CN1861722A - Process of preparing ester from rosin and acrylate - Google Patents
Process of preparing ester from rosin and acrylate Download PDFInfo
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- CN1861722A CN1861722A CN 200610085332 CN200610085332A CN1861722A CN 1861722 A CN1861722 A CN 1861722A CN 200610085332 CN200610085332 CN 200610085332 CN 200610085332 A CN200610085332 A CN 200610085332A CN 1861722 A CN1861722 A CN 1861722A
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Abstract
A process to make the ester with the rosin and the acrylate includes: first the rosin is dissolved in the benzol and react with the acyl reagent for 3h under 50DEG C to change the carboxyl into the acyl chloride; second the rosin acyl chloride react with the acrylate for 3h under 50DEG C to get the rosin ester. The percent conversion of the acrylate can reach above 90%, the reactive byproduct is also the important chemical material; the rosin ester has the good polymeric activeness, so it can be used for composing the high molecular polymer to improve the heat and chemical resistance.
Description
Technical field
The present invention relates to a kind of method of producing ester by rosin and acrylate.
Technical background
Rosin has many excellent characteristic, as anticorrosion, moistureproof, insulation, bonding, emulsification, softening etc.Before 1700 in the Shennong's Herbal with rosin as drug use.According to statistics, the rosin purposes has kind more than 400.Since the nearly century, rosin and deep processing modified product thereof are widely used in many fields such as coating, tackiness agent, printing ink, papermaking, rubber, foodstuff additive and biological products.The rosiny chemistry utilizes by directly utilizing rosin mixture primary products to utilize the special-purpose tandem product direction of the pure product exploitation of rosin derivative to develop to the degree of depth.The Abietyl modified application performance that not only can improve product, the while also can be improved the added value of rosin resource, is devoted to rosin chemical modification utilization research both at home and abroad always.
Ternary phenanthrene ring structure in the rosin molecular skeleton has certain rigid, if can be incorporated into resistance toheat and the chemical resistance that removes to improve effectively polymkeric substance in the polymer to it.Acrylic ester polymer is a kind of range of application polymkeric substance very widely, as organic glass (polymethylmethacrylate), Pressure sensitive adhesive tape (multipolymer of butyl acrylate-Isooctyl acrylate monomer-methyl methacrylate).Rosin is applied in the acrylic ester polymer as tackifying resin usually and goes, but this only is a kind of mechanical blending, and the two fails to realize chemical bonding, As time goes on, it is bad that the performance of blend can become, and this blend and underuse characteristics on the rosin molecular structure.If can might successfully be implemented in the purpose of introducing rosin ternary phenanthrene ring structure on the macromolecular chain connecting polymerisable group by the chemical bonding effect on the rosin molecular skeleton.
Rosin is the mixture of a series of resinous acids, and comprise main the composition such as pimaric acid, isopimaric acid, palustric acid, abietic acid, neoabietic acid, dehydroabietic acid etc.They all contain two keys (conjugation or non-conjugated) of a ternary phenanthrene ring frame, carboxyl side group and different loci and quantity.Rosin has multiple common derivative on the basis of not destroying the rosin molecular skeleton, as staybelite, nilox resin, maleated rosin, acrylic acid rosin etc.
Carboxyl in the rosin acid, the same with other monocarboxylic acid, can generate corresponding ester class with multiple alcohols reaction.But because carboxyl is positioned on the tertiary carbon atom, have bigger sterically hinderedly, making it esterification needs higher or than the reaction conditions that causes that generally esterification is more fierce.The principal item of rosin ester is rosin monobasic alcohol ester, rosin binary alcohol esters, rosin triol ester and rosin quaternary alcohol ester.Their synthetic method is in the rosin fusion and has under the condition of catalyzer, generates corresponding rosin ester class with alcohols (more than 250 ℃) direct esterification at high temperature.Esterification of rosin esterification is a balanced reaction, need improve temperature of reaction and vacuumize the water of removing the reaction generation in the reaction later stage and carry out to impel reaction forward.
Because acrylate is thermopolymerization easily at high temperature, so this patent can not adopt above-mentioned enzymatic synthesis condition.
