CN111393631B - Synthesis method of secondary alcohol polyoxyethylene ether - Google Patents
Synthesis method of secondary alcohol polyoxyethylene ether Download PDFInfo
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- CN111393631B CN111393631B CN202010473011.7A CN202010473011A CN111393631B CN 111393631 B CN111393631 B CN 111393631B CN 202010473011 A CN202010473011 A CN 202010473011A CN 111393631 B CN111393631 B CN 111393631B
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- secondary alcohol
- polyoxyethylene ether
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- alcohol polyoxyethylene
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- 150000003333 secondary alcohols Chemical class 0.000 title claims abstract description 114
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 37
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- CSEGCHWAMVIXSA-UHFFFAOYSA-L cyclopenta-1,3-diene;hafnium(4+);dichloride Chemical compound [Cl-].[Cl-].[Hf+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 CSEGCHWAMVIXSA-UHFFFAOYSA-L 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 3
- 238000003786 synthesis reaction Methods 0.000 claims 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 238000001816 cooling Methods 0.000 description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- -1 cyclopentadienyl anion Chemical class 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 238000005485 electric heating Methods 0.000 description 12
- 239000004310 lactic acid Substances 0.000 description 12
- 235000014655 lactic acid Nutrition 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012968 metallocene catalyst Substances 0.000 description 11
- HKOLRKVMHVYNGG-UHFFFAOYSA-N tridecan-2-ol Chemical compound CCCCCCCCCCCC(C)O HKOLRKVMHVYNGG-UHFFFAOYSA-N 0.000 description 11
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 description 9
- 238000007789 sealing Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical group CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2654—Aluminium or boron; Compounds thereof
-
- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
-
- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2672—Nitrogen or compounds thereof
-
- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method of secondary alcohol polyoxyethylene ether, mainly solve the technical problem that the secondary alcohol conversion rate is low or the secondary alcohol residue in the secondary alcohol polyoxyethylene ether product is large in the prior art, through adopting the synthetic method of the secondary alcohol polyoxyethylene ether, including in the presence of catalyst, using secondary alcohol as initiator, initiating ethylene oxide polymerization reaction to obtain the secondary alcohol polyoxyethylene ether product, wherein the catalyst includes component A and/or component B; the component A is piperidine oxide; the component B comprises: (1) metallocenes and (2) alkylalumoxanes; the technical scheme that the metal in the metallocene is selected from IVB group transition metal elements better solves the technical problem, and can be used in the industrial production of secondary alcohol polyoxyethylene ether.
Description
Technical Field
The invention relates to a method for synthesizing secondary alcohol polyoxyethylene ether.
Background
The secondary alcohol polyoxyethylene ether is a product obtained by initiating ethylene oxide polymerization by taking a secondary alcohol as an initiator in the presence of a catalyst. The secondary alcohol polyoxyethylene ether has excellent penetration, emulsifying agent, wetting and cleaning agent, does not contain APEO, can be used in combination with other various anionic, nonionic and cationic surfactants, has superior synergistic effect, can greatly reduce the consumption of the auxiliary agent, and achieves good cost performance. At present, the problems of low conversion rate of secondary alcohol polyoxyethylene ether and high residual amount of secondary alcohol seriously affect the yield and productivity of products, so a method for improving the conversion rate of the secondary alcohol polyoxyethylene ether is hopefully to be found.
As used herein, the term "metallocene catalyst" is intended to mean an organometallic complex of a group IVB transition metal (e.g., Ti, Zr, Hf) bonded to at least one Cp (cyclopentadienyl anion ligand) or Cp derivative, i.e., a metallocene, as the main component, and an alkylaluminoxane or an organoboride (e.g., B (C) 6 F 5 ) 3 ) As an auxiliary component. Among the above metallocenes, titanocene dichloride, zirconocene dichloride and the like are common. The alkylaluminoxane is widely used, and examples thereof include methylaluminoxane (abbreviated to MAO), ethyl-modified MAO (abbreviated to MMAO-Et), and isobutyl-modified MAO (MMAO-i-Bu). Metallocene catalysts are commonly used in olefin polymerization reactions, but have not been found to be useful in the polymerization of secondary alcohols as initiatorsThe use in ring opening polymerization of alkylene oxides.
