CN104370774A - Rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof - Google Patents
Rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof Download PDFInfo
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- CN104370774A CN104370774A CN201410547344.4A CN201410547344A CN104370774A CN 104370774 A CN104370774 A CN 104370774A CN 201410547344 A CN201410547344 A CN 201410547344A CN 104370774 A CN104370774 A CN 104370774A
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- rosinyl
- carbamate
- ammonium salt
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- salt derivative
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- 0 CC(C1(C2CC3C(C)(CCC4)C(CC5)C4(C)C(O*C(*O4)OC4=O)=O)C(OC)=O)C2=CC35C1C(O*C(CO1)OC1=O)=O Chemical compound CC(C1(C2CC3C(C)(CCC4)C(CC5)C4(C)C(O*C(*O4)OC4=O)=O)C(OC)=O)C2=CC35C1C(O*C(CO1)OC1=O)=O 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N CC(CO1)OC1=O Chemical compound CC(CO1)OC1=O RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a rosinyl carbamate quaternary ammonium salt derivative and a preparation method thereof. According to the method, maleopimaric acid epoxy resin is subjected to a reaction with CO2 under the action of a catalyst to synthesize rosinyl cyclic carbonate, the rosinyl cyclic carbonate is subjected to a reaction with an amine compound to prepare rosinyl carbamate, and further, the novel rosinyl quaternary ammonium salt derivative containing the carbamate group is obtained by a quaternization reaction. The rosinyl carbamate quaternary ammonium salt derivative prepared by the method is low in raw material cost, wide in source, and safe and non-toxic in preparation process; and because the carbamate polar group having an antibacterial activity is introduced into a molecular structure, the rosinyl carbamate quaternary ammonium salt derivative has good water solubility, good biocompatibility and excellent antibacterial and bactericidal properties, and can be used in the fields of antibacterial agents, bactericidal agents and the like.
Description
The divisional application that the present invention is application number 201310222679.4, name is called the application of " preparation method of a kind of rosinyl cyclic carbonate ester and quaternary ammonium salt antibiotic derivative thereof ".
Technical field
The invention discloses a kind of rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof, particularly relate to and a kind ofly react with rosinyl carbamate and brominated alkanes the method preparing rosinyl carbamate quaternary ammonium salt derivative.
Background technology
Rosin is a kind of important natural resource, and have biodegradable, renewable and wide material sources, lower-price characteristic, its main component is resinous acid, containing groups such as triatomic ring luxuriant and rich with fragrance skeleton, double bond and carboxylic acids in molecular structure.By to rosin chemical structure modification, dissimilar derivative can be prepared.Wherein, rosinyl cationic quaternary compound is subject to extensive concern because of the advantage such as low toxicity, nonirritant and good emulsifying power, inhibition power, antibacterial and fungicidal activity.But traditional quarternary ammonium salt compound difficult degradation, easily cause environmental pollution.Now there are some researches show, in quaternary ammonium salt molecular structure, introduce ether, ester, acid amides, carbamate and hydroxyl isopolarity functional group can improve the water-soluble of compound and biological degradability effectively, makes that it is more green, environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of rosinyl carbamate quaternary ammonium salt derivative and preparation method thereof.
The present invention is by the following technical solutions: a kind of rosinyl carbamate quaternary ammonium salt derivative, and its structural formula is:
n＝2～5，m＝2～22。
Described rosinyl carbamate quaternary ammonium salt derivative reacts preparation in organic solvent with rosinyl carbamate and brominated alkanes, and reaction formula is:
Described brominated alkanes is for containing C
2~ C
22the brominated alkanes of alkyl.
Described temperature of reaction is 60 ~ 100 DEG C, and the reaction times is 5 ~ 24h.
Beneficial effect of the present invention:
1. the present invention with renewable resources rosin for raw material prepares biomass-based cyclic carbonate ester, carbamate and quaternary ammonium salt derivative thereof, raw materials cost is low, wide material sources, safe preparation process, nontoxic, and the cyclic carbonate ester of preparation, rosinyl carbamate and quaternary ammonium salt derivative thereof have biodegradability, environmental friendliness.
2. the rosinyl carbamate quaternary ammonium salt derivative prepared of the present invention, because introducing the carbamate polar group with anti-microbial activity in molecular structure, thus has antibacterial, the bactericidal property of well water-soluble, biocompatibility and excellence.
Accompanying drawing explanation
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-rosinyl carboxylamine ester quat (QAS-a).
The infrared spectrogram of Fig. 4 n-hexyl-rosinyl carboxylamine ester quat (QAS-b).