When adopting elder generation that rosin is carried out this gentle relatively reaction conditions of chloride resterification, can avoid the auto-polymerization of acrylate and the generation of other unfavorable side reaction.
Rosin, staybelite, nilox resin, maleated rosin and acylting agent are carried out acyl chloride reaction; generate chloride compounds; again with the esters of acrylic acid reaction that contains hydroxyl; on the rosin molecular skeleton, introduce acrylate group, just can contain the macromole of ternary phenanthrene ring (rosin group) structure with a series of incompatible preparation of compound copolymerization that contains two keys.
Summary of the invention
The invention provides a kind of thermopolymerization that can avoid acrylate, simple to operate and cheap for manufacturing cost produce the method for ester by rosin and acrylate, the polymkeric substance that the ester copolymerization that is made by the present invention forms has the advantage of good heat resistance.
The present invention adopts following technical scheme:
The first step: the rosiny acyl chloride reaction is dissolved in the rosin of 100 parts of quality in the benzene solvent of 10-500 part quality, the acylting agent of 1-70 part quality is dissolved in the benzene solvent of 1-70 part quality, the acylting agent drips of solution is added to mixing and stirring in the rosin solution, reaction times 1-6 hour, temperature of reaction maintains between 30 ℃-80 ℃, this reaction makes the carboxyl in the rosin be converted into acid chloride groups, above-mentioned solution is filtered to remove impurity, benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the rosin acyl chlorides thus;
Second step: the rosin acyl chlorides of 100 parts of quality that the esterification of rosin acyl chlorides will make is dissolved in the benzene solvent of 10-500 part quality, the acrylate that contains hydroxyl of 1-60 part quality is added drop-wise to mixes in the rosin solution of acid chloride and stir; Reaction times 1-6 hour, temperature of reaction maintained between 30 ℃-80 ℃, and this reaction makes acyl chlorides and hydroxyl reaction generate ester group, and benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares rosin (acrylate) ester thus.
The synthetic route chart of nilox resin (vinylformic acid-2-hydroxyethyl ester) ester
Ultimate principle of the present invention: the ternary phenanthrene ring structure in the rosin molecular skeleton has certain rigid, if can be incorporated into resistance toheat and the chemical resistance that removes to improve effectively polymkeric substance in the polymer to it.Acrylic ester polymer is a kind of range of application polymkeric substance very widely, rosin is applied in the acrylic ester polymer as tackifying resin usually and goes, but this only is a kind of mechanical blending, the two fails to realize chemical bonding, As time goes on, it is bad that the performance of blend can become, and this blend and underuse the rosin characteristics of molecular structure.If can might successfully be implemented in the purpose of introducing rosin ternary phenanthrene ring structure on the macromolecular chain connecting polymerisable group by the chemical bonding effect on the rosin molecular skeleton.Rosin and acylting agent are carried out acyl chloride reaction; generate chloride compounds; again with the acrylate generation esterification that contains hydroxyl; can on the rosin molecular skeleton, introduce the group (acrylate or methacrylate based group) of free redical polymerization, promptly can obtain containing the acrylic ester polymer of ternary phenanthrene ring structure afterwards with a series of compound copolymerization that contains two keys.Be the reaction mechanism of nilox resin and Hydroxyethyl acrylate prepared in reaction nilox resin (vinylformic acid-2-hydroxyethyl ester) ester shown in the last figure.The first step reaction is that resinous acid and the phosphorus trichloride reaction in the nilox resin generates corresponding resinous acid acyl chlorides, and this reaction is quantitatively carried out; The reaction of second step is that resinous acid acyl chlorides and vinylformic acid-2-hydroxyethyl ester carry out esterification, generates the product of expection, i.e. nilox resin (2-Hydroxy ethyl acrylate) ester.
The rosin that uses among the present invention is a kind of in gum resin, staybelite, nilox resin, the maleated rosin.
Rosiny acyl chloride reaction of the present invention, acylting agent are a kind of in phosphorus trichloride, phosphorus pentachloride or the thionyl chloride.
