CN103111324B - Application of bromine or iodine-containing haloid and method for synthesizing methyl three-long-chain aliphatic group quaternary ammonium salt derivative - Google Patents
Application of bromine or iodine-containing haloid and method for synthesizing methyl three-long-chain aliphatic group quaternary ammonium salt derivative Download PDFInfo
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- CN103111324B CN103111324B CN201310030396.XA CN201310030396A CN103111324B CN 103111324 B CN103111324 B CN 103111324B CN 201310030396 A CN201310030396 A CN 201310030396A CN 103111324 B CN103111324 B CN 103111324B
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Abstract
The invention discloses application of bromine or iodine-containing haloid and a method for synthesizing a methyl three-long-chain aliphatic group quaternary ammonium salt derivative. According to the application, the bromine or iodine-containing haloid serving as a catalyst is used for catalyzing reaction between three-long-chain aliphatic group tertiary amine and dimethyl carbonate to prepare the methyl three-long-chain aliphatic group quaternary ammonium salt derivative. By the preparation method, under the conditions that the temperature is 90-130 DEG C and the pressure is 0.8-4.5 MPa, the three-long-chain aliphatic group tertiary amine and the dimethyl carbonate react for 4 to 12 hours under the catalysis of the bromine or iodine-containing haloid, so that the methyl three-long-chain aliphatic group quaternary ammonium salt derivative is obtained. By the method, the three-long-chain aliphatic group tertiary amine with large space bit resistance is used for synthesizing the methyl three-long-chain aliphatic group quaternary ammonium salt derivative, so that characteristics of high yield and high purity are achieved. Materials which pollute the environment and corrode equipment are not used, and resources of materials used for synthesizing the quaternary ammonium salt derivative biological materials are widened; and the preparation technology is simple.
Description
Technical field
The present invention relates to the application of haloid and the method for synthesizing methyl three long-chain fat alkyl quaternary ammonium salt derivatives containing bromine or iodine, belong to the synthetic field of organic catalysis.
Background technology
Quarternary ammonium salt compound containing long-chain fat tertiary amine is the very important organic chemicals of a class, as bactericide, washing agent, extractant and antistatic additive etc., is mainly used in petrochemical industry, agricultural chemicals, medical and health, weaving, hydrometallurgy and daily use chemicals industry etc.The ammonium agent of the cationic quaternary ammonium salt derivative of current industrial use mainly contains chloromethanes, halogenation benzyl, dimethyl suflfate, but these reagent are poisonous and equipment is existed to corrosion.Dimethyl carbonate is a kind of novel Green Chemistry reagent, within 1992, in Europe, as non-toxicant, register, in its molecular structure, containing the substitute that methyl can be used as dimethyl suflfate, halide, is a kind of environment-friendly and green raw material that existingization " cleaning procedure " requires that meets.The 1950's, Werntz just started to carry out the quaterisation research of the short chain tertiary amine of dimethyl carbonate, and it mainly represents it is the quaternized of trimethylamine, triethylamine and tri-n-butylamine and dimethyl carbonate.With trimethylamine and dimethyl carbonate, make quaternary ammonium salt, be then hydrolyzed to tetramethyl ammonium hydrogen carbonate, then manufacture high-purity TMAH through electrolysis, realized industrialization.Triethylamine and dimethyl carbonate that Mori and his colleague are 1: 1 in 1991 propositions by mol ratio, do at methyl alcohol under the condition of solvent in autoclave, in 115 ℃, under 0.41MPa, to react 12h, and the conversion ratio of triethylamine can reach 95%.Gary tri-n-butylamine and dimethyl carbonate in 2005, be dissolved in 85mL methyl alcohol, and reaction temperature is 135 ℃～145 ℃, and pressure is 0.69MPa.The productive rate of methyl carbonic acid ester quat can reach 91%～96%.Li Qiu in 2007 is little etc., and use long-chain fat tertiary amine and dimethyl carbonate are put into autoclave, add low-carbon alcohols solvent simultaneously, be warming up to 130 ℃～160 ℃, keep reaction pressure 0.5MPa～1.5MPa, react 4～10 hours, obtain ester quat, Geng Tao in 2010 etc. carry out quaterisation to Dodecyl Dimethyl Amine, in optimal conditions, the quaternary ammonium rate of the monoalkyl tertiary amine of different carbon chain lengths all reaches more than 98%, and two carbon ten and two carbon 18 tertiary amines because of sterically hindered large its conversion ratio lower, be respectively 88.09% and 68.77%, the method that they provide is not suitable for the methyl quaterisation of three long-chain fat alkyl tertiary amines and dimethyl carbonate.For the research with dimethyl carbonate and the quaternized synthetic three long-chain fat alkyl quaternary ammonium salt derivatives of three long-chain fat alkyl tertiary amines, there is not yet document and have successfully report.
