CN101249400B - Maleated rosin based quaternaries cation surface active agent and method of preparing the same - Google Patents
Maleated rosin based quaternaries cation surface active agent and method of preparing the same Download PDFInfo
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- CN101249400B CN101249400B CN200810073532.2A CN200810073532A CN101249400B CN 101249400 B CN101249400 B CN 101249400B CN 200810073532 A CN200810073532 A CN 200810073532A CN 101249400 B CN101249400 B CN 101249400B
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Abstract
The invention relates to a maleated rosin radical quaternary ammonium salt-type cationic surfactant and a preparation method thereof. The maleated rosin radical quaternary ammonium salt cationic surfactant is prepared with maleated rosin, epichlorohydrin and organic amine through reaction under the base catalysis. The maleated rosin radical quaternary ammonium salt-type cationic surfactant is characterized in that a low carbon chain alcohol is used as the solvent, and the maleated rosin, the epichlorohydrin and the organic amine react under the base catalysis; alkylation and quaterisation are completed simultaneously in one step operation, thus getting the target compound. The product has high foamability and is capable of sterilization, which can be used in the fields of textile, printing and dying, sterilization, froth flotation, metal inhibition and so on, and can be used for preparing cationic dispersion rosin sizing agents.
Description
Technical field:
The present invention relates to a kind of is raw material with the maleic rosin, prepares a kind of maleated rosin based quaternaries cation surface active agent and preparation method thereof, belongs to field of fine chemical.
Background technology:
China is rosin big producing country, and aboundresources is cheap, for preparation degradable environment-friendly type chemical products provide good material base.By chemical reaction rosin is carried out deep processing, expand new purposes, the new material that processability is superior becomes the important research direction of development China ROSIN INDUSTRY, and surfactant industry is exactly a key areas of its application.In recent years, the work of rosin-based surfactant mainly concentrates on anion and the non-ionic surface active agent, about the report of the synthetic and aspect of performance of its cationic surfactant also few.
By the cationic surfactant that rosin synthesized all is the quaternary compound basically.Common synthetic method has following: (1) rosin acid and epichlorohydrin reaction generate intermediate, form quaternary ammonium salt with the ammonium reaction then; Also can prepare corresponding quaternary ammonium salt cationic surfactant by rosin acid is quaternized again after the glycidol esterification.(2) epoxy radicals alkanes material and tertiary amine generate intermediate earlier, this intermediate generates cation colophony type surfactant (3) with the rosin reaction again and earlier obtains rosin amine by rosin acid, further makes quaternary ammonium salt cationic surfactant with the quaternary ammonium salt reaction again., Wang Yan modest as the Song Zhan of China Forests Science Academe Forests Chemical Industry Research Institute is raw material with dehydrogenation abietic acid, neoabietic acid, rosin ammonium etc., with prepared in reaction Abietyl quaternary ammonium salt compounds such as epoxychloropropane, organic amine, benzyl chloride, cylite, dimethyl suflfate ([P]. Abietyl quaternary ammonium salt compounds and preparation method thereof, CN97106924.7).The Wei Xiao of Guangzhou Inst of Chemistry, Chinese Academy of Sciences favour, Liao Shizhen, Cao Derong, Dong Shaofeng are raw material with the acrylic acid modified rosin, under the phase transfer catalyst effect, obtain quaternizing agent with epichlorohydrin reaction, and then under the uniform temperature condition, two kinds of abietyl double quaternary ammonium salt type cationic surfactant (synthetic and performances of abietyl bis-quaternary ammonium salt cationic surfactant have been synthesized with triethylamine and pyridine reaction respectively, [J]. fine chemistry industry, 2003, Vol.20, No.9); The