The esterification of rosin acyl chlorides of the present invention, the acrylate that is adopted are the esters of acrylic acid that contains hydroxyl.
Rosiny acyl chloride reaction of the present invention, solvent account for about the 10-90% of whole system, and rosin carries out acyl chloride reaction with acylting agent under different temperature, reaction times, seek best acylting agent and reaction conditions; With acrylate that contains hydroxyl or methacrylic ester reaction, generate the esterification products of rosin acyl chlorides afterwards.
Compare with the technology of preparing of existing rosin ester, have the following advantages:
1. the present invention can avoid the thermopolymerization of esters of acrylic acid fully, and the transformation efficiency of acrylate is reached more than 90%.
2. step of the present invention is few, simple to operate, and byproduct of reaction phosphorous acid, hydrogenchloride etc. are important chemical material, and economic benefit is good.
3. raw material used in the present invention is gum resin, staybelite, nilox resin, maleated rosin etc., and raw material is cheap and easy to get, and product has higher added value.
4. the present invention adopts benzene solvent, and its solubility property is good, and no coupling product generates, and reaction can the underpressure distillation recycling after finishing.
5. acylting agent used in the present invention is phosphorus trichloride, phosphorus pentachloride or thionyl chloride, reacts completely, and by product is easy to remove or reclaims, and pollutes for a short time, and product postprocessing is simple.
6. acrylate used in the present invention is acrylate or the methacrylic ester that contains hydroxyl.The acrylate group radical polymerization that contains in the product active higher is easy to generate the macromole that contains ternary phenanthrene ring with other monomer (vinylbenzene, methyl methacrylate etc.) copolymerization.
Rosin (acrylate) ester of the present invention preparation has excellent comprehensive performances, as polymerization, anticorrosion, moistureproof, insulation, bonding, softening etc.Can be widely used in many fields such as coating, tackiness agent, printing ink, papermaking.
Description of drawings
Fig. 1 is the infrared absorption comparison diagram of nilox resin and nilox resin acyl chlorides.
Fig. 2 is the infrared absorption variation diagram of each group in the acyl chloride reaction process of nilox resin.
Fig. 3 is the variation of the relative content of carboxyl and acid chloride groups in the reaction process.
Fig. 4 is the infrared absorption variation diagram in the nilox resin esterification of acyl chloride reaction process.
The gas chromatography-mass spectrography spectrogram of Fig. 5 nilox resin and nilox resin (vinylformic acid-2-hydroxyethyl ester) ester.
The mass spectrum of Fig. 6 dehydroabietic acid.
The mass spectrum of Fig. 7 dihydropimaric acid.
The mass spectrum of Fig. 8 dehydroabietic acid (vinylformic acid-2-hydroxyethyl ester) ester.
The mass spectrum of Fig. 9 dihydropimaric acid (vinylformic acid-2-hydroxyethyl ester) ester.
Embodiment
A kind ofly produce the method for ester, may further comprise the steps by rosin and acrylate:
The first step: the rosiny acyl chloride reaction is dissolved in the rosin of 100 parts of quality in the benzene solvent of 10-500 part quality, the acylting agent of 1-70 part quality is dissolved in the benzene solvent of 1-70 part quality, the acylting agent drips of solution is added to mixing and stirring in the rosin solution, reaction times 1-6 hour, temperature of reaction maintains between 30 ℃-80 ℃, this reaction makes the carboxyl in the rosin be converted into acid chloride groups, above-mentioned solution is filtered to remove impurity, (vacuum tightness is 0.1MPa in underpressure distillation, solution temperature is 80 ℃) the recovery benzene solvent, make the rosin acyl chlorides thus, the variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor;
In the present embodiment, rosin is a kind of in rosin, nilox resin, staybelite, maleated rosin or the acrylic acid rosin, and the rosin quality umber is 100 parts; Acylting agent is a kind of in thionyl chloride, phosphorus trichloride, the phosphorus pentachloride, and the mass fraction of acylting agent can be 1 part, 15 parts, 23 parts, 42 parts, 54 parts, 62 parts, 70 parts; Solvent is a benzene solvent, accounts for the 10-90% of whole reaction system; Temperature of reaction can be 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃; Reaction times can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours.After reaction finishes, above-mentioned solution is filtered removal impurity, benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the rosin acyl chlorides thus.
