CN115536830A - Wide molecular weight distribution fatty alcohol random polyether and preparation method thereof - Google Patents
Wide molecular weight distribution fatty alcohol random polyether and preparation method thereof Download PDFInfo
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- CN115536830A CN115536830A CN202211260311.2A CN202211260311A CN115536830A CN 115536830 A CN115536830 A CN 115536830A CN 202211260311 A CN202211260311 A CN 202211260311A CN 115536830 A CN115536830 A CN 115536830A
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- fatty alcohol
- random polyether
- molecular weight
- weight distribution
- polyether
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- 229920000570 polyether Polymers 0.000 title claims abstract description 89
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 87
- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 238000007872 degassing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000543 intermediate Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001514 detection method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 1
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CBEVANLIGJVSHZ-UHFFFAOYSA-N n,n'-diheptyl-n,n'-dimethylbutanediamide Chemical compound CCCCCCCN(C)C(=O)CCC(=O)N(C)CCCCCCC CBEVANLIGJVSHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C08G65/2648—Alkali metals 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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a preparation method of a random polyether of fatty alcohol with wide molecular weight distribution, which comprises the following steps: mixing strong base catalyst with fatty alcohol, introducing N 2 Dehydrating for 1-2 h at the temperature of 115-120 ℃ and the vacuum degree of ≧ 0.095MPa, adding olefin oxide for reaction at the temperature of 90-130 ℃, degassing and discharging to obtain an aliphatic alcohol random polyether intermediate; removing impurity ions from the fatty alcohol random polyether intermediate after adsorption and filtration to obtain the product with K removed + 、Na + A fatty alcohol random polyether intermediate with impurity ions; mixing the fatty alcohol random polyether intermediate without impurity ions with an acidic auxiliary agent, and introducing N 2 Dehydrating for 1-2 h under the conditions that the temperature is 115-120 ℃ and the vacuum degree is not less than-0.095 MPa, adding DMC, heating to 120-150 ℃, adding alkylene oxide, degassing and discharging to obtain the fatty alcohol random polyether. The fatty alcohol random polyether obtained by the invention has wider range compared with the fatty alcohol random polyether prepared by directly catalyzing with DMC or strong base under the same reaction condition, and the molecular weight distribution coefficient can break through1.2, or even higher.
Description
Technical Field
The invention relates to the field of fine chemical engineering for synthesizing a surfactant, in particular to fatty alcohol random polyether with wide molecular weight distribution and a preparation method thereof.
Background
The traditional fatty alcohol polyether preparation method adopts strong base as a catalyst, such as sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, metal potassium, sodium and the like, and due to the reaction characteristic of the strong base catalyst, the speed of chain initiation reaction is lower than that of chain growth reaction, so that polyether chains are grown before all initiators are not completely converted into a unitary adduct, and the final product has initiator residues and very wide adduct molecular weight distribution.
Compared with the traditional alkali catalyst, the double metal cyanide catalyst (DMC) is adopted to synthesize polyether, and because the hydroxyl and the active center in the system have high-speed chain transfer, the terminal group rearrangement in polymerization is eliminated, the reduction of hydroxyl functionality is avoided, and the polyether has the advantages of high molecular weight, low unsaturation degree, high average functionality degree, narrow molecular weight distribution and the like.
Based on the principle, the molecular weight distribution characteristics of the fatty alcohol polyether synthesized by the two single catalysts are obvious, and the molecular weight distribution characteristics are basically fixed in respective specific areas and are difficult to expand to a larger range. However, from the application field of polyether, the systems required to be met are various, so that the molecular weight distribution of fatty alcohol polyether is also required to be diversified, and the narrow-distribution polyether is not limited. In order to meet the compatibility requirements, the market also seeks wide-distribution polyethers, and it is necessary to flexibly adjust the molecular weight distribution of the fatty alcohol polyether.
Disclosure of Invention
In view of the above, the present invention aims to provide a fatty alcohol random polyether with a wide molecular weight distribution and a preparation method thereof, aiming at the limitation of the molecular weight distribution of the fatty alcohol random polyether prepared by the existing process.
