CN103450054B - The preparation method of BDO gemini di-sec-octyl succinate sodium sulfonate - Google Patents

The preparation method of BDO gemini di-sec-octyl succinate sodium sulfonate Download PDF

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CN103450054B
CN103450054B CN201310375651.4A CN201310375651A CN103450054B CN 103450054 B CN103450054 B CN 103450054B CN 201310375651 A CN201310375651 A CN 201310375651A CN 103450054 B CN103450054 B CN 103450054B
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sec
bdo
octyl
gemini
double
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CN103450054A (en
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华平
李建华
喻红梅
施磊
鞠剑峰
戴宝江
方略韬
张海滨
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NANTONG HONGSHEN CHEMICAL CO Ltd
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Nantong University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of 1, the preparation method of 4 butanediol gemini di-sec-octyl succinate sodium sulfonate, comprise the following steps: maleic anhydride and 1, two hydroxy combinings on 4 butanediols carry out single-esterification and generate 1, the double maleic mono-ester of 4 butanediols, 1, the double maleic mono-ester of 4 butanediols carries out double esterification reaction with sec-octyl alcohol again and obtains 1, the double maleic acid di-sec-octyl of 4 butanediols, the double maleic acid di-sec-octyl of last Isosorbide-5-Nitrae butanediol carries out conjugate addition sulfonating reaction with sodium sulfite again and prepares product；Wherein, the catalyst of double esterification reaction is carbon-based solid acid catalyst.The present invention easily operates, method easy, the feature of environmental protection is good.

