CN111875475B - High-carbon heterogeneous fatty alcohol and preparation method and application thereof - Google Patents
High-carbon heterogeneous fatty alcohol and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-carbon heterogeneous fatty alcohol and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Preparing high-carbon isomerism olefin chloride by reacting high-carbon isomerism olefin with sulfonyl chloride; (2) Mixing and reacting the high-carbon isomeric olefine chloride prepared in the step (1) with a strong alkaline catalyst and dibutyl sodium naphthalene sulfonate to prepare high-carbon isomeric enol; (3) And (3) carrying out hydrogenation reaction on the high-carbon isomeric enol prepared in the step (2) to prepare the high-carbon isomeric fatty alcohol. The structure is that
Wherein R is 1 And R is 2 Selected from branched saturated alkyl groups of 1 to 8 carbon atoms, R 1 And R is 2 The structures may be the same or different; preferably, said R 1 And R is 2 The total number of carbon atoms is 8 to 16. The invention has simple synthesis process, easily obtained raw materials, less side reaction and definite product structure, is especially suitable for preparing the narrow molecular weight distribution primary alcohol polyoxyethylene ether and the derivatives thereof, and has good emulsifying, wetting and low-temperature performances.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a preparation method and application of high-carbon isomeric fatty alcohol.
Background
Fatty alcohol is a basic raw material of the surfactant, and can enable the surfactant to have the functional characteristics of better washing, wetting, rust prevention, permeation, dispersion, emulsification, softness, static resistance and the like. In the prior art, fatty alcohol used for preparing fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether sulfate and ester lubricating oil/plasticizer is generally fatty alcohol with carbon number more than or equal to 8, and is mainly divided into the following steps: 1) Natural fatty alcohol is full linear chain even carbon primary alcohol; 2) Ethylene oligomerization-oxidation-hydrolysis alcohols, more than 95% of which are linear even primary alcohols; 3) Alcohols from the hydroformylation of linear alpha olefins, more than 75% of which are linear primary alcohols; 4) Alcohols from propylene/butene oligomer-hydroformylation-hydrogenation, 100% branched primary alcohols, are mixtures of various degrees of branching and carbon chain structures; 5) Alcohols prepared by oxidation of alpha-olefins or paraffins/linear alkanes, the vast majority of carbon chain structures being linear secondary alcohols; 6) The structure of the Guerbet alcohol is primary alcohol with a linear alkyl branched chain, wherein the Guerbet alcohol is prepared by aldol condensation-hydrogenation of aldehyde obtained by hydroformylation of propylene or butylene or by Guerbet reaction of low-carbon linear alcohol.
The high carbon isomeric fatty alcohol is a primary alcohol with a long branched chain structure at the beta position. Compared with straight-chain fatty alcohol, the high-carbon heterogeneous fatty alcohol has the following characteristics: 1) Has high molecular weight and low irritation; 2) A branched structure with a high degree of branching, which remains in a liquid state at extremely low temperatures; 3) The volatility is small; 4) Belongs to primary alcohol, has active property and can prepare various derivatives; 5) Saturated alcohol, has higher stability than other unsaturated products, and has good oxidation stability, hydrolysis resistance and good color at high temperature. Based on the characteristics, the high-carbon heterogeneous fatty alcohol is widely applied to the fields of cosmetics, textile printing and dyeing auxiliary agents, fiber oil agents, printing ink auxiliary agents, high-grade lubricating oil additives and the like.
The prior high-carbon isomerism fatty alcohol preparation mainly adopts isomerism olefin as a raw material and synthesizes corresponding fatty alcohol through carbonylation reaction, but the reaction is carried out under the condition of high temperature and high pressure (more than 20 MPa), and the used catalyst is noble metal cobalt, ruthenium and the like, so that the problems of high fixed investment, difficult separation of impurities and low product yield exist. In addition, the preparation methods of the isomerised fatty alcohols reported in the literature are as follows: the method comprises the steps of synthesizing by an n-alcohol isomerization method, an isomeric fatty acid hydrogenation method, an isomeric fatty acid methyl ester hydrogenation method and the like. However, these methods have the disadvantages of large difference in structure of raw materials, low yield of product alcohol and high hydrocarbon content. For example, patent CN1587244a uses mixed octenes as raw materials to prepare isononaldehyde through carbonylation reaction, and corresponding isononanol can be obtained through hydrogenation, and the disadvantages of high reaction temperature, high pressure, high catalyst price and the like exist; patent CN105646149A takes normal alcohol as a raw material to prepare isomeric alcohol through isomerization, and has the defects of complex process, multiple three wastes and the like. The product prepared by the method has the problem of low purity, can not meet the requirements of some high-grade cosmetics on raw materials, and prevents further application of high-carbon heterogeneous fatty alcohol.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of high-carbon isomerism fatty alcohol with a novel structure, which has the advantages of simple process, high product yield and high purity, in particular to the olefin chlorination process in the method, which can react with high conversion rate at normal temperature and normal pressure without a catalyst.