Summary of the invention
One object of the present invention is to provide the application containing the haloid of bromine or iodine, and the haloid that contains bromine or iodine is applied to catalysis three long-chain fat alkyl tertiary amines and dimethyl carbonate generation quaterisation, obtains high-purity, the product of high yield.
The object of the present invention is to provide a kind of high yield, high-purity, method with three long-chain fat alkyl tertiary amine synthesizing methyl three long-chain fat alkyl quaternary ammonium salt derivatives of large space steric hindrance, the method has avoided using environmental pollution and the raw material to equipment corrosion, the source of raw material and the type of quaternary ammonium salt derivative anion that have expanded synthetic quaternary ammonium salt derivative, preparation technology is simple.
The invention provides the application containing the haloid of bromine or iodine, this application is that the haloid containing bromine or iodine is applied to catalysis three long-chain fat alkyl tertiary amines as catalyst and dimethyl carbonate is prepared methyl three long-chain fat alkyl quaternary ammonium salt derivatives.
Described is one or more that have in quaternary ammonium halides salt, NaBr, NaI, KBr and the KI of formula 1 structure containing bromine or iodine haloid catalyst;
Formula 1
R
4, R
5and R
6be selected from independently of one another C
8~ C
18aliphatic group in a kind of;
X is selected from bromine atoms or iodine atom a kind of.
Three described long-chain fat alkyl tertiary amines have formula 2 structures:
Formula 2
R
1, R
2and R
3be selected from independently of one another C
8~ C
18aliphatic group in a kind of.
Preferred quaternary ammonium halides salt, R in formula 1
4, R
5and R
6independently be selected from separately C
8~ C
18alkyl in a kind of.
Quaternary ammonium halides salt more preferably, R in formula 1
4, R
5and R
6independently be selected from separately C
8~ C
18linear paraffin base in a kind of.
Preferred three long-chain fat alkyl tertiary amines, R in formula 2
1, R
2and R
3independently be selected from separately C
8~ C
18alkyl in a kind of.
Most preferred three long-chain fat alkyl tertiary amines, R in formula 2
1, R
2and R
3independently be selected from separately C
8~ C
18linear paraffin base in a kind of.
Most preferred quaternary ammonium halides salt, the R in formula 1
4, R
5, R
6with the R in formula 2
1, R
2, R
3structural formula is identical respectively; The R in the quaternary ammonium halides salt catalyst of selecting
4, R
5and R
6with R in reaction substrate three long-chain fat alkyl tertiary amines
1, R
2and R
3match.
The present invention also provides the method that contains the haloid catalytic synthesis of methyl three long-chain fat alkyl quaternary ammonium salt derivatives of bromine or iodine described in the above-mentioned application of a kind of use, the method is to be 90 ℃～130 ℃ in temperature, pressure is under the condition of 0.8～4.5MPa, three long-chain fat alkyl tertiary amines and dimethyl carbonate, reacting 4～12h containing under the haloid catalyst of bromine or iodine, are obtained.
The consumption of described haloid catalyst is 0.5%～8% of reaction system gross mass; Be preferably 3～6%.
