CN103304534A - Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof - Google Patents
Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of rosinyl cyclic carbonate and a quaternary ammonium salt antibacterial derivative thereof. The preparation method comprises the following steps of: reacting maleopimaric acid epoxy resin with CO2 under the action of a catalyst, so as to synthesize rosinyl cyclic carbonate; reacting the rosinyl cyclic carbonate with an amino compound to prepare rosinyl carbamic acid ester; and further carrying out a quaterisation reaction so as to obtain a novel rosinyl quaternary ammonium salt antibacterial derivative containing carbamic acid ester groups. The rosinyl quaternary ammonium salt antibacterial derivative is low in raw material cost, wide in resource and safe and non-toxic in preparation process; as carbamic acid ester polar groups with antibacterial activity are introduced into the molecular structure, the quaternary ammonium salt antibacterial derivative has good water solubility, biocompatibility and excellent antibacterial and bactericidal performances, and can be applied to fields of antibacterial, bactericides and the like.
Description
Technical field
The invention discloses the preparation method of a kind of rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof, relate in particular to a kind of with maleopimaric acid Resins, epoxy and CO
2The preparation method of prepared in reaction rosinyl cyclic carbonate ester and amido-containing acid ester group quaternary ammonium salt derivative thereof.
Background technology
Rosin is a kind of important natural resource, has biodegradable, renewable and wide material sources, lower-price characteristic, and its main component is resinous acid, contains groups such as the luxuriant and rich with fragrance skeleton of triatomic ring, two key and carboxylic acid in the molecular structure.By to the rosin chemical structure modification, can prepare dissimilar derivatives.Wherein, cationic quarternary ammonium salt compound is subjected to extensive concern because of advantages such as low toxicity, nonirritant and good emulsifying power, inhibition power, antibiotic and fungicidal activities.But traditional quarternary ammonium salt compound difficult degradation, easily cause environmental pollution.Existing studies show that introduced the water-soluble and biological degradability that ether, ester, acid amides, carbamate and hydroxyl isopolarity functional group can improve compound effectively in the quaternary ammonium salt molecular structure, make its more green, environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt antibiotic derivative and preparation method.
The present invention is by the following technical solutions: a kind of rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt derivative thereof, the structural formula of described rosinyl cyclic carbonate ester is
The structural formula of described rosinyl carbamate is
N=2～5; The structural formula of described Abietyl quaternary ammonium salt derivative is
N=2～5, m=2～22.
A kind of method for preparing rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt derivative thereof, described rosinyl cyclic carbonate ester is with maleopimaric acid Resins, epoxy and CO
2Prepared in reaction under the effect of catalyzer, reaction formula is:
Formula one
Described catalyzer is the compound system of metal halide/vicinal diol compound, and the mass ratio of metal halide and adjacent glycol is 1:0.1～1:2.Wherein, metal halide is lithiumbromide (LiBr), lithium chloride (LiCl), potassiumiodide (KI), Potassium Bromide (KBr), zinc bromide (ZnBr
2) in a kind of, consumption is 0.1～5% of maleopimaric acid Resins, epoxy quality; Adjacent glycols compound is ethylene glycol, 1,2-propylene glycol, a kind of in 1, the 2-butyleneglycol.
The reaction of preparation rosinyl cyclic carbonate ester is with N-Methyl pyrrolidone or N, and dinethylformamide is solvent, and maleopimaric acid Resins, epoxy is placed closed reactor, feeds CO
2To pressure be 0.5～5MPa, 80～150 ℃ the reaction 2～24h.
Described rosinyl carbamate is prepared in reaction in organic solvent with rosinyl cyclic carbonate ester and amino-complex, and reaction formula is:
Formula two
Described amino-complex is (CH
3)
2NR
1NH
2, wherein, R
1Be C
2～C
5Alkyl, described temperature of reaction is 25～100 ℃, reaction times 2～8h.
Described amino-complex is N, N-dimethylamino quadrol, N, N-dimethylaminopropylamine, 4-dimethylamino butylamine etc.
Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, the tetrahydrofuran (THF).