2,2,6, 6-tetramethylpiperidine oxide (TEMPO for short) can be used as an oxidation catalyst in the selective oxidation reaction of oxidizing a primary alcohol to an aldehyde and a secondary alcohol to a ketone in the presence of an oxidizing agent, but is not reported to be used in the ring-opening polymerization reaction of alkylene oxide using a secondary alcohol as an initiator.
Disclosure of Invention
The invention aims to solve the technical problem that the secondary alcohol residue in a secondary alcohol polyoxyethylene ether product obtained by the reaction of a secondary alcohol and ethylene oxide under the condition of a catalyst is large in the prior art, and provides a synthetic method of the secondary alcohol polyoxyethylene ether.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a synthesis method of secondary alcohol polyoxyethylene ether comprises the steps of initiating ethylene oxide polymerization reaction by taking a secondary alcohol as an initiator in the presence of a catalyst to obtain a secondary alcohol polyoxyethylene ether product, wherein the catalyst comprises a component A and/or a component B;
the component A is piperidine oxide;
the component B comprises:
(1) a metallocene;
(2) alkylaluminoxane;
the metal in the metallocene is selected from group IVB transition metal elements.
Compared with the conventional alkaline or acidic catalyst, the catalyst adopted in the synthesis method can effectively improve the conversion rate of the secondary alcohol or reduce the residual amount of the secondary alcohol in the secondary alcohol polyoxyethylene ether product.
In the above technical solution, preferably, the piperidine oxide has the following structural formula one:
wherein R1-R10 are independently selected from H or C1-C10 alkyl, but R1-R4 are not H at the same time; it is further preferred that R1 and R2 are not both H, and R3 and R4 are not both H; it is further preferred that none of R1-R4 is H, and the piperidine oxide in this case may be, for example only, a 2,2,6, 6-tetraalkylpiperidine oxide. Preferably, the hydrocarbyl group is an alkyl or aryl group. Examples of the alkyl group include, but are not limited to, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, a C7 alkyl group, a C8 alkyl group, a C9 alkyl group, and a C10 alkyl group. In a specific embodiment, 2,6, 6-tetramethylpiperidine oxide is used as piperidine oxide, just by analogy.
In the above technical solution, the metallocene of component (1) is a complex of elements of IVB group transition metals (such as Ti, Zr, Hf), and the ligand contains at least one Cp (short for cyclopentadienyl anion ligand) or Cp derivative. By way of example only, the metallocene is selected from the group consisting of titanocene dichloride (formula Cp) 2 TiCl 2 ) Zirconocene dichloride (molecular formula is Cp) 2 ZrCl 2 ) And hafnocene dichloride (formula Cp) 2 HfCl 2 ) At least one of the group of substances. In terms of equivalents only, the metallocene used in the specific embodiment is titanocene dichloride.
In the above technical solution, the alkyl group in the alkylaluminoxane is preferably at least one selected from the group consisting of C1 to C8 alkyl groups. Such as, but not limited to, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, and C8 alkyl. As examples of the specific substance, alkylaluminoxane may be, but not limited to, methylaluminoxane (abbreviated to MAO), ethyl-modified MAO (abbreviated to MMAO-Et), isobutyl-modified MAO (MMAO-i-Bu) and the like. In terms of ratios only, methylaluminoxane is used in the specific embodiment.
In the above technical solution, it is preferable that the catalyst comprises both component a and component B, and component a and component B tend to enhance each other in terms of reducing secondary alcohol residue. It is further preferred that the weight ratio of component A to component B is 0.01 to 100, such as but not limited to 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 1, 2, 5, 8, 10, 20, 50, 80, 100, etc., preferably 0.02 to 50, more preferably 0.05 to 20, most preferably 0.1 to 10, most preferably 0.1 to 5.
In the above aspect, the group IVB transition metal element is preferably at least one element selected from the group consisting of Ti, Zr, and Hf, and more preferably the group IVB transition metal element includes Ti.
In the above technical solution, the weight ratio of the alkylaluminoxane to the metallocene is preferably 0.005-0.05. Such as but not limited to 0.01, 0.02, 0.03, 0.04, and the like. In one embodiment, the weight ratio of the alkylaluminoxane to the metallocene is 0.01, and the alkylaluminoxane and the metallocene are collectively referred to as "metallocene catalyst".