The invention also aims to provide the application of the compound serving as a surfactant in daily chemicals, pesticides and paint industries and the application of the compound in preparing the primary alcohol polyoxyethylene ether with narrow molecular weight distribution and the derivatives thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
a preparation method of high-carbon heterogeneous fatty alcohol comprises the following steps:
(1) Preparing high-carbon isomerism olefin chloride by reacting high-carbon isomerism olefin with sulfonyl chloride;
(2) Mixing and reacting the high-carbon isomeric olefine chloride prepared in the step (1) with a strong alkaline catalyst and dibutyl sodium naphthalene sulfonate to prepare high-carbon isomeric enol;
(3) And (3) preparing the high-carbon isomeric fatty alcohol by hydrogenation reaction of the high-carbon isomeric enol prepared in the step (2).
In the preparation method, in the step (1), the carbon number of the high-carbon isoolefin is 8-16; the high-carbon isoolefin can be prepared from propylene, n-isobutene, n-isopentene, n-isohexene, n-isoheptene, n-isooctene and the like through oligomerization, for example, C8 olefin and C12 olefin can be obtained by dimerization and trimerization of isobutene under an acidic catalyst, the method for preparing the high-carbon isoolefin through oligomerization is the prior art, and specific conditions for preparing the high-carbon isoolefin through oligomerization are not particularly required.
In some examples, the higher isoolefin is triisobutene and/or tetraisobutene.
In the preparation method, in the step (1), the molar ratio of the high-carbon isoolefin to the sulfonyl chloride is 0.5-1.5: 1, preferably 0.8 to 1.2:1.
in the preparation method, in the step (1), the reaction conditions are as follows: the reaction temperature is 20-80 ℃, preferably 30-60 ℃; the reaction time is 2 to 6 hours, preferably 3 to 5 hours.
In some examples, step (1) of the present invention is carried out by stirring the higher isoolefin to a reaction temperature, and then slowly adding (preferably dropwise adding) the sulfonyl chloride for a period of from 0.5 to 2 hours, preferably from 0.5 to 1 hour, the period of time for which the sulfonyl chloride is added being within the reaction time.
In order to facilitate the reaction, the reaction process of step (1) of the present invention preferably further comprises a gas separation operation, for example in some examples the treatment may be carried out by pumping the gas into aqueous alkali, which may be NaOH or NaHCO, using a vacuum pump 3 The concentration of the aqueous solution is preferably 20 to 30% by weight.
In some examples, after the reaction in step (1) of the present invention is completed, the reaction solution further includes a washing treatment, and the specific method is as follows: after the reaction solution was cooled, it was washed with saturated aqueous NaCl solution, aqueous NaOH solution (20 wt%) and saturated aqueous NaCl solution in this order until it became neutral.
In the preparation method, in the step (2), the strong alkaline catalyst is a guanidine compound, preferably a guanidine compound with an alkyl chain having 1-2 carbon atoms; in some examples, the guanidine compound is more preferably tetramethylguanidine and/or tetraethylguanidine; the addition amount of the strong alkaline catalyst is 0.5-1.0 wt%, preferably 0.6-0.8 wt% of high carbon isomeric olefine chloride.
In the preparation method, in the step (2), the addition amount of the dibutyl sodium naphthalene sulfonate is 0.1 to 0.6 weight percent, preferably 0.2 to 0.5 weight percent, of high carbon isomeric alkene chloride. The dibutyl sodium naphthalene sulfonate can further increase the compatibility of the basic catalyst and high-carbon isomeric olefine chloride, and improve the catalytic activity.
In the preparation method, in the step (2), the reaction conditions are as follows: the reaction pressure is 2-10 MPaG, preferably 4-6 MPaG, the reaction temperature is 50-150 ℃, preferably 80-120 ℃, and the reaction time is 1-5 h, preferably 2-4 h.
In some examples, after the reaction in the step (2) is completed, the method further comprises the steps of adding water into the reaction solution for washing, standing and layering, removing the sodium dibutylnapthyl sulfonate, and collecting an organic phase to obtain the target product high-carbon isomeric enol.
In the preparation method, in the step (3), the hydrogenation reaction conditions are as follows: the reaction pressure is 2-10 MPaG, preferably 4-6 MPaG, the reaction temperature is 50-150 ℃, preferably 80-120 ℃, and the reaction time is 1-5 h, preferably 2-4 h.
In the preparation method of the present invention, in the step (3), the hydrogenation reaction is performed under the action of a catalyst, and the catalyst is a hydrogenation catalyst, and in some examples, a hydrogenation catalyst such as raney nickel, supported nickel and the like, preferably raney nickel, may be used. The catalyst is used in an amount of 1 to 5wt%, preferably 1 to 3wt%, of the high carbon isomeric enol.