In order to achieve the technical purpose, the technical scheme adopted by the application is as follows:
in a first aspect, the present invention provides a process for the preparation of a broad molecular weight distribution fatty alcohol random polyether, said process comprising the steps of:
step 1, mixing strong base catalyst and fatty alcohol, and introducing N 2 Dehydrating for 1-2 h at the temperature of 115-120 ℃ and the vacuum degree of ≧ 0.095MPa, adding olefin oxide for reaction at the temperature of 90-130 ℃, degassing and discharging to obtain an aliphatic alcohol random polyether intermediate;
step 2, adsorbing the fatty alcohol random polyether intermediate, and then filtering to remove impurity ions to obtain a fatty alcohol random polyether intermediate without impurity ions;
step 3, mixing the fatty alcohol random polyether intermediate with impurity ions removed and an acidic auxiliary agent, and introducing N 2 Dehydrating for 1-2 h under the conditions that the temperature is 115-120 ℃ and the vacuum degree is not less than-0.095 MPa, adding a double metal cyanide catalyst DMC, heating to 120-150 ℃, adding alkylene oxide, degassing and discharging to obtain the fatty alcohol random polyether.
Further, the fatty alcohol in the step 1 is at least one of straight chain or branched chain fatty alcohol with the carbon number of 10-18.
Further, the strong base catalyst in step 1 is at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, metal potassium and metal sodium, and the dosage of the strong base catalyst is 1-5% of the total weight of the fatty alcohol and the olefin oxide.
Furthermore, the molecular weight of the fatty alcohol random polyether intermediate in the step 1 is 20-30% of that of the finished fatty alcohol random polyether.
Further, the adsorption process in step 2 is as follows: adding distilled water and acetic acid into the fatty alcohol random polyether intermediate in the step 1, mixing and stirring at 50-70 ℃ for 20-30 min, adding an adsorbent, adsorbing and stirring at 70-80 ℃ for 30-60 min; dehydrating at 100-115 deg.c and vacuum degree not less than-0.095 MPa to water content less than 0.05%; the distilled water amount is 2-10% of the mass of the fatty alcohol random polyether intermediate.
Further, the adsorbent consists of an adsorbent main body and a modified ligand, wherein the adsorbent main body is alpha-Al 2 O 3 At least one of amorphous silicon dioxide, magnesium silicate, aluminum silicate or magnesium aluminum silicate; the ligand is at least one of magnesium acetate, calcium chloride, copper chloride, potassium chloride, magnesium nitrate or aluminum nitrate; the addition amount of the adsorbent accounts for 0.1-1% of the mass of the fatty alcohol random polyether intermediate.
Further, the acidic auxiliary agent in step 3 is at least one of phosphoric acid, sulfuric acid, acetic acid, citric acid, nitric acid, hydrochloric acid and formic acid.
Further, the dosage of DMC in the step 3 is 10-100 ppm of the total mass of the molecular weight of the finished fatty alcohol random polyether; the mass ratio of the acidic auxiliary agent to the DMC in the step 3 is (1-10): 1.
Preferably, the alkylene oxide described in step 1 and step 3 is a mixture of ethylene oxide and propylene oxide.
Preferably, the ethylene oxide mass is 10 to 30% of the total mass of the alkylene oxide.
In a second aspect, the invention provides a wide molecular weight distribution fatty alcohol random polyether, wherein the molecular weight distribution coefficient of the fatty alcohol random polyether is 1.2-1.5, and the wide molecular weight distribution fatty alcohol random polyether is prepared by the preparation method of the wide molecular weight distribution fatty alcohol random polyether.
The invention has the following beneficial effects:
1. the invention can obtain fatty alcohol random polyether with wider molecular weight distribution, and has wider molecular weight distribution coefficient which can break through 1.2 and even higher than fatty alcohol random polyether prepared by directly using DMC or strong base catalysis under the same reaction condition.
2. The invention can also control the molecular weight distribution of the fatty alcohol random polyether by adjusting the mass ratio of the acid additive to the DMC, thereby meeting the compatibility requirement of the market on the diversification of the molecular weight distribution of the fatty alcohol polyether.
3. In the invention, the intermediate is obtained by catalyzing with a strong base catalyst, which is used for controlling the by-product of the product. Because the by-product is generated when the DMC one-step method is directly used for catalysis under the acidic auxiliary agent, the most intuitive embodiment is that the reaction liquid is turbid, the intermediate is obtained by first catalyzing with the strong base catalyst, and the appearance of the product obtained by DMC catalysis after adsorption treatment is clear.
Detailed Description
In the description of the present invention, it should be noted that those who do not specify specific conditions in the examples are performed according to conventional conditions or conditions recommended by manufacturers. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The molecular weight distribution of the fatty alcohol random polyether is detected by GPC and expressed by D (Mw/Mn), and the detection conditions are combined by columns
(length 65 cm), temperature 30 ℃, THF as mobile phase, flow rate of 1ml/min, sample concentration of 10g/L, RI detector.