Described Abietyl quaternary ammonium salt derivative is prepared in reaction in organic solvent with rosinyl carbamate and bromo alkane, and reaction formula is:
Formula three
Described bromo alkane is for containing C
2～C
22The bromo alkane of alkyl.
Described temperature of reaction is 60～100 ℃, and the reaction times is 5～24h.
Beneficial effect of the present invention:
1. the present invention is the biomass-based cyclic carbonate ester of feedstock production, carbamate and quaternary ammonium salt derivative thereof with renewable resources rosin, raw materials cost is low, wide material sources, safe preparation process, nontoxic, and cyclic carbonate ester, carbamate and the quaternary ammonium salt derivative thereof of preparation have biodegradability, environmental friendliness.
2. the Abietyl quaternary ammonium salt antibiotic derivative of the present invention preparation has the carbamate polar group of anti-microbial activity because introducing in the molecular structure, thereby has well water-soluble, biocompatibility and excellent antibiotic, bactericidal property.
Description of drawings
The infrared spectrogram of Fig. 1 rosinyl cyclic carbonate ester (R-C).
The infrared spectrogram of Fig. 2 rosinyl carbamate (R-Ca).
The infrared spectrogram of Fig. 3 n-propyl-Abietyl quaternary ammonium salt (QAS-a).
The infrared spectrogram of Fig. 4 n-hexyl-Abietyl quaternary ammonium salt (QAS-b).
The infrared spectrogram of Fig. 5 dodecyl-Abietyl quaternary ammonium salt (QAS-c).
Embodiment
Maleopimaric acid Resins, epoxy of the present invention is pressed reference (thermosetting resin, 1996,11 (2), 19-22.) the method preparation in.
The preparation method of a kind of rosinyl cyclic carbonate ester and amido-containing acid ester based quaternary ammonium salt derivative thereof.
This method realizes by following steps:
The first step in autoclave, is dissolved in a certain amount of N-Methyl pyrrolidone or N with maleopimaric acid Resins, epoxy and the catalyzer of certain mass, dinethylformamide, and the sealing back feeds CO
2To pressure be 0.5～5MPa, 80～150 ℃ the reaction 2～24h prepare the rosinyl cyclic carbonate ester, the reaction as shown in Equation 1.
Described catalyzer is the compound system of metal halide/adjacent glycols compound, and the mass ratio of metal halide and adjacent glycols compound is 1:0.1～1:2.Wherein, metal halide is lithiumbromide (LiBr), lithium chloride (LiCl), potassiumiodide (KI), Potassium Bromide (KBr), zinc bromide (ZnBr
2) in a kind of, consumption is 0.1～5% of maleopimaric acid Resins, epoxy quality; Adjacent glycols compound is ethylene glycol, 1,2-propylene glycol, 1,2-butyleneglycol etc.; Described reaction pressure the best is 2MPa, and temperature of reaction the best is 120 ℃, and reaction times the best is 7h.
Second step was dissolved in a small amount of organic solvent with the rosinyl cyclic carbonate ester, and mixes with the ratio 1:1 of amino-complex by amount of substance, reacted 2～8h down at 25～100 ℃ and prepared the rosinyl carbamate, and reaction as shown in Equation 2.
Formula 2
Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, the tetrahydrofuran (THF); Described amino-complex is (CH
3)
2NR
1NH
2, wherein, R
1Be C
2～C
5Alkyl; As N, N-dimethylamino quadrol, dimethylaminopropylamine, 4-dimethylamino butylamine etc.; Described temperature of reaction is 25～100 ℃, reaction times 2～8h; Described temperature of reaction the best is 70 ℃, and reaction times the best is 2h.
The 3rd step was dissolved in a small amount of organic solvent with the rosinyl carbamate, and mixes than 1:1 by amount of substance with bromo alkane, reacted 5～24h down at 60～100 ℃ and prepared the Abietyl quaternary ammonium salt derivative, and reaction as shown in Equation 3.