Second step: the rosin acyl chlorides of 100 parts of quality that the esterification of rosin acyl chlorides will make is dissolved in the benzene solvent of 10-500 part quality, the acrylate that contains hydroxyl of 1-60 part quality is added drop-wise to mixes in the rosin solution of acid chloride and stir; Reaction times 1-6 hour, temperature of reaction maintained between 30 ℃-80 ℃, and this reaction makes acyl chlorides and hydroxyl reaction generate ester group, and benzene solvent is reclaimed in underpressure distillation, prepares rosin (acrylate) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
In the present embodiment, the mass fraction of rosin acyl chlorides is 100 parts; The used acrylate of esterification is acrylate or the methacrylic ester that contains hydroxyl, as vinylformic acid-2-hydroxyethyl ester, vinylformic acid-3-hydroxy-propyl ester, a kind of in methacrylic acid-2-hydroxyethyl ester, the methacrylic acid-3-hydroxy-propyl ester, the mass fraction of acrylic ester monomer can be 1 part, 15 parts, 30 parts, 37 parts, 42 parts, 53 parts, 60 parts; Solvent is a benzene solvent, accounts for the 10-90% of whole system; Temperature of reaction can be 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃; Reaction times can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours.After reaction finishes, benzene solvent is reclaimed in above-mentioned solution decompression distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepare rosin (acrylate) ester thus.
The first step: the acyl chloride reaction of gum resin:
Earlier 50g gum resin is joined in the 50g benzene, after treating fully to dissolve, the phosphorus trichloride with 6.83g is dissolved in the 6.83g benzene again, and the phosphorus trichloride drips of solution is added to mixed and stirring in the gum resin solution, reacts 2 hours, and temperature of reaction maintains 60 ℃.After reaction finishes above-mentioned solution is filtered removal phosphorous acid precipitation, benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the gum resin acyl chlorides thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A rosin 50 grams
B benzene 50 grams
C phosphorus trichloride 6.83 grams
D benzene 6.83 grams
Products therefrom is the gum resin acyl chlorides, and yield is 94%.
Second step: the esterification of gum resin acyl chlorides:
Elder generation joins 40g gum resin acyl chlorides in the 40g benzene, after treating fully to dissolve, drips 14.7g methacrylic acid-2-hydroxyethyl ester and mixes and stirring to the gum resin solution of acid chloride, and the reaction times is 2 hours, and temperature of reaction maintains 60 ℃.After reaction finished, benzene solvent was reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares gum resin (methacrylic acid-2-hydroxyethyl ester) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A gum resin acyl chlorides 40 grams
C methacrylic acid-2-hydroxyethyl ester 14.7 grams
Products therefrom is gum resin (methacrylic acid-2-hydroxyethyl ester) ester, and yield is 93%.
Embodiment 3
The first step: the acyl chloride reaction of nilox resin:
Earlier the 50g nilox resin is joined in the 50g benzene, after treating fully to dissolve, the phosphorus trichloride with 6.83g is dissolved in the 6.83g benzene again, and the phosphorus trichloride drips of solution is added to mixed and stirring in the nilox resin solution, reacts 3 hours, and temperature of reaction maintains 50 ℃.After reaction finishes above-mentioned solution is filtered removal phosphorous acid precipitation, benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the nilox resin acyl chlorides thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A nilox resin 50 grams
B benzene 50 grams
C phosphorus trichloride 6.83 grams
D benzene 6.83 grams
Products therefrom is the nilox resin acyl chlorides, and yield is 96%.