The molecular weight of the fatty alcohol random polyether intermediate is controlled to be 20-30% of that of the finished product fatty alcohol random polyether by an alkali catalysis process, and the feeding amount of fatty alcohol and oxyalkylene in the synthesis process is determined according to the designed molecular weight of the finished product fatty alcohol random polyether. And then carrying out adsorption treatment on the intermediate, and then catalyzing by using DMC under an acidic auxiliary agent to produce the random polyether with the wide-distribution fatty alcohol. The intermediate is constructed in the process, the generation of byproducts can be effectively controlled, and the cost is saved.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The embodiment relates to a preparation method of fatty alcohol random polyether with wide molecular weight distribution, which comprises the following steps:
step 1, step 3.36g of catalyst KOH and 500g of C 18 -C 16 Adding alcohol into a 2.5L polymerization reaction kettle, dehydrating for 1.5h under the conditions of 115-120 ℃ and-0.096 Mpa, then heating to 115 ℃, continuously adding a uniform mixture of 136g of ethylene oxide and 483g of propylene oxide, keeping the reaction temperature at 115-120 ℃ in the reaction control stage, continuing the reaction until the pressure drop is stable after the mixture is added, finally cooling and degassing to 60 ℃, and filtering to obtain C 18 -C 16 Alcohol random polyether intermediate (design molecular weight 600);
step 2, 500gC was placed in a 1000mL four-necked glass flask 18 -C 16 Adding 1.6g of acetic acid (98 wt%) and 15g of distilled water into an alcohol random polyether intermediate, heating and stirring at 60 ℃ for 30 minutes, then adding 1.5g of an adsorbent mainly containing aluminum magnesium silicate/ligand calcium chloride, stirring and adsorbing at 75 ℃ for 60 minutes, gradually heating to 115 ℃, vacuumizing and dehydrating for 4 hours, filtering after the dehydration is finished and the water content is less than 0.04%, and obtaining the product with pH =6.95, K and K + 、Na + Post-treated C with contents of 10ppm or less 18 -C 16 An alcohol random polyether intermediate;
step 3, post-treating 300g of C 18 -C 16 Adding alcohol random polyether intermediate and acid auxiliary agent phosphoric acid which accounts for 60ppm of the total mass of a target product in a kettle into a 2.5L polymerization reaction kettle, dehydrating for 1.5h under the conditions of 115-120 ℃ and-0.096 Mpa, then adding DMC which accounts for 40ppm of the total mass of the target product in the kettle (keeping the mass ratio of the auxiliary agent to the DMC to be 1.5) 18 -C 16 Alcohol random polyether finished product (design molecular weight 2200) with yield of 97.2%. Molecular weight distribution D =1.20 by GPC detection.
Example 2
Step 1, adding 2.07g of catalyst KOH and 350g of lauryl alcohol into a 2.5L polymerization reaction kettle, dehydrating for 1.5h under the conditions of 115-120 ℃ and-0.096 Mpa, then heating to 115 ℃ and continuously adding a uniform mixture of 137g of ethylene oxide and 549g of propylene oxide, keeping the reaction temperature at 115-120 ℃ in a reaction control stage, continuing to react after the mixture is added until the pressure drop is stable, finally cooling and degassing to 60 ℃, and filtering to obtain a lauryl alcohol random polyether intermediate (with the designed molecular weight of 550);
step 2, adding 500g of lauryl alcohol random polyether intermediate into a 1000mL four-neck glass flask, simultaneously adding 1.10g of acetic acid (98 wt%) and 20g of distilled water, heating and stirring at 60 ℃ for 30 minutes, then adding 1.2g of adsorbent of main body aluminum silicate/ligand calcium acetate, stirring and adsorbing at 70 ℃ for 60 minutes, gradually heating to 110 ℃, vacuumizing and dehydrating for 3 hours, filtering after the dehydration is finished and the water content is less than 0.04%, and obtaining the product with pH =7.02, K + 、Na + A post-treated lauryl alcohol random polyether intermediate with a content of 10ppm or less;
and 3, putting 150g of the post-treated lauryl alcohol intermediate and acid auxiliary agent sulfuric acid which accounts for 100ppm of the total mass of the target product in the kettle into a 2.5L polymerization reaction kettle, dehydrating for 1.5h under the conditions of 115-120 ℃ and-0.096 MPa, then adding DMC (the mass ratio of the auxiliary agent to the DMC is kept at 2.5. Molecular weight distribution D =1.23 by GPC detection.
Example 3
The amount of the acid additive in example 2 was changed to 120ppm of the acid additive based on the total mass of the target product, and the mass ratio of the additive to DMC was maintained at 3. Molecular weight distribution D =1.27 by GPC detection. The yield reaches 97.1 percent.
