candle to synthesize
Base oil, therefore can only recover the oil synthetic base oil in the special dimension of high request standard.Wherein polyethers is exactly in synthetic base oil
One kind, have many advantages, such as that thermal oxidation stability is high, thermal decomposition temperature is high, resistance to low temperature is good.
Common polyethers synthetic base oil in the market, mostly uses greatly glycerin polyether and butylol polyether.The work of polyethers synthesis
For skill generally using glycerol or n-butanol as initiator, the alkali metal class such as KOH, NaOH is catalyst, and propylene oxide or epoxy third is added
Alkane reacts into polyethers crude product with ethylene oxide mixture, and deionized water, phosphoric acid neutralization is added after synthesizing crude product, adds magnesium silicate
The absorption of the polyethers adsorbent such as class, filtering waits until polyethers finished product after deviating from moisture by heating.This kind of polyethers is placed (half for a long time
Month or more) can acid value it is higher, generate sour regurgitation phenomenon, cause the lubricating oil made to corrode metal material serious, corrosion index is not
It is able to satisfy requirement；Another defect is the glycerol or butylol polyether that can only synthesize viscosity index (VI)≤220.In order to overcome two above
Defect, this patent are used as lubricating oil using triethanolamine class initiator (monoethanolamine, diethanol amine, triethanolamine) synthesizing polyether
Base oil.
Triethanolamine class polyethers is to be with the mixture of one or more of triethanolamine, diethanol amine, monoethanolamine
Initiator is reacted with propylene oxide mixture with propylene oxide or ethylene oxide under the action of catalyst and is obtained.Triethanolamine is poly-
Ether can be used as lube base oil, the demulsifier of oil recovery, flex foam, rigid foam, elastomeric material etc..
Has the research report of some pairs of triethanolamine polyethers at present.107573499 A of patent CN discloses one kind and is used for
The synthetic method of the crude oil demulsifier triethanolamine block polyether of oil recovery, using KOH as catalyst, triethanolamine is initiator, point
Step addition ethylene oxide, propylene oxide synthesize triethanolamine block polyether.The crude oil demulsifier molecular structure is simple, in grease cream
Diffusion velocity is fast in shape liquid, and flocculation agglutinating power is strong, and energy rapid damage crude oil emulsion droplet interfaces film, phase separation is fast, takes off
Water rate is high, and oil-water interfaces are clear, and middle layer is few, not wall built-up, and sewage with oil is few, and the aqueous saliferous of purification oil is few, and oily water purification is clear.
106008954 B of patent CN discloses a kind of polyether polyol with high activity for polyurethane fast demoulding system,
Using hydramine or toluenediamine as initiator, ethylene oxide or propylene oxide are chain extender, and KOH or NaOH are catalyst synthesizing polyether
Polyalcohol, amido polyether polyol activity is high, good for release property in refrigerator insulation system, can fast demoulding, and with penta
Alkane Miscibility is good, utmostly shortens the production cycle, improves production efficiency.
It is more that 107057051 A of patent CN discloses a kind of high activity polyether that synthesis is used for polyurethane fast demoulding system
The preparation method of first alcohol, using triethylene diamine or triethanolamine as initiator, KOH or NaOH are catalyst, ethylene oxide or ring
Ethylene Oxide is chain extender, and polyether polyol obtained has the characteristics that good fluidity, quick solidifying, intensity are high.
101240062 B of patent CN discloses a kind of synthetic method of triethanolamine block polyether, with triethanolamine, ring
Ethylene Oxide, ethylene oxide are raw material, under catalyst (KOH, NaOH, sodium methoxide class) effect under propylene oxide be first added gathered
Reaction is closed, ethylene oxide is then added and carries out polymerization reaction and be made, triethanolamine block polyether obtained has excellent resistance to
High temperature and alkaline resistance properties can prepare the product for meeting various requirement viscosity；For the processing of polyurethane foam plastics, its foaming is anti-
Should be mild, it is easy to control.
Summary of the invention
It is right it is an object of the invention to overcome existing lubricating oil polyethers (glycerin polyether, butylol polyether etc.) to be easy sour regurgitation
The deficiency for the prior arts such as equipment easily causes corrosion, and viscosity index (VI) is not easy to improve, provides one kind and is easy to industrializing implementation, gained produces
Product are not easy sour regurgitation, do not cause to corrode to equipment, and viscosity index (VI) is high, and pour point is low, the preparation side of the stable triethanolamine polyethers of quality
Method, concrete scheme are as follows:
A kind of synthetic method of organic amine polyethers, includes the following steps: (1) in triethanolamine, diethanol amine, monoethanolamine
One or more of mixtures is initiator, uses self-catalysis or catalyst one for catalyst, adds propylene oxide or epoxy
Propane reacts synthesis low molecular weight triethanolamine class polyethers with the mixture of ethylene oxide；(2) low molecule obtained in step (1)
Polypropylene glycol is added in amount triethanolamine class polyethers, catalyst two is added, propylene oxide or propylene oxide and ethylene oxide is added
Mixture reaction, obtain triethanolamine class polyethers crude product；(3) the triethanolamine class polyethers crude product vacuum for obtaining step (2)
Unreacted epoxy monomer is removed, deionized water is then added and stirs stratification, neutralizer is added in the polyethers layer separated
It neutralizes, absorption is dehydrated and is obtained by filtration triethanolamine polyethers finished product.
Catalyst one in the step (1) be potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide etc. it is one of or
Several mixtures, dosage are the mixing of the initiator and step (1) oxypropylene or propylene oxide and ethylene oxide of step (1)
The 1 of object total weight ~ 10 ‰.
The mixture ethylene oxide of the propylene oxide and ethylene oxide of the step (1) and (2) and the weight of propylene oxide
Measuring ratio is 0:100 ~ 30:70.
Low molecular weight triethanolamine class polyethers molecular weight is 300 ~ 1500 in the step (1), the reaction of the step (1)
Temperature is 70-130 DEG C.
