CN117164842B - Preparation method of narrow-distribution isomeric alcohol polyoxyethylene ether - Google Patents
Preparation method of narrow-distribution isomeric alcohol polyoxyethylene ether Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 45
- 238000009826 distribution Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 21
- 150000003077 polyols Chemical class 0.000 claims abstract description 21
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011206 ternary composite Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- -1 magnesium carboxylate Chemical class 0.000 claims description 22
- 208000005156 Dehydration Diseases 0.000 claims description 19
- 238000006297 dehydration reaction Methods 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 16
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 7
- CXVRRNGQUSTOIV-UHFFFAOYSA-N [Co](C#N)C#N.[Zn] Chemical compound [Co](C#N)C#N.[Zn] CXVRRNGQUSTOIV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000009736 wetting Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 230000032683 aging Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 239000012467 final product Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000007789 sealing Methods 0.000 description 8
- 229940087291 tridecyl alcohol Drugs 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ZXKXJHAOUFHNAS-FVGYRXGTSA-N (S)-fenfluramine hydrochloride Chemical compound [Cl-].CC[NH2+][C@@H](C)CC1=CC=CC(C(F)(F)F)=C1 ZXKXJHAOUFHNAS-FVGYRXGTSA-N 0.000 description 1
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention provides a preparation method of narrow-distribution isomeric alcohol polyoxyethylene ether, which is characterized in that the isomeric alcohol polyoxyethylene ether is prepared by reacting isomeric alcohol with ethylene oxide in the presence of a ternary composite catalyst, wherein the ternary composite catalyst comprises an alkaline earth metal-polyether polyol complex catalyst, a double metal cyanide catalyst and a phosphazene catalyst. The invention also provides the narrow-distribution isomeric alcohol polyoxyethylene ether and application thereof. The preparation method provided by the invention can obviously improve the physicochemical properties of the obtained isomeric alcohol polyoxyethylene ether, has the advantages of narrow molecular weight distribution, low pour point, low free alcohol content and almost no high molecular weight component, and can obtain good wetting permeability and emulsifying property when being used as a surfactant. In addition, the preparation method provided by the invention has the advantages of simple and convenient process, easiness in operation, mild and easily-controlled reaction conditions and small catalyst consumption, so that the production cost can be greatly reduced, and the production efficiency can be improved.
Description
Technical Field
The invention relates to the field of chemical preparation, in particular to a preparation method of narrow-distribution isomeric alcohol polyoxyethylene ether, the narrow-distribution isomeric alcohol polyoxyethylene ether prepared by the preparation method and application thereof.
Background
The isomeric alcohol polyoxyethylene ether is a polymer formed by adding isomeric alcohol and Ethylene Oxide (EO) to different degrees, belongs to a nonionic surfactant, mainly comprises isomeric polyoxyethylene lauryl ether, isomeric polyoxyethylene undecyl ether, isomeric polyoxyethylene tridecyl ether and the like, has stronger emulsifying capacity and excellent wetting permeability, and can be applied to the fields of textile printing and dyeing, industrial cleaning, personal care products, pesticide assistants and the like.
The isomeric alcohol polyoxyethylene ether is mainly prepared by starting from isomeric alcohol and reacting with ethylene oxide under the action of alkaline catalysts such as potassium hydroxide, sodium hydroxide and the like, and the product prepared by the method is wide in molecular weight distribution, high in free alcohol content, large in product smell, poor in low-temperature fluidity, and relatively inconvenient to use, and the drying room material is usually needed when the temperature is low in winter. Therefore, developing a new synthesis process for preparing the narrow-distribution heterogeneous alcohol polyoxyethylene ether product with low pour point and high solid content is important.
Chinese patent CN 109679085B reports a narrow-distribution random polyether and a preparation method thereof, which prepares the narrow-distribution random polyether by a step-by-step catalysis method, firstly mixes an initiator containing active hydrogen and a first catalyst, polymerizes with epoxide, ages and degass to prepare an intermediate, and then mixes and adducts epoxide with a second catalyst to prepare the narrow-distribution random polyether, the molecular weight distribution coefficient of the product is less than 1.06, however, the method has longer aging time in the process of preparing the intermediate, and the preparation process is more complicated, thereby prolonging the reaction period, and further increasing the production cost. Chinese patent application CN 106084197A reports a preparation method of narrow-distribution polyether, which is characterized in that a composite catalyst is used for controlling the reaction temperature and time and catalyzing small molecular alcohols such as ethylene glycol and propylene oxide to polymerize to prepare the narrow-distribution polyether, but the process is not suitable for catalyzing an ethylene oxide system, mainly because double metal cyanide is used for catalyzing ethylene oxide to easily generate high molecular weight components, the comprehensive performance of the product is reduced, and the product is easily layered and is unfavorable for downstream application.