In the above technical solution, the secondary alcohol is preferably at least one of the group consisting of a secondary alcohol of C8, a secondary alcohol of C9, a secondary alcohol of C10, a secondary alcohol of C11, a secondary alcohol of C12, a secondary alcohol of C13, a secondary alcohol of C14, a secondary alcohol of C15, a secondary alcohol of C16, a secondary alcohol of C17, and a secondary alcohol of C18.
In the technical scheme, the molar ratio of the total feeding amount of the polymerization reaction ethylene oxide to the feeding amount of the secondary alcohol is preferably 3-10. Such as, but not limited to, a molar ratio of 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and the like.
In the above technical scheme, the reaction temperature is preferably 50 to 150 ℃, for example, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like. And/or the pressure of the reaction is 0.05 to 0.5MPa, such as but not limited to 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, and the like.
The key to the process of the invention is the choice of catalyst, which can be reasonably chosen by the person skilled in the art without any inventive effort with regard to the amount of catalyst used and the relevant process conditions. By way of example only, the catalyst may be used in an amount of 0.05 to 0.8% by weight, specifically 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75% and the like, more preferably 0.05 to 5% by weight, based on the total weight of the secondary alcohol polyoxyethylene ether product.
In the synthesis method of the secondary alcohol polyoxyethylene ether, when the catalyst adopts mixed components, the mixing sequence of the catalyst, the mixing before adding the catalyst into a polymerization reaction system or the in-situ mixing after adding the catalyst into the polymerization reaction system are not particularly limited, and the technical effects can be obtained. In the same way, in the specific embodiment of the invention, when the catalyst adopts mixed components, the mixed components are mixed in advance and then added into the polymerization reaction system. The method comprises the following steps: (i) when the catalyst only adopts the composition of the component B in the specific embodiment, the catalyst is obtained by adding alkyl aluminoxane into the mixing sequence of metallocene according to the required proportion and mixing; (ii) when the catalyst comprises both component A and component B, the mixing sequence is such that (2) is added to (1) and then component A is added in the desired ratio.
Unless otherwise specified, the pressures described herein are in terms of gauge pressure.
The secondary alcohol residue in the secondary alcohol polyoxyethylene ether product is determined by gas chromatography.
The inventors have experimentally found that, using the method described herein, the conversion of secondary alcohols is high or the amount of residual secondary alcohols in the secondary alcohol polyoxyethylene ether product is low, especially when the catalyst comprises both component a and component B, which have an interactive promoting effect on increasing the conversion of secondary alcohols or reducing the amount of residual secondary alcohols in the secondary alcohol polyoxyethylene ether product.
The present invention will be further described with reference to the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE ]
Adding 200g of sec-tridecanol and 1g of potassium hydroxide into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing with nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 45% by weight.
[ example 1 ]
Adding 200g of sec-tridecanol and 0.5g of metallocene catalyst into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to 120 ℃ and the reaction pressure to 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 26% by weight.
[ example 2 ]
Adding 200g of sec-tridecanol and 1g of metallocene catalyst into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing with nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to 120 ℃ and the reaction pressure to 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography, and was found to be 15% by weight.
[ example 3 ]
Adding 200g of sec-tridecanol and 1.5g of metallocene catalyst into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to 120 ℃ and the reaction pressure to 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography, and found to be 10% by weight.
[ example 4 ] A method for producing a polycarbonate
200g of secondary tridecanol and 0.5g of 2,2,6, 6-tetramethyl piperidine oxide are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the reaction kettle is pumped out and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more, the curing reaction is finished, and 1g of lactic acid is added for neutralization when the cooling temperature is 60 ℃, so as to obtain the secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography, and found to be 32% by weight.
[ example 5 ]
Putting 200g of sec-tridecanol and 1g of 2,2,6, 6-tetramethyl piperidine oxide into a 1-pressure-rising reaction kettle with a stirring electric heating outer sleeve and an internal water cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing with nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reaction kettle, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reaction kettle does not drop any more, indicating that the curing reaction is finished, cooling the reaction temperature to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography, and found to be 24% by weight.
