CN105801752B - A kind of copolymer of β carypohyllenes maleic anhydride and preparation method and application - Google Patents
A kind of copolymer of β carypohyllenes maleic anhydride and preparation method and application Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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Abstract
The invention provides a kind of β carypohyllenes copolymer-maleic anhydride and preparation method and application, described copolymer has anhydride bond, and carrying out copolymerization with maleic anhydride for β carypohyllenes is made.It is under nitrogen protection, by β carypohyllenes and maleic anhydride according to material proportion 4:1~1:6, it is dissolved in solvent or directly body mixes, and radical initiator is added, then reaction obtains β carypohyllene copolymer-maleic anhydrides under conditions of heating.β carypohyllenes copolymer-maleic anhydride can be widely used in the industries such as coating, cosmetics, food.The β carypohyllenes copolymer-maleic anhydride of the present invention is subjected to saponification, obtains a kind of anion surfactant.Reaction condition of the present invention is gentle, and technique is simple, is easy to industrialized production.
Description
Technical field
The present invention relates to polymer preparation, and in particular to a kind of β-carypohyllene-copolymer-maleic anhydride and preparation method thereof
With application.
Technical background
China's masson pine pine resin yield is big, ranks the first in the world.Masson pine rosin is carried out into distillation can obtain lightweight pine
Fuel-economizing, heavy turpentine and rosin.Research at present for lightweight turpentine oil and rosin is a lot, and industrialized product also compares
It is more, but the research research for heavy turpentine is still deficienter, and industrialization product is few, causes heavy turpentine
Price is constantly in low state.Main component is longifolene and β-carypohyllene in heavy turpentine.Wherein, β-carypohyllene contains
Amount can reach 19% or so, and research and utilization is carried out to β-carypohyllene, and the utilization rate that become more meticulous to raising heavy turpentine has important
Meaning.
β-carypohyllene belongs to bicyclic sequiterpene type compound, and its molecular formula is C15H24, structural formula is as follows：
At present, in terms of the research for β-carypohyllene is concentrated mainly on the synthesis of pharmacological activity and essence and flavoring agent.And incite somebody to action
β-carypohyllene polymerize to form copolymer with maleic anhydride, and by its it is saponified apply in terms of surfactant, at present, have not seen
Relevant report.Similar report has Shen Minmin, Qiu Zhenmin etc. [A of CN 1900129] to disclose one kind in dicyandiamide solution, heating
Under the conditions of, method that nopinene and copolymer-maleic anhydride are prepared using radical initiator；Gloomy [the gloomy β-pinane of Li Jie of Li Jie
The synthesis of alkene/copolymer-maleic anhydride and application study [J] Zhongshan University postgraduate's academic periodical (natural science, medicine)
.2009,30(2):78-84] progress nopinene and maleic anhydride polymerisation in different temperatures, different medium are have studied, and
Copolymer is hydrolyzed with ammoniacal liquor and self assembly, has obtained the low particle up to 400nm of particle diameter；Cheng Jianhua etc. [Cheng Jianhua, 5
By the emperor himself, Wang Xiaojun, synthesis and application and research [J] the Liaoning chemical industry of water soluble dispersing agents maleic anhydride of styrene (SMA) are waited
.2001,30(8):328-329] use solvent method synthesizing styrene-maleic anhydride type (SMA) aqueous dispersion agent.But this
A little methods are all not involved with the copolymer of β-carypohyllene-maleic anhydride.
The content of the invention
The invention provides a kind of β-carypohyllene and copolymer-maleic anhydride and preparation method and application.β-carypohyllene with
Copolymer-maleic anhydride will be used widely in industries such as coating, cosmetics, food.
The technical scheme is that：A kind of copolymer of β-carypohyllene-maleic anhydride, using solvent polymerization method or straight
Connect mass polymerization to be copolymerized to obtain with maleic anhydride by β-carypohyllene, the ratio between amount of β-carypohyllene and maleic anhydride material is
4:1~1:6.