The infrared spectrogram of Fig. 5 dodecyl-rosinyl carboxylamine ester quat (QAS-c).
Embodiment
Maleopimaric acid epoxy resin of the present invention presses the method preparation in reference (thermosetting resin, 1996,11 (2), 19-22.).
The preparation method of a kind of rosinyl cyclic carbonate ester and carbamate quaternary ammonium salt derivative thereof.
The method is realized by following steps:
The first step, in autoclave, is dissolved in a certain amount of N-Methyl pyrrolidone or DMF by the maleopimaric acid epoxy resin of certain mass and catalyzer, passes into CO after sealing
2be 0.5 ~ 5MPa to pressure, prepare rosinyl cyclic carbonate ester at 80 ~ 150 DEG C of reaction 2 ~ 24h, reaction as shown in Equation 1.
Described catalyzer is the compound system of metal halide/vicinal diamines compounds, and the mass ratio of metal halide and vicinal diamines compounds 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 one, consumption is 0.1 ~ 5% of maleopimaric acid epoxy resin quality; Vicinal diamines compounds is ethylene glycol, 1,2-PD, 1,2-butyleneglycol etc.; Described reaction pressure the best is 2MPa, and temperature of reaction the best is 120 DEG C, and reaction times the best is 7h.
Second step, is dissolved in a small amount of organic solvent by rosinyl cyclic carbonate ester, and mixes with the ratio 1:1 of amino-complex by amount of substance, and at 25 ~ 100 DEG C, react 2 ~ 8h prepare rosinyl carbamate, reaction as shown in Equation 2.
Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, tetrahydrofuran (THF); Described amino-complex is (CH
3)
2nR
1nH
2, wherein, R
1for C
2~ C
5alkyl; As N, N-dimethylamino quadrol, dimethylaminopropylamine, 4-dimethylamino butylamine etc.; Described temperature of reaction is 25 ~ 100 DEG C, reaction times 2 ~ 8h; Described temperature of reaction the best is 70 DEG C, and reaction times the best is 2h.
3rd step, is dissolved in a small amount of organic solvent by rosinyl carbamate, and mixes than 1:1 by amount of substance with brominated alkanes, and at 60 ~ 100 DEG C, react 5 ~ 24h prepare rosinyl carbamate quaternary ammonium salt derivative, reaction as shown in Equation 3.
Described organic solvent is any one in methyl alcohol, ethanol, sherwood oil, acetone, cyclobutanone, ethyl acetate, tetrahydrofuran (THF); Described brominated alkanes is for containing C
2~ C
22the bromo alkyl of alkyl, more preferably containing C
2~ C
16the bromo alkyl of alkyl, as n-propyl bromide, bromo normal hexane, bromododecane, bromohexadecane, isobutane bromide, bromo-iso-octane etc.; Described temperature of reaction the best is 70 DEG C, and reaction times the best is 12h.
Embodiment 1
In 1L autoclave, add 200g maleopimaric acid epoxy resin, 2g lithiumbromide, 1g ethylene glycol and 70mLN-methyl-2-pyrrolidone (NMP), be warming up to 120 DEG C, pass into CO2 to certain pressure, emptying after leak detection.Repetitive operation three times, thoroughly gets rid of air in still, passes into CO
2keep pressure at 2MPa, stirring reaction 7h.After having reacted, remaining CO in emptying still
2, poured out while hot by product, with hot wash removing catalyzer and NMP, underpressure distillation removing moisture obtains rosinyl cyclic carbonate ester (R-C).The oxirane value of assay products, obtaining its epoxy group(ing) transformation efficiency is 98.6%.
Product rosinyl cyclic carbonate ester (R-C) in embodiment 1
1h NMR (500MHz, CDCl
3, δ ppm): δ 5.37 (– C=CH –); δ 4.87 ~ 5.08 (methine hydrogens of cyclic carbonategroup); δ 4.02 ~ 4.23 (methylene hydrogens of cyclic carbonate group); δ 4.26 ~ 4.65 (O – CH2 –); 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 in embodiment 1
13c NMR (500MHz, CDCl
3, δ ppm): δ 177.9,172.1,171.9 (carbonylcarbon); 154.7 (cyclicarbonate carbon); δ 147.3,123.3 (– C=C –); δ 73.9 (methine carbons of cyclic carbonate); δ 66.0 (O – CH
2–); δ 63.3 (methylenecarbons of cyclic carbonate); δ 55.7,53.8,49.3,47.3,40.9,37.5,36.5,34.5,32.3,30.5,28.2,21.6,21.1,20.2,19.5,17.4,16.7,16.5,15.5.