Catalyst two in the step (2) be potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide etc. it is one of or
Several mixtures, dosage are epoxy third in the low molecular weight triethanolamine class polyethers, polypropylene glycol and step (2) of step (2)
The 1 of the total weight of the mixture of alkane or propylene oxide and ethylene oxide ~ 10 ‰.
The molecular weight of polypropylene glycol is 5 ~ 50 times of low molecular weight triethanolamine class polyethers molecular weight in the step (2),
Additional amount is the 0.5 ~ 50% of the triethanolamine class polyethers weight of low molecular weight.
Triethanolamine class polyethers molecular weight is 2000 ~ 20000 in the step (2), and the reaction temperature of the step (2) is
70-140℃。
The polyethers adsorbent being added in adsorption step in the step (3) is magnesium silicate, alumina silicate or magnesium silicate and silicic acid
The mixture of aluminium, additional amount are 0.5 ~ the 5 ‰ of triethanolamine polyethers finished weight, and the neutralizer in the step (3) is phosphoric acid.
The molecular weight of the triethanolamine polyethers finished product is 2000-20000.
A kind of triethanolamine polyethers finished product that the preparation method using above-mentioned triethanolamine class polyethers is prepared as
Application in terms of lubricating oil.
Triethanolamine polyethers finished product molecular weight produced by the present invention is 2000-20000, and product is not easy sour regurgitation, moistens for doing
Lubricating oil to equipment without causing to corrode, and the viscosity index (VI) of product can accomplish >=220, pour point≤- 38 DEG C.
When initiator is triethanolamine, reaction equation of the invention are as follows:
。
When initiator is diethanol amine, reaction equation of the invention are as follows:
。
When initiator is monoethanolamine, reaction equation of the invention are as follows:
。
Step (2) of the present invention is related to the reaction equation of polypropylene glycol are as follows:
。
The synthetic method of triethanolamine class polyethers of the invention, using two-step method.The first step is urged using self-catalysis or KOH etc.
Agent catalyzes and synthesizes the low molecular polyether that molecular weight is 300-1500, and second step is birdsed of the same feather flock together in first step low molecular weight triethanolamine
On the basis of ether, a certain proportion of polypropylene glycol is added, and the molecular weight of polypropylene glycol is low molecular weight triethanolamine class polyethers
5-50 times, add epoxide reaction and obtain high molecular weight triethanolamine polyethers crude product.The polypropylene glycols amount of addition
It is 5-50 times of low molecular weight triethanolamine polyethers, in order to have a certain proportion of high-molecular-weight poly the third two when synthesizing finished product
Alcohol polyethers (being 5-50 times of triethanolamine class polyethers polyethers), high molecular weight polypropylene glycol polyethers can be improved triethanolamine and birds of the same feather flock together
The viscosity index (VI) of ether finished product, so that the viscosity temperature characteristic of product is more preferable, viscosity index (VI) can be greatly improved；Due to triethanolamine class polyethers
Amido key between can form hydrogen bond so that triethanolamine class polyethers pour point, freezing point are few compared with hydrogen bond between polypropylene glycols molecular weight
Or the product height of hydrogen bond cannot be formed, there are a certain proportion of polypropylene glycol polyethers to enable to product in triethanolamine class polyethers
Pour point reduce.Since propoxyl group quantity is significantly larger than ethyoxyl quantity, product in the triethanolamine class polyethers of this patent
Not soluble in water for oil-soluble, polyethers crude product refining is layered out polyethers layer (buck layer is reusable) using first washing, and K+、
Na+Equal metal ions are dissolved in water in buck layer, wash off most metal ion (K+、Na+Deng), it adds a small amount of phosphoric acid and gathers
Ether adsorbent carries out exquisite post-processing, compared to the phosphoric acid and polyethers adsorbent needed for refining in traditional direct acid adding with post-processing
Dosage can be greatly lowered, that is, reduce three wastes generation, and can reduce production cost.Triethanolamine class polyethers is due to itself being alkali
Property substance will not generate corrosion and destruction to equipment when being used as lubricating oil so be not easy sour regurgitation.
The present invention uses one or more of triethanolamine, diethanol amine, monoethanolamine mixture for initiator, with two
Footwork synthesis.First use self-catalysis or potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide etc. for one of or several mixing
Object is that catalyst synthesizes triethanolamine class polyether oligomers；Certain ratio is added on low molecular weight triethanolamine class polyether-based plinth again
The polypropylene glycol of example certain molecular weight is added epoxides and synthesizes triethanolamine class polyethers crude product with potassium methoxide etc. for catalyst,
Deionized water washing is added after synthesis crude product and is layered out polyethers layer and buck layer, buck layer is applied, and a small amount of phosphoric acid is added in polyethers layer
With polyethers adsorbent adsorption refining, purification triethanolamine class polyethers is obtained after dewatering and filtering.The polyethers of this method preparation is for moistening
Lubricating oil is able to solve existing lubricating oil polyethers and is easy sour regurgitation, causes the problem of damage equipment is corroded to equipment, and can prepare
The viscosity-temperature characteristics of viscosity index (VI) >=230 good lubricating oil triethanolamine class polyethers.Polyethers refining methd is layered using first washing, then
A small amount of acid and adsorbent is added, quantity of three wastes can be greatly reduced, and production cost can be reduced.Compared with prior art, have with
Lower outstanding advantages and good effect:
1, the triethanolamine class polyethers synthesized using technical solution of the present invention, viscosity index (VI) height (>=220), viscosity temperature characteristic is good, inclines
Point is low, and is not likely to produce sour regurgitation (since triethanolamine class polyethers itself has alkalescent) for lubricating oil, will not make to equipment
At corrosion.
2, the triethanolamine class polyethers synthesized using technical solution of the present invention, triethanolamine class polyethers molecular weight can be
2000-20000。
3, the simple process of triethanolamine class polyethers is prepared, post-processing is layered out polyethers layer, the amount of adding water using first washing
Phosphoric acid and adsorbent purification, buck layer is reusable, greatly reduces three wastes generation, reduces production cost.