Example 4
The amount of the acid additive in example 2 was changed to 160ppm of the acid additive based on the total mass of the target product, and the mass ratio of the additive to DMC was maintained at 4. Molecular weight distribution D =1.32 by GPC detection. The yield reaches 97.0 percent.
Example 5
The amount of the acid additive in example 2 was changed to 400ppm of the acid additive based on the total mass of the target product, and the mass ratio of the additive to DMC was maintained at 10. Molecular weight distribution D =1.47 by GPC detection. The yield reaches 97.1 percent.
Comparative example 1
Adding 5.3g of catalyst KOH and 150g of lauryl alcohol into a 2.5L polymerization reaction kettle, heating and stirring, dehydrating for 1.5h under the conditions of 115-120 ℃ and-0.096 Mpa, then continuously adding a uniform mixture of 325g of ethylene oxide and 1299g of propylene oxide, keeping the reaction temperature at 115-120 ℃ in the reaction control stage, continuing to react until the pressure drop is stable after the mixture is added, finally cooling and degassing to 60 ℃, and filtering to obtain the lauryl alcohol random polyether (with the designed molecular weight of 2200) with the yield of 97.5%. . Molecular weight distribution D =1.13 by GPC detection.
Comparative example 2
Adding 150g of lauryl alcohol into a 2.5L polymerization reaction kettle, heating and stirring, dehydrating for 1.5h at 115-120 ℃ and under the condition of-0.096 Mpa, then adding DMC accounting for 40ppm of the total mass of a target product in the kettle, heating to 130 ℃, continuously adding a uniform mixture of 325g of ethylene oxide and 1299g of propylene oxide, keeping the reaction temperature at 130-135 ℃ in a reaction control stage, continuing to react until the pressure drop is stable after the mixture is added, finally cooling and degassing to 60 ℃, and filtering to obtain the lauryl alcohol random polyether (the designed molecular weight is 2200) with the yield of 97.7%. Molecular weight distribution D =1.04 by GPC detection.
Comparative example 3
The fatty alcohol of comparative example 1 was changed to C 12 -C 14 The alcohol, catalyst KOH was changed to 4.9g, alkylene oxide was changed to a homogeneous blend of 450g ethylene oxide and 1050g propylene oxide, and the other conditions were unchanged. Molecular weight distribution D =1.16 by GPC detection. The yield reaches 97.3 percent.
Comparative example 4
The fatty alcohol in comparative example 2 was C 12 -C 14 The alcohol and the olefin oxide were changed to a homogeneous mixture of 450g of ethylene oxide and 1050g of propylene oxide, and the other conditions were unchanged. Molecular weight distribution D =1.03 by GPC detection. The yield reaches 97.5 percent.
Comparative example 5
The fatty alcohol of comparative example 1 was changed to C 18 -C 16 Alcohol, catalyst KOHThe amount was changed to 3.7g, the alkylene oxide to a homogeneous blend of 238g of ethylene oxide and 843g of propylene oxide, and the other conditions were unchanged. Molecular weight distribution D =1.15 by GPC detection. The yield reaches 97.3 percent.
Comparative example 6
The fatty alcohol in comparative example 2 was changed to C 18 -C 16 The alcohol and alkylene oxide were changed to a homogeneous mixture of 238g of ethylene oxide and 843g of propylene oxide, the other conditions being unchanged. Molecular weight distribution D =1.05 by GPC detection. The yield reaches 97.4 percent.
Comparative example 7
150g of lauryl alcohol and acid auxiliary agent phosphoric acid which accounts for 60ppm of the total mass of the target product in the kettle are added into a 2.5L polymerization reaction kettle, and other conditions are not changed. Molecular weight distribution D =1.22 by GPC detection. The product has turbid appearance and white suspended substances, and the yield only reaches 95.3 percent.