Description

The preparation method of BDO gemini di-sec-octyl succinate sodium sulfonate
Technical field
The present invention relates to the preparation method of a kind of BDO gemini di-sec-octyl succinate sodium sulfonate.
Background technology
BDO gemini di-sec-octyl succinate sodium sulfonate is to design strand surfactant sulfo group in the molecule Succinic acid Zhong Xin ester sodium salt, as the ion head of parents' molecule, is formed by connecting by chemical bond through linking group BDO Gemini surface active agent.Its surface activity, in addition to all advantages with strand surfactant, also has lower surface The most higher surface activity of tension force.Owing to its special structural table reveals the performance of uniqueness, thus it is more widely applied.With Isosorbide-5-Nitrae- Butanediol, maleic anhydride and sec-octyl alcohol are that BDO gemini di-sec-octyl succinate sodium sulfonate prepared by raw material, this product Report without document before items.
Summary of the invention
It is an object of the invention to provide a kind of easy operation, the BDO Shuangzi succinum that method is easy, the feature of environmental protection is good The preparation method of acid di-sec-octyl sodium sulfonate.
The technical solution of the present invention is:
The preparation method of a kind of BDO gemini di-sec-octyl succinate sodium sulfonate, is characterized in that: include following step Rapid: maleic anhydride and two hydroxy combinings on BDO carry out single-esterification and generate the double maleic acid list of BDO Ester, the double maleic mono-ester of BDO carries out double esterification reaction again with sec-octyl alcohol, and to obtain the double maleic acid di-secondary of BDO pungent Ester, the double maleic acid di-sec-octyl of last BDO carries out conjugate addition sulfonating reaction with sodium sulfite again and prepares product； Wherein, the catalyst of double esterification reaction is carbon-based solid acid catalyst.
During single-esterification, maleic anhydride and BDO mol ratio are 2.15:1.0.
During double esterification reaction, sec-octyl alcohol addition is 1.00 1.05 by the mol ratio of maleic anhydride Yu sec-octyl alcohol.
During sulfonating reaction, the consumption of sodium sulfite presses maleic anhydride and NaHSO3Mol ratio be 1.00 1.05.
Reaction equation:
The present invention easily operates, method easy, the feature of environmental protection is good.
1, BDO gemini di-sec-octyl succinate sodium sulfonate is a kind of new Gemini surface active agent, currently without Directly related document was reported.
2, the present invention uses carbon-based solid acid (the immobilized p-methyl benzenesulfonic acid of starch) to make catalyst for esterification reaction, catalyst manufacture Simply, cheap, and esterification products only need to be carried out simple filtration just can separating catalyst, the catalyst of separation is repeatable Use.Avoiding liquid acid catalyst to be difficult to separate with product, etching apparatus, the catalyst such as metal solid is sour make trouble and valency The shortcomings such as lattice are high.
3, this technique need not when double esterification reaction additional make water entrainer and double esterification reaction often such as toluene equal solvent Pressure carries out being esterified dehydration.Avoiding existing Shuangzi sulphosuccinates of preparing needs additional water entrainer maybe to need to use decompression The method of dehydration, decreases the requirement to equipment of reducing pressure, the consumption decreasing raw material and distillation except the operation of toluene.
4, this technique is when esterification, directly ethylene glycol and cis-butenedioic anhydride is reacted, is not required to added acetone etc. and makees cosolvent, keep away Having exempted from original technique needs added acetone to make cosolvent, needs distillation except the work of acetone at the end of decreasing the consumption of raw material and reaction Sequence, it also avoid environmental pollution.
5, the single, double reaction time of esterification of the present invention is short, has effectively contained the phenomenon that double ester hydrolysis and product color are deepened.
6, the most additional phase transfer catalyst of sulfonating reaction, utilizes and controls double esterification reaction esterification yield, by double esterification reaction Monoesters in become salt as phase transfer catalyst.Decrease the impurity of product and the utilization rate of equipment.
Accompanying drawing explanation
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Fig. 1 is the infrared spectrogram of BDO gemini di-sec-octyl succinate sodium sulfonate.
Fig. 2 is the mass spectrum of BDO gemini di-sec-octyl succinate sodium sulfonate.
Detailed description of the invention
The preparation method of a kind of BDO gemini di-sec-octyl succinate sodium sulfonate, comprises the following steps: the first step Single-esterification (I), weighs BDO and horse in the ratio that maleic anhydride and BDO mol ratio are 2.15:1.0 Carrying out anhydride to add in the reactor being furnished with agitator, thermometer and reflux condensing tube, be passed through nitrogen, in 10min, stirring is warming up to 110 DEG C and timing, maintain the temperature at 110 DEG C ± 2 DEG C reaction 2.0h, and single-esterification terminates.Second step double esterification reaction (II), Adding sec-octyl alcohol on same table apparatus, addition is claimed in the ratio that mol ratio is 1.00 1.05 of maleic anhydride with sec-octyl alcohol Take, add and account for the carbon-based solid acid catalyst of cis-butenedioic anhydride quality 1% and (add by m (p-methyl benzenesulfonic acid): m (starch)=1 2 in beaker Entering soluble starch and p-methyl benzenesulfonic acid, heating distilled water dissolves.Treat solution clear, be cooled to room temperature, steam with rotating Send out instrument and flash to sticky shape colloid, insert in Muffle furnace carbonization 8h at 200 DEG C.Grind, cross 80 mesh sieves, i.e. obtain carbon-based solid Acid catalyst), to load onto water knockout drum, continue to be passed through nitrogen, in 10min, be warming up to 200 ± 2 DEG C and timing, period constantly separates life The water become, reacts 3h, and double esterification reaction terminates (esterification yield is 94%-96%).Product is cooled to 50 ± 10 DEG C, is recovered by filtration and urges Agent, reusable after recovery.Filtrate is neutralized to pH=7 ± 0.5 with the NaOH aqueous solution of 30%.3rd step sulfonating reaction (III), adding aqueous solution of sodium bisulfite on same table apparatus, the amount of sodium sulfite presses maleic anhydride and NaHSO3Rub You weigh than the ratio being 1.00 1.05, and aqueous solution of sodium bisulfite quality presses the 1.0 of double esterification product theory yield extraordinarily Enter.Being passed through nitrogen, in the lower 10min of stirring, oil bath is warmed up to 120 ± 2 DEG C of insulations, is stirred vigorously, and system azeotropic at 104 DEG C is anti- Answer 2.5h, i.e. obtain product.Sulfonated tail gas SO2Absorb with sig water.
Surface tension γ is surveyed with Zibo Zi Fen Instrument Ltd. CL-3 type automatic tension analyzerCMCDense with critical micell Degree CMC；Nicolet company of U.S. AVATAR-370 Fourier transformation infrared spectrometer surveys infrared spectrum；Thermo company of the U.S. Trace DSQ-GC/MS type list quadrupole rod gas chromatograph-mass spectrometer (GC-MS) surveys mass spectrum.
Product structure is verified
1) infrared analysis
The infrared spectrogram of BDO gemini di-sec-octyl succinate sodium sulfonate is as shown in Figure 1.
In figure, 2956.44.cm-1For-CH3Antisymmetric stretching vibration, 2931.27cm-1For-CH2Antisymmetry flexible shake Dynamic 2859.18cm-1For-CH3Symmetrical stretching vibration, 1732.09cm-1For the stretching vibration of C=O, 1378.76cm-1Left and right is C-CH3Deformation vibration, 1224.53cm-1Asymmetric stretching vibration 1047.67cm for C-O-C-1Shake for the symmetry of C-O is flexible Dynamic, 500～600cm-1Stretching vibration for C-S.Prove the functional group having target product structure in the product of synthesis.
2) mass spectral analysis
The mass spectrum of BDO gemini di-sec-octyl succinate sodium sulfonate is as shown in Figure 2.
In figure, m/z335.98 is that target product sloughs two Na+The fragment ion formed；M/z257.72 is target product Slough two-SO3The fragment ion that Na is formed；M/z81.03 is that target product sloughs functional group's fragment ion.
According to above characterization result, the product of synthesis is target product BDO Shuangzi succinic acid di-sec-octyl sulphur Acid sodium.
The surface property of product and application performance
The product BDO gemini di-sec-octyl succinate sodium sulfonate of synthesis under optimum process condition is carried out table Face performance and application performance measure, and result is as shown in table 1.
Table 11,4-butanediol gemini di-sec-octyl succinate sodium sulfonate surface property and application performance
The toxicity testing result of product
The toxicity testing result of BDO gemini di-sec-octyl succinate sodium sulfonate is as shown in table 2.
The toxicity testing result of table 2:1,4-butanediol gemini di-sec-octyl succinate sodium sulfonate
As can be seen from Table 2: it is little, weak that BDO gemini di-sec-octyl succinate sodium sulfonate belongs to low toxicity, zest The material of sensitization.