Second step: the esterification of nilox resin acyl chlorides:
Elder generation joins 40g nilox resin acyl chlorides in the 40g benzene, after treating fully to dissolve, drips 13.1g vinylformic acid-2-hydroxyethyl ester and mixes and stirring to the nilox resin solution of acid chloride, and the reaction times is 3 hours, and temperature of reaction maintains 50 ℃.After reaction finished, benzene solvent was reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares nilox resin (vinylformic acid-2-hydroxyethyl ester) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A nilox resin acyl chlorides 40 grams
C vinylformic acid-2-hydroxyethyl ester 13.1 grams
Products therefrom is nilox resin (vinylformic acid-2-hydroxyethyl ester) ester cpds, and yield is 95%.
With reference to Fig. 1, in the acyl chloride reaction of nilox resin, after the hydroxyl that links to each other with the carboxylic carbonyl is replaced by the chlorine atom, because the chlorine atom has stronger electron-withdrawing power, make two key increases (carbonyl is difficult for changing toward singly-bound) of carbonyl, cause the infrared absorption frequency of carbonyl to rise.The infrared signature of carboxylic carbonyl is absorbed in 1695cm in the nilox resin
-1The place, the infrared signature of carbonyl absorbs then at 1793cm in the nilox resin acyl chlorides
-1The place.Unreacted nilox resin is at 1695cm in the reaction system
-1The place also has a less absorption.
With reference to Fig. 2, along with the carrying out of acylation reaction, 1695cm
-1The infrared absorption at place diminishes 1793cm gradually
-1The infrared absorption at place becomes big gradually.
With reference to Fig. 3, transmissivity among Fig. 2-wave number infrared spectrum is converted into absorbancy-wave number infrared spectrum and calculates 1793cm-1,1695cm-1 and the absorption peak area at 1464cm-1 place and carry out normalized, can obtain in the reaction process-COCl ,-COOH group and-CH
2The variation synoptic diagram of the area ratio of-group absorption peak.From figure as can be seen ,-COOH content descends rapidly in 60 minutes of reaction, slowly is reduced to almost constantly subsequently again, and-COCl content prolongs in time to be on the increase to almost constant.React that each group relative content no longer changes after 120 minutes.Test-results shows that rosiny acylation reaction speed is very fast, and transformation efficiency is higher.
With reference to Fig. 4, as seen from Figure 4,1793cm
-1The peak (COCl) prolong in time and constantly reduce, until last disappearance; 1730cm
-1(COOR) prolong to continue become big in time, showing constantly has ester group to generate in the reaction process at the peak.Meanwhile the hydroxyl absorption peak at 3400cm-1 place diminishes gradually and disappears.
With reference to Fig. 5, the main composition of nilox resin is dehydroabietic acid and dihydropimaric acid, the main composition that retention time in gas-chromatography is respectively 10.53min and 10.23min product is dehydroabietic acid (vinylformic acid-2-hydroxyethyl ester) ester and dihydropimaric acid (vinylformic acid-2-hydroxyethyl ester) ester, and their retention time is respectively 20.44min and 19.92min.In product, fail to detect dehydroabietic acid and dihydropimaric acid.
With reference to Fig. 6, the molecular weight that can learn the methyl dehydroabietate is 314, and is consistent with the result of theoretical prediction.
With reference to Fig. 7, the molecular weight of dihydropimaric acid methyl esters is 318, and is consistent with the result of theoretical prediction.
With reference to Fig. 8, the molecular weight of dehydroabietic acid (vinylformic acid-2-hydroxyethyl ester) ester is 398, and is consistent with the result of theoretical prediction.
With reference to Fig. 9, the molecular weight of dihydropimaric acid (vinylformic acid-2-hydroxyethyl ester) ester is 402, and is consistent with the result of theoretical prediction.
Table 1 list in reactant, intermediate product and the final product the chemical shift of each group.