From comparative examples 1, 3 and 5, the molecular weight distribution D of the random polyether of fatty alcohol prepared by using the strong base catalyst KOH is between 1.1 and 1.2; from comparative examples 2, 4 and 6, it can be seen that the molecular weight distribution D of the random polyether of fatty alcohol prepared with the catalyst DMC is stabilized within 1.1. The molecular weight distribution characteristics of the fatty alcohol random polyether synthesized by the two single catalysts are obvious, and the fatty alcohol random polyether is basically fixed in respective specific areas and is difficult to expand to a larger range; from comparative example 7, it can be seen that there is a significant by-product in the direct DMC-catalyzed synthesis of fatty alcohol random polyethers in the presence of acidic adjuvants. Through the preparation method introduced by the invention, the wide-distribution aliphatic alcohol random polyether with the molecular weight distribution D of 1.2 can be synthesized by constructing polyether intermediates and utilizing the limiting effect of an acidic auxiliary agent on DMC in examples 1, 2, 3 and 4, and no by-product is generated, which is difficult to achieve by the comparative example method. In addition, the method can also synthesize polyether with specific molecular weight distribution by adjusting the proportion of the auxiliary agent and the catalyst so as to meet diversified compatibility requirements.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of fatty alcohol random polyether with wide molecular weight distribution is characterized in that: the method comprises the following steps:
step 1, mixing strong base catalyst and fatty alcohol, introducing N 2 Dehydrating for 1-2 h at the temperature of 115-120 ℃ and the vacuum degree of ≧ 0.095MPa, adding olefin oxide to react at the temperature of 90-130 ℃, degassing and discharging to obtain a fatty alcohol random polyether intermediate;
step 2, adsorbing the fatty alcohol random polyether intermediate, and then filtering to remove impurity ions to obtain a fatty alcohol random polyether intermediate without impurity ions;
step 3, mixing the fatty alcohol random polyether intermediate with impurity ions removed and an acidic auxiliary agent, and introducing N 2 Dehydrating for 1-2 h under the conditions that the temperature is 115-120 ℃ and the vacuum degree is not less than-0.095 MPa, adding a double metal cyanide catalyst DMC, heating to 120-150 ℃, then adding alkylene oxide, degassing and discharging to obtain the fatty alcohol random polyether.
2. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 1, wherein: the fatty alcohol is at least one of straight chain or branched chain fatty alcohol with the carbon number of 10-18.
3. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 1, wherein: the strong base catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, metal potassium and metal sodium, and the dosage of the strong base catalyst is 1-5 per mill of the total weight of the fatty alcohol and the olefin oxide.
4. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 1, wherein: the molecular weight of the fatty alcohol random polyether intermediate is 20-30% of that of the finished fatty alcohol random polyether.
5. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 1, wherein: the adsorption process comprises the following steps: adding distilled water and acetic acid into the aliphatic alcohol random polyether intermediate in the step 1, mixing and stirring at 50-70 ℃ for 20-30 min, adding an adsorbent, and adsorbing and stirring at 70-80 ℃ for 30-60 min; dehydrating at 100-115 deg.c and vacuum degree not less than-0.095 MPa to water content less than 0.05%; the distilled water amount is 2-10% of the mass of the fatty alcohol random polyether intermediate.
6. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 5, wherein: the adsorbent consists of an adsorbent main body and a modified ligand, wherein the adsorbent main body is alpha-Al 2 O 3 At least one of amorphous silicon dioxide, magnesium silicate, aluminum silicate or magnesium aluminum silicate; the ligand is at least one of magnesium acetate, calcium chloride, copper chloride, potassium chloride, magnesium nitrate or aluminum nitrate; the addition amount of the adsorbent accounts for 0.1-1% of the mass of the fatty alcohol random polyether intermediate.
7. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 1, wherein: the dosage of DMC is 10-100 ppm of the total mass of the molecular weight of the finished product fatty alcohol random polyether; the mass ratio of the acidic auxiliary agent to the DMC is (1-10): 1.
8. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 7, wherein: the acidic auxiliary agent is at least one of phosphoric acid, sulfuric acid, acetic acid, citric acid, nitric acid, hydrochloric acid and formic acid.
9. The method for preparing a random polyether of fatty alcohol with broad molecular weight distribution as claimed in claim 1, wherein: the oxyalkylene is a mixture of ethylene oxide and propylene oxide, and the mass of the ethylene oxide accounts for 10-30% of the total mass of the oxyalkylene.
10. A broad molecular weight distribution fatty alcohol random polyether characterized by: the fatty alcohol random polyether has a molecular weight distribution coefficient of 1.2-1.5, and is obtained by the preparation method of any one of claims 1-9.
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| CN107200837A (en) * | 2016-03-18 | 2017-09-26 | 淮安巴德聚氨酯科技有限公司 | A kind of method that utilization dmc catalyst circulation prepares PPG |
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| CN114437335A (en) * | 2022-02-24 | 2022-05-06 | 浙江皇马科技股份有限公司 | Synthesis method of fatty alcohol polyether defoamer with wide molecular weight distribution |
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| CN107200837A (en) * | 2016-03-18 | 2017-09-26 | 淮安巴德聚氨酯科技有限公司 | A kind of method that utilization dmc catalyst circulation prepares PPG |
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| CN113831525A (en) * | 2021-10-18 | 2021-12-24 | 浙江皇马科技股份有限公司 | Preparation method of nonionic fatty alcohol polyether for defoaming agent |
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