Solvent in described solvent polymerization method includes tetrahydrofuran, dioxane, cyclohexanone, acetone, dimethylbenzene, toluene
In any one.
The method for preparing the copolymer of described β-carypohyllene-maleic anhydride, under nitrogen protection, β-carypohyllene and Malaysia
Acid anhydrides in the presence of radical initiators, 10 minutes to 6 hours of heating response, obtains β-carypohyllene-maleic anhydride
Thing.
Described radical initiator is organic peroxide initiator or azo-initiator.
Described radical initiator is benzoyl peroxide or di-t-butyl peroxide.
The dosage of described radical initiator is the 1%~15% of the amount of β-carypohyllene and maleic anhydride total material.
Reaction temperature is 80 DEG C~180 DEG C.
The copolymer of described β-carypohyllene-maleic anhydride is in coating, cosmetics, the application in food service industry.
A kind of surfactant of the copolymer based on described β-carypohyllene-maleic anhydride, by β-carypohyllene-maleic acid
Anhydride copolymer carries out saponification using alkali compounds and obtains described anion surfactant.
Described alkali compounds is sodium hydroxide.
Beneficial effect
1. widened β-carypohyllene to become more meticulous utilization ways, with the polymer obtained by maleic anhydride and its saponified
The industries such as coating, cosmetics, food can be widely used in.
2. organic solvent used can recycle in reaction, running cost is relatively low.
3. mild condition of the present invention, the reaction time is very fast, and post processing is simple.
4. synthetic method of the present invention is simple, easy to operate, available for industrialized production.
Brief description of the drawings
Fig. 1 is that β-carypohyllene-copolymer-maleic anhydride (B) prepared by embodiment 1 and compareing for raw material β-carypohyllene (A) are red
External spectrum figure, 1857.48cm in figure-1、1779.60cm-1For the characteristic bimodal of anhydride group, and the intensity at low frequency peak compares high frequency
Peak is big, and this shows that anhydride group is cyclic structure, also exactly this explanation β-carypohyllene and maleic acid of the construction unit of maleic anhydride
There occurs copolyreaction for acid anhydride.
Fig. 2 is thermal weight loss (TG) curve of β-carypohyllene-copolymer-maleic anhydride prepared by embodiment 1.β-China pink in figure
Temperature of the alkene-copolymer-maleic anhydride weight-loss ratio at 10%, 50%, 90% is respectively 350 DEG C, 403 DEG C, 440 DEG C, shows this
Polymer has good heat resistance.
Fig. 3 is β-saponified surface tension of carypohyllene-copolymer-maleic anhydride and saponified concentration prepared by embodiment 1
Relation, as seen from the figure when saponified concentration is in 15gL-1During left and right, the surface tension of water is remarkably decreased, and shows that this is saponified
It can be used as a kind of good anion surfactant.
Embodiment
The following examples are the further explanations to the present invention, rather than limit the scope of the present invention.
A kind of preparation method of the copolymer of β-carypohyllene-maleic anhydride, under nitrogen protection, by β-carypohyllene and Malaysia
Acid anhydrides is according to material proportion 4:1~1:6, it is dissolved in solvent or directly body mixes, and radical initiator is added, Ran Hou
10 minutes to 6 hours are reacted under conditions of heating, obtain β-carypohyllene-copolymer-maleic anhydride.
Solvent in above-mentioned solvent polymerization method is tetrahydrofuran, dioxane, cyclohexanone, acetone, dimethylbenzene, toluene,
Preferable solvent is dioxane and cyclohexanone.The dosage of solvent is 1~2 times of β-carypohyllene and maleic anhydride total amount.
Above-mentioned β-carypohyllene and maleic anhydride are 4 according to material proportion:1~1:6, more excellent material ratio is 2:1~1:2.
Above-mentioned radical initiator is organic peroxide initiator or azo-initiator.Preferably peroxidating
Benzoyl, di-t-butyl peroxide.The dosage of radical initiator be the amount of β-carypohyllene and maleic anhydride total material 1%~
15%.
