CN101864051A - Maleic anhydride acidation chitosan salt/nature rubber graft copolymer and preparation method thereof - Google Patents
Maleic anhydride acidation chitosan salt/nature rubber graft copolymer and preparation method thereof Download PDFInfo
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- CN101864051A CN101864051A CN201010192035A CN201010192035A CN101864051A CN 101864051 A CN101864051 A CN 101864051A CN 201010192035 A CN201010192035 A CN 201010192035A CN 201010192035 A CN201010192035 A CN 201010192035A CN 101864051 A CN101864051 A CN 101864051A
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- maleic anhydride
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Abstract
The invention provides maleic anhydride acidation chitosan salt/nature rubber graft copolymer and a preparation method thereof. The method comprises the following steps: adding stabilizing agent non-ionic surface active agents Peregal-O into concentrated natural rubber for maintaining the stability and the temperature rise of the nature rubber; regulating the pH value of the maleic anhydride acidation chitosan salt solution between 8 and 12; then, adding obtained materials into the nature rubber; adding triggering agents of one kind or two kinds of materials in benzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, sulphur, cumene hydroperoxide, potassium peroxydisulfate and N, N-methylene-bisacrylamide; carrying out stilling standing for 24 hours; adding activating agents of tetraethylenepentamine; continuously raising the temperature; carrying out reaction for 2 to 24 hours at the temperature between 60 and 125 DEG C; and obtaining the milky maleic anhydride acidation chitosan salt/nature rubber graft copolymer. The copolymer has good antibacterial property, good physiological activity, good hydrophilcity and good heat resistance performance, and further widens the application range of the nature rubber in the fields of medical sanitation and the like.
Description
One, technical field
The present invention relates to the chemical modification of natural polymer, particularly natural rubber and maleic anhydride acylation chitosan (MCS) salt graft copolymer and the preparation method.
Two, background technology
Chitosan is a kind of natural biological degradation material, good biocompatibility and nontoxic.Studies show that chitosan not only has outside the superiority such as biodegradability and low cytotoxicity, also have unique cross-cell membrane ability and receive much concern.But, greatly having limited it and used widely because chitosan is water insoluble, water-soluble chitosan is the focus of chitosan derivatives research at present.MCS is a kind of water-solubility chitosan derivative, also is that a kind of complex polyelectrolyte particle has good water-absorbent.Lot of domestic and international scholar synthesizes it and should be used as a large amount of research.It is catalyzer that Chinese patent CN98110568.8 discloses with yellow soda ash, is medium with water, makes water-soluble maleoyl chitosan sodium (MCS-Na) under the normal temperature, and uses it for the main raw material of makeup.Employing ceric ammonium nitrates such as Shu Hongying are initiator, microwave radiation, and with N, dinethylformamide (DMF) is a reaction medium, has synthesized the graft copolymer (Nanjing aviation college journal, 4:64-67,2008) of chitosan and maleic anhydride.Usefulness acetic acid such as Wang Zhouyu and acetone are that solvent dissolves chitosan and maleic anhydride respectively, with chitosan the N-acylation reaction take place under homogeneous phase condition, have prepared serial water-solubility chitosan derivative (applied chemistry, 19 (10): 1002-1004,2002).Dong Yanming etc. are dissolved in the DMF solution with maleic anhydride, and nitrogen protection is down reacted for 130 ℃ to react under the condition in 3 hours with chitosan and made, and its crystal habit is studied.[Xiamen University's journal (natural science edition), 6:824-827,2004; Polymer International, 55:1444-1449,2006].Li Yongzhen etc. study the preparation and the resistance toheat thereof of maleoyl chitosan sodium, find behind the maleylation resistance toheat be greatly improved (polymer material science and engineering, 2:164-166,2009).