Formula 3
Described organic solvent is any one in methyl alcohol, ethanol, sherwood oil, acetone, cyclobutanone, ethyl acetate, the tetrahydrofuran (THF); Described bromo alkane is for containing C
2～C
22The bromo alkyl of alkyl more preferably contains C
2～C
16The bromo alkyl of alkyl is as n-propyl bromide, bromo normal hexane, bromododecane, bromohexadecane, isobutane bromide, bromo-iso-octane etc.; Described temperature of reaction the best is 70 ℃, and reaction times the best is 12h.
In the 1L autoclave, add 200g maleopimaric acid Resins, epoxy, 2g lithiumbromide, 1g ethylene glycol and 70mL N-Methyl pyrrolidone (NMP), be warming up to 120 ℃, feed CO
2To certain pressure, leak detection back emptying.Air in the still is thoroughly got rid of in repetitive operation three times, feeds CO
2Keep-up pressure at 2MPa stirring reaction 7h.After reaction is finished, remaining CO in the emptying still
2, product is poured out while hot, remove catalyzer and NMP with hot wash, underpressure distillation is removed moisture and is got the rosinyl cyclic carbonate ester.The oxirane value of assay products, getting its epoxy group(ing) transformation efficiency is 98.6%.
Product rosinyl cyclic carbonate ester among the embodiment 1
1H NMR (500MHz, CDCl
3, δ ppm): δ 5.37 (– C=CH –); δ 4.87～5.08 (methine hydrogens of cyclic carbonate group); δ 4.02～4.23 (methylene hydrogens of cyclic carbonate group); δ 4.26～4.65 (O – CH
2–); δ 2.95～3.00 (CH – C=); δ 2.87～2.91 (CH – C=O); δ 2.52～2.65 (CH – CH
3); δ 1.05～1.86 (CH
2, CH
3).
Product rosinyl cyclic carbonate ester among the embodiment 1
13C NMR (500MHz, CDCl
3, δ ppm): δ 177.9,172.1,171.9 (carbonyl carbon); (154.7 cyclicarbonate carbon); δ 147.3,123.3 (– C=C –); δ 73.9 (methine carbons of cyclic carbonate); δ 66.0 (O – CH2 –); δ 63.3 (methylene carbons of cyclic carbonate); δ 55.7,53.8, and 49.3,47.3,40.9,37.5,36.5,34.5,32.3,30.5,28.2,21.6,21.1,20.2,19.5,17.4,16.7,16.5,15.5.
The infrared spectrogram of product rosinyl cyclic carbonate ester is seen accompanying drawing 1, IR:2932,2868cm among the embodiment 1
-1(CH
2, CH
3); 1791cm
-1(C=O); 1724cm
-1(C=O); 1457,1388cm
-1(CH
3, CH
2); 1161,1095,1049cm
-1(C – O – C).
Embodiment 2
In having the four-hole round-bottomed flask of agitator, thermometer and reflux condensing tube, add 40g rosinyl cyclic carbonate ester, 40mL ethanol, be warming up to 70 ℃ under stirring, treat the dissolving of rosinyl cyclic carbonate ester, drip the 11.5g dimethylaminopropylamine, TLC follows the tracks of reaction, reacts completely to cyclic carbonate ester.The underpressure distillation desolventizing, thick product gets the brown solid product, i.e. the rosinyl carbamate through ethanol/re-crystallizing in ethyl acetate purifying.
Product rosinyl carbamate among the embodiment 2
1H NMR (500MHz, CDCl
3, δ ppm): δ 5.37 (– C=CH –); δ 3.64～4.39 (O – CH
2–, CH – OH, CH
2– OH, O – CH); δ 3.14～3.36(N – CH
2–); δ 2.85～2.95 (CH – C=O); δ 2.54～2.65 (CH – CH
3); δ 2.21 (N – CH
3); δ 1.04～1.80 (CH
2, CH
3).
Product rosinyl carbamate among the embodiment 2
13C NMR (500MHz, CDCl
3, δ ppm): δ 178.5,173.3,172.1 (carbonyl carbon); (156.8 NH – CO); δ 148.3,123.6 (– C=C –); δ 62.5～72.5 (O – CH
2–, CH – OH, CH
2– OH); δ 56.7 (N – CH
2–); δ 45.1 (N – CH
3); δ 53.8,52.1, and 49.2,47.1,39.4,37.5,36.3,34.9,32.4,30.5,29.4,26.9,21.6,21.1,20.2,19.5,17.4,16.7,16.5,15.5.