In table 1 nilox resin (vinylformic acid-2-hydroxyethyl ester) the ester building-up process
13The C-NMR analytical results
| δ c(ppm) | |||||
| δ c＞160 | 150＞δ c＞100 | ||||
| Test value | Theoretical value [12] | Test value | Theoretical value [12] | ||
| Disproportionated rosin disproportionated rosin acyl chlorides 2-hydroxyethyl acrylate disproportionated rosin (2-hydroxyethyl acrylate) ester | -COOH -benzyl and -C＝C- -COCl -benzyl and -C＝C- belong to disproportional rosin molecular architecture -COO- belong to 2-HEA -C＝C- -COOR -benzyl and -C＝C- belong to disproportional rosin molecular architecture -C＝C- belong to 2-HEA | 186.0、185.7 181.5、181.3 165.9 178.0、177.7： 169.6 | 185-160 182-165 175-155 175-155 | 146.7、145.6、137.4、 134.6、126.9、126.1、 124.1、123.9 146.6、 146.1、145.6、 137.0、134.6、 1282、 126.9、126.2、124.1、 123.8 130.8、127.5 146.4、 146.3、145.3、 137.2、134.2、 127.9、 126.5、125.6、123.8、 123.6- 130.8、127.6 | 110-150 110-150 110-150 110-150 110-150 |
The chemical shift of the carbonyl carbon in the nilox resin is 186.0 and 185.7ppm, the chemical shift of carbonyl carbon is 181.5 and 181.3ppm in the nilox resin acyl chlorides, and the chemical shift of the carbonyl carbon in nilox resin (vinylformic acid-2-hydroxyethyl ester) ester is 178.0 and 177.7ppm.The chemical shift of carbonyl carbon is different and variation has taken place along with the group that links to each other with carbonyl in reaction process, and this is consistent (δ with the theoretical prediction result
C-COO hour185-160ppm; δ
C-COCl182-165ppm; δ
C-COOR175-155ppm).The chemical shift of the carbon-carbon double bond in the Hydroxyethyl acrylate is respectively 127.5 and 130.8ppm, and the chemical shift of carbon-carbon double bond is respectively 127.6 and 130.8ppm in nilox resin (vinylformic acid-2-hydroxyethyl ester) ester.This explanation above-mentioned pair of key in reaction process is not damaged.
Embodiment 4
The first step: the acyl chloride reaction of nilox resin:
Earlier the 50g nilox resin is joined in the 50g dimethylbenzene, after treating fully to dissolve, the phosphorus pentachloride with 31.28g is dissolved in the 31.28g dimethylbenzene again, splashes in the above-mentioned flask with dropping funnel, reacts 5 hours, and temperature of reaction maintains 40 ℃.After reaction finishes above-mentioned solution is filtered removal phosphorous oxychloride precipitation, xylene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the nilox resin acyl chlorides thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A nilox resin 50 grams
B toluene 50 grams
C phosphorus pentachloride 31.28 grams
D dimethylbenzene 31.28 grams
Products therefrom is the nilox resin acyl chlorides, and yield is 92%.
Second step: the esterification of nilox resin acyl chlorides:
Elder generation joins 40g nilox resin acyl chlorides in the 40g dimethylbenzene, after treating fully to dissolve, drips 14.69g vinylformic acid-3-hydroxy-propyl ester and mixes and stirring to the nilox resin solution of acid chloride, and the reaction times is 5 hours, and temperature of reaction maintains 40 ℃.After reaction finished, xylene solvent was reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares nilox resin (vinylformic acid-3-hydroxy-propyl ester) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A nilox resin acyl chlorides 40 grams
C vinylformic acid-3-hydroxy-propyl ester 14.7 grams
Products therefrom is nilox resin (vinylformic acid-3-hydroxy-propyl ester) ester, and yield is 92%.
The first step: the acyl chloride reaction of nilox resin:
Earlier the 50g nilox resin is joined in the 50g toluene, after treating fully to dissolve, the thionyl chloride with 26.78g is dissolved in the 26.78g toluene again, and the thionyl chloride drips of solution is added to mixed and stirring in the nilox resin solution, reacts 6 hours, and temperature of reaction maintains 30 ℃.After reaction finishes above-mentioned solution is filtered, toluene solvant and unnecessary thionyl chloride are reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), make the nilox resin acyl chlorides thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A nilox resin 50 grams
B toluene 50 grams
C thionyl chloride 26.78 grams
D toluene 26.78 grams
Products therefrom is the nilox resin acyl chlorides, and yield is 96%.