Three described long-chain fat alkyl tertiary amines and mol ratio 1.0:1.5～6 of dimethyl carbonate; Be preferably 1.0:3.0～6.0.
Reaction described in the present invention is carried out in low-carbon alcohols solvent.
Described low-carbon alcohols solvent load is 30%～150% of trialkyl fat tertiary amine quality; Be preferably 40%～100%.
Described low-carbon alcohols solvent is: in absolute methanol, absolute ethyl alcohol, isopropyl alcohol, ethylene glycol or propane diols one or more.
The synthetic methyl three long-chain fat alkyl quaternary ammonium salt derivatives of preparation method of the present invention have formula 3 structures,
Formula 3
R
1, R
2and R
3be selected from independently of one another C
8~ C
18aliphatic group in a kind of.
Preferred methyl three long-chain fat alkyl quaternary ammonium salt derivatives, R
1, R
2and R
3be selected from independently of one another C
8~ C
18alkyl in a kind of.
Methyl three long-chain fat alkyl quaternary ammonium salt derivatives more preferably, R
1, R
2and R
3be selected from independently of one another C
8~ C
18linear paraffin base in a kind of.
Preferred synthetic method is to be 90 ℃～130 ℃ in temperature, pressure is under the condition of 0.8～4.5MPa, three long-chain fat alkyl tertiary amines and the dimethyl carbonate with formula 1 structure are joined in the reactor of short chain alcohol solvent, add the haloid catalyst containing bromine or iodine, after reaction 4～12h, cooling, decompression steams solvent and unreacted dimethyl carbonate, obtains.
The route of the quaternary ammonium salt that the present invention's three long-chain fat base tertiary amines and dimethyl carbonate generate is as follows:
The synthetic methyl three long-chain fat alkyl quaternary ammonium salt derivatives of the present invention are cationic surfactant, the characteristic with cation performance activating agent, can be used for the fields such as petrochemical industry, agricultural chemicals, medical and health, weaving, hydrometallurgy, mineral floating and day chemical industry.
Know-why of the present invention: halogen anion has good nucleophilicity, particularly I
-and Br
-; Inventor finds, containing the bromine or iodine anion in the slaine of bromine or iodine, the quaterisation of fat-based tertiary amine and dimethyl carbonate is had to catalytic action first by great many of experiments; On this basis, inventor has further studied the quaterisation of three long-chain fat alkyl tertiary amines and dimethyl carbonate, and has successfully made to high yield, high-purity first containing C
8~ C
18the quaternary ammonium compound of three long-chain fat alkyl; But halogen metal salt compounds solubility in organic solvent is little, the catalytic efficiency of catalyst is not very high; Inventor attempts replacing halogen metal salt with quaternary ammonium halides salt, has overcome catalysts solubility little, the problem that catalytic efficiency is not high, and high productivity has obtained containing C too
8~ C
18the quaternary ammonium compound of three long-chain fat alkyl, but exist again cation in the catalyst of minute quantity to enter product, the high product of purity requirement is had to the impact of quality; Inventor considers to use the corresponding halogen quaternary ammonium salt identical with three aliphatic chains of reaction substrate three long-chain fat alkyl tertiary amines to do all problems that catalyst has overcome above-mentioned catalytic reaction through repeatedly studying, prepare high yield, the highly purified quaternary ammonium salt derivative product that contains three long-chain fat alkyl.
The inventive method is compared with prior art and have the following advantages: the present invention adopts the haloid of brominated and iodine as catalyst three long-chain fat alkyl tertiary amines and dimethyl carbonate generation quaterisation first, has obtained very high conversion ratio and yield; This technique is used environmental protection material carbon dimethyl phthalate to substitute has corrosion and poisonous quaternizing agent halomethane, dimethyl suflfate etc. to equipment, has avoided the pollution of environment and the corrosion to equipment; The method equipment investment and operating cost are low, have the premium properties of good be converted into chlorion type, bromide ion type, sulfate ion type, carbanion type, bicarbonate radical type quaternary ammonium salt derivative; The method has expanded the type of quaternary ammonium salt derivative anion, also for preparation does not provide preferred feedstock containing the high purity quaternary ammonium hydrate of inorganic salts.