The infrared spectrogram of product rosinyl carbamate (R-Ca) is seen accompanying drawing 2, IR:3338cm among the embodiment 2
-1(– OH); 2943,2866cm
-1(CH
2, CH
3); 1716cm
-1(C=O); 1530cm
-1(N – H); 1461,1385cm
-1(CH
3, CH
2); 1140cm
-1(N – C); 1101,1038cm
-1(C – O – C).
With a small amount of organic solvent dissolution of rosinyl carbamate of method for preparing, the ratio 1:1 by amount of substance mixes with bromo alkane, reacts 5～24h down at 60～100 ℃.Concrete grammar is seen embodiment 3～5.
Embodiment 3
In the four-hole boiling flask that thermometer, agitator, prolong are housed, add 20.0g rosinyl carbamate, 40mL ethanol, be stirred to dissolving fully, be warming up to 70 ℃, drip the 1.87g n-propyl bromide, back flow reaction 15h.The underpressure distillation desolventizing, thick product gets the dark brown solid product, i.e. n-propyl-Abietyl quaternary ammonium salt derivative through ethanol/re-crystallizing in ethyl acetate.
Product n-propyl-Abietyl quaternary ammonium salt derivative among the embodiment 3
1H NMR (500MHz, CDCl
3, δ ppm): δ 5.34 (– C=CH –); δ 3.45～4.30 (O – CH
2–, CH – OH, CH
2– OH, O – CH); δ 3.18～3.32 (NH – CH
2–); δ 3.05 (N
+– CH
3); δ 2.87～2.91 (N
+– CH
2); δ 2.79～2.85 (CH – C=O); δ 2.60～2.69 (N
+– CH
2); δ 2.48～2.58 (CH – CH
3); δ 0.90～1.98 (CH
2, CH
3).
Product n-propyl-Abietyl quaternary ammonium salt derivative among the embodiment 3
13C NMR (500MHz, CDCl
3, δ ppm): δ 178.2,173.6,172.7 (carbonyl carbon); (156.9 NH – CO); δ 147.7,123.9 (– C=C –); δ 61.6～72.5 (O – CH
2–, CH – OH, CH
2– OH, N
+– CH
2); δ 49.8 (N
+– CH
3); δ 55.3,49.4, and 48.2,42.8,37.4,36.6,35.4,34.5,32.3,30.2,28.4,25.7,22.9,21.5,20.2,19.4,17.1,16.5,16.0,15.6,9.6.
The infrared spectrogram of product among the embodiment 3 (QAS-a) n-propyl-Abietyl quaternary ammonium salt derivative is seen accompanying drawing 3, IR:3324cm
-1(– OH); 2944,2869cm
-1(CH
2, CH
3); 1712cm
-1(C=O); 1528cm
-1(N – H); 1461,1386cm
-1(CH
3, CH
2); 1177cm
-1(N
+– C); 1150cm
-1(N – C); 1103,1042cm
-1(C – O – C).
Embodiment 4
In the four-hole boiling flask that thermometer, agitator, prolong are housed, add 40.0g rosinyl carbamate, 40mL ethanol, be stirred to dissolving fully, be warming up to 70 ℃, Dropwise 5 .02g bromo normal hexane, back flow reaction 12h.The underpressure distillation desolventizing, thick product gets the dark brown solid product, i.e. n-hexyl-Abietyl quaternary ammonium salt derivative through ethanol/re-crystallizing in ethyl acetate.
Product n-hexyl-Abietyl quaternary ammonium salt derivative among the embodiment 4
1H NMR (500MHz, CDCl
3, δ ppm): δ 5.37 (– C=CH –); δ 3.48～4.27 (O – CH
2–, CH – OH, CH
2– OH, O – CH); δ 3.17～3.35 (NH – CH
2–); δ 3.08 (N
+– CH
3); δ 2.87～2.93 (N
+– CH
2); δ 2.75～2.83 (CH – C=O); δ 2.54～2.65 (N
+– CH
2); δ 2.36～2.43 (CH – CH
3); δ 0.91～1.99 (CH
2, CH
3).