4. the temperature of the application is lower to be no more than 140 DEG C, reaction condition is more mild, and the application is in low molecular weight rank
Duan Caiyong lower temperature, uses higher temperature when molecular weight is high, so that the triethanolamine class polyethers molecular weight of the application synthesis is
2000-20000。
5. joined polypropylene glycol in the application step (2), polypropylene glycol itself has ehter bond and c-c key, will not generate
Hydrogen bond, pour point is lower, and triethanolamine class polyethers has between amido or amido and water or ehter bond, can form hydrogen bond, pour point is relatively
Height, polypropylene glycol, which is added, can be improved, the application performance of product, the lower use environment of adaptive temperature.
Specific embodiment
The preparation of reaction kettle before implementing: first washing 2.5L high-pressure stirring reaction kettle several times with distilled water, until clean,
Reaction kettle is dried, is cooled to spare after room temperature.
The preparation of low molecular weight triethanolamine class polyethers
Embodiment 1
Triethanolamine 248, KOH4.5g is added in 2.5L high-pressure stirring reaction kettle, is vacuumized with vacuum pump, using N2It displaces
Air in reaction kettle, after displacement three times, at vacuum degree >=-0.096MPa, the dehydration that heats up when vacuumizing is to 120 DEG C of material
Heat preservation dehydration 1 hour afterwards.Dehydration is finished, and is cooled to 85 DEG C and is continuously added into propylene oxide 1252g.Reaction temperature is controlled in 80-100
DEG C, reacting kettle inner pressure is in -0.05 ~ 0.40MPa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.It has reacted
Finish, vacuum outgas, vacuum >=-0.098MPa keeps blowing after 10min to obtain low molecular weight triethanolamine polyethers.Product index:
Chemical determination hydroxyl value is 189.1(mgKOH/g), molecular weight 890.1.
Embodiment 2
Monoethanolamine 261 is added in 2.5L high-pressure stirring reaction kettle, is vacuumized with vacuum pump, using N2It displaces in reaction kettle
Air, displacement three times after, at vacuum degree >=-0.096MPa, close vacuum be warming up to 70 DEG C after be continuously added into propylene oxide
With mixture 1239g(the ethylene oxide 300g, propylene oxide 939g of ethylene oxide).Control reaction temperature at 70-100 DEG C, instead
Answer in kettle pressure in -0.05 ~ 0.40Mpa, the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction, vacuum
Degassing, vacuum >=-0.098MPa keep blowing after 10min to obtain low molecular weight monoethanolamine polyethers.Product index: chemical method is surveyed
Determining hydroxyl value is 488(mgKOH/g), molecular weight 345.
Embodiment 3
Diethanol amine 112, KOH4.0g is added in 2.5L high-pressure stirring reaction kettle, is vacuumized with vacuum pump, using N2It displaces
Air in reaction kettle after displacement three times, is dehydrated being heated up at vacuum degree >=-0.096MPa when vacuumizing to material 110
Heat preservation dehydration 1 hour after DEG C.Dehydration is finished, and is cooled to 85 DEG C and is continuously added into propylene oxide 1252g.Reaction temperature is controlled in 80-120
DEG C, reacting kettle inner pressure is in -0.05 ~ 0.40Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.It has reacted
Finish, vacuum outgas, vacuum >=-0.098MPa keeps blowing after 10min to obtain low molecular weight diethanol amine polyethers.Product index:
Chemical determination hydroxyl value is 122.4(mgKOH/g), molecular weight 1375.
Comparative example 1
Glycerol 184, KOH4.0g is added in 2.5L high-pressure stirring reaction kettle, is vacuumized with vacuum pump, using N2Displace reaction
Air in kettle after displacement three times, is dehydrated heat up at vacuum degree >=-0.096MPa when vacuumizing to after 110 DEG C of material
Heat preservation dehydration 1 hour.Dehydration is finished, and is cooled to 85 DEG C and is continuously added into propylene oxide 1316g.Control reaction temperature at 80-120 DEG C,
Reacting kettle inner pressure is in -0.05 ~ 0.40Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction, very
Sky degassing, vacuum >=-0.098MPa keep blowing after 10min to obtain low molecular weight glycerin polyether.Product index: chemical determination
Hydroxyl value is 227.5(mgKOH/g), molecular weight 740.
Comparative example 2
N-butanol 261, KOH4.0g is added in 2.5L high-pressure stirring reaction kettle, is vacuumized with vacuum pump, using N2It displaces anti-
Answer the air in kettle, after displacement three times, at vacuum degree >=-0.096MPa, close vacuum heating dehydration to after 70 DEG C persistently plus
Enter mixture 1239g(the ethylene oxide 300g, propylene oxide 939g of propylene oxide and ethylene oxide).Control reaction temperature exists
70-120 DEG C, reacting kettle inner pressure is in -0.05 ~ 0.40Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.Instead
It should finish, vacuum outgas, vacuum >=-0.098MPa keeps blowing after 10min to obtain low molecular weight n-butanol polyethers.Product refers to
Mark: chemical determination hydroxyl value is 136.8(mgKOH/g), molecular weight 410.
Embodiment 4
Triethanolamine 248 is added in 2.5L high-pressure stirring reaction kettle, sodium methoxide 1.2g is vacuumized with vacuum pump, using N2It sets
The air in reaction kettle is changed, after displacement three times, at vacuum degree >=-0.096MPa, heats up and is dehydrated to material when vacuumizing
Heat preservation dehydration 1 hour after 120 DEG C.Dehydration is finished, and is cooled to 85 DEG C and is continuously added into propylene oxide 1252g.Reaction temperature is controlled in 80-
100 DEG C, reacting kettle inner pressure is in -0.05 ~ 0.40MPa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.Reaction
It finishes, vacuum outgas, vacuum >=-0.098MPa keeps blowing after 10min to obtain low molecular weight triethanolamine polyethers.Product refers to
Mark: chemical determination hydroxyl value is 191.5(mgKOH/g), molecular weight 879.0.