In some examples, after the reaction of step (3) of the present invention is completed, the method further comprises filtering and separating the catalyst, and then obtaining the corresponding high-carbon isomeric fatty alcohol product through rectification and separation. Preferably, in the embodiments of the present invention, specific rectification separation conditions employed for isomerising dodecanol are: the theoretical plate number of the rectifying tower is 28, the reflux ratio is 2, the operation is carried out under reduced pressure of 2KPa, and the fraction of the part with the temperature of 115-118 ℃ at the top of the tower is collected; the specific rectification separation conditions adopted by the isohexadecanol are as follows: the theoretical plate number of the rectifying tower is 28, the reflux ratio is 2, the operation is carried out under 500Pa, and the fraction with the temperature of 141-148 ℃ at the top of the tower is collected.
In the present invention, the high-carbon isomeric fatty alcohol obtained by the above-mentioned preparation method can be represented by the structure
Wherein R is 1 And R is 2 Selected from branched saturated alkyl groups of 1 to 8 carbon atoms, R 1 And R is 2 The structures may be the same or different; preferably, said R 1 And R is 2 The total number of carbon atoms is 8-16; more preferably, the R 1 And R is R 2 Is any one of the following combinations: r is R 1 is-CH 3 And R is 2 is-CH 2 CH(CH 3 ) 2 or-CH 2 C(CH 3 ) 3 ；R 1 And R is R 2 Identical, all are-CH 2 CH(CH 3 ) 2 or-CH 2 C(CH 3 ) 3 ；R 1 is-CH 2 C(CH 3 ) 3 And R is 2 is-CH 2 C(CH 3 ) 2 CH 2 CH(CH 3 ) 2 。
In the embodiment of the invention, the high-carbon isomerised fatty alcohol prepared by the method is isomerised dodecanol or isomerised hexadecanol.
For example, the substituent R in the structural formula of the high-carbon isomerised fatty alcohol 1 And R is R 2 Are all-CH 2 C(CH 3 ) 3 For example, the reaction mechanism for preparing the isomerised dodecanol from the raw material triisobutene is as follows:
steps (1) and (2)
Step (3)
Similarly, when the higher isomeric fatty alcohols are of the formula R 1 is-CH 2 C(CH 3 ) 3 ，R 2 is-CH 2 C(CH 3 ) 2 CH 2 C(CH 3 ) 3 Namely, when the raw material is tetraisobutene, the isohexadecanol can be prepared and has the structure of
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In another aspect, the invention provides the application of the high-carbon heterogeneous fatty alcohol prepared by the method in the field of surfactant preparation.
The high-carbon heterogeneous fatty alcohol disclosed by the invention is suitable for preparing primary alcohol polyoxyethylene ether and derivatives thereof, has narrow molecular weight distribution, and has good emulsifying, wetting and low-temperature performances as a surfactant.
A primary alcohol polyoxyethylene ether has the following structure:
wherein n has a value of 3 to 30, preferably 3 to 10;
R 1 and R is 2 Introduced from the above-mentioned higher isomeric fatty alcohols, which are defined as the same as those in the above-mentioned higher isomeric fatty alcohols of the present invention, namely: r is R 1 And R is 2 Selected from branched saturated alkyl groups of 1 to 8 carbon atoms, R 1 And R is 2 The structures may be the same or different; preferably, said R 1 And R is 2 The total number of carbon atoms is 8-16; more preferably, the R 1 And R is R 2 Is any one of the following combinations: r is R 1 is-CH 3 And R is 2 is-CH 2 CH(CH 3 ) 2 or-CH 2 C(CH 3 ) 3 ；R 1 And R is R 2 Identical, all are-CH 2 CH(CH 3 ) 2 or-CH 2 C(CH 3 ) 3 ；R 1 is-CH 2 C(CH 3 ) 3 And R is 2 is-CH 2 C(CH 3 ) 2 CH 2 CH(CH 3 ) 2 。
The primary alcohol polyoxyethylene ether of the invention has the following preferable structure:
the preparation method of the primary alcohol polyoxyethylene ether comprises the following steps: the high-carbon isomeric fatty alcohol reacts with ethylene oxide and/or propylene oxide to obtain the primary alcohol polyoxyethylene ether, wherein the addition number of the primary alcohol polyoxyethylene ether is 3-10, and the addition number refers to the number of EO and/or PO structures connected to the high-carbon isomeric fatty alcohol.
In the preparation method of the primary alcohol polyoxyethylene ether, the molar ratio of the high-carbon isomeric fatty alcohol to the ethylene oxide and/or the propylene oxide is 1:3 to 10;
in the preparation method of the primary alcohol polyoxyethylene ether, the reaction is carried out under the action of a catalyst, and the catalyst is selected from an acidic catalyst BF 3 Isopropyl alcohol complex catalyst, BF 3 Methanol Complex catalyst, BF 3 One or more of diethyl ether complex catalyst and the like, preferably BF 3 Isopropanol complex catalyst. Preferably, the catalyst is used in an amount of 0.05 to 0.5% of the molar amount of the high carbon isomeric fatty alcohol.