Zhang Guangyou of Nanjing Forestry University, Zhang Pukang, a uncommon dam etc. are raw material with the disproportionation rosin, from disproportionation rosin, extract the dehydrogenation abietic acid earlier, and then as raw material and epichlorohydrin reaction generation dehydrogenation abietic acid ethylene oxidic ester, generate abietyl double quaternary ammonium salt type cationic surfactant N-(3-dehydrogenation fir acyl-oxygen-2-hydroxyl) propyl group-N with the trimethylamine hydrochloride reaction more at last, N, N-trimethyl sal-ammoniac (N-(3-dehydrogenation fir acyl-oxygen-2-hydroxyl) propyl group-N, N, synthetic and character [J] chemistry of forest product and the industry of N-trimethyl ammonium chloride, 1994, (S1).The Zhang Jian of South China Science ﹠ Engineering University, what North Sea, Li Junrong, Qian Liying etc. generate intermediate earlier with epoxy radicals alkanes material and tertiary amine, this intermediate again with rosin reaction generate cation colophony type surfactant ([J]. paper science and technology, 2005, Vol.24, No.6).Beijing Institute of Light Industry beam dream orchid, Ye Jianfeng is raw material with the dehydroabietylamine, with formic acid, formolite reaction elder generation synthesization of dimethyl dehydroabietylamine, with benzyl chloride, dimethyl suflfate has synthesized N respectively again, N-dimethyl-N-benzyl-N-dehydrogenated rosin ammonium chloride and N, N, N-trimethyl-two kinds of abietyl cationic surfactants of N-dehydrogenation rosin-base methyl sulfate ammonium ([J]. chemistry world, 2000, No.3).Azanylization that the above method is included and quaterisation all are to operate in two steps to finish, and contained quaternary ammonium group is 1 or 2 in the product, are mono-quaternaries or bi-quaternary ammonium salt compounds.
Summary of the invention:
The objective of the invention is to relate to a kind of chemical general formula is the maleated rosin based quaternaries cation surface active agent of (I) and preparation method thereof.It is to react gained by maleic rosin and epoxychloropropane, organic amine under base catalysis.It is characterized in that with low carbon chain alcohol be solvent, azanylization and quaterisation are finished simultaneously maleic rosin and epoxychloropropane, organic amine in single stepping and obtained maleated rosin based three quarternary ammonium salt compounds of chemical formula for (I).
(I) in the formula, R:-CH
3, or-C
2H
5
Described organic amine is that trimethylamine, triethylamine or Diethylenetriamine (claim diethylentriamine again; Diethylenetriamine; 2,2 '-the diaminourea diethylamide; 2,2 '-the two ethamine of imido grpup).
Described low carbon chain alcohol is ethanol, propyl alcohol or isopropyl alcohol, perhaps their mixture, for example mixture of ethanol and isopropyl alcohol, propyl alcohol and isopropyl alcohol etc.
Described alkali is NaOH or potassium hydroxide.
Preparation method's technology of above-described maleated rosin based quaternaries cation surface active agent is as follows: maleic rosin, alcohol, alkali, epoxychloropropane, organic amine are mixed, be warming up to 60～110 ℃, reaction down 12～30 hours refluxes, reaction finishes, be neutralized to neutrality with hydrochloric acid, by distillation or decompression distillation alcohol is steamed again, promptly obtain maleated rosin based quaternaries cation type surfactant.Product is brown viscous liquid shape, good water solubility.
The ratio of the amount of substance of described maleic rosin, epoxychloropropane, organic amine, alcohol, alkali is: 1: 5～7: 3～5: 10～30: 1.5～3.
In the above-mentioned preparation process, after reaction finishes pure and mild unreacted epoxychloropropane, organic amine are passed through distillation or decompression distillation recycling.
The prepared maleated rosin based quaternaries cation type surfactant of the present invention is water-soluble good, no Kraft point in 0～100 ℃ of scope, foaming characteristic is strong, has bactericidal action, can be used for fields such as weaving, printing and dyeing, sterilization, froth flotation, corrosion inhibition for metal, also can be used for preparing cationic dispersion rosin size.