Product n-hexyl-Abietyl quaternary ammonium salt derivative among the embodiment 4
13C NMR (500MHz, CDCl
3, δ ppm): δ 178.2,173.4,173.2 (carbonyl carbon); (156.8 NH – CO); δ 147.7,123.7 (– C=C –); δ 61.5～72.2 (O – CH
2–, CH – OH, CH
2– OH, N
+– CH
2); δ 49.6 (N
+– CH
3); δ 52.0,48.8, and 48.2,41.9,40.5,37.1,36.9,36.0,35.3,32.0,31.7,30.5,25.2,22.9,22.5,21.7,21.1,19.2,16.2,15.0,12.5.
The Infrared Characterization of product among the embodiment 4 (QAS-b) n-hexyl-rosinyl quaternary ammonium-salt derivative is seen accompanying drawing (4), IR:3338cm
-1(– OH); 2930,2868cm
-1(CH
2, CH
3); 1713cm
-1(C=O); 1531cm
-1(N – H); 1464,1386cm
-1(CH
3, CH
2); 1177cm
-1(N
+– C); 1149cm
-1(N – C); 1104,1039cm
-1(C – O – C).
Embodiment 5
In the four-hole boiling flask that thermometer, agitator, prolong are housed, add 30.0g rosinyl carbamate, 40mL ethanol, be stirred to dissolving fully, be warming up to 75 ℃, Dropwise 5 .69g bromo n-dodecane, back flow reaction 17h.The underpressure distillation desolventizing, ethanol/re-crystallizing in ethyl acetate gets the dark brown solid product, i.e. dodecyl-Abietyl quaternary ammonium salt derivative.
Product dodecyl among the embodiment 5-Abietyl quaternary ammonium salt derivative (QAS-c)
1HNMR (500MHz, CDCl
3, δ ppm): δ 5.39 (– C=CH –); δ 3.58～4.33 (O – CH
2–, CH – OH, CH
2– OH, O – CH); δ 3.24～3.37 (NH – CH
2–); δ 3.13 (N
+– CH
3); δ 2.85～2.94 (N
+– CH
2); δ 2.73～2.83 (CH – C=O); δ 2.51～2.62 (N
+– CH
2); δ 2.36～2.42 (CH – CH
3); δ 0.89～2.00 (CH
2, CH
3).
Product dodecyl-Abietyl quaternary ammonium salt derivative among the embodiment 5
13C NMR (500MHz, CDCl
3, δ ppm): δ 178.2,173.4,172.8 (carbonyl carbon); (156.8 NH – CO); δ 147.6,124.0 (– C=C –); δ 61.5～72.5 (O – CH
2–, CH – OH, CH
2– OH, N
+– CH
2); δ 49.8 (N
+– CH
3); δ 52.1,48.8, and 48.2,42.0,37.1,36.2,35.3,34.2,32.1,31.3,29.0,28.9,28.7,28.5,25.7,22.6,22.0,21.8,21.2,20.1,19.3,16.4,15.7,15.0,12.8.
The infrared spectrogram of product dodecyl-Abietyl quaternary ammonium salt derivative is seen accompanying drawing 5, IR:3329cm among the embodiment 5
-1(– OH); 2923,2853cm
-1(CH
2, CH
3); 1715cm
-1(C=O); 1530cm
-1(N – H); 1465,1386cm
-1(CH
3, CH
2); 1177cm
-1(N
+– C); 1150cm
-1(N – C); 1103,1038cm
-1(C – O – C).