Embodiment 5
Diethanol amine 112, NaOH13.0g is added in 2.5L high-pressure stirring reaction kettle, is vacuumized with vacuum pump, using N2Displacement
Fall the air in reaction kettle, after displacement three times, is dehydrated being heated up at vacuum degree >=-0.096MPa when vacuumizing to material
Heat preservation dehydration 1 hour after 110 DEG C.Dehydration is finished, and is cooled to 85 DEG C and is continuously added into propylene oxide 1252g.Reaction temperature is controlled in 80-
120 DEG C, reacting kettle inner pressure is in -0.05 ~ 0.40Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.Reaction
It finishes, vacuum outgas, vacuum >=-0.098MPa keeps blowing after 10min to obtain low molecular weight diethanol amine polyethers.Product refers to
Mark: chemical determination hydroxyl value is 125.6(mgKOH/g), molecular weight 1340.
Low molecular weight triethanolamine polyethers index
| Embodiment one | Embodiment two | Embodiment three | Comparative example 1 | Comparative example 2 | |
| Hydroxyl value (mgKOH/g) | 189.1 | 488 | 122.4 | 227.5 | 136.8 |
| Molecular weight | 890.1 | 345 | 1375 | 740 | 410 |
The preparation of triethanolamine class polyethers finished product
1. different polyether types are compared as time change acid value changes
Embodiment 6:
The low molecular weight triethanolamine polyethers 250g of embodiment 1 is added in 2.5L reaction kettle, molecular weight is poly- the third the two of 6000
Alcohol 15g, potassium methoxide 1.3g, using N2The air in reaction kettle is displaced, after displacement three times, at vacuum degree >=-0.096MPa,
Be warming up to when vacuumizing 90 DEG C of elimination reactions generation methanol, the retention time 1 hour.After dealcoholysis, it is continuously added into epoxy
Propane and ethylene oxide mixture 1235g(ethylene oxide 370g, propylene oxide 865).Control reaction temperature at 80-125 DEG C, instead
Answer in kettle pressure in -0.02 ~ 0.4Mpa, the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction uses
After vacuum >=-0.098MPa keeps 10min, stratification after deionized water 525g stirring 20min is added in vacuum outgas.It separates
Polyethers layer in phosphoric acid 2.1g, magnesium silicate 2.2g, diatomite 0.5g is added, stirring after twenty minutes, is warming up to 100-115 DEG C, takes out
After vacuum removal moisture, it is cooled to 60 DEG C and triethanolamine polyethers finished product is obtained by filtration.Product analysis detection: chemical determination hydroxyl value
For 33.0mgKOH/g, molecular weight 5101, acid value 0.01mgKOH/g, K+Content 1.5ppm.
Comparative example 3:
The glycerin polyether 116g, potassium methoxide 9.0g, using N of comparative example 1 are added in 2.5L reaction kettle2It displaces in reaction kettle
After displacement three times, at vacuum degree >=-0.096MPa, the methanol of 90 DEG C of elimination reactions generation is warming up to when vacuumizing for air,
Retention time 1 hour.After dealcoholysis, it is continuously added into propylene oxide 1384g.Reaction temperature is controlled at 80-125 DEG C, reaction kettle
Interior pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction, using vacuum
After vacuum >=-0.098MPa keeps 10min, stratification after deionized water 520g stirring 20min is added in degassing.What is separated is poly-
Phosphoric acid 2.3g, magnesium silicate 2.2g, diatomite 0.5g are added in ether layer, stirring after twenty minutes, is warming up to 100-115 DEG C, vacuumizes
After removing moisture, it is cooled to 60 DEG C and glycerin polyether finished product is obtained by filtration.Product analysis detects: chemical determination hydroxyl value is
16.1mgKOH/g, molecular weight 3485, acid value 0.03mgKOH/g, K+Content 1.6ppm.
Comparative example 4
The butylol polyether 209g, potassium methoxide 6.0g, using N of comparative example 2 are added in 2.5L reaction kettle2It displaces in reaction kettle
After displacement three times, at vacuum degree >=-0.096MPa, the methanol of 90 DEG C of elimination reactions generation is warming up to when vacuumizing for air,
Retention time 1 hour.After dealcoholysis, it is continuously added into propylene oxide 1291g.Reaction temperature is controlled at 80-125 DEG C, reaction kettle
Interior pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction, using vacuum
After vacuum >=-0.098MPa keeps 10min, stratification after deionized water 520g stirring 20min is added in degassing.What is separated is poly-
Phosphoric acid 2.5g, magnesium silicate 2.2g, diatomite 0.5g are added in ether layer, stirring after twenty minutes, is warming up to 100-115 DEG C, vacuumizes
After removing moisture, it is cooled to 60 DEG C and butylol polyether finished product is obtained by filtration.Product analysis detects: chemical determination hydroxyl value is
20.4mgKOH/g, molecular weight 2750, acid value 0.04mgKOH/g, K+Content 1.5ppm.
The sample of embodiment 6, comparative example 3 and comparative example 4 is used into 3 bottle airtight packages with model respectively, at room temperature
On the same platform for placing laboratory, as time change detects the variation of its acid value, experimental result is as follows:
Sample changes over time acid value testing result
| Original value | 10 days | 20 days | 30 days | |
| Embodiment 6 | 0.01 | 0.01 | 0.01 | 0.01 |
| Comparative example 3 | 0.03 | 0.12 | 0.85 | 1.8 |
| Comparative example 4 | 0.04 | 0.15 | 0.88 | 2.1 |
As can be seen from the above table, the butylol polyether of the glycerin polyether of comparative example 3 and comparative example 4, with the extension acid of standing time
Value increases quickly, and sour regurgitation phenomenon is serious, and the serious product of sour regurgitation can cause serious corrosion etc. to destroy for lubricating oil to equipment；
And the triethanolamine polyethers of embodiment 4, with the extension of standing time, acid value is basically unchanged, because its own is the object of meta-alkalescence
Matter will not cause corrosion to damage so being not easy sour regurgitation to equipment.