Therefore, although a certain progress is made on the technological improvement of the narrow-distribution heterogeneous alcohol polyoxyethylene ether product, the ideal product effect still cannot be achieved, and corresponding research needs to be further carried out.
Disclosure of Invention
In order to make up the defects in the prior art, the invention aims to provide a preparation method of the narrow-distribution isomeric alcohol polyoxyethylene ether, and the narrow-distribution isomeric alcohol polyoxyethylene ether can be prepared by the preparation method, has excellent comprehensive performance and is favorable for improving the emulsifying performance.
The invention also aims to provide the narrow-distribution isomeric alcohol polyoxyethylene ether and application thereof.
The first aspect of the invention provides a preparation method of narrow-distribution isomeric alcohol polyoxyethylene ether, which comprises the following steps: the heterogeneous alcohol polyoxyethylene ether is prepared by reacting C6-C20 heterogeneous alcohol with ethylene oxide in the presence of a ternary composite catalyst, wherein the ternary composite catalyst comprises an alkaline earth metal-polyether polyol complex catalyst, a double metal cyanide catalyst and a phosphazene catalyst.
The preparation method provided by the invention adopts a novel ternary composite catalyst, and takes the isomeric alcohol as an initiator to carry out polymerization reaction with ethylene oxide, thereby preparing the isomeric alcohol polyoxyethylene ether with narrow distribution. In the ternary composite catalyst, the alkaline earth metal-polyether polyol complex catalyst and the phosphazene catalyst are relatively mild, and can control the middle and front section of the polymerization reaction to generate high molecular weight components difficultly, so that the molecular weight distribution of the polymer is controlled, but partial isomerised alcohol cannot participate in the polymerization reaction at the moment, so that the residual alcohol is consumed in the final section of the reaction through the catalysis of the high-activity double metal cyanide catalyst, and the content of free alcohol in a target product is reduced.
Based on the method, the isomeric alcohol polyoxyethylene ether prepared by the invention has the advantages of narrow molecular weight distribution, low free alcohol content, no obvious smell, low pour point, low viscosity, good low-temperature fluidity and convenient use. In addition, the isomeric alcohol polyoxyethylene ether prepared by the invention hardly contains high molecular weight components, and has excellent adaptability under a high-concentration formula.
In the preparation method provided by the invention, the ternary composite catalyst can be composed of an alkaline earth metal-polyether polyol complex catalyst, a double metal cyanide catalyst and a phosphazene catalyst. In some preferred embodiments, the alkaline earth metal-polyether polyol complex catalyst, double metal cyanide catalyst, and phosphazene catalyst may be in a mass ratio of 0.2 to 3:0.5 to 5:1. Specifically, when the phosphazene catalyst is 1 part by mass, the alkaline earth metal-polyether polyol complex catalyst may be about 0.2, about 0.5, about 0.8, about 1.0, about 1.2, about 1.5, about 1.8, about 2.0, about 2.2, about 2.5, about 2.8 or about 3.0 parts by mass, and the double metal cyanide catalyst may be about 0.5, about 1.0, about 1.5, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5 or about 5.0 parts by mass, or any part by mass interval.
In the preparation method provided by the invention, the dosage of the ternary composite catalyst can be 0.001-0.25 wt% of the total mass of the isomeride and the ethylene oxide. In some preferred embodiments, the ternary complex catalyst may be used in an amount of 0.005 to 0.1 wt% by weight of the total mass of the isomeric alcohol and ethylene oxide, for example, about 0.005 wt%, about 0.008 wt%, about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.04 wt%, about 0.05 wt%, about 0.06 wt%, about 0.07 wt%, about 0.08 wt%, about 0.09 wt%, about 0.1 wt%, or any mass ratio interval.