In the preparation method of the primary alcohol polyoxyethylene ether, the reaction conditions are as follows: the reaction temperature is 50-80 ℃ and the reaction time is 1-4 h.
In some examples, the high-carbon isomerised fatty alcohol adopted by the invention is isomerised dodecanol or isomerised hexadecanol, and the primary alcohol polyoxyethylene ether is prepared by using the isomerised dodecanol or isomerised hexadecanol as a raw material, and the specific steps are as follows: heating the isomerism dodeca/hexadecanol to 100-110 ℃ for dehydration for 0.2-1 h (such as 0.5 h), cooling to below 50 ℃, adding an acidic catalyst BF 3 The isopropanol complex catalyst is stirred for 5-30 min (e.g. 10 min) and the nitrogen is rapidly displaced twice. Heating to 50-80 deg.c (e.g. 70 deg.c), adding 3-6 times (e.g. 3 times) of ethylene oxide and/or propylene oxide to the molar amount of fatty alcohol, wherein the catalyst amount is 0.05-0.5% of the molar amount of isomeric fatty alcohol, reacting to unchanged pressure, separating the catalyst from the reaction product through standing and layering, neutralizing with alkali solution, washing with water, and filtering to obtain the target product.
In the existing high-carbon isomerism fatty alcohol preparation process, olefin is subjected to hydroformylation and hydrogenation to prepare isomerism alcohol, in the high-temperature high-pressure hydroformylation reaction process, relatively wide molecular weight distribution occurs due to the reasons of olefin isomerism and the like, and the olefin chlorination reaction only generates corresponding allyl chloride, so that the structure is unique. Therefore, the primary alcohol polyoxyethylene ether prepared by the invention has the advantage of narrow molecular weight distribution, and has better emulsifying, wetting and low-temperature performances compared with the linear alcohol because of a large number of branched chain structures in the raw material isomeric fatty alcohol. Can be used as a surfactant in daily chemicals, pesticides and paint industries or used as a lubricant or plasticizer in daily chemicals, lubricating oil and high molecular polymer production and processing industries.
The technical scheme of the invention has the beneficial effects that:
the synthesis process is simple, the sources of the raw material high-carbon isomerism olefin are rich and easy to obtain, the side reaction is less, the purity of the prepared high-carbon isomerism fatty alcohol is more than 99%, and the yield is more than 90%; the product has definite structure, is especially suitable for preparing the narrow molecular weight distribution primary alcohol polyoxyethylene ether and the derivatives thereof, and has good emulsifying, wetting and low temperature performances.
Detailed Description
The method of the present invention is described in detail below with reference to examples, but it should be understood that the scope of the present invention includes, but is not limited to, such examples.
Sources of reagents in examples and comparative examples:
triisobutene, tetraisobutene: wanhua chemistry;
sodium hydroxide: technical grade, aladine;
sulfonyl chloride (SO) 2 Cl 2 ): allatin;
tetramethyl guanidine, tetraethyl guanidine: allatin;
sodium dibutylnaphthalene sulfonate: allatin;
hydrogenation catalyst (Raney 3110): grace company;
BF 3 isopropanol complex catalyst: allatin;
unless otherwise indicated, all other starting materials were common commercial products and all reagents were analytically pure.
The analytical instruments and methods employed for the examples and comparative products were as follows:
nuclear magnetism: varian-NMR 300, chemical shifts are indicated in ppm;
gas chromatograph: agilent-7820:
gas chromatographic column: DB-5 capillary column with the thickness of 0.25mm multiplied by 30m, detector FID, vaporizing chamber temperature of 280 ℃, column box temperature of 280 ℃, FID detector temperature of 300 ℃, argon current-carrying capacity of 2.1mL/min, hydrogen flow of 30mL/min, air flow of 400mL/min and sample injection amount of 1.0 mu L. The conversion of olefins and the selectivity of the products were calculated using an area normalization method. Heating program: preheating to 40 deg.C, maintaining for 5min, and heating from 40 deg.C to 280 deg.C at 15 deg.C/min for 2min.
Surfactant performance test method: emulsification time: GB/T6369-2008); wetting time: GB/T11983-2008); degradability for 7 days: GB/T15818-2018.