Influence of the polypropylene glycol polyethers to product is added in the second step process
Embodiment 7
The low molecular weight triethanolamine polyethers 250g of embodiment 1 is added in 2.5L reaction kettle, molecular weight is poly- the third the two of 6000
Alcohol 15g, KOH 4.5g, using N2The air in reaction kettle is displaced, after displacement three times, at vacuum degree >=-0.096MPa, side
Vacuumize side be warming up to 110 DEG C of elimination reactions generation water, the retention time 1 hour.After dealcoholysis, it is continuously added into propylene oxide
1235g.Reaction temperature is controlled at 90-130 DEG C, reacting kettle inner pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, directly
It is no longer reduced to only to pressure.After vacuum >=-0.098MPa keeps 10min, deionization is added using vacuum outgas in end of reaction
Water 525g stirs stratification after 20min.Phosphoric acid 2.1g, magnesium silicate 2.2g are added in the polyethers layer separated, diatomite 0.5g is stirred
Mix after twenty minutes, be warming up to 100-115 DEG C, vacuumize removing moisture after, be cooled to 60 DEG C be obtained by filtration triethanolamine polyethers at
Product.Product analysis detection: chemical determination hydroxyl value is 33.0mgKOH/g, and molecular weight 5101, acid value 0.01mgKOH/g inclines
- 41 DEG C of point, viscosity index (VI) 250.
Comparative example 5
Low molecular weight triethanolamine polyethers 250g, the KOH 4.5g of embodiment 1 is added in 2.5L reaction kettle, using N2It displaces
At vacuum degree >=-0.096MPa, 110 DEG C of elimination reactions are warming up to when vacuumizing after displacement three times for air in reaction kettle
The water of generation, the retention time 1 hour.After dehydration, it is continuously added into propylene oxide 1237g.Reaction temperature is controlled in 80-125
DEG C, reacting kettle inner pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction,
Using vacuum outgas, after vacuum >=-0.098MPa keeps 10min, stratification after deionized water 525g stirring 20min is added.
Phosphoric acid 2.1g, magnesium silicate 2.2g, diatomite 0.5g are added in the polyethers layer separated, stirring after twenty minutes, is warming up to 100-115
DEG C, after vacuumizing removing moisture, it is cooled to 60 DEG C and triethanolamine polyethers finished product is obtained by filtration.Product analysis detection: chemical method is surveyed
Determine hydroxyl value be 33.2mgKOH/g, molecular weight 5070, acid value 0.01mgKOH/g, -34 DEG C of pour point, viscosity index (VI) 231.
Embodiment 8
The low molecular weight monoethanolamine polyethers 86g of embodiment 2, the polypropylene glycol that molecular weight is 5000 are added in 2.5L reaction kettle
12g, potassium methoxide 8.0g, using N2The air in reaction kettle is displaced, after displacement three times, at vacuum degree >=-0.096MPa, side
Vacuumize side be warming up to 100 DEG C of elimination reactions generation methanol, the retention time 1 hour.After dealcoholysis, it is continuously added into epoxy third
Alkane and ethylene oxide mixture 1902g(ethylene oxide 285g, propylene oxide 1617).Control reaction temperature at 90-130 DEG C, instead
Answer in kettle pressure in -0.02 ~ 0.4Mpa, the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction uses
After vacuum >=-0.098MPa keeps 10min, stratification after deionized water 700g stirring 20min is added in vacuum outgas.It separates
Polyethers layer in phosphoric acid 2.1g, magnesium silicate 2.2g, diatomite 0.5g is added, stirring after twenty minutes, is warming up to 100-115 DEG C, takes out
After vacuum removal moisture, it is cooled to 60 DEG C and monoethanolamine polyethers finished product is obtained by filtration.Product analysis detection: chemical determination hydroxyl value
For 22.7mgKOH/g, molecular weight 7415, acid value 0.01mgKOH/g, -43 DEG C of pour point, viscosity index (VI) 262.
Comparative example 6
The low molecular weight monoethanolamine polyethers 86g of embodiment 2, the polypropylene glycol that molecular weight is 5000 are added in 2.5L reaction kettle
12g, potassium methoxide 8.0g, using N2The air in reaction kettle is displaced, after displacement three times, at vacuum degree >=-0.096MPa, side
Vacuumize side be warming up to 100 DEG C of elimination reactions generation methanol, the retention time 1 hour.After dealcoholysis, it is continuously added into epoxy third
Alkane and ethylene oxide mixture 1895g(ethylene oxide 284g, propylene oxide 1611).Control reaction temperature at 80-125 DEG C, instead
Answer in kettle pressure in -0.02 ~ 0.4Mpa, the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction uses
After vacuum >=-0.098MPa keeps 10min, stratification after deionized water 700g stirring 20min is added in vacuum outgas.It separates
Polyethers layer in phosphoric acid 2.5g, magnesium silicate 2.2g, diatomite 0.5g is added, stirring after twenty minutes, is warming up to 100-115 DEG C, takes out
After vacuum removal moisture, it is cooled to 60 DEG C and monoethanolamine polyethers finished product is obtained by filtration.Product analysis detection: chemical determination hydroxyl value
For 22.6mgKOH/g, molecular weight 7448, acid value 0.01mgKOH/g, -33 DEG C of pour point, viscosity index (VI) 243.
Embodiment 9
The low molecular weight diethanol amine polyethers 150g of embodiment 3 is added in 2.5L reaction kettle, molecular weight is poly- the third the two of 10000
Alcohol 30g, NaOH 9.0g, using N2The air in reaction kettle is displaced, after displacement three times, at vacuum degree >=-0.096MPa,
Be warming up to when vacuumizing 120 DEG C of elimination reactions generation water, the retention time 1 hour.After dealcoholysis, it is continuously added into epoxy third
Alkane 1320g.Reaction temperature is controlled at 90-140 DEG C, reacting kettle inner pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding,
Until pressure is no longer reduced to only.End of reaction, using vacuum outgas, after vacuum >=-0.098MPa keeps 10min, addition go from
Stratification after sub- water 350g stirring 20min.Addition phosphoric acid 2.1g, magnesium silicate 2.2g, diatomite 0.5g in the polyethers layer separated,
Stirring after twenty minutes, is warming up to 100-115 DEG C, after vacuumizing removing moisture, is cooled to 60 DEG C and diethanol amine polyethers is obtained by filtration
Finished product.Product analysis detection: chemical determination hydroxyl value be 15.3mgKOH/g, molecular weight 11000, acid value 0.01mgKOH/g,
- 43 DEG C of pour point, viscosity index (VI) 272.