The specific embodiment
Describe the present invention in detail by following examples:
Embodiment 1 is with the 50g maleic rosin, 100～150ml ethanol and 8gNaOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and NaOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 20～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 2 is with the 50g maleic rosin, 150～200ml propyl alcohol and 8gNaOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and NaOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 22～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 3 is with the 50g maleic rosin, 150～200ml isopropyl alcohol and 8gNaOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and NaOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 22～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 4 is with the 50g maleic rosin, 100ml ethanol, 100ml propyl alcohol and 8gNaOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and NaOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 22～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 5 is with the 50g maleic rosin, 100ml ethanol, 100ml isopropyl alcohol and 8gNaOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and NaOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 22～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 6 is with the 50g maleic rosin, the 100m propyl alcohol, 100ml isopropyl alcohol and 8gNaOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and NaOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 22～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 7 joins 50g maleic rosin, 100～150ml ethanol and 10gKOH in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and KOH solid have dissolved, add 60g epoxychloropropane and 40g triethylamine again, be warming up to 75～90 ℃, back flow reaction 20～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation steams isopropyl alcohol and unreacted epoxychloropropane, triethylamine, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 8 joins 50g maleic rosin, 100～150ml ethanol and 10gKOH in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and KOH solid have dissolved, add 60g epoxychloropropane and 36g trimethylamine again, be warming up to 75～90 ℃, back flow reaction 20～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation steams isopropyl alcohol and unreacted epoxychloropropane, triethylamine, can obtain the about 120g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 9 is with the 50g maleic rosin, 100～150ml ethanol and 10gKOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and KOH solid have dissolved, add 60g epoxychloropropane and 40g Diethylenetriamine again, be warming up to 75～90 ℃, back flow reaction 20～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Embodiment 10 is with the 50g maleic rosin, 100～150ml isopropyl alcohol and 10gKOH join in the four-necked bottle that has agitator and reflux condensing tube successively, start agitator, after treating that maleic rosin and KOH solid have dissolved, add 60g epoxychloropropane and 40g Diethylenetriamine again, be warming up to 75～90 ℃, back flow reaction 20～30 hours, stop reaction, while hot reaction system is transferred in the Rotary Evaporators, decompression distillation is with isopropyl alcohol and unreacted epoxychloropropane, triethylamine steams, can obtain the about 123g of title compound, be the sepia viscous liquid, productive rate about 98%.
Claims (2)
1. maleated rosin based quaternaries cation surface active agent, it is characterized in that: its chemical general formula is suc as formula shown in (I):
In (I) formula, R:-CH
3, or-C
2H
5
2. the preparation method of the described maleated rosin based quaternaries cation surface active agent of claim 1, it is characterized in that: with low carbon chain alcohol is solvent, earlier with maleic rosin, alcohol, alkali mixed dissolution, add epoxychloropropane, organic amine then, be warming up to 60～110 ℃, reaction down 12～30 hours refluxes, azanylization and quaterisation are finished in single stepping simultaneously, reaction finishes, alcohol is distilled, obtain the maleated rosin based quaternaries cation type surfactant of chemical formula for (I);
Described organic amine is trimethylamine, triethylamine or Diethylenetriamine;
Described low carbon chain alcohol is ethanol, propyl alcohol or isopropyl alcohol, perhaps the mixture of ethanol and propyl alcohol, ethanol and isopropyl alcohol, propyl alcohol and isopropyl alcohol;
The ratio of the amount of substance of described maleic rosin, epoxychloropropane, organic amine, alcohol, alkali is: 1: 5～7: 3～5: 10～30: 1.5～3.
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| CN101628212A (en) * | 2009-08-04 | 2010-01-20 | 郑州大学 | New cationic surfactant containing boron and preparation method thereof |
| CN103250740A (en) * | 2013-06-04 | 2013-08-21 | 常州和方环保科技有限公司 | Mildew inhibitor, and preparation method and application method thereof |
| CN103304534B (en) * | 2013-06-05 | 2014-12-10 | 中国林业科学研究院林产化学工业研究所 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
| CN103788723B (en) * | 2014-02-27 | 2015-06-24 | 新疆大学 | Modified soapstone, quaternary ammonium polylactide/fulvate modified soapstone composite material and preparation methods and products thereof |
| CN111821911A (en) * | 2020-07-27 | 2020-10-27 | 福州大学 | Quaternary ammonium salt rosin-based Gemini surfactant and preparation method thereof |
| CN113582862B (en) * | 2021-08-31 | 2023-11-10 | 广州安赛化工有限公司 | Rosin-based quaternary ammonium salt for preparing multifunctional cooling water biocide, preparation method and application thereof |
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| 张国利.马来松香三季铵盐的合成及其在纳米阳离子分散松香胶制备中的应用.广西大学硕士毕业论文.2007, * |
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