NR can with the reaction of many unsaturated compounds, but study early, more and what have significant practical applications is the reaction of itself and maleic anhydride.As far back as nineteen thirty-nine, it is initiator that Bacon and Farmer etc. just find with a small amount of benzoyl peroxide (BPO), to plasticate NR and maleic anhydride places benzene or toluene solvant, hour just can obtain product (the Rubber Chem.AndTechnol. of white or light yellow hardened resin shape at 100 ℃ of following stoichiometric numbers, 12 (2): 200-209,1939).The Judd people etc. adopt solution method, are initiator with BPO, use maleic anhydride graft natural rubber latex [China Synthetic Rubber Industry, 28 (3): 200-204,2005; Elastomerics, 14 (5): 1-5,2004].
Though NR is the macromolecular material that is used as medical elastomer the earliest, because NR do not have antibacterial and physiologically active, and wetting ability and resistance toheat are relatively poor; Do not have the function side group in its molecular structure, do not have can with other drug bonded active site.These defectives have limited its application at field of medicaments widely.
Three, summary of the invention
The object of the present invention is to provide a kind of have germ resistance, physiologically active, wetting ability and stable on heating MCS and NR graft copolymer and preparation method thereof, further widen the range of application of natural rubber in fields such as health cares.
NR/MCS graft copolymer of the present invention is characterized in that it comprises following components by weight portions:
By 100 parts of the concentrated natural latexes of dried glue;
0.1～60 part of maleic anhydride acylation chitosan salt.
In order to prepare NR/MCS graft copolymer graft copolymer of the present invention, also can select to add stablizer, activator, one or both initiators of following weight part:
1.0～5.0 parts of stablizers;
0.01～0.8 part of initiator;
0.01～0.3 part in activator.
Weight part of the present invention can be known content units such as gram or kilogram.
Initiator of the present invention is benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, sulphur, hydrogen phosphide cumene, Potassium Persulphate, N, a kind of in the N-methylene-bisacrylamide or two kinds, activator is a tetraethylenepentamine, and stablizer is nonionogenic tenside peregal " O ".
The preparation method of NR/MCS graft copolymer of the present invention is as follows:
In concentrated natural latex, add stablizer nonionogenic tenside peregal " O ", make latex keep stable, heat up.Regulate maleic anhydride acylation chitosan salts solution pH value between the 8-12; it is joined in the above-mentioned natural rubber latex then; and add initiator benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, sulphur, hydrogen phosphide cumene, Potassium Persulphate, N; in the N-methylene-bisacrylamide one or both were parked 24 hours.Adding the activator tetraethylenepentamine, continue to heat up, is under 60 ℃～125 ℃ in temperature, reacts 2-24 hour, makes lactous maleic anhydride acylation chitosan salt/nature rubber graft copolymer.
Four, Fa Ming key problem in technology point
Key problem in technology point of the present invention is:
1, the selection of initiator (system).Because the present invention utilizes two keys on the MCS side base and two key generation copolyreaction of natural rubber, thus to the requirement of initiator than higher.Because reaction is carried out under emulsion system, first-selected water miscible initiator potassium persulfate has been used tertbutyl peroxide, benzoyl peroxide, hydrogen phosphide cumene, Diisopropyl azodicarboxylate then.In order to improve cross-linking effect, also added N,N methylene bis acrylamide.
2, the kind of MCS salt.It must be water miscible that solution method requires used MCS salt, as sodium salt, sylvite, ammonium salt, zinc salt, magnesium salts, calcium salt etc.The present invention has selected ammonium salt, sodium salt, sylvite, zinc salt and calcium salt to react.
3, the selection of temperature of reaction.The initiation that temperature of reaction should satisfy initiator requires to guarantee again the stability of reacting.Therefore, the kind of the temperature of reaction and initiator has substantial connection.Show that through experimental result vs. temperature of the present invention is as shown in table 1.