Embodiment 6
The anti-microbial property test of rosinyl carbamate and quaternary ammonium salt antibiotic derivative thereof: the 1. preparation of bacteria suspension: four kinds of experiments such as staphylococcus aureus, intestinal bacteria, subtilis and bacillus thuringiensis are inoculated on the beef-protein medium inclined-plane with bacterium, 37 ℃ of activation 24h, streptomyces microflavus is inoculated on the Gao Shi I medium slant, 28 ℃ of activation 3d, respectively each bacterial classification of picking is in right amount in sterilized water with transfering loop then, and the bacterial classification concentration that makes bacteria suspension is 10
5～10
6CFU/mL.2. the preparation of filter paper and processing: prepare the filter paper dick of some amount diameter 5.0mm with punch tool, 121 ℃ of rearmounted oven for drying of sterilization 20min are standby.Getting the filter paper of sterilization back oven dry with aseptic nipper, be immersed in 12h in the testing compound solution of various different concns respectively, is blank simultaneously with the coordinative solvent.With the ultraviolet 30min that sterilizes.30min drains before using.3. adopt the filter paper method that compound is carried out the bacteriostatic activity test: under the aseptic technique, drawing bacteria suspension 0.1mL with aseptic straw drips on corresponding plate culture medium surface, smearing even back with spreading rod places the filter paper that will be immersed in behind the 30min in the different solutions and is attached to every ware and contains on the bacterium flat board, 5 filter paper of every ware, evenly distribute, behind staphylococcus aureus, intestinal bacteria, subtilis and 37 ℃ of constant temperature culture 24h of bacillus thuringiensis, 28 ℃ of constant temperature culture 3d of streptomyces microflavus, measure its antibacterial circle diameter with the right-angled intersection method, relatively fungistatic effect.More than experiment repeats twice, data average (seeing Table 1).
The antibacterial circle diameter of table 1 rosinyl carbamate and quaternary ammonium salt derivative thereof (mm)
Wherein, QAS-a is n-propyl-Abietyl quaternary ammonium salt; QAS-b is n-hexyl-Abietyl quaternary ammonium salt; QAS-c is dodecyl-Abietyl quaternary ammonium salt; R-Ca is the rosinyl carbamate.
Rosinyl carbamate and quaternary ammonium salt derivative thereof that the present invention is prepared all have better antibacterial activity to staphylococcus aureus, intestinal bacteria, subtilis, bacillus thuringiensis and streptomyces microflavus.
Claims (9)
1. a rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof is characterized in that:
The structural formula of described rosinyl cyclic carbonate ester is:
The structural formula of described rosinyl carbamate is:
The structural formula of described Abietyl quaternary ammonium salt antibiotic derivative is:
N=2～5, m=2～22.
2. prepare the method for the described rosinyl cyclic carbonate ester of claim 1 and quaternary ammonium salt antibiotic derivative thereof, it is characterized in that: described rosinyl cyclic carbonate ester is with maleopimaric acid Resins, epoxy and CO
2Prepared in reaction under the effect of catalyzer, reaction formula is:
3. the method for preparing rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof as claimed in claim 2 is characterized in that: reaction is with N-Methyl pyrrolidone or N, and dinethylformamide is solvent, feeds CO in closed reactor
2To pressure be 0.5～5MPa, 80～150 ℃ the reaction 2～24h.
4. the method for preparing rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof as claimed in claim 2, it is characterized in that: described catalyzer is to be that Primary Catalysts, adjacent glycols compound are the compound system of promotor with the metal halide, and the mass ratio of metal halide and adjacent glycols compound is 1:0.1～1:2; Wherein, described metal halide is a kind of in lithiumbromide, lithium chloride, potassiumiodide, Potassium Bromide, the zinc bromide, and consumption is 0.1～5% of maleopimaric acid Resins, epoxy quality; Described adjacent glycols compound is ethylene glycol, 1,2-propylene glycol, a kind of in 1, the 2-butyleneglycol.
5. prepare the method for the described rosinyl cyclic carbonate ester of claim 1 and quaternary ammonium salt antibiotic derivative thereof, it is characterized in that: described rosinyl carbamate is prepared in reaction in organic solvent with rosinyl cyclic carbonate ester and amino-complex, and reaction formula is:
6. the method for preparing rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof as claimed in claim 5, it is characterized in that: described amino-complex is (CH
3)
2NR
1NH
2, wherein, R
1Be C
2～C
5Alkyl; Described temperature of reaction is 25～100 ℃, reaction times 2～8h; Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, the tetrahydrofuran (THF).