In the preparation method provided by the invention, the alkaline earth metal-polyether polyol complex catalyst is prepared by reacting an alkaline earth metal compound with a polyether polyol, wherein the alkaline earth metal compound can be one or more of magnesium oxide, magnesium hydroxide, magnesium carboxylate, calcium oxide, calcium hydroxide, calcium carboxylate, barium oxide, barium hydroxide, strontium oxide and strontium hydroxide, and the polyether polyol is polyethylene glycol and/or diethylene glycol monoethyl ether. The complex catalyst of the present invention is an alkaline earth metal catalyst as described in chinese patent application CN 116102728A (the entire disclosure of which is incorporated herein by reference).
In some preferred embodiments, the alkaline earth metal-polyether polyol complex catalyst may be prepared by a process comprising:
(1) Adding alkaline earth metal compound into polyether polyol under inert atmosphere, controlling the temperature to be 80-150 ℃ (preferably 90-120 ℃, such as 100 ℃, 110 ℃, 130 ℃ or 140 ℃ and the like), and stirring for reaction;
(2) The temperature is reduced to 10-90 ℃ (preferably 20-50 ℃, such as 30 ℃, 40 ℃, 60 ℃, 70 ℃ or 80 ℃ and the like), inorganic oxy acid (such as phosphoric acid, nitric acid or sulfuric acid, preferably sulfuric acid) is dripped into the reaction liquid in the step (1), and the alkaline earth metal-polyether polyol complex catalyst is obtained through stirring reaction.
In the step (1), the weight ratio of the alkaline earth metal compound to the polyether polyol is 0.05:1 to 1:1, preferably 0.1:1 to 1:1.
In the step (1), the stirring reaction time is 2 to 6. 6 h.
In the step (2), the molar ratio of the alkaline earth metal compound to the inorganic oxy acid is 10:1 to 1:1, preferably 4:1 to 1.2:1.
In the step (2), the stirring reaction time is 1 to 24 and h.
In the step (2), a reduced pressure distillation is performed to remove impurities before the catalyst is obtained, the conditions of the reduced pressure distillation being: the temperature is 120-240 ℃, the pressure is-0.05 Mpa to-0.098 Mpa, and the time is 1-8 h.
In the preparation method provided by the invention, the double metal cyanide catalyst can be a catalyst represented by the following general formula:
X 3 [Y(CN) 6 ] 2 ·(XZ 2 )·3A·2B
wherein X, Y each independently represents Zn, fe, al, co, cu, cr, mn or Pb, and X and Y are different from each other; z represents Cl - Or Br (Br) - The method comprises the steps of carrying out a first treatment on the surface of the A represents tert-butanol or n-butanol; b represents glycerol.
In some preferred embodiments, the double metal cyanide catalyst may be one or more of a zinc aluminum cyanide catalyst, a zinc cobalt cyanide catalyst, an aluminum chromium cyanide catalyst, a manganese aluminum cyanide catalyst, a cobalt chromium cyanide catalyst. In some more preferred embodiments, the double metal cyanide catalyst is Cr 3 [Al(CN) 6 ] 2 ·(CrCl 2 ) 3 t-butanol 2 Glycerol, zn 3 [Co(CN) 6 ] 2 ·(ZnCl 2 ) 3 t-butanol 2 Glycerol, mn 3 [Al(CN) 6 ] 2 ·(MnCl 2 ) One or more of 3 t-butanol 2 glycerol.
In the preparation method provided by the invention, the phosphazene catalyst can be phosphazene oxide and/or phosphazene salt.
In some preferred embodiments, the phosphazene catalyst may be a phosphazene salt [ (C) 6 H 11 )CH 3 N] 4 P + BF 4 - And/or hexaphenoxy cyclotriphosphazene.
The double metal cyanide catalysts and phosphazene catalysts described in the present invention are those described in chinese patent application CN 106084197a (the entire disclosure of which is incorporated herein by reference). Can be a commercial product or can be self-made by referring to the literature.
In the preparation method provided by the invention, the isomerised alcohol can be one or more of isooctanol, isononanol, isomerised dodecanol, isomerised undecanol, isomerised tridecanol and isomerised hexadecanol.
In the preparation method provided by the invention, the mass ratio of the isomeric alcohol to the ethylene oxide can be 1:0.5-2. In some preferred embodiments, the mass ratio of the isomeric alcohol to ethylene oxide may be from 1:0.7 to 1.8.