Table 1 vs. temperature
| Initiator | Potassium Persulphate | Tertbutyl peroxide | Benzoyl peroxide | Hydrogen phosphide cumene | Diisopropyl azodicarboxylate |
| Kick off temperature/℃ | ??60 | ??60 | ??80 | ??125 | ??80 |
4, the ratio of MCS salt and NR consumption.The affiliation that adds of MCS salts solution has influence on the stability of latex system, generally needs to add stablizer.But the adding of stablizer can have influence on the performance of product again, and therefore, the ratio of MCS salt and NR consumption is to need to select.The ratio of best MCS salt and NR consumption surpasses 60% demixing phenomenon takes place easily between 0.1%～60%.
5, the pH value of MCS salts solution.MCS salt is a kind of complex polyelectrolyte particle, and the pH value has determined its solvability and stability, and therefore, different types of MCS salt needs different pH values.Simultaneously, the pH value of MCS is also relevant with the pH value of the natural rubber latex that will add, and take all factors into consideration and select.The present invention determines that suitable pH value scope is 8-12.
Five, beneficial effect of the present invention
Maleic anhydride acylation chitosan salt/nature rubber graft copolymer of the present invention has following advantage:
1, can improve the wetting ability of natural rubber after MCS salt and the natural rubber copolymerization.Owing to introduced the chitosan derivatives that has hydrophilic side group, made the wetting ability of multipolymer be improved.The contact angle data are as shown in the table after the graft copolymerization:
Table 2 contact angle test result
| Sample number into spectrum | Contact angle/° |
| ??NR | ??116 |
| ??NR/MCS-1 | ??110 |
| ??NR/MCS-2 | ??98 |
| ??NR/MCS-3 | ??72 |
| ??NR/MCS-4 | ??68 |
| ??NR/MCS-5 | ??55 |
| ??NR/MCS-6 | ??52 |
2, the anti-microbial property after the graft copolymerization is improved.Chitosan itself has the excellent antibiotic performance, and these performances will obtain keeping after the graft copolymerization.Therefore, multipolymer can be used as medicine equipment, food product pack etc. sanitation and hygiene are required than higher field.Select for use intestinal bacteria and staphylococcus aureus that the polymkeric substance glued membrane is carried out antibacterial experiment, the result is as follows:
Table 3 antibacterial experiment result
3, the thermotolerance that draws multipolymer by thermogravimetric analysis increases than natural rubber.The thermogravimetric analysis result is as shown in table 4:
Table 4 multipolymer heat analysis data
| Sample | ??T o/℃ | ??T p/℃ | ??T f/℃ |
| ??NR | ??385.2 | ??410.8 | ??436.3 |
| ??NR/MCS-1 | ??385.9 | ??411.6 | ??437.2 |
| ??NR/MCS-2 | ??385.7 | ??411.2 | ??436.9 |
| Sample | ??T o/℃ | ??T p/℃ | ??T f/℃ |
| ??NR/MCS-3 | ??408.9 | ??433.7 | ??453.8 |
| ??NR/MCS-4 | ??402.6 | ??426.9 | ??448.5 |
| ??NR/MCS-5 | ??405.7 | ??429.8 | ??451.2 |
| ??NR/MCS-6 | ??426.5 | ??452.0 | ??475.3 |
4,, can improve the mechanical property of natural rubber owing to the crosslinked action of MCS salt.Show through experimental result: the zinc salt of MCS and the reinforced effects of calcium salt are better than sodium salt and sylvite.
Table 5 multipolymer tensile property test result
5, multipolymer use main raw material---chitin and natural rubber all are natural macromolecular materials, and human body is had no side effect, avoided of the harm of chemosynthesis polymer to human body.
6, the preparation method of maleic anhydride acylation chitosan salt/nature rubber graft copolymer of the present invention, technological process is simple, and copolyreaction is carried out under emulsion system, and is workable.
Six, embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.Except as otherwise noted, the umber that hereinafter adopts is dry weight part.
Example one
Take by weighing 3 parts of chitosans, the water that adds 300 parts, magnetic agitation, alternately add 0.5 part maleic anhydride and 0.5 part yellow soda ash every half hour, repeat 4 times, reaction is 6 hours under the room temperature, sodium hydroxide solution is regulated the pH value to alkalescence, remove by filter unreacted chitosan, not small molecular weight impurity is removed in the reaction solution dialysis, preparation MCS-Na salts solution.