Comparative example 7
Low molecular weight diethanol amine polyethers 150g, the NaOH 9.0g of embodiment 3 is added in 2.5L reaction kettle, using N2Displacement
Fall the air in reaction kettle, after displacement three times, at vacuum degree >=-0.096MPa, it is anti-that 120 DEG C of removings are warming up to when vacuumizing
The water that should be generated, the retention time 1 hour.After dealcoholysis, it is continuously added into propylene oxide 1310g.Reaction temperature is controlled in 110-
125 DEG C, reacting kettle inner pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.It has reacted
Finish, using vacuum outgas, after vacuum >=-0.098MPa keeps 10min, standing point after deionized water 350g stirring 20min is added
Layer.Phosphoric acid 2.1g, magnesium silicate 2.2g, diatomite 0.5g are added in the polyethers layer separated, stirring after twenty minutes, is warming up to 100-
It 115 DEG C, after vacuumizing removing moisture, is cooled to 60 DEG C and diethanol amine polyethers finished product is obtained by filtration.Product analysis detection: chemical method
Measurement hydroxyl value be 15.3mgKOH/g, molecular weight 11148, acid value 0.01mgKOH/g, -33 DEG C of pour point, viscosity index (VI) 256.
Embodiment 10
The low molecular weight diethanol amine polyethers 100g of embodiment 3 is added in 2.5L reaction kettle, molecular weight is poly- the third the two of 12000
Alcohol 25g, sodium methoxide 13.5g, using N2The air in reaction kettle is displaced, after displacement three times, in vacuum degree >=-0.096MPa
Under, be warming up to when vacuumizing 110 DEG C of elimination reactions generation methanol, the retention time 1 hour.After dealcoholysis, it is continuously added into
Propylene oxide 1375g.Reaction temperature is controlled at 90-140 DEG C, reacting kettle inner pressure in -0.02 ~ 0.4Mpa, after adding heat preservation after
Continuous reaction, until pressure is no longer reduced to only.End of reaction is added after vacuum >=-0.098MPa keeps 10min using vacuum outgas
Enter deionized water 300g and stirs stratification after 20min.Phosphoric acid 2.1g, magnesium silicate 2.2g, diatom are added in the polyethers layer separated
Native 0.5g, stirring after twenty minutes, are warming up to 100-115 DEG C, after vacuumizing removing moisture, are cooled to 60 DEG C and diethanol is obtained by filtration
Amine polyethers finished product.Product analysis detection: chemical determination hydroxyl value is 10.7mgKOH/g, and molecular weight 15732, acid value is
0.01mgKOH/g, -42 DEG C of pour point, viscosity index (VI) 280.
Comparative example 8
Low molecular weight diethanol amine the polyethers 100g, sodium methoxide 13.5g, using N of embodiment 3 are added in 2.5L reaction kettle2It sets
It changes the air in reaction kettle and at vacuum degree >=-0.096MPa, 110 DEG C of removings is warming up to when vacuumizing after displacement three times
The methanol that reaction generates, the retention time 1 hour.After dealcoholysis, it is continuously added into propylene oxide 1358g.Control reaction temperature exists
110-125 DEG C, reacting kettle inner pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.Instead
It should finish, it is quiet after addition deionized water 300g stirring 20min after vacuum >=-0.098MPa keeps 10min using vacuum outgas
Set layering.Phosphoric acid 2.5g, magnesium silicate 2.2g, diatomite 0.5g are added in the polyethers layer separated, stirring after twenty minutes, is warming up to
It 100-115 DEG C, after vacuumizing removing moisture, is cooled to 60 DEG C and triethanolamine polyethers finished product is obtained by filtration.Product analysis detection: change
Method measure hydroxyl value be 10.8mgKOH/g, molecular weight 15586, acid value 0.01mgKOH/g, -32 DEG C of pour point, viscosity index (VI)
262。
Dose influence table of the polypropylene glycol polyethers to product
| Polypropylene glycol accounting (%) * | Molecular weight product | Viscosity index (VI) | Pour point (DEG C) | |
| Embodiment 7 | 6 | 5101 | 250 | -41 |
| Comparative example 5 | - | 5070 | 231 | -34 |
| Embodiment 8 | 13.9 | 7415 | 262 | -43 |
| Comparative example 6 | - | 7448 | 243 | -33 |
| Embodiment 9 | 20 | 11000 | 272 | -43 |
| Comparative example 7 | - | 11148 | 256 | -33 |
| Embodiment 10 | 25 | 15732 | 280 | -42 |
| Comparative example 8 | - | 15586 | 262 | -32 |
* the mass ratio of low molecular weight triethanolamine class polyethers polypropylene glycol accounting: is accounted for for the polypropylene glycol of addition
From upper table, statistics indicate that, the triethanolamine class polyethers of close molecular weight adds higher molecular weight polypropylene glycol in low molecule
It measures in triethanolamine class polyethers, the product that epoxide reaction obtains is added, compared to the triethanolamine class for not having addition polymerization propylene glycol
Polyethers viscosity index (VI) is higher by 10 or more, and low 7 DEG C of pour point or more, can be suitably used for the lower working environment of temperature, and viscosity temperature characteristic
It is more excellent.
The supplementary product consumptions such as post processing mode and adsorbent are to industry Index Influence
The preparation of triethanolamine polyethers crude product
Low molecular weight triethanolamine polyethers 337g, the KOH 6.1g of embodiment 1 is added in 2.5L reaction kettle, using N2It displaces
At vacuum degree >=-0.096MPa, 110 DEG C of elimination reactions are warming up to when vacuumizing after displacement three times for air in reaction kettle
The water of generation, the retention time 1 hour.After dehydration, it is continuously added into propylene oxide 1670g.Reaction temperature is controlled in 80-125
DEG C, reacting kettle inner pressure is in -0.02 ~ 0.4Mpa, and the reaction was continued for heat preservation after adding, until pressure is no longer reduced to only.End of reaction,
Using vacuum outgas, vacuum >=-0.098MPa is cooled to 60 DEG C of blowing packagings after keeping 10min, obtains polyethers crude product.