In the preparation method provided by the invention, the preparation method can further comprise the following steps: and in the presence of the ternary composite catalyst, carrying out dehydration treatment on the isomeric alcohol, then heating to a first temperature, introducing first ethylene oxide for reaction, heating to a second temperature, introducing second ethylene oxide for reaction, heating to a third temperature, and introducing third ethylene oxide for reaction to obtain the isomeric alcohol polyoxyethylene ether.
The preparation method provided by the invention adopts a three-stage gradual heating mode, and is matched with an alkaline earth metal-polyether polyol complex catalyst and a phosphazene catalyst for mild reaction in the middle-front stage reaction, and double metal cyanide catalyst is activated at high temperature in the final stage reaction to catalyze the residual alcohol reaction.
In some preferred embodiments, the temperature of the dehydration treatment is 70 to 80 ℃, the dehydration time is 1 to 3 h (more preferably 1 to 1.5 h), and the post-dehydration moisture content is less than 1 wt%.
In some preferred embodiments, the first temperature is 110 to 125 ℃, the second temperature is 125 to 145 ℃, the third temperature is 145 to 160 ℃, and the third temperature is higher than the second temperature, and the second temperature is higher than the first temperature. In some more preferred embodiments, the first temperature is 110 to 125 ℃, the second temperature is 130 to 135 ℃, and the third temperature is 150 to 155 ℃.
In some preferred embodiments, the first ethylene oxide is passed for a post reaction of 0.1 to 0.25 h, the second ethylene oxide is passed for a reaction of 0.3 to 0.6 h, and the third ethylene oxide is passed for a reaction of 0.1 to 0.25 h.
In some preferred embodiments, the first ethylene oxide, the second ethylene oxide, and the third ethylene oxide comprise 3 to 25 wt%, 70 to 90 wt%, and 3 to 25 wt% of the total mass of the ethylene oxide, respectively. In some more preferred embodiments, the first ethylene oxide, the second ethylene oxide, and the third ethylene oxide comprise 5 to 15 wt%, 75 to 85 wt%, and 5 to 20 wt% of the total mass of the ethylene oxide, respectively.
In some preferred embodiments, after the third ethylene oxide is introduced and reacted, the aging may be continued for a period of time to allow the ethylene oxide to react completely, for example, 0.2 to 0.8 h may be aged at 140 to 150 ℃ until the pressure in the reaction vessel is no longer decreasing.
The second aspect of the invention provides a narrow-distribution isomeric alcohol polyoxyethylene ether, which is prepared by the preparation method according to any one of the technical schemes.
The isomeric alcohol polyoxyethylene ether prepared by the preparation method of the invention has excellent properties such as narrow molecular weight distribution, low pour point, no gel, low free alcohol content and almost no high molecular weight component.
In some preferred embodiments, the isomeric alcohol polyoxyethylene ether has a molecular weight distribution index PDI of less than 1.08.
In a third aspect, the present invention provides the use of the narrow-distribution isomeric alcohol polyoxyethylene ether according to any of the above technical schemes as a nonionic surfactant.
The isomeric alcohol polyoxyethylene ether prepared by the preparation method has excellent properties, thus having good wetting permeability and emulsifying property, being very suitable for being used as a nonionic surfactant and being completely suitable for a high-concentration formula system.
The technical scheme provided by the invention has the following advantages:
(1) According to the preparation method provided by the invention, the novel ternary composite catalyst is adopted to prepare the narrow-distribution isomeric alcohol polyoxyethylene ether, and the various properties of the obtained isomeric alcohol polyoxyethylene ether can be obviously improved through the combined use of catalyst components with different activities and different types.
(2) Based on excellent properties, the isomeric alcohol polyoxyethylene ether prepared by the preparation method provided by the invention is particularly suitable for being used as a nonionic surfactant, can obtain good wetting permeability and emulsifying property, and has excellent adaptability even to a high-concentration formula system, so that the isomeric alcohol polyoxyethylene ether has wide application prospects in the fields of daily chemical products, process cleaning, textile printing and dyeing, personal care products, pesticide auxiliaries and the like.
(3) The preparation method provided by the invention has the advantages of simple and convenient process, easy operation, mild and easily controlled reaction conditions, small catalyst consumption, convenient removal and no need of complex post-treatment procedures, thus greatly reducing the production cost and improving the production efficiency, and being very suitable for industrial scale production.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
The sources of the catalysts used in the examples and comparative examples of the present invention are as follows:
other materials or reagents are commercially available unless otherwise specified.