Example 1:
the preparation method of the isomerism dodecanol comprises the following steps:
100g of triisobutene was charged into a 500mL three-necked flask, the temperature was raised to 30℃under mechanical stirring, 67g of sulfonyl chloride (molar ratio of triisobutene to sulfonyl chloride 1.2:1) was slowly added dropwise, and the resulting exhaust SO was obtained 2 HCl was pumped into 25wt% sodium bicarbonate in water for 2h, after which the sulfonyl chloride was added dropwise and the reaction was continued at 30℃for 4h. After cooling, transferring the reaction solution into a separating funnel, and washing the reaction solution to be neutral by adopting a saturated NaCl aqueous solution, a 20wt% NaOH aqueous solution and a saturated NaCl aqueous solution in sequence to obtain 117.3g of isomeric dodecene chloride;
mixing the isomerism dodecene chloride, 0.7g of tetramethyl guanidine and 0.23g of dibutyl sodium naphthalene sulfonate, adding the mixture into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 5MPaG and 100 ℃, cooling the reaction liquid to room temperature, adding deionized water for washing twice, standing and layering to obtain an organic layer and a water layer, wherein the organic layer is 101.8g of the isomerism dodecenol of the target product;
adding the isomerism dodecanol into a hydrogenation reaction kettle, adding 3.05g of Raney3110 catalyst, reacting for 2 hours at the temperature of 3MPaG and 80 ℃, filtering the catalyst after the reaction is finished, and carrying out reduced pressure distillation to obtain 100.7g of colorless transparent liquid, namely isomerism dodecanol (theoretical plate number of a rectifying tower is 28, reflux ratio is 2, reduced pressure 2KPaG operation is carried out, fraction of the temperature of the top of the tower is collected at 115-118 ℃), and the total yield is 91%.
The number average molecular weight of the prepared isomerism dodecanol is 186g/mol measured by a WATER gel permeation chromatograph;
nuclear magnetic analysis: 1 H NMR(300MHz，CDCL3)：δ＝0.94(s,CH 3 ,18H)，1.17(d,CH 2 ,4H)，1.56(m,1H)，3.49(d,CH 2 ,2H)，3.65(brs,OH,1H)， 13 C-NMR(300MHz,CDCl3)：δ＝66.8，45.7，31.5，30.1；
elemental analysis (%): c,77.35; h,14.06; o,8.59;
the test hydroxyl value is 301mgKOH/g, namely monohydric alcohol;
the purity of the gas chromatography analysis was 99.1%.
The structure of the obtained isomerised dodecanol is as follows:
example 2:
the preparation method of the isomerism dodecanol comprises the following steps:
100g of triisobutene was added to a 500mL three-necked flask, the temperature was raised to 40℃with mechanical stirring, 80g of sulfonyl chloride (molar ratio of triisobutene to sulfonyl chloride 1:1) was slowly added dropwise, and the resulting exhaust SO was obtained 2 HCl was pumped into 25wt% sodium bicarbonate in water for 1h, after which the sulfonyl chloride was added dropwise and the reaction was continued at 40℃for 3h. After cooling, transferring the reaction solution to a separating funnel, and washing the reaction solution to be neutral by adopting a saturated NaCl aqueous solution, a 20wt% NaOH aqueous solution and a saturated NaCl aqueous solution in sequence to obtain 118.1g of isomerism dodecene chloride;
mixing the isomerism dodecene chloride, 0.8g of tetramethyl guanidine and 0.35g of dibutyl sodium naphthalene sulfonate, adding into a high-pressure reaction kettle, reacting for 4 hours at the temperature of 4MPaG and 80 ℃, cooling the reaction liquid after the reaction, adding deionized water for washing twice, standing and layering to obtain an organic layer and a water layer, wherein the organic layer is 102.3g of target product isomerism dodecenol;
adding the isomerism dodecanol into a hydrogenation reaction kettle, adding 2.1g Raney3110 catalyst, reacting for 3 hours at the temperature of 4MPaG and 100 ℃, filtering the catalyst after the reaction is finished, and distilling under reduced pressure to obtain 101.4g colorless transparent liquid, namely isomerism dodecanol, wherein the total yield is 92%.
The prepared isomeric dodecanol has a test hydroxyl value of 300mgKOH/g, namely monohydric alcohol;
the purity of the gas chromatography analysis was 99.2%.
Example 3:
the preparation method of the isomerism dodecanol comprises the following steps:
100g of triisobutene was charged into a 500mL three-necked flask, the temperature was raised to 50℃under mechanical stirring, 100g of sulfonyl chloride (molar ratio of triisobutene to sulfonyl chloride: 0.8:1) was slowly added dropwise, and the resulting exhaust SO was obtained 2 HCl was pumped into 25wt% sodium bicarbonate in water with a vacuum pump, and after 0.5h the sulfonyl chloride was added dropwise, and the reaction was continued at 50℃for 1.5h. After cooling, transferring the reaction solution into a separating funnel, and washing the reaction solution to be neutral by adopting a saturated NaCl aqueous solution, a 20wt% NaOH aqueous solution and a saturated NaCl aqueous solution in sequence to obtain 119.7g of isomerism dodecene chloride;
mixing the isomerism dodecene chloride, 1.0g of tetramethyl guanidine and 0.5g of dibutyl sodium naphthalene sulfonate, adding into a high-pressure reaction kettle, reacting for 5 hours at the temperature of 3MPaG and 60 ℃, cooling the reaction liquid after the reaction, adding deionized water for washing twice, standing and layering to obtain an organic layer and a water layer, wherein the organic layer is 103.1g of target product isomerism dodecenol;
adding the isomerism dodecanol into a hydrogenation reaction kettle, adding 1g of Raney3110 catalyst, reacting for 4 hours at the temperature of 5MPaG and 120 ℃, filtering the catalyst after the reaction is finished, and distilling under reduced pressure to obtain 102.1g of colorless transparent liquid, namely isomerism dodecanol, wherein the total yield is 92%.