Second step: the esterification of nilox resin acyl chlorides:
Elder generation joins 40g nilox resin acyl chlorides in the 40g toluene, after treating fully to dissolve, drips 16.5g methacrylic acid-3-hydroxy-propyl ester and mixes and stirring to the nilox resin solution of acid chloride, and the reaction times is 6 hours, and temperature of reaction maintains 30 ℃.After reaction finished, toluene solvant was reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares nilox resin (methacrylic acid-3-hydroxy-propyl ester) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A nilox resin acyl chlorides 40 grams
B toluene 40 grams
C methacrylic acid-3-hydroxy-propyl ester 16.5 grams
Products therefrom is nilox resin (methacrylic acid-3-hydroxy-propyl ester) ester, and yield is 91%.
Embodiment 6
The first step: the acyl chloride reaction of staybelite:
Earlier the 50g staybelite is joined in the 50g benzene, after treating fully to dissolve, again with in the molten fourth 6.83g benzene of the phosphorus trichloride of 6.83g, the phosphorus trichloride drips of solution is added to mixed and stirring in the staybelite solution, reacted 4 hours, temperature of reaction maintains 50 ℃.After reaction finishes above-mentioned solution is filtered removal phosphorous acid precipitation, benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the staybelite acyl chlorides thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A staybelite 50 grams
B benzene 50 grams
C phosphorus trichloride 6.83 grams
D benzene 6.83 grams
Products therefrom is the staybelite acyl chlorides, and yield is 93%.
Second step: the esterification of staybelite acyl chlorides:
Elder generation joins 40g staybelite acyl chlorides in the 40g toluene, after treating fully to dissolve, drips 13.1g vinylformic acid-2-hydroxyethyl ester and mixes and stirring to the staybelite solution of acid chloride, and the reaction times is 4 hours, and temperature of reaction maintains 50 ℃.After reaction finished, benzene solvent was reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares staybelite (vinylformic acid-2-hydroxyethyl ester) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A staybelite acyl chlorides 40 grams
C vinylformic acid-2-hydroxyethyl ester 13.1 grams
Products therefrom is staybelite (vinylformic acid-2-hydroxyethyl ester) ester cpds, and yield is 92%.
Embodiment 7
The first step: the acyl chloride reaction of maleated rosin:
Earlier the 50g maleated rosin is joined in the 100g benzene, after treating fully to dissolve, the thionyl chloride with 20.58g is dissolved in the 20.58g benzene again, and the thionyl chloride drips of solution is added to mixed and stirring in the maleated rosin solution, reacts 3 hours, and temperature of reaction maintains 60 ℃.After reaction finishes above-mentioned solution is filtered, benzene solvent and excessive thionyl chloride are reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), make the maleated rosin acyl chlorides thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A maleated rosin 50 grams
B chlorine sulfoxide 20.58 grams
C benzene 20.58 grams
Products therefrom is the maleated rosin acyl chlorides, and yield is 97%.
Second step: the esterification of maleated rosin acyl chlorides:
Elder generation joins 40g maleated rosin acyl chlorides in the 100g benzene, after treating fully to dissolve, drips 12.03g methacrylic acid-3-hydroxy-propyl ester and mixes and stirring to the maleated rosin solution of acid chloride, and the reaction times is 3 hours, and temperature of reaction maintains 60 ℃.After reaction finished, benzene solvent was removed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares maleated rosin (methacrylic acid-3-hydroxy-propyl ester) ester thus.The variation of group infrared absorption is analyzed in sampling half an hour at interval in the reaction process with the infrared spectra tracking monitor.
Proportioning:
A maleated rosin acyl chlorides 40 grams
B methacrylic acid-3-hydroxypropyl acrylate 12.03 grams
Products therefrom is maleated rosin (methacrylic acid-3-hydroxy-propyl ester) ester, and yield is 93%.