[ example 6 ]
200g of sec-tridecanol and 1.5g of 2,2,6, 6-tetramethyl piperidine oxide are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the reaction kettle is pumped out and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more, the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature is 60 ℃, and a secondary alcohol polyoxyethylene (6) ether product is obtained.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 19% by weight.
[ example 7 ] A method for producing a polycarbonate
200g of sec-tridecanol and 1g of catalyst (consisting of 0.5g of metallocene catalyst and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide) are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the high-pressure reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and the secondary alcohol polyoxyethylene (6) ether product is obtained.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 7% by weight.
[ example 8 ]
200g of sec-tridecanol and 1.5g of catalyst (consisting of 0.5g of metallocene catalyst and 1g of 2,2,6, 6-tetramethylpiperidine oxide) are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the high-pressure reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is introduced into a slow reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and a secondary alcohol polyoxyethylene (6) ether product is obtained.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 4% by weight.
[ example 9 ] A method for producing a polycarbonate
Adding 200g of sec-tridecanol and 2g of catalyst (consisting of 0.5g of metallocene catalyst and 1.5g of 2,2,6, 6-tetramethylpiperidine oxide) into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil pipe, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature of 120 ℃ and the reaction pressure of 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, maintaining the reaction temperature until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, and adding 1g of lactic acid for neutralization when the cooling temperature reaches 60 ℃ to obtain the secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 2% by weight.
[ example 10 ]
200g of sec-tridecanol and 1.5g of catalyst (consisting of 1g of metallocene catalyst and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide) are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the high-pressure reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and the secondary alcohol polyoxyethylene (6) ether product is obtained.
The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 5% by weight.
[ example 11 ] A method for producing a polycarbonate
Putting 200g of sec-tridecanol and 2g of catalyst (consisting of 1.5g of metallocene catalyst and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide) into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature of 120 ℃ and the reaction pressure of 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reaction kettle does not drop any more to indicate that the aging reaction is finished, cooling the reaction temperature to 60 ℃, adding 1g of lactic acid for neutralization to obtain a secondary alcohol polyoxyethylene (6) ether product.
The secondary alcohol residue in the product was measured by gas chromatography, and found to be 3% by weight.
Claims (14)
1. A synthesis method of secondary alcohol polyoxyethylene ether comprises the steps of initiating ethylene oxide polymerization reaction by taking a secondary alcohol as an initiator in the presence of a catalyst to obtain a secondary alcohol polyoxyethylene ether product, wherein the catalyst comprises a component A and a component B;
the component A is piperidine oxide;
the component B comprises:
(1) a metallocene; and
(2) alkylaluminoxane;
the metal in the metallocene is selected from IVB transition metal elements;
the piperidine oxide is according to the following structural formula one:
wherein R is 1 ～R 10 Independently selected from H or C1-C10 hydrocarbon groups, with the proviso that R is 1 ～R 4 Not H at the same time;
the weight ratio of the component A to the component B is 0.01-100.
2. A process for the synthesis of secondary alcohol polyoxyethylene ethers as claimed in claim 1, wherein R is 1 And R 2 Not being H at the same time, and R 3 And R 4 Not H at the same time.
3. A process for the synthesis of secondary alcohol polyoxyethylene ethers as claimed in claim 2, wherein R is 1 ～R 4 Are not all H.
4. The method for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the metallocene is at least one selected from the group consisting of titanocene dichloride, zirconocene dichloride and hafnocene dichloride.
5. A process for synthesizing a secondary alcohol polyoxyethylene ether as claimed in claim 1, wherein the alkyl group of the alkylaluminoxane is at least one selected from the group consisting of C1-C8 alkyl groups.
6. The method for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the weight ratio of the component A to the component B is 0.02-50.
7. The method for synthesizing secondary alcohol polyoxyethylene ether as claimed in claim 6, wherein the weight ratio of component A to component B is 0.05-20
8. The method for synthesizing secondary alcohol polyoxyethylene ether according to claim 7, wherein the weight ratio of the component A to the component B is 0.1-10.
9. A process for the synthesis of a secondary alcohol polyoxyethylene ether according to claim 1, wherein the group IVB transition metal element is at least one selected from the group consisting of Ti, Zr and Hf.