The prepared isomeric dodecanol has a test hydroxyl value of 300mgKOH/g, namely monohydric alcohol;
the purity of the gas chromatography analysis was 99.1%.
Example 4:
the preparation method of the isomeric hexadecanol comprises the following steps:
100g of tetraisobutylene was charged into a 500mL three-necked flask, the temperature was raised to 60℃under mechanical stirring, 101g of sulfonyl chloride (molar ratio of tetraisobutylene to sulfonyl chloride 0.6:1) was slowly added dropwise, and the resulting exhaust SO was obtained 2 HCl was pumped into 25wt% sodium bicarbonate in water with a vacuum pump, and after 1.5h the sulfonyl chloride was added dropwise, and the reaction was continued at 60℃for 1.5h. Cooling and then cooling the reaction solutionTransferring to a separating funnel, and washing sequentially with saturated NaCl aqueous solution, 20wt% NaOH aqueous solution and saturated NaCl aqueous solution until the mixture is neutral to obtain 111.5g of isomeric hexadecene chloride;
mixing the isomeric hexadecene chloride, 1.0g of tetramethyl guanidine and 0.56g of dibutyl sodium naphthalene sulfonate, adding into a high-pressure reaction kettle, reacting for 5 hours at the temperature of 6MPaG and 120 ℃, cooling the reaction liquid after the reaction, adding deionized water for washing twice, standing and layering to obtain an organic layer and a water layer, wherein the organic layer is 99.8g of target product isomeric hexadecene alcohol;
adding the isomeric hexadecanol into a hydrogenation reaction kettle, adding 3g of Raney3110 catalyst, reacting for 3 hours at the temperature of 8MPaG and 140 ℃, filtering the catalyst after the reaction is finished, and carrying out reduced pressure distillation to obtain 98.3g of colorless transparent liquid, namely the isomeric hexadecanol (the theoretical plate number of a rectifying tower is 28, the reflux ratio is 2, the operation is carried out under reduced pressure of 500 and PaG, and the fraction of 141-148 ℃ on the top of the tower is collected), wherein the total yield is 92%.
The number average molecular weight of the prepared isohexadecanol is 242g/mol measured by a WATER gel permeation chromatograph;
nuclear magnetic analysis: 1 H NMR(300MHz，CDCL3)：δ＝0.94(s,CH 3 ,24H)，1.17(d,CH 2 ,6H)，1.56(m,1H)，3.62(d,CH 2 ,2H)，3.65(brs,OH,1H)， 13 C-NMR(300MHz,CDCl3)：δ＝66.8，45.7，32.6，31.5，30.4；
elemental analysis (%): c,79.27; h,14.14; o,6.60;
the test hydroxyl value is 233mgKOH/g, namely monohydric alcohol;
the purity of the gas chromatography analysis was 99.4%.
The structure of the obtained isomeric hexadecanol is as follows:
example 5:
the preparation method of the isomeric hexadecanol comprises the following steps:
100g of tetraisobutylene was added to a 500mL three-necked flask, the temperature was raised to 70℃under mechanical stirring, and 60g of tetraisobutylene was slowly added dropwiseSulfonyl chloride (molar ratio of tetraisobutylene to sulfonyl chloride 1:1), the resulting off-gas SO 2 HCl was pumped into 25wt% sodium bicarbonate in water with a vacuum pump, and after 1.5h the sulfonyl chloride was added dropwise, and the reaction was continued at 70℃for 0.5h. After cooling, transferring the reaction solution into a separating funnel, and washing the reaction solution to be neutral by adopting a saturated NaCl aqueous solution, a 20wt% NaOH aqueous solution and a saturated NaCl aqueous solution in sequence to obtain 100.5g of isomerism dodecene chloride;
mixing the above-mentioned isomerism hexadecene chloride, 1.1g tetraethylguanidine and 0.67g dibutyl sodium naphthalene sulfonate, adding into a high-pressure reaction kettle, reacting for 2 hours at 10MPaG and 150 ℃, cooling the reaction liquid after the reaction, adding deionized water to wash twice, standing and layering to obtain an organic layer and a water layer, wherein the organic layer is 97.8g of target product isomerism hexadecene alcohol;
adding the isomeric hexadecanol into a hydrogenation reaction kettle, adding 1.5g of Raney3110 catalyst, reacting for 2 hours at the temperature of 6MPaG and 150 ℃, filtering the catalyst after the reaction is finished, and distilling under reduced pressure to obtain 95.4g of colorless transparent liquid, namely the isomeric hexadecanol, wherein the total yield is 90%.