Claims (1)

1. a BDO gemini di-sec-octyl succinate sodium sulfonate, is characterized in that:
BDO gemini di-sec-octyl succinate sodium sulfonate surface property and application performance
The toxicity testing result of BDO gemini di-sec-octyl succinate sodium sulfonate
Preparation method comprises the following steps: first step single-esterification, is 2.15 by maleic anhydride and BDO mol ratio: The ratio of 1.0 weighs BDO and maleic anhydride adds in the reactor being furnished with agitator, thermometer and reflux condensing tube, Being passed through nitrogen, in 10min, stirring is warming up to 110 DEG C and timing, maintains the temperature at 110 DEG C ± 2 DEG C reaction 2.0h, single-esterification Terminate；Second step double esterification reaction, adds sec-octyl alcohol on same table apparatus, addition press maleic anhydride and sec-octyl alcohol mole Weigh than the ratio being 1.00 1.05, add the carbon-based solid acid catalyst accounting for cis-butenedioic anhydride quality 1%, load onto water knockout drum, continue Being passed through nitrogen, be warming up to 200 ± 2 DEG C and timing in 10min, period constantly separates the water of generation, reacts 3h, and double esterification reaction is tied Bundle, esterification yield is 94%-96%；Product is cooled to 50 ± 10 DEG C, catalyst is recovered by filtration, reusable after recovery；Filter Liquid is neutralized to pH=7 ± 0.5 with the NaOH aqueous solution of 30%；3rd step sulfonating reaction, adds sulfurous acid on same table apparatus Hydrogen sodium water solution, the amount of sodium sulfite presses maleic anhydride and NaHSO3The ratio that mol ratio is 1.00 1.05 weigh, sulfurous Acid hydrogen sodium water solution quality presses 1.0 times of additions of double esterification product theory yield；It is passed through nitrogen, oil bath liter in the lower 10min of stirring Temperature, to 120 ± 2 DEG C of insulations, is stirred vigorously, and system is azeotropic reaction 2.5h at 104 DEG C, i.e. obtains product；Sulfonated tail gas SO2With Sig water absorbs；
The preparation method of described carbon-based solid acid catalyst: press p-methyl benzenesulfonic acid in beaker: the mass ratio of starch=1 2 adds Soluble starch and p-methyl benzenesulfonic acid, heating distilled water dissolves；Treat solution clear, be cooled to room temperature, use rotary evaporation Instrument flashes to sticky shape colloid, inserts in Muffle furnace carbonization 8h at 200 DEG C；Grind, cross 80 mesh sieves, i.e. obtain carbon-based solid acid Catalyst.
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CN201310375651.4A CN103450054B (en) 2013-08-26 2013-08-26 The preparation method of BDO gemini di-sec-octyl succinate sodium sulfonate
CN201610835064.2A CN106431996B (en) 2013-08-26 2013-08-26 The preparation method of 1,4 good butanediol gemini di-sec-octyl succinate sodium sulfonates of the feature of environmental protection
CN201610840146.6A CN106431997B (en) 2013-08-26 2013-08-26 The preparation method of easy-operating 1,4 butanediol gemini di-sec-octyl succinate sodium sulfonate

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CN106431996B (en) * 2013-08-26 2017-10-31 南通大学 The preparation method of 1,4 good butanediol gemini di-sec-octyl succinate sodium sulfonates of the feature of environmental protection
CN105566505B (en) * 2015-12-16 2017-09-22 中铁十二局集团有限公司 A kind of preparation method of starch sulphonic acid ester
CN109627168A (en) * 2019-01-02 2019-04-16 江苏理工学院 A kind of preparation method of tributyl citrate
CN110563867B (en) * 2019-09-25 2020-06-02 清华大学 Preparation method of high molecular weight high cis content polybutylene maleate
CN113637153B (en) * 2021-10-18 2022-03-22 常熟耐素生物材料科技有限公司 Multi-block polyether type high-molecular surfactant and preparation method and application thereof
CN114736144B (en) * 2022-04-27 2023-10-13 武汉百科药物开发有限公司 Industrial preparation method of docusate calcium

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CN103086928A (en) * 2013-02-04 2013-05-08 南通大学 Sodium 1,4-butanediol bissulfosuccinate laurylpolyoxyethene (3) isooctyl sulfonate and its preparation method
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