The percentages used in the examples and comparative examples of the present invention are mass percentages unless otherwise specified.
EXAMPLE 1 preparation of isomeric decaol polyoxyethylene ethers
Adding the composite catalyst of which the mass ratio is 0.1 percent relative to the total mass of the isomeric dodecanol and the ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of a calcium-based catalyst to an aluminum-chromium cyanide catalyst to a phosphazene salt catalyst is 0.8:1.3:1, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 70-75 ℃ for 1 h, introducing 20 g ethylene oxide when the temperature is raised to 110 ℃, reacting for 0.1 h, then introducing 365 g ethylene oxide when the temperature is raised to 130 ℃ and reacting for 0.5 h, continuously raising the temperature to 150 ℃, introducing the residual ethylene oxide for 47 g and reacting for 0.1 h, ageing at 140-150 ℃ for 0.5 h until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain a final product.
EXAMPLE 2 preparation of isomeric tridecanol polyoxyethylene ethers
Adding the composite catalyst of the isomeric tridecanol 393 g and 0.005 percent relative to the total mass of the isomeric tridecanol and the ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of the magnesium-based catalyst to the zinc-cobalt cyanide catalyst to the phosphazene salt catalyst is 1.8:2.5:1, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 75-80 ℃ for 1.2 h, introducing 61 g ethylene oxide and reacting for 0.2 h when the temperature rises to 120 ℃, then introducing 516 g ethylene oxide and reacting for 0.5 h when the temperature rises to 130 ℃, continuously introducing the residual ethylene oxide for 30 g and reacting for 0.1 h when the temperature continues to rise to 145 ℃, then aging for about 0.5 h at 140-150 ℃ until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain the final product.
EXAMPLE 3 preparation of isomeric decaol polyoxyethylene ethers
Adding 360 g of isomerism dodecanol and a composite catalyst accounting for 0.07 percent of the total mass of isomerism dodecanol and ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of a calcium-based catalyst to an aluminum-chromium cyanide catalyst to a phosphazene oxide catalyst is 2.9:0.6:1, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 70-75 ℃ for 1 h, introducing 32 g ethylene oxide when the temperature is raised to 110 ℃, reacting for 0.1 h, then raising the temperature to 135 ℃, introducing 512 g ethylene oxide, reacting for 0.6 h, continuously raising the temperature to 155 ℃, introducing the residual ethylene oxide for 96 g, reacting for 0.15h, ageing for 0.5 h at 140-150 ℃ until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain a final product.
EXAMPLE 4 preparation of isomerised undecylenic alcohol polyoxyethylene ether
Adding the composite catalyst of the isomerism undecanol 494 g and 0.03 percent relative to the total mass of the isomerism undecanol and the ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of a calcium-based catalyst to an aluminum-chromium cyanide catalyst to a phosphazene oxide catalyst is 0.2:4.6:1, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 75-80 ℃ for 1.5 h, introducing 26 g ethylene oxide when the temperature rises to 115 ℃ and reacting for 0.1 h, then introducing 379 g ethylene oxide when the temperature rises to 130 ℃ and reacting for 0.4 h, continuously heating to 155 ℃ and introducing the residual ethylene oxide 101 g and reacting for 0.15h after the reaction, ageing at 140-150 ℃ for about 0.5 h until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain the final product.
EXAMPLE 5 preparation of isomeric tridecanol polyoxyethylene ethers
Adding the composite catalyst of the isotridecyl alcohol 476 and g which is 0.008 percent relative to the total mass of the isotridecyl alcohol and the ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of a magnesium-based catalyst to a zinc cobalt cyanide catalyst to a phosphazene salt catalyst is 1.2:0.8:1, after the reaction kettle is closed, nitrogen is replaced three times, then negative pressure dehydration is carried out at 75-80 ℃ for 1.3 h, when the temperature is raised to 125 ℃, 55 g ethylene oxide is introduced and reacted for 0.1 h, then the temperature is raised to 135 ℃ and 393 g ethylene oxide is introduced and reacted for 0.35 h, after the reaction, the temperature is continuously raised to 150 ℃, the residual ethylene oxide is introduced for 76 g and reacted for 0.1 h, then the pressure in the reaction kettle is not reduced any more after ageing for 0.5 h at 140-150 ℃, and discharging is carried out after cooling to 60 ℃ so as to obtain the final product.