To drc is to add 1 part of nonionogenic tenside peregal " O " in 100 parts the concentrated natural latex, makes latex keep stable; Take by weighing the solution 50mL that contains 20 parts of MCS-Na salt; regulate pH value to 8; under the magnetic agitation condition, it is added drop-wise in the natural rubber latex, adds 0.5 part of benzoyl peroxide then, 0.1 part of N; the N-methylene-bisacrylamide; parked 24 hours, and added 0.01 part of tetraethylenepentamine, be warming up to 80 ℃; reacted 2 hours, and made lactous maleic anhydride acylation chitosan sodium/nature rubber graft copolymer.Shop film drying, unreacted MCS-Na is removed in alkali cleaning, washing, drying.The contact angle that records copolymer adhesive film is 110 °, and bacteriostasis rate is 77.5%, the beginning cracking temperature: 385.9 ℃, and tensile strength: 4.16MPa.
Example two
6 parts maleic anhydrides are dissolved among 100 parts the DMF, add 3 parts of chitosans, N
2Protection is warming up to 130 ℃ of reactions 2 hours down, and reaction solution is poured in the mixture of ice and water, and precipitation, suction filtration, ether wash for several times, vacuum-drying, preparation maleic anhydride acylation chitosan (MCS); The MCS that obtains is become MCS-Ga solution with the aqua calcis prepared in reaction.
To drc is to add 5 parts of nonionogenic tenside peregals " O " in 100 parts the concentrated natural latex, makes latex keep stable; Take by weighing the solution 50mL that contains 30 parts of MCS-Ga; regulate pH value to 9; under the magnetic agitation condition, it is added drop-wise in the natural rubber latex; add 0.01 part of tertbutyl peroxide then; parked 24 hours, and added 0.3 part and add tetraethylenepentamine, be warming up to 80 ℃; reacted 10 hours, and made lactous maleic anhydride acylation chitosan calcium/nature rubber graft copolymer.Shop film drying, unreacted MCS-Ga is removed in alkali cleaning, washing, drying.The contact angle that records co-polymer membrane is 98 °, and bacteriostasis rate is 82.5%, the beginning cracking temperature: 385.7 ℃, and tensile strength: 4.23MPa.
Example three
Take by weighing 2 parts of chitosans, add the acetum 120mL of 2% (mass fraction), stir dissolving down 1 hour, form homogeneous phase solution; Take by weighing 4 parts maleic anhydride, make it to be dissolved in the 5mL acetone, stir adding reactor down, at room temperature reacted 12 hours, product is purified with the acetone extracting, vacuum-drying then, preparation maleic anhydride acylation chitosan (MCS); Get the solution 50mL that contains 1.0 parts of MCS, add ZnO0.5 part, preparation maleic anhydride acylation chitosan zinc solution.
To drc is to add 3 parts of nonionogenic tenside peregals " O " in 100 parts the concentrated natural latex, makes latex keep stable; Take by weighing the solution 50mL that contains 1 part of MCS-Zn; regulate pH value to 12; under the magnetic agitation condition, it is added drop-wise in the natural rubber latex; add 0.8 part of hydrogen phosphide cumene then; parked 24 hours, and added 0.3 part and add tetraethylenepentamine, be warming up to 125 ℃; reacted 10 hours, and made lactous maleic anhydride acylation chitosan calcium/nature rubber graft copolymer.Shop film drying, unreacted MCS-Zn is removed in alkali cleaning, washing, drying.The contact angle that records copolymer adhesive film is 72 °, and bacteriostasis rate is 85%, the beginning cracking temperature: 408.9 ℃, and tensile strength: 5.68MPa.