The test hydroxyl value of the prepared isohexadecanol is 233mgKOH/g, namely monohydric alcohol;
the purity of the gas chromatography analysis was 99.1%.
Comparative example 1:
based on the embodiment 1 of the invention, the preparation method of the isomerised dodecanol comprises the steps of 2) hydrolysis reaction, namely replacing a tetramethylguanidine catalyst with sodium hydroxide, and 2) specifically comprises the following steps:
117.3g of the isomeric dodecene chloride prepared in the step 1) of the example 1 and 1.4g of 50wt% sodium hydroxide aqueous solution are mixed and then added into a high-pressure reaction kettle to react for 3 hours at the temperature of 5MPaG and 100 ℃, the reaction liquid is cooled, washed twice by adding deionized water, then is left standing and layered, an organic layer and a water layer are obtained, the organic layer is the target product isomeric dodecene alcohol and unreacted alkene chloride, and the alkene chloride conversion rate is only 40% through gas phase analysis.
Example 6:
a preparation method of a surfactant comprises the following steps:
adding the isomerism dodecanol prepared in the embodiment 1 into a reaction kettle, heating to 100-110 ℃ for dehydration for 0.5h, cooling to below 50 ℃, and adding an acidic catalyst BF 3 The isopropanol complex catalyst was stirred for 10min and purged twice with nitrogen. Heating to 70 ℃, adding ethylene oxide with 3 times of the mole amount of fatty alcohol, wherein the catalyst is 0.1% of the mole amount of the isomeric dodecanol, reacting for 2 hours until the system pressure is unchanged, separating the catalyst from a reaction product through standing layering, neutralizing with alkali liquor, washing with water, and filtering to obtain a target product
The addition number is 3.
Elemental analysis (%): c,67.88; h,12.03; o,20.09;
nuclear magnetic analysis: 1 H NMR(300MHz，CDCL3)：δ＝0.94(s,CH 3 ,18H)，1.17(d,CH 2 ,4H)，1.80(m,1H)，3.33-3.56(d,CH 2 ,14H)，3.65(brs,OH,1H)， 13 C-NMR(300MHz,CDCl3)：δ＝79.7，70.4，46.0，31.5，30.1，27.9。
the heterogeneous fatty alcohol-polyoxyethylene ether prepared in this example was tested as a surfactant in terms of emulsifying property, wetting property, dissolution property and degradability as shown in table 1 below.
Example 7:
a preparation method of a surfactant, which is different from example 6 only in that the raw material of isomerised dodecanol is replaced by isomerised hexadecanol prepared in example 4 to obtain a target product
The addition number is 3.
Elemental analysis (%): c,70.54; h,12.38; o,17.08;
nuclear magnetic analysis: 1 H NMR(300MHz，CDCL3)：δ＝0.94(s,CH 3 ,24H)，1.17(d,CH 2 ,6H)，1.80(m,1H)，3.56(d,CH 2 ,14H)，3.65(brs,OH,1H)， 13 C-NMR(300MHz,CDCl3)：δ＝79.7，70.4，61.3，46.0，32.6，31.5，30.1，28.2。
the heterogeneous fatty alcohol-polyoxyethylene ether prepared in this example was tested as a surfactant in terms of emulsifying property, wetting property, dissolution property and degradability as shown in table 1 below.
Comparative examples 2 to 3:
comparative examples 2 and 3 the starting materials in examples 6 and 7 were respectively replaced with straight-chain dodecanol (1-dodecanol, exxon Mobil Co., USA) and straight-chain hexadecanol (1-hexadecanol) under the same conditions to give the desired product C 12 H 25 -O(CH 2 CH 2 O) 3 H C 16 H 33 -O(CH 2 CH 2 O) 3 H. Its performance as a surfactant was then tested for emulsifying, wetting, dissolving and degrading properties, and the results are given in table 1 below.
Comparative example 4:
a surfactant is prepared by the following method:
adding the isohexadecanol prepared in the patent CN201610098967 into a reaction kettle, heating to 100-110 ℃ for dehydration for 0.5h, cooling to below 50 ℃, and adding an acidic catalyst BF 3 The isopropanol complex catalyst was stirred for 10min and purged twice with nitrogen. Heating to 70 ℃, adding ethylene oxide with 3 times of the mole amount of fatty alcohol, wherein the catalyst dosage is 0.1% of the mole amount of the isomeric fatty alcohol, reacting until the system pressure is unchanged, separating the catalyst from a reaction product through standing delamination, neutralizing with alkali liquor, washing with water, and filtering to obtain a target product
The emulsion, wetting, dissolution and degradation properties were then tested and the results are given in table 1 below.
TABLE 1
From the data in table 1, it can be seen that: the product obtained by the invention is used as a surfactant, the emulsification time is longer than that of a comparative example, the wetting time is shorter than that of the comparative example, the concentration of gel in water at 0 ℃ is higher, and the product obtained by the invention has better emulsification performance and wetting performance, and has better low-temperature performance and is not easy to gel in cold water.