Comparative example 1 preparation of isomeric decaol polyoxyethylene ether
Adding the isomeric dodecanol 560-g and an aluminum-chromium cyanide catalyst accounting for 0.1% of the total mass of the isomeric dodecanol and the ethylene oxide into a self-priming stirring reaction kettle, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 70-75 ℃ for 1-h, introducing 20-g ethylene oxide when the temperature is raised to 135 ℃ and reacting for 0.1-h, then introducing the residual ethylene oxide 412-g at the temperature of 150 ℃ and reacting for 0.55-h, then aging at 140-150 ℃ for about 0.5-h until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain the final product.
Comparative example 2 preparation of isomeric decaol polyoxyethylene ether
Adding a potassium hydroxide catalyst which is 0.35 percent of the total mass of the isomeric dodecanol and the ethylene oxide into a self-priming stirring reaction kettle, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 70-75 ℃, introducing 32 g ethylene oxide when the temperature is increased to 140 ℃ and reacting 0.1 h, then raising the temperature to 155 ℃, introducing the rest ethylene oxide 608 g and reacting 0.95 h, aging until the pressure in the reaction kettle is not reduced after the reaction is finished, cooling to 60 ℃, adding 3.6 g acetic acid for neutralization, continuously stirring for 15 min, discharging, adding the taken intermediate product about 1 kg into a three-mouth flask, adding a magnesium silicate adsorbent 10 g, adsorbing 1 h at the temperature of 100 ℃ and the rotating speed of 1000 rpm/min, filtering the adsorbed intermediate product through a pressurizing filter, and filtering under the pressure of 0.35 MPa to obtain a final product.
Comparative example 3 preparation of isomeric tridecanol polyoxyethylene ether
Adding the isomeric tridecyl alcohol 393 g and a zinc cobalt cyanide/phosphazene salt composite catalyst which is 0.08 percent relative to the total mass of the isomeric tridecyl alcohol and the ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of the zinc cobalt cyanide catalyst to the phosphazene salt catalyst is 2.5:1, after the reaction kettle is closed, nitrogen is replaced for three times, then negative pressure dehydration is carried out at 75-80 ℃ for 1.2 h, when the temperature is raised to 135 ℃, 61 g ethylene oxide is introduced and reacted for 0.25 h, then the temperature is raised to 145 ℃, the residual ethylene oxide 546 g is introduced and reacted for 0.55 h, then aging is carried out at 140-150 ℃ for about 0.5 h until the pressure in the reaction kettle is not reduced, and then discharging after cooling to 60 ℃ is carried out, thus obtaining the final product.
Comparative example 4 preparation of isomeric decaol polyoxyethylene ether
Adding the isomeric dodecanol 418 g and a manganese aluminum cyanide/phosphazene salt composite catalyst accounting for 0.005 percent of the total mass of the isomeric dodecanol and the ethylene oxide into a self-priming stirring reaction kettle, wherein the mass ratio of the manganese aluminum cyanide catalyst to the phosphazene salt catalyst is 3.2:1, after the reaction kettle is closed, nitrogen is replaced for three times, then negative pressure dehydration is carried out at 70-75 ℃ for 1.5 h, 29 g ethylene oxide is introduced when the temperature is raised to 130 ℃ and reacted for 0.15h, then the temperature is raised to 130 ℃, 553 g residual ethylene oxide is introduced and reacted for 0.6 h, then aging is carried out at 140-150 ℃ for about 0.5 h until the pressure in the reaction kettle is not reduced, and discharging after cooling to below 60 ℃ to obtain a final product.
Comparative example 5 preparation of isomeric decaol polyoxyethylene ether
Adding the isomeric dodecanol 560 g and a calcium-based catalyst accounting for 0.08 percent of the total mass of the isomeric dodecanol and the ethylene oxide into a self-priming stirring reaction kettle, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 70-75 ℃ for 1 h, introducing 20 g ethylene oxide when the temperature is raised to 135 ℃ and reacting for 0.1 h, then introducing the residual ethylene oxide 412 g at the temperature of 150 ℃ and reacting for 0.65 h, then aging at 140-150 ℃ for about 0.5 h until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain the final product.