Above-mentioned reaction temperature is 80 DEG C~180 DEG C.Preferable reaction temperature is 80 DEG C~155 DEG C.
Contain anhydride bond in the polymer of gained of the invention, saponification is carried out using alkali compounds, a kind of the moon can be obtained
Ionic surface active agent.
Above-mentioned alkali compounds is sodium hydroxide.
Embodiment 1
Equipped with thermometer, 10.38g β-carypohyllene is added in the 100ml three-necked flasks of magnetic stir bar, 4.90g's
Maleic anhydride, 0.584g di-t-butyl peroxide and 30.6g cyclohexanone.Under the protection of nitrogen, 150 DEG C are warming up to, instead
1h is answered, then stops reaction, reactant is poured into a large amount of methanol, white precipitate is separated out, is then filtered, obtain white powder
Last shape solid, after drying, measure quality 11.1g, yield 72.63%.GPC measures molecular weight of copolymer MnFor 1404, MwFor
3249.Then take 2g copolymers to be added in the single-necked flask equipped with the NaOH solution that mass fraction is 5%, be heated to reflux to saturating
It is bright, then reactant is poured into a large amount of methanol and separates out white precipitate, filter, be dried to obtain it is saponified, to saponified carry out table
Face tension detection, is as a result shown in Fig. 3.
Embodiment 2
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 0.438g di-t-butyl peroxide and 22.93g's
Cyclohexanone.Under the protection of nitrogen, 145 DEG C are warming up to, reacts 1h, other conditions are with embodiment 1, the copolymer substance finally obtained
Measure as 11.1g, yield 79.83%.
Embodiment 3
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 0.584g di-t-butyl peroxide and 30.57g's
Cyclohexanone.Under the protection of nitrogen, 150 DEG C are warming up to, reacts 10min, other conditions are with embodiment 1, the copolymerization finally obtained
Amount of substance is 9.6g, yield 62.81%.
Embodiment 4
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 0.584g di-t-butyl peroxide and 30.57g's
Cyclohexanone.Under the protection of nitrogen, 150 DEG C are warming up to, reacts 4h, other conditions are with embodiment 1, the copolymer substance finally obtained
Measure as 10.4g, yield 68.05%.
Embodiment 5
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 0.365g di-t-butyl peroxide and 15.29g's
Cyclohexanone.Under the protection of nitrogen, 150 DEG C are warming up to, reacts 1h, other conditions are with embodiment 1, the copolymer substance finally obtained
Measure as 13.5g, yield 88.33%.
Embodiment 6
Add 10.38g β-carypohyllene, 2.46g maleic anhydride, 0.513g di-t-butyl peroxide and 25.67g's
Cyclohexanone.Under the protection of nitrogen, 150 DEG C are warming up to, reacts 4h, other conditions are with embodiment 1, the copolymer substance finally obtained
Measure as 2.8g.
Embodiment 7
Add 5.19g β-carypohyllene, 4.91g maleic anhydride, 0.438g di-t-butyl peroxide and 20.186g's
Cyclohexanone.Under the protection of nitrogen, 150 DEG C are warming up to, reacts 4h, other conditions are with embodiment 1, the copolymer substance finally obtained
Measure as 6.6g.
Embodiment 8
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 1.211g benzoyl peroxide and the two of 30.57g
The ring of oxygen six.Under the protection of nitrogen, 80 DEG C are warming up to, reacts 4h, then stops reaction, reactant is poured into a large amount of absolute ethyl alcohols
In, white precipitate is separated out, is then filtered, obtains white powdery solids, after drying, measures quality 7.2g, yield
47.11%.GPC measures molecular weight MnFor 3647, MwFor 13249.
Embodiment 9
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 1.939g benzoyl peroxide and 15.29g ring
Hexanone.Under the protection of nitrogen, it is warming up to, 100 DEG C, reacts 4h, other conditions are with embodiment 8, the copolymer substance finally obtained
Measure as 9.8g, yield 64.12%.