10. The method for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the weight ratio of the alkylaluminoxane to the metallocene is 0.005-0.05.
11. The method for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the secondary alcohol is at least one selected from the group consisting of a secondary alcohol of C8, a secondary alcohol of C9, a secondary alcohol of C10, a secondary alcohol of C11, a secondary alcohol of C12, a secondary alcohol of C13, a secondary alcohol of C14, a secondary alcohol of C15, a secondary alcohol of C16, a secondary alcohol of C17 and a secondary alcohol of C18.
12. The method for synthesizing a secondary alcohol polyoxyethylene ether as claimed in claim 1, wherein the molar ratio of the total amount of ethylene oxide to the secondary alcohol in the polymerization reaction is 3 to 10.
13. The method for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the reaction temperature is 50-150 ℃.
14. The method for synthesizing a secondary alcohol polyoxyethylene ether as claimed in claim 1, wherein the reaction pressure is 0.05-0.5 MPa.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3357970A (en) * | 1964-06-10 | 1967-12-12 | Pfizer & Co C | Oxyalkylation of solid polyols |
| US6303832B1 (en) * | 1999-11-09 | 2001-10-16 | Basf Aktiengesellschaft | Oxyalkylation of alkanols with alkylene oxides |
| CN1439669A (en) * | 1998-05-14 | 2003-09-03 | 巴斯福股份公司 | Preparation for mixture containing carbodiimide and polyurethane |
| JP2005298463A (en) * | 2004-04-07 | 2005-10-27 | Matsumoto Yushi Seiyaku Co Ltd | Ring-opening polymerization method |
| WO2009056513A1 (en) * | 2007-10-30 | 2009-05-07 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a polyether polyol suitable for preparing rigid polyurethane foams |
| JP2011153112A (en) * | 2010-01-28 | 2011-08-11 | Kao Corp | Method for producing (poly)glyceryl ether |
| CN108117639A (en) * | 2016-11-30 | 2018-06-05 | 中国石油天然气股份有限公司 | Unsaturated fatty alcohol polyoxyethylene polyoxypropylene block copolymer and preparation method and application |
| CN108250426A (en) * | 2018-03-07 | 2018-07-06 | 上海五伦化工科技有限公司 | The preparation method and process for purification of secondary aliphatic alcohol polyoxyethylene ether |
| WO2018209069A1 (en) * | 2017-05-10 | 2018-11-15 | Dow Global Technologies Llc | Catalyst complex |
| CN109503825A (en) * | 2018-11-19 | 2019-03-22 | 上海多纶化工有限公司 | The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether |
-
2020
- 2020-05-29 CN CN202010473011.7A patent/CN111393631B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3357970A (en) * | 1964-06-10 | 1967-12-12 | Pfizer & Co C | Oxyalkylation of solid polyols |
| CN1439669A (en) * | 1998-05-14 | 2003-09-03 | 巴斯福股份公司 | Preparation for mixture containing carbodiimide and polyurethane |
| US6303832B1 (en) * | 1999-11-09 | 2001-10-16 | Basf Aktiengesellschaft | Oxyalkylation of alkanols with alkylene oxides |
| JP2005298463A (en) * | 2004-04-07 | 2005-10-27 | Matsumoto Yushi Seiyaku Co Ltd | Ring-opening polymerization method |
| WO2009056513A1 (en) * | 2007-10-30 | 2009-05-07 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a polyether polyol suitable for preparing rigid polyurethane foams |
| JP2011153112A (en) * | 2010-01-28 | 2011-08-11 | Kao Corp | Method for producing (poly)glyceryl ether |
| CN108117639A (en) * | 2016-11-30 | 2018-06-05 | 中国石油天然气股份有限公司 | Unsaturated fatty alcohol polyoxyethylene polyoxypropylene block copolymer and preparation method and application |
| WO2018209069A1 (en) * | 2017-05-10 | 2018-11-15 | Dow Global Technologies Llc | Catalyst complex |
| CN108250426A (en) * | 2018-03-07 | 2018-07-06 | 上海五伦化工科技有限公司 | The preparation method and process for purification of secondary aliphatic alcohol polyoxyethylene ether |
| CN109503825A (en) * | 2018-11-19 | 2019-03-22 | 上海多纶化工有限公司 | The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether |
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