Comparative example 6 preparation of isomeric decaol polyoxyethylene ether
Adding 310-g of isomeric dodecanol and 0.15% of phosphazene catalyst relative to the total mass of isomeric dodecanol and ethylene oxide into a self-priming stirring reaction kettle, sealing the reaction kettle, replacing nitrogen for three times, then carrying out negative pressure dehydration at 70-75 ℃ for 1-h, introducing 35-g ethylene oxide when the temperature is raised to 110 ℃ and reacting for 0.2-h, then introducing 655-g of residual ethylene oxide when the temperature is raised to 120 ℃ and reacting for 5.2-h, then aging at 140-150 ℃ for about 0.5-h until the pressure in the reaction kettle is not reduced, cooling to below 60 ℃, and discharging to obtain the final product.
Test case
The molecular weight distribution index, pour point, viscosity, free alcohol content, high EO product content, emulsifying property, etc. of the isomeric alcohol polyoxyethylene ethers prepared in each example and comparative example were tested, and the test results are shown in table 1.
TABLE 1 Performance test results
Note that:
1) The high EO product is an abnormally high molecular weight component with EO number greater than 20 generated during the reaction;
2) The method for evaluating the emulsifying property comprises the following steps: the oil agent is liquid paraffin, the concentration of the emulsifier is 1.0 g/L, the rotating speed is 1000 rpm, the time is 2 min, and the water-oil two-phase layering time (unit: s) is examined.
As can be seen from comparative example 1, if only double metal cyanide is used as the catalyst, the catalytic activity is high, and high molecular weight polyether is easy to generate, so that the obtained polyoxyethylene ether product has wide molecular weight distribution, high free alcohol content and high EO product content, and the polyoxyethylene ether product is easy to delaminate, and has poor stability and emulsifying property when being used in a downstream high-concentration formula.
As can be seen from comparative example 2, if an alkali hydroxide is used as a catalyst, the catalytic activity is low, and the obtained polyether product has a broad molecular weight distribution and undesirable effects such as pour point, viscosity, free alcohol content, etc. And the alkaline hydroxide is required to be subjected to neutralization, desalination and other treatment steps, and the post-treatment process is complicated.
As can be seen from comparative examples 3 and 4, if double metal cyanide and phosphazene are used as binary catalysts, the resulting polyether product is still poor in terms of molecular weight distribution, free alcohol content and the like, and the emulsifying property is still not ideal.
As can be seen from comparative example 5, if only an alkaline earth metal-polyether polyol complex catalyst is used, the molecular weight distribution of the resulting polyether product is slightly broad, the free alcohol content is too high, and a small amount of high molecular weight component is also generated, and the emulsifying property is also poor.
As can be seen from comparative example 6, if only phosphazene catalyst is used, the molecular weight distribution of the obtained polyether product is obviously narrowed, and indexes such as free alcohol content, high EO product content and the like are improved, but the emulsifying property is still not ideal, the reaction time is too long (more than 5 h), the catalyst dosage is also large, the production efficiency is low, and the industrial production is not favored.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.
Claims (19)
1. The preparation method of the narrow-distribution isomeric alcohol polyoxyethylene ether is characterized in that the isomeric alcohol polyoxyethylene ether is prepared by reacting C6-C20 isomeric alcohol with ethylene oxide in the presence of a ternary composite catalyst, wherein the ternary composite catalyst comprises an alkaline earth metal-polyether polyol complex catalyst, a double metal cyanide catalyst and a phosphazene catalyst.
2. The method of preparing according to claim 1, wherein the three-way composite catalyst consists of an alkaline earth metal-polyether polyol complex catalyst, a double metal cyanide catalyst, and a phosphazene catalyst.
3. The method according to claim 1, wherein the mass ratio of the alkaline earth metal-polyether polyol complex catalyst, double metal cyanide catalyst and phosphazene catalyst is 0.2 to 3:0.5 to 5:1.
4. The preparation method according to claim 1, wherein the amount of the ternary composite catalyst is 0.001 to 0.25. 0.25 wt% of the total mass of the isomeric alcohol and the ethylene oxide.
5. The preparation method according to claim 4, wherein the amount of the ternary composite catalyst is 0.005 to 0.1. 0.1 wt% of the total mass of the isomeric alcohol and the ethylene oxide.