In embodiment 1, the infrared spectra of product rosinyl cyclic carbonate ester (R-C) is shown in accompanying drawing 1, IR:2932,2868cm
-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
With in four mouthfuls of round-bottomed flasks of agitator, thermometer and reflux condensing tube, add 40g rosinyl cyclic carbonate ester, 40mL ethanol, under stirring, be warming up to 70 DEG C, treat that rosinyl cyclic carbonate ester dissolves, drip 11.5g dimethylaminopropylamine, TLC follows the tracks of reaction, reacts completely to cyclic carbonate ester.Underpressure distillation is except desolventizing, and thick product, through ethanol/re-crystallizing in ethyl acetate purifying, obtains brown solid, i.e. rosinyl carbamate (R-Ca).
Product rosinyl carbamate (R-Ca) in 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 (R-Ca) in 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 53.8,52.1,49.2,47.1,39.4,37.5,36.3,34.9,32.4,30.5,29.4,26.9,21.6,21.1,20.2,19.5,17.4,16.7,16.5,15.5.
In embodiment 2, the infrared spectra of product rosinyl carbamate (R-Ca) is shown in accompanying drawing 2, IR:3338cm
-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).
The a small amount of organic solvent dissolution of rosinyl carbamate prepared by aforesaid method, mixes with the ratio 1:1 of brominated alkanes by amount of substance, at 60 ~ 100 DEG C, react 5 ~ 24h.Concrete grammar is shown in 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 and dissolve completely, be warming up to 70 DEG C, drip 1.87g n-propyl bromide, back flow reaction 15h.Underpressure distillation is except desolventizing, and thick product, through ethanol/re-crystallizing in ethyl acetate, obtains dark brown solid product, i.e. n-propyl-rosinyl carboxylamine ester quat (QAS-a).
Product n-propyl in embodiment 3-rosinyl carboxylamine ester quat (QAS-a)
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 in embodiment 3-rosinyl carboxylamine ester quat (QAS-a)
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 55.3,49.4,48.2,42.8,37.4,36.6,35.4,34.5,32.3,30.2,28.4,25.7,22.9,21.5,20.2,19.4,17.1,16.5,16.0,15.6,9.6.
The infrared spectra of product (QAS-a) n-propyl in embodiment 3-rosinyl carboxylamine ester quat (QAS-a) is shown in 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 and dissolve completely, be warming up to 70 DEG C, drip 5.02g bromo normal hexane, back flow reaction 12h.Underpressure distillation is except desolventizing, and thick product, through ethanol/re-crystallizing in ethyl acetate, obtains dark brown solid product, i.e. n-hexyl-rosinyl carboxylamine ester quat (QAS-b).
Product n-hexyl in embodiment 4-rosinyl carboxylamine ester quat (QAS-b)
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 in embodiment 4-rosinyl carboxylamine ester quat (QAS-b)
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 52.0,48.8,48.2,41.9,40.5,37.1,36.9,36.0,35.3,32.0,31.7,30.5,25.2,22.9,22.5,21.7,21.1,19.2,16.2,15.0,12.5.
The infrared spectra of product (QAS-b) n-hexyl in embodiment 4-rosinyl carboxylamine ester quat (QAS-b) is shown in 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 and dissolve completely, be warming up to 75 DEG C, drip 5.69g N-dodeeyl bromide, back flow reaction 17h.Underpressure distillation is except desolventizing, and ethanol/re-crystallizing in ethyl acetate, obtains dark brown solid product, i.e. dodecyl-rosinyl carboxylamine ester quat (QAS-c).
Product dodecyl in embodiment 5-rosinyl carboxylamine ester quat (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 in embodiment 5-rosinyl carboxylamine ester quat (QAS-c)
13cNMR (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 52.1,48.8,48.2,42.0,37.1,36.2,35.3,34.2,32.1,31.3,29.0,28.9,28.7,28.5,25.7,22.6,22.0,21.8,21.2,20.1,19.3,16.4,15.7,15.0,12.8.