Claims (19)
1. The preparation method of the high-carbon heterogeneous fatty alcohol is characterized by comprising the following steps:
(1) Preparing high-carbon isomerism olefin chloride by reacting high-carbon isomerism olefin with sulfonyl chloride;
(2) Mixing and reacting the high-carbon isomeric olefine chloride prepared in the step (1) with a strong alkaline catalyst and dibutyl sodium naphthalene sulfonate to prepare high-carbon isomeric enol, wherein the strong alkaline catalyst is a guanidine compound;
(3) And (3) preparing the high-carbon isomeric fatty alcohol by hydrogenation reaction of the high-carbon isomeric enol prepared in the step (2).
2. The process according to claim 1, wherein in the step (1), the higher isoolefin has 8 to 16 carbon atoms;
the mol ratio of the high-carbon isoolefin to the sulfonyl chloride is 0.5-1.5: 1, a step of;
the reaction conditions are as follows: the reaction temperature is 20-80 ℃ and the reaction time is 2-6 hours;
the reaction process also comprises a gas separation operation, wherein the gas separation operation adopts a vacuum pump to pump gas into alkali liquor.
3. The process according to claim 2, wherein the higher isoolefin is triisobutene and/or tetraisobutene.
4. The process according to claim 2, wherein the molar ratio of higher isoolefin to sulfonyl chloride is from 0.8 to 1.2:1.
5. the preparation method according to claim 2, wherein the reaction temperature is 30 to 60 ℃; the reaction time is 3-5 h.
6. The process of claim 1, wherein in step (1), the sulfonyl chloride is added for a period of time ranging from 0.5 to 2 hours.
7. The method according to claim 6, wherein the sulfonyl chloride is added for 0.5 to 1 hour.
8. The method according to claim 1, wherein in the step (2), the strong basic catalyst is a guanidine compound having 1 to 2 carbon atoms in the alkyl chain;
the reaction conditions are as follows: the reaction pressure is 2-10 MPaG, the reaction temperature is 50-150 ℃ and the reaction time is 1-5 h.
9. The method according to claim 8, wherein the guanidine compound is tetramethylguanidine and/or tetraethylguanidine.
10. The preparation method according to claim 8, wherein the reaction pressure is 4-6 MPaG, the reaction temperature is 80-120 ℃, and the reaction time is 2-4 hours.
11. The method according to claim 1, wherein in the step (2), the addition amount of the strong basic catalyst is 0.5 to 1.0wt% of the high carbon isomeric olefine chloride;
the addition amount of the dibutyl sodium naphthalene sulfonate is 0.1-0.6wt% of high-carbon isomeric alkene chloride.
12. The method according to claim 11, wherein in the step (2), the addition amount of the strong basic catalyst is 0.6 to 0.8wt% of the high carbon isomeric olefine chloride;
the addition amount of the dibutyl sodium naphthalene sulfonate is 0.2-0.5 wt% of high-carbon isomeric olefine chloride.
13. The process of claim 1, wherein in step (3), the hydrogenation reaction conditions are: the reaction pressure is 2-10 MPaG, the reaction temperature is 50-150 ℃ and the reaction time is 1-5 h;
the hydrogenation reaction is carried out under the action of a catalyst, wherein the catalyst is a hydrogenation catalyst; the dosage of the catalyst is 1-5 wt% of the high-carbon isomeric enol.
14. The preparation method according to claim 13, wherein the reaction pressure is 4-6 MPaG, the reaction temperature is 80-120 ℃, and the reaction time is 2-4 hours.
15. The method according to claim 13, wherein the hydrogenation catalyst is raney nickel or supported nickel.
16. The method according to claim 13, wherein the catalyst is used in an amount of 1 to 3wt% of the higher isomeric enol.
17. A primary alcohol polyoxyethylene ether has the following structure:
18. a method for preparing the primary alcohol polyoxyethylene ether according to claim 17, which is characterized in that the high-carbon isomeric fatty alcohol prepared by the method according to any one of claims 1 to 16 reacts with ethylene oxide and/or propylene oxide to obtain the primary alcohol polyoxyethylene ether;
the reaction is carried out under the action of a catalyst selected from acid catalyst BF 3 Isopropyl alcohol complex catalyst, BF 3 Methanol Complex catalyst, BF 3 One or more of the ether complex catalysts.
19. The process according to claim 18, wherein the molar ratio of higher isomeric fatty alcohols to ethylene oxide and/or propylene oxide is 1:3 to 10;
the catalyst is BF 3 Isopropanol complex catalyst; the dosage of the catalyst is 0.05 to 0.5 percent of the molar weight of the high-carbon heterogeneous fatty alcohol;
the reaction conditions are as follows: the reaction temperature is 50-80 ℃ and the reaction time is 1-4 h.
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