Embodiment 10
Add 10.38g β-carypohyllene, 4.90g maleic anhydride, 0.438g di-t-butyl peroxide and 22.93g's
Cyclohexanone.Under the protection of nitrogen, 145 DEG C are warming up to, reacts 1h, other conditions are with embodiment 1, the copolymer substance finally obtained
Measure as 11.1g, yield 79.83%.
Embodiment 11
Add 22.7g β-carypohyllene, 9.807g maleic anhydride, 0.098g di-t-butyl peroxide.In nitrogen
Under protection, 150 DEG C are warming up to, react 10min, then stop reaction, by tetrahydrofuran to entering in reactant, dissolve consolidating for generation
Body, after having dissolved, pour into a large amount of absolute ethyl alcohols and separate out white precipitate, then filtered, obtain white powdery solids, do
After dry, quality 21g, yield 68.50% are measured.
Claims (7)
1. a kind of copolymer of β-carypohyllene-maleic anhydride, it is characterised in that using solvent polymerization method or direct polymerisation in bulk
β-carypohyllene is copolymerized to obtain by method with maleic anhydride, and the ratio between amount of β-carypohyllene and maleic anhydride material is 4:1~1:6；Institute
Solvent in the solvent polymerization method stated includes any one in tetrahydrofuran, dioxane, cyclohexanone, acetone, dimethylbenzene, toluene
Kind；Specific method be under nitrogen protection, β-carypohyllene and maleic anhydride in the presence of radical initiators, heating response 10
Minute to 6 hours, obtains β-carypohyllene-copolymer-maleic anhydride；Described radical initiator be benzoyl peroxide or
Di-t-butyl peroxide.
2. prepare the method for the copolymer of β-carypohyllene-maleic anhydride described in claim 1, it is characterised in that protect in nitrogen
Under shield, β-carypohyllene and maleic anhydride in the presence of radical initiators, 10 minutes to 6 hours of heating response, obtain β-
Carypohyllene-copolymer-maleic anhydride；Described radical initiator is benzoyl peroxide or di-t-butyl peroxide.
3. the method for the copolymer according to claim 2 for preparing β-carypohyllene-maleic anhydride, it is characterised in that：It is described
The dosage of radical initiator be the 1% ~ 15% of the amount of β-carypohyllene and maleic anhydride total material.
4. the method for the copolymer according to claim 2 for preparing β-carypohyllene-maleic anhydride, it is characterised in that：Reaction
Temperature is 80 DEG C ~ 180 DEG C.
5. the copolymer of β-carypohyllene-maleic anhydride described in claim 1 is in coating, cosmetics, the application in food service industry.
6. a kind of surfactant of the copolymer of β-carypohyllene-maleic anhydride based on described in claim 1, its feature exist
In：β-carypohyllene-copolymer-maleic anhydride is subjected to saponification using alkali compounds and obtains anion surfactant.
7. the surfactant according to claim 6 based on β-carypohyllene-copolymer-maleic anhydride, it is characterised in that：
Described alkali compounds is sodium hydroxide.
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| CN106832125A (en) * | 2017-03-16 | 2017-06-13 | 中国林业科学研究院林产化学工业研究所 | A kind of heavy turpentine copolymer-maleic anhydride, modifier and preparation method and application |
| CN110698126A (en) * | 2019-10-15 | 2020-01-17 | 福建船政交通职业学院 | High-performance building material and preparation method thereof |
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| CN1900129A (en) * | 2006-07-17 | 2007-01-24 | 中国科学院广州化学研究所 | Process for synthesizing beta-pinene/maleic anhydride copolymer |
| US9303111B2 (en) * | 2011-11-01 | 2016-04-05 | Lubrizol Advanced Materials, Inc. | Acrylate-olefin copolymers, methods for producing same and compositions utilizing same |
| CN103449954B (en) * | 2013-08-27 | 2015-04-15 | 梧州市松桦化学品有限公司 | Preparation method of high-purity longifolene |
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