Accompanying drawing explanation
[Fig. 1] is that the product of the embodiment of the present invention 1 and the infrared spectrum comparison diagram of raw material: a are the infrared spectrogram of raw material N235; B is carbonic acid mono-methyl quaternary ammonium salt infrared spectrogram; C is sulphation quaternary ammonium salt infrared spectrogram.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1:
Measure 240mlN235,240ml dimethyl carbonate, 120ml absolute methanol, take 24.0g(bromination trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 125 ℃, 2.4 ~ 4.0MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.N235 conversion ratio is 93.84%.
Infrared spectrum characterization
Adopt KBr coated wafer embrane method to carry out infrared spectrum characterization, raw material N235 (a), carbonic acid mono-methyl quaternary ammonium salt (b) and sulphation quaternary ammonium salt (c), gained infrared absorption spectroscopy is as shown in Figure 1;
In Fig. 1, compare with a, b is at 1668cm
-1the characteristic absorption peak that has occurred carbonyl, simultaneously at 1289cm
-1the characteristic absorption peak that has occurred C-O-C; In c, the characteristic peak of carbonyl, C-O-C all disappears.
Embodiment 2:
Measure 240mlN235,240ml dimethyl carbonate, 120ml absolute methanol, take 25.0g(bromination trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 110 ℃, 1.1 ~ 2.4MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.N235 conversion ratio is 99.39%.
Embodiment 3:
Measure 240ml trioctylphosphine tertiary amine, 240ml dimethyl carbonate, 120ml absolute methanol, add 27.8g(bromination trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 115 ℃, 1.75 ~ 2.7MPa reaction 6 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.Trioctylphosphine tertiary amine conversion ratio is 97.19%.
Embodiment 4:
Measure 240ml trioctylphosphine tertiary amine, 240ml dimethyl carbonate, 120ml absolute methanol, add 28.0g(iodate trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 110 ℃, 1.75 ~ 2.7MPa reaction 6 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of trioctylphosphine tertiary amine is 98.78%.
Embodiment 5:
Measure 240ml dioctyl dodecyl tertiary amine, 240ml dimethyl carbonate, 100ml absolute methanol, add 28.0g(iodate dioctyl dodecyl methyl quaternary ammonium salt) catalyst, add in 1L autoclave, be warming up to 130 ℃, after 2.4 ~ 4.0MPa reaction reaction in 8 hours stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.Dioctyl dodecyl tertiary amine conversion ratio is 98.28%.
Embodiment 6:
Measure 240ml dioctyl decyl tertiary amine, 240ml dimethyl carbonate, 100ml absolute methanol, add 28.0g(bromination dioctyl decyl methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 130 ℃, 2.4 ~ 4.2MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of dioctyl decyl tertiary amine is 96.0%.
Embodiment 7:
Measure 240ml N235,240ml dimethyl carbonate, 120ml absolute methanol, adds 10.0gKI catalyst, add in 1L autoclave, be warming up to 120 ℃, 1.0～1.2MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of N235 is 88.0%.
Embodiment 8:
Measure 240ml dioctyl octadecyl tertiary amine, 240ml dimethyl carbonate, 120ml absolute methanol, add 28.0g(iodate dioctyl octadecyl methyl quaternary ammonium salt) catalyst, add in 1L autoclave, be warming up to 130 ℃, 2.4～4.0.MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of dioctyl octadecyl tertiary amine is 98.0%.
Embodiment 9:
Measure 240mlN235,240ml dimethyl carbonate, 100ml absolute methanol, add 20g(iodate trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 130 ℃, after 2.4 ~ 4.0MPa reaction reaction in 8 hours stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of N235 is 91.67%.
Embodiment 10:
Measure 240mlN235,240ml dimethyl carbonate, 120ml absolute methanol, add 14.0g(bromination trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 130 ℃, 1.1 ~ 1.6MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.N235 conversion ratio is 83.33%.