Claims (5)
1. produce the method for ester by rosin and acrylate for one kind, it is characterized in that may further comprise the steps:
The first step: the rosiny acyl chloride reaction is dissolved in the rosin of 100 parts of quality in the benzene solvent of 10-500 part quality, the acylting agent of 10-70 part quality is dissolved in the benzene solvent of 10-70 part quality, the acylting agent drips of solution is added to mixing and stirring in the rosin solution, reaction times 1-6 hour, temperature of reaction maintains between 30 ℃-80 ℃, this reaction makes the carboxyl in the rosin be converted into acid chloride groups, above-mentioned solution is filtered to remove impurity, benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), makes the rosin acyl chlorides thus;
Second step: the rosin acyl chlorides of 100 parts of quality that the esterification of rosin acyl chlorides will make is dissolved in the benzene solvent of 10-500 part quality, the acrylate that contains hydroxyl of 1-60 part quality is added drop-wise to mixes in the rosin solution of acid chloride and stir; Reaction times 1-6 hour, temperature of reaction maintained between 30 ℃-80 ℃, and this reaction makes acyl chlorides and hydroxyl reaction generate ester group, and benzene solvent is reclaimed in underpressure distillation (vacuum tightness is that 0.1MPa, solution temperature are 80 ℃), prepares rosin (acrylate) ester thus.
2. according to claim 1ly produce the method for ester, it is characterized in that said rosin is a kind of in gum resin, nilox resin, staybelite or the maleated rosin by rosin and acrylate.
3. according to claim 1ly a kind ofly produce the method for ester, it is characterized in that said benzene solvent is a kind of in benzene, toluene or the dimethylbenzene by rosin and acrylate.
4. according to claim 1ly produce the method for ester, it is characterized in that acylting agent is a kind of in phosphorus trichloride, phosphorus pentachloride or the thionyl chloride by rosin and acrylate.
5. according to claim 1ly produce the method for ester by rosin and acrylate, the used acrylate that contains hydroxyl of esterification that it is characterized in that the rosin acyl chlorides is a kind of in vinylformic acid-2-hydroxyethyl ester, vinylformic acid-3-hydroxy-propyl ester, methacrylic acid-2-hydroxyethyl ester or the methacrylic acid-3-hydroxy-propyl ester.
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| JP2009120542A (en) * | 2007-11-15 | 2009-06-04 | Chisso Corp | Polymerizable abietic acid derivative |
| CN101066918B (en) * | 2006-12-22 | 2010-05-19 | 中国林业科学研究院林产化学工业研究所 | Process of preparing double functional group acrylate based on acrylic rosin |
| CN101016437B (en) * | 2007-03-02 | 2011-01-26 | 桂林工学院 | Method of preparing esterified substance by rosin and hydroxyl acrylate |
| CN101215445B (en) * | 2007-12-28 | 2011-03-16 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| CN101492591B (en) * | 2008-08-13 | 2011-08-17 | 中国林业科学研究院林产化学工业研究所 | Acrylic acid or methylpropenoic acid rosin derivative ester synthesis method |
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| CN101066918B (en) * | 2006-12-22 | 2010-05-19 | 中国林业科学研究院林产化学工业研究所 | Process of preparing double functional group acrylate based on acrylic rosin |
| CN101016437B (en) * | 2007-03-02 | 2011-01-26 | 桂林工学院 | Method of preparing esterified substance by rosin and hydroxyl acrylate |
| JP2009120542A (en) * | 2007-11-15 | 2009-06-04 | Chisso Corp | Polymerizable abietic acid derivative |
| CN101215445B (en) * | 2007-12-28 | 2011-03-16 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| CN101492591B (en) * | 2008-08-13 | 2011-08-17 | 中国林业科学研究院林产化学工业研究所 | Acrylic acid or methylpropenoic acid rosin derivative ester synthesis method |
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| CN102659598A (en) * | 2012-05-23 | 2012-09-12 | 桂林理工大学 | Method for preparing ester compound by colophony and glycidyl methacrylate |
| CN103232349A (en) * | 2013-03-28 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Rosin or rosin derivative long chain flexible monomer preparation method |
| CN104497175A (en) * | 2014-12-17 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | Rosin-based ATRP initiator and preparation method and applications thereof |
| CN104497175B (en) * | 2014-12-17 | 2017-01-25 | 中国林业科学研究院林产化学工业研究所 | Rosin-based ATRP initiator and preparation method and applications thereof |
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