7. as claim 5 or the 6 described methods that prepare rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof, it is characterized in that: described amino-complex is N, any in N-dimethylamino quadrol, dimethylaminopropylamine or the 4-dimethylamino butylamine.
8. the method for preparing the described rosinyl cyclic carbonate ester of claim 1 and quaternary ammonium salt antibiotic derivative thereof, it is characterized in that: described Abietyl quaternary ammonium salt antibiotic derivative is prepared in reaction in organic solvent with rosinyl carbamate and bromo alkane, and reaction formula is:
N=2～5, m=2～22.
9. the method for preparing rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof as claimed in claim 8, it is characterized in that: described bromo alkane is C
2～C
22Bromo alkane, temperature of reaction is 60～100 ℃, the reaction times is 5～24h; Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, ethyl acetate, tetrahydrofuran (THF), benzene, the toluene.
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| CN201410547344.4A CN104370774B (en) | 2013-06-05 | 2013-06-05 | A kind of rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104645874A (en) * | 2015-02-05 | 2015-05-27 | 中国林业科学研究院林产化学工业研究所 | Rosin-based choline quaternary ammonium salt surfactant and preparation method thereof |
| CN105061388A (en) * | 2015-08-04 | 2015-11-18 | 中国林业科学研究院林产化学工业研究所 | Gallate base cyclic carbonate, non-isocyanate polyurethane and preparation method thereof |
| CN105504272A (en) * | 2016-01-22 | 2016-04-20 | 中国林业科学研究院林产化学工业研究所 | POSS modified rosin nonisocyanate polyurethane and preparation method of nonisocyanate polyurethane |
| CN115260046A (en) * | 2022-08-22 | 2022-11-01 | 贵州大学 | Abietate compound and preparation method and application thereof |
| CN115417970A (en) * | 2022-09-21 | 2022-12-02 | 中国林业科学研究院林产化学工业研究所 | Transparent rosin-based self-repairing polyurethane elastomer and synthesis method and application thereof |
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| CN103113552B (en) * | 2013-01-22 | 2015-02-25 | 中国科学院宁波材料技术与工程研究所 | Rosin-based chain extender and preparation method thereof |
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| CN101249400A (en) * | 2008-04-09 | 2008-08-27 | 广西大学 | Maleated rosin based quaternaries cation surface active agent and method of preparing the same |
| CN101914029A (en) * | 2010-06-03 | 2010-12-15 | 东北林业大学 | Preparation method of rosin-based Gemini surface active agent |
| CN102206324A (en) * | 2011-03-29 | 2011-10-05 | 中国科学院宁波材料技术与工程研究所 | Full-biobased epoxy resin composition and condensate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104645874A (en) * | 2015-02-05 | 2015-05-27 | 中国林业科学研究院林产化学工业研究所 | Rosin-based choline quaternary ammonium salt surfactant and preparation method thereof |
| CN105061388A (en) * | 2015-08-04 | 2015-11-18 | 中国林业科学研究院林产化学工业研究所 | Gallate base cyclic carbonate, non-isocyanate polyurethane and preparation method thereof |
| CN105504272A (en) * | 2016-01-22 | 2016-04-20 | 中国林业科学研究院林产化学工业研究所 | POSS modified rosin nonisocyanate polyurethane and preparation method of nonisocyanate polyurethane |
| CN115260046A (en) * | 2022-08-22 | 2022-11-01 | 贵州大学 | Abietate compound and preparation method and application thereof |
| CN115417970A (en) * | 2022-09-21 | 2022-12-02 | 中国林业科学研究院林产化学工业研究所 | Transparent rosin-based self-repairing polyurethane elastomer and synthesis method and application thereof |
| CN115417970B (en) * | 2022-09-21 | 2024-05-24 | 中国林业科学研究院林产化学工业研究所 | Transparent rosin-based self-repairing polyurethane elastomer and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
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| CN104370774A (en) | 2015-02-25 |
| CN103304534B (en) | 2014-12-10 |
| CN104370773B (en) | 2016-01-20 |
| CN104370773A (en) | 2015-02-25 |
| CN104370774B (en) | 2016-01-20 |
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