6. The preparation method according to claim 2, wherein the alkaline earth metal-polyether polyol complex catalyst is prepared by reacting an alkaline earth metal compound with a polyether polyol, wherein the alkaline earth metal compound is one or more of magnesium oxide, magnesium hydroxide, magnesium carboxylate, calcium oxide, calcium hydroxide, calcium carboxylate, barium oxide, barium hydroxide, strontium oxide and strontium hydroxide, and the polyether polyol is polyethylene glycol and/or diethylene glycol monoethyl ether; and/or
The double metal cyanide catalyst is a catalyst represented by the following general formula:
X 3 [Y(CN) 6 ] 2 ·(XZ 2 )·3A·2B
wherein X, Y each independently represents Zn, fe, al, co, cu, cr, mn or Pb, and X and Y are different from each other, Z represents Cl - Or Br (Br) - A represents tert-butanol or n-butanol, and B represents glycerol; and/or
The phosphazene catalyst is phosphazene oxide and/or phosphazene salt.
7. The method of claim 6, wherein the double metal cyanide catalyst is one or more of a zinc aluminum cyanide catalyst, a zinc cobalt cyanide catalyst, an aluminum chromium cyanide catalyst, a manganese aluminum cyanide catalyst, and a cobalt chromium cyanide catalyst.
8. The method of claim 7, wherein the double metal cyanide catalyst is Cr 3 [Al(CN) 6 ] 2 ·(CrCl 2 ) 3 t-butanol 2 Glycerol, zn 3 [Co(CN) 6 ] 2 ·(ZnCl 2 ) 3 t-butanol 2 Glycerol, mn 3 [Al(CN) 6 ] 2 ·(MnCl 2 ) One or more of 3 t-butanol 2 glycerol.
9. The method according to claim 6, wherein the phosphazene catalyst is a phosphazene salt [ (C) 6 H 11 )CH 3 N] 4 P + BF 4 - And/or hexaphenoxy cyclotriphosphazene.
10. The method of claim 1, wherein the isomeric alcohols are one or more of isooctanol, isononanol, isomeric dodecanol, isomeric undecanol, isomeric tridecanol, isomeric hexadecanol; and/or
The mass ratio of the isomeric alcohol to the ethylene oxide is 1:0.5-2.
11. The preparation method according to any one of claims 1 to 10, characterized in that the preparation method comprises the following process: and in the presence of the ternary composite catalyst, carrying out dehydration treatment on the isomeric alcohol, then heating to a first temperature, introducing first ethylene oxide for reaction, heating to a second temperature, introducing second ethylene oxide for reaction, heating to a third temperature, and introducing third ethylene oxide for reaction to obtain the isomeric alcohol polyoxyethylene ether.
12. The method according to claim 11, wherein the dehydration treatment is carried out at a temperature of 70 to 80 ℃ for a dehydration time of 1 to 3 h, and the water content after dehydration is less than 1 wt%.
13. The method of claim 11, wherein the first temperature is 110-125 ℃, the second temperature is 125-145 ℃, the third temperature is 145-160 ℃, and the third temperature is higher than the second temperature, and the second temperature is higher than the first temperature.
14. The method of claim 13, wherein the first temperature is 110-125 ℃, the second temperature is 130-135 ℃, and the third temperature is 150-155 ℃.
15. The method of claim 11, wherein the first ethylene oxide, the second ethylene oxide, and the third ethylene oxide comprise 3 to 25 wt%, 70 to 90 wt%, and 3 to 25 wt% of the total mass of the ethylene oxide, respectively.
16. The method of claim 15, wherein the first ethylene oxide, the second ethylene oxide, and the third ethylene oxide comprise 5 to 15 wt%, 75 to 85 wt%, and 5 to 20 wt% of the total mass of the ethylene oxide, respectively.
17. A narrow distribution of isomeric alcohol polyoxyethylene ethers prepared by the process of any one of claims 1-16.
18. The isomeric alcohol-polyoxyethylene ether according to claim 17, wherein the isomeric alcohol-polyoxyethylene ether has a molecular weight distribution index PDI of less than 1.08.
19. Use of the narrowly distributed isomeric alcohol polyoxyethylene ether of claim 17 or 18 as a nonionic surfactant.
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| WO2022048099A1 (en) * | 2020-09-01 | 2022-03-10 | 万华化学集团股份有限公司 | Method for preparing narrow-distribution triethanolamine block polyether, block polyether, and use thereof |
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