In embodiment 5, the infrared spectra of product dodecyl-Abietyl quaternary ammonium salt (QAS-c) is shown in accompanying drawing 5, IR:3329cm
-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 beef-protein medium inclined-plane with bacterium, 37 DEG C of activation 24h, streptomyces microflavus is inoculated in Gao Shi I medium slant, 28 DEG C of activation 3d, then distinguish each bacterial classification of picking in right amount in sterilized water with transfering loop, make the bacterial classification concentration of bacteria suspension be 10
5~ 10
6cFU/mL.2. the preparation of filter paper and process: the filter paper dick preparing some amount diameter 5.0mm with punch tool, 121 DEG C of rearmounted oven for drying of sterilizing 20min are for subsequent use.Getting the filter paper of sterilizing post-drying with aseptic nipper, be immersed in 12h in the testing compound solution of various different concns respectively, is simultaneously blank with coordinative solvent.Use ultraviolet sterilization 30min.Front 30min is used to drain.3. filter paper enzyme is adopted to carry out bacteriostatic activity test to compound: under aseptic technique, draw bacteria suspension 0.1mL with aseptic straw to drip at corresponding slat chain conveyor primary surface, smear evenly with spreading rod and after placement 30min, the filter paper be immersed in different solutions is attached to every ware containing on bacterium flat board, every ware 5 filter paper, be uniformly distributed, after staphylococcus aureus, intestinal bacteria, subtilis and bacillus thuringiensis 37 DEG C of constant temperature culture 24h, streptomyces microflavus 28 DEG C of constant temperature culture 3d, measure its antibacterial circle diameter with right-angled intersection method, compare fungistatic effect.More than test repetition twice, data average (see table 1).
The antibacterial circle diameter (mm) of table 1 rosinyl carbamate and quaternary ammonium salt derivative thereof
Wherein, QAS-a is n-propyl-rosinyl carboxylamine ester quat; QAS-b is n-hexyl-rosinyl carboxylamine ester quat; QAS-c is dodecyl-rosinyl carboxylamine ester quat; R-Ca is rosinyl carbamate.
Rosinyl carbamate prepared by the present invention and quaternary ammonium salt derivative thereof all have good anti-microbial activity to staphylococcus aureus, intestinal bacteria, subtilis, bacillus thuringiensis and streptomyces microflavus.
Claims (3)
1. a rosinyl carbamate quaternary ammonium salt derivative, is characterized in that: the structural formula of rosinyl carbamate quaternary ammonium salt derivative is:
2. prepare the method for rosinyl carbamate quaternary ammonium salt derivative according to claim 1, it is characterized in that: described rosinyl carbamate quaternary ammonium salt derivative reacts preparation in organic solvent with rosinyl carbamate and brominated alkanes, and reaction formula is:
3. prepare the method for rosinyl carbamate quaternary ammonium salt derivative as claimed in claim 2, it is characterized in that: described brominated alkanes is C
2~ C
22brominated alkanes, temperature of reaction is 60 ~ 100 DEG C, and the reaction times is 5 ~ 24h; Described organic solvent is any one in sherwood oil, methyl alcohol, ethanol, acetone, ethyl acetate, tetrahydrofuran (THF), benzene, toluene.
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| CN201410547344.4A Expired - Fee Related 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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| 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 |
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| CN104645874B (en) * | 2015-02-05 | 2017-03-15 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl choline quaternary surfactant and preparation method thereof |
| CN105061388B (en) * | 2015-08-04 | 2017-06-23 | 中国林业科学研究院林产化学工业研究所 | A kind of gallic acid basic ring carbonic ester, non-isocyanate polyurethane and preparation method thereof |
| CN115260046B (en) * | 2022-08-22 | 2023-06-27 | 贵州大学 | Rosin acid ester compound and preparation 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 |
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| EP0599265A1 (en) * | 1992-11-24 | 1994-06-01 | Takeda Chemical Industries, Ltd. | Antibacterial, antifungal compound and its production method |
| US20040236119A1 (en) * | 2003-04-24 | 2004-11-25 | Jurgen Van Holen | Process using a cyclic carbonate reactant and beta-hydroxyurethanes thereby obtained |
| CN1796435A (en) * | 2004-12-22 | 2006-07-05 | 中国科学院化学研究所 | Modified butanediol ester poly succinic acid and synthetic method |
| CN103113552A (en) * | 2013-01-22 | 2013-05-22 | 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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| CN101249400B (en) * | 2008-04-09 | 2011-07-20 | 广西大学 | Maleated rosin based quaternaries cation surface active agent and method of preparing the same |
| CN101914029B (en) * | 2010-06-03 | 2013-07-03 | 东北林业大学 | Preparation method of rosin-based Gemini surface active agent |
| CN102206324B (en) * | 2011-03-29 | 2012-12-12 | 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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2013
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| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104370773A (en) | 2015-02-25 |
| CN103304534B (en) | 2014-12-10 |
| CN104370774B (en) | 2016-01-20 |
| CN104370773B (en) | 2016-01-20 |
| CN103304534A (en) | 2013-09-18 |
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