Embodiment 11:
Measure 240mlN235,240ml dimethyl carbonate, 100ml anhydrous isopropyl alcohol, add 20.0g(iodate trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 130 ℃, after 1.1 ~ 1.65MPa reaction reaction in 8 hours stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of N235 is 70.67%.
Embodiment 12:
Measure 240mlN235,240ml dimethyl carbonate, 120ml absolute ethyl alcohol, add 14.0g(bromination trioctylphosphine methyl quaternary ammonium) catalyst, add in 1L autoclave, be warming up to 130 ℃, 1.1 ~ 1.6MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.N235 conversion ratio is 73.33%.
Embodiment 13:
Measure 240ml trioctylphosphine tertiary amine, 240ml dimethyl carbonate, 120ml absolute methanol, add 24.0g(bromination trioctylphosphine methyl quaternary ammonium and 2.0gKBr) catalyst, add in 1L autoclave, be warming up to 120 ℃, 2.4～4.4MPa reaction 8 hours, after reaction stops, cooling, decompression steams solvent and unreacted dimethyl carbonate.The conversion ratio of trioctylphosphine tertiary amine is 98.33%.Under stirring, the sulfuric acid that adds 260ml3.0mol/L by 1:1 (V/V), after having reacted, separates organic phase.By 3 * 260ml diluted sodium hydroxide solution washing organic phase, till being washed till wash water and being neutrality, separate organic phase, decompression steams the water in organic phase, obtains sulphation trioctylphosphine methyl quaternary ammonium.
Claims (3)
1. the method containing the haloid catalytic synthesis of methyl three long-chain fat alkyl quaternary ammonium salt derivatives of bromine or iodine, it is characterized in that, in temperature, it is 90 ℃～130 ℃, pressure is under the condition of 0.8～4.5MPa, three long-chain fat alkyl tertiary amines and dimethyl carbonate, reacting 4～12h containing under the haloid catalyst of bromine or iodine, are obtained;
The described haloid catalyst containing bromine or iodine is the quaternary ammonium halides salt with formula 1 structure;
Three described long-chain fat alkyl tertiary amines have formula 2 structures;
R
1, R
2, R
3, R
4, R
5and R
6independently be selected from separately C
8～C
18linear paraffin base in a kind of;
R in formula 1
4, R
5, R
6with the R in formula 2
1, R
2, R
3structural formula is identical respectively;
X is selected from bromine atoms or iodine atom a kind of.
2. method according to claim 1, is characterized in that, the consumption of described haloid catalyst is 0.5%～8% of reaction system gross mass.
3. method according to claim 1, is characterized in that, three described long-chain fat alkyl tertiary amines and mol ratio 1.0:1.5～6 of dimethyl carbonate.
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| CN105503612B (en) * | 2015-11-30 | 2017-08-01 | 中南大学 | Ammonium salt of six alkyl triethylene of tetramethyl four and its preparation method and application |
| CN107118104B (en) * | 2017-05-10 | 2019-06-28 | 中南大学 | A kind of preparation method of three long aliphatic hydrocarbon chain ammonium carbonate salts of methyl |
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| UA76478C2 (en) * | 2001-07-09 | 2006-08-15 | Лонза Інк. | In situ methods of preparing quaternary ammonium alkylcarbonates |
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN100436402C (en) * | 2006-08-24 | 2008-11-26 | 中国日用化学工业研究院 | Synthesis of fat tertiary amine quaternary ammonium salt derivative |
| CN102816075A (en) * | 2012-08-24 | 2012-12-12 | 四川大学 | Preparation method of long-chain quaternary ammonium surfactant |
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Effective date of registration: 20181119 Address after: 414517 Pingjiang Industrial Park, Yueyang City, Hunan Province Patentee after: Hunan macro state Mstar Technology Ltd Address before: 410083 932 south foot Road, Yuelu District, Changsha, Hunan Patentee before: Central South University |
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