Crude product derived above is divided into 6 parts of each 330g, is post-processed with different process, specific as follows:
Method 1: first deionized water 100g is added to be warming up to 60 DEG C of stratification after mixing evenly in crude product, the polyethers layer branched away
0.3g phosphoric acid, polyethers adsorbent magnesium silicate 0.4g, diatomite is added in (buck layer reusable in wash new polyethers crude product)
After mixing evenly, heating carries out vacuum dehydration to 0.15g, when temperature rises to 115 DEG C, after vacuum >=-0.098Mpa is kept for 1 hour,
Cooling is filtered to obtain polyethers finished product.
Method 2: first adding deionized water 150 to be warming up to 60 DEG C of stratification after mixing evenly in crude product, poly- what is branched away
0.3g phosphoric acid, polyethers adsorbent magnesium silicate 0.4g, diatom is added in ether layer (buck layer reusable in wash new polyethers crude product)
After mixing evenly, heating carries out vacuum dehydration to native 0.15g, and when temperature rises to 115 DEG C, vacuum >=-0.098Mpa is kept for 1 hour
Afterwards, cooling is filtered to obtain polyethers finished product.
Method 3: first adding deionized water 200 to be warming up to 60 DEG C of stratification after mixing evenly in crude product, poly- what is branched away
0.25g phosphoric acid, polyethers adsorbent magnesium silicate 0.4g, diatom is added in ether layer (buck layer reusable in wash new polyethers crude product)
After mixing evenly, heating carries out vacuum dehydration to native 0.15g, and when temperature rises to 115 DEG C, vacuum >=-0.098Mpa is kept for 1 hour
Afterwards, cooling is filtered to obtain polyethers finished product.
Method 4: add deionized water 32g in crude product, add 2.05g phosphoric acid, polyethers adsorbent magnesium silicate 2.0g, diatomite
1.5g is neutralized after mixing evenly, and heating carries out vacuum dehydration, and when temperature rises to 115 DEG C, vacuum >=-0.098Mpa is kept for 1 hour
Afterwards, cooling is filtered to obtain polyethers finished product.
Method 5: add deionized water 32g in crude product, add 1.8g phosphoric acid, polyethers adsorbent magnesium silicate 2.0g, diatomite
1.5g is neutralized after mixing evenly, and heating carries out vacuum dehydration, and when temperature rises to 115 DEG C, vacuum >=-0.098Mpa is kept for 1 hour
Afterwards, cooling is filtered to obtain polyethers finished product.
Method 6: add deionized water 32g in crude product, add 2.05g phosphoric acid, polyethers adsorbent magnesium silicate 1.3g, diatomite
1.0g is neutralized after mixing evenly, and heating carries out vacuum dehydration, and when temperature rises to 115 DEG C, vacuum >=-0.098Mpa is kept for 1 hour
Afterwards, cooling is filtered to obtain polyethers finished product.
The index of above six kinds of processing methods is as follows:
Phosphoric acid, polyethers adsorbent usage amount and the product index of six kinds of processing methods
From it was found from upper table correlation data: using in the method 4, method 5, method 6 of conventional method, the product of only method 4 is transparent, K+
Content < 5ppm, and method 5 is since the phosphoric acid of addition is inadequate, K+Potassium dihydrogen phosphate crystallization cannot be completely formed to be removed by filtration, made
It obtains and contains 61ppm K in finished product+, and turbid appearance；Method 6, cannot be potassium dihydrogen phosphate whole since adsorbent is using deficiency
Absorption, residual fraction makes K+ content for 56ppm in finished product, and turbid appearance.And layering is first washed using this patent method,
Method 1, the method 2, the resulting finished product of method 3 of acid adding processing again, K+Residual quantity is all within 2ppm, and phosphoric acid additional amount only has
15% or so of conventional method 4, adsorbent magnesium silicate diatomite dosage only have 20% or so of conventional method method 4, and diatomite dosage is only
There is 10% or so of conventional method method 4.Show largely reduce phosphoric acid, magnesium silicate, silicon using the fine purification treatment process of this patent
Diatomaceous earth dosage.
Claims (10)
1. a kind of synthetic method of organic amine polyethers, it is characterised in that include the following steps: (1) with triethanolamine, diethanol amine,
The mixture of one or more of monoethanolamine is initiator, uses self-catalysis or catalyst one for catalyst, adds ring
Ethylene Oxide or propylene oxide react synthesis low molecular weight triethanolamine class polyethers with the mixture of ethylene oxide；(2) in step (1)
Polypropylene glycol is added in obtained low molecular weight triethanolamine class polyethers, catalyst two is added, propylene oxide or epoxy third is added
Alkane is reacted with the mixture of ethylene oxide, obtains triethanolamine class polyethers crude product；(3) the triethanolamine class for obtaining step (2)
Then the unreacted epoxy monomer of polyethers crude product vacuum removal is added deionized water and stirs stratification, in the polyethers layer separated
Middle addition neutralizer neutralizes, and absorption is dehydrated and is obtained by filtration triethanolamine polyethers finished product.
2. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: urging in the step (1)
Agent one is the one of which such as potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide or several mixtures, and dosage is step (1)
1 ~ the 10 ‰ of the total weight of the mixture of initiator and step (1) oxypropylene or propylene oxide and ethylene oxide.
3. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: the step (1) and (2)
The weight ratio of the mixture ethylene oxide and propylene oxide of propylene oxide and ethylene oxide is 0:100 ~ 30:70.
4. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: low point in the step (1)
Son amount triethanolamine class polyethers molecular weight is 300 ~ 1500, and the reaction temperature of the step (1) is 70-130 DEG C.
5. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: urging in the step (2)
Agent two is the one of which such as potassium methoxide, sodium methoxide, potassium hydroxide, sodium hydroxide or several mixtures, and dosage is step (2) use
Low molecular weight triethanolamine class polyethers, polypropylene glycol and step (2) oxypropylene or propylene oxide and ethylene oxide it is mixed
Close 1 ~ the 10 ‰ of object total weight.
6. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: poly- third in the step (2)
The molecular weight of glycol is 5 ~ 50 times of low molecular weight triethanolamine class polyethers molecular weight, and additional amount is the triethanolamine of low molecular weight
The 0.5 ~ 50% of class polyethers weight.
7. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: three second in the step (2)
Alcamines pfpe molecule amount is 2000 ~ 20000, and the reaction temperature of the step (2) is 70-140 DEG C.
8. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: absorption in the step (3)
The polyethers adsorbent being added in step is the mixture of magnesium silicate, alumina silicate or magnesium silicate and alumina silicate, and additional amount is three ethyl alcohol
0.5 ~ the 5 ‰ of amine polyethers finished weight, the neutralizer in the step (3) are phosphoric acid.
9. a kind of synthetic method of organic amine polyethers as described in claim 1, it is characterised in that: the triethanolamine polyethers at
The molecular weight of product is 2000-20000.
10. a kind of triethanolamine polyethers finished product that the synthetic method using organic amine polyethers described in claim 1 is prepared
Application in terms of as lubricating oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810946984.0A CN109206607A (en) | 2018-08-20 | 2018-08-20 | A kind of synthetic method and its application of organic amine polyethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810946984.0A CN109206607A (en) | 2018-08-20 | 2018-08-20 | A kind of synthetic method and its application of organic amine polyethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109206607A true CN109206607A (en) | 2019-01-15 |
Family
ID=64989314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810946984.0A Pending CN109206607A (en) | 2018-08-20 | 2018-08-20 | A kind of synthetic method and its application of organic amine polyethers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206607A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347428A (en) * | 1999-04-14 | 2002-05-01 | 拜尔公司 | Polyol mixture for preparation of rigid polyurethane foams |
| CN103025792A (en) * | 2010-05-27 | 2013-04-03 | 陶氏环球技术有限责任公司 | Methods for producing crosslinkable silyl group-containing polyoxyalkylene polymers |
| CN103183820A (en) * | 2011-12-29 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Preparation method of polyoxyethylene/propylene ether with low polyethylene/propylene glycol content |
| CN107057051A (en) * | 2017-01-23 | 2017-08-18 | 山东诺威新材料有限公司 | High activity rigid foam polyether polyatomic alcohol and preparation method thereof |
-
2018
- 2018-08-20 CN CN201810946984.0A patent/CN109206607A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347428A (en) * | 1999-04-14 | 2002-05-01 | 拜尔公司 | Polyol mixture for preparation of rigid polyurethane foams |
| CN103025792A (en) * | 2010-05-27 | 2013-04-03 | 陶氏环球技术有限责任公司 | Methods for producing crosslinkable silyl group-containing polyoxyalkylene polymers |
| CN103183820A (en) * | 2011-12-29 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Preparation method of polyoxyethylene/propylene ether with low polyethylene/propylene glycol content |
| CN107057051A (en) * | 2017-01-23 | 2017-08-18 | 山东诺威新材料有限公司 | High activity rigid foam polyether polyatomic alcohol and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102733155B1 (en) | Alkoxylated secondary alcohol | |
| US20070164252A1 (en) | Refrigerating machine oil composition | |
| WO2020133062A1 (en) | Method for preparing reactive sealant resin | |
| CN115124709A (en) | Polyether demulsifier with decyltetradecanol as starting agent, preparation method and application thereof | |
| CN104531206B (en) | Environmental-protecting and high-efficient type low temperature condensate oil emulsion splitter and preparation method thereof | |
| CN105061750A (en) | High-double bond content allyl polyether production method | |
| CN107304161A (en) | A kind of laruyl alcohol alkyl ether and preparation method thereof and drilling fluid | |
| CN106753284B (en) | A kind of viscosity reducer for crude oil and preparation method thereof | |
| CN107118756A (en) | A kind of efficient thick-oil thinner and preparation method thereof | |
| CN111139040B (en) | Temperature response type aluminum-based plugging treating agent for drilling fluid and preparation method thereof | |
| CN105330831A (en) | Polyether polyol used for polyurethane single-component grouting materials and preparation method and application thereof | |
| CN108165303B (en) | Crude oil demulsifier and preparation method and use method thereof | |
| CN109232876A (en) | A kind of preparation method of ethylol amine polyethers | |
| CN109206607A (en) | A kind of synthetic method and its application of organic amine polyethers | |
| CN107043463A (en) | Humic acid condensation polymer and preparation method thereof | |
| CN102898640B (en) | Preparation method of octafluoropentyl alcohol polyoxyethylene ether | |
| CN111378107B (en) | Preparation method of reactive sealant resin | |
| CN106085577A (en) | A kind of medical apparatus and instruments soluble oil and preparation method thereof | |
| CN109438692A (en) | A kind of synthetic method of phosphonitrile polyethers | |
| CN115558096A (en) | Comb-type cardanol polyether demulsifier, and preparation method and application thereof | |
| CN106467562A (en) | A kind of aminoacid sugar ester, its preparation method and its application | |
| CN110643340B9 (en) | High-efficiency water-soluble viscosity-reduction oil washing agent for heavy oil thermal recovery and preparation method thereof | |
| CN109679636B (en) | Method for discharging liquid and gas production by adopting oil-resistant solid foam discharging agent composition | |
| CN109681171B (en) | Method for discharging liquid and producing gas by adopting solid foam water discharging agent composition | |
| CN110499185A (en) | A kind of racemosus type macromolecule demulsification host agent and base oildeemulsifier in high performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 312000 No. 8, Jingqi East Road, Shangyu economic and Technological Development Zone, Hangzhou Bay, Shangyu District, Shaoxing City, Zhejiang Province Applicant after: Zhejiang Real Madrid Shangyi New Material Co.,Ltd. Address before: 312000 Shangyu Economic and Technological Development Zone, Hangzhou Bay, Shangyu District, Shaoxing City, Zhejiang Province Applicant before: ZHEJIANG HUANGMA NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190115 |