Example four
6 parts maleic anhydrides are dissolved among 100 parts the DMF, add 3 parts of chitosans, N
2Protection is warming up to 130 ℃ of reactions 2 hours down, and reaction solution is poured in the mixture of ice and water, and precipitation, suction filtration, ether wash for several times, vacuum-drying.The MCS that obtains is become MCS-K solution with the potassium hydroxide solution prepared in reaction.
To drc is to add 3 parts of nonionogenic tenside peregals " O " in 100 parts the concentrated natural latex, makes latex keep stable; Take by weighing the solution 50mL that contains 15 parts of MCS-K; regulate pH value to 10; under the magnetic agitation condition, it is added drop-wise in the natural rubber latex; add 0.5 part of Potassium Persulphate then; parked 24 hours, and added 0.2 part and add tetraethylenepentamine, be warming up to 60 ℃; reacted 24 hours, and made lactous maleic anhydride acylation chitosan potassium/nature rubber graft copolymer.Shop film drying, unreacted MCS-K is removed in alkali cleaning, washing, drying.The contact angle that records copolymer adhesive film is 68 °, and bacteriostasis rate is 89.16%, the beginning cracking temperature: 402.6 ℃, and tensile strength: 8.59MPa.
Example five
Take by weighing 2 parts of chitosans, add the acetum 120mL of 2% (mass fraction), stir dissolving down 1 hour, form homogeneous phase solution.Take by weighing 4 parts maleic anhydride, make it to be dissolved in the 5mL acetone, stir adding reactor down, at room temperature reacted 12 hours, product is purified with the acetone extracting, vacuum-drying then.The MCS that obtains is dissolved in the ammoniacal liquor ammonium salt of preparation maleic anhydride acylation chitosan.
To drc is to add 2 parts of nonionogenic tenside peregals " O " in 100 parts the concentrated natural latex, makes latex keep stable; Take by weighing and contain 0.1 part of MCS-NH
4Solution 50mL; regulate pH value to 12; under the magnetic agitation condition, it is added drop-wise in the natural rubber latex; add 0.5 part of initiator Diisopropyl azodicarboxylate then; parked 24 hours, and added 0.25 part and add tetraethylenepentamine, be warming up to 80 ℃; reacted 12 hours, and made lactous maleic anhydride acylation chitosan ammonium/nature rubber graft copolymer.Shop film drying, unreacted MCS-NH is removed in alkali cleaning
4, washing, drying.The contact angle that records copolymer adhesive film is 55 °, and bacteriostasis rate is 93.33%, the beginning cracking temperature: 405.7 ℃, and tensile strength: 9.65MPa.
Example six
Take by weighing 2 parts of chitosans, be dissolved in 100 part 5% the acetic acid solution, stirred 1 hour, add 100 parts of methyl alcohol then.The maleic anhydride that is dissolved in a spot of acetone is added drop-wise in the chitosan solution for 12 parts, and powerful the stirring under the room temperature reacted 12 hours, and reaction solution is poured in a large amount of acetone, and vacuum-drying obtains MCS; MCS and MgO prepared in reaction MCS-Mg salt.
To drc is to add 2.5 parts of nonionogenic tenside peregals " O " in 100 parts the concentrated natural latex, makes latex keep stable; Take by weighing the solution 50mL that contains 60 parts of MCS-Mg; regulate pH value to 10; under the magnetic agitation condition, it is added drop-wise in the natural rubber latex; add 0.5 part of initiator benzoyl peroxide then; parked 24 hours, and added 0.1 part and add tetraethylenepentamine, be warming up to 80 ℃; reacted 24 hours, and made lactous maleic anhydride acylation chitosan magnesium/nature rubber graft copolymer.Shop film drying, unreacted MCS-Mg is removed in alkali cleaning, washing, drying.The contact angle that records copolymer adhesive film is 52 °, and bacteriostasis rate is 97.50%, the beginning cracking temperature: 426.5 ℃, and tensile strength: 8.23MPa.
Claims (3)
1. maleic anhydride acylation chitosan salt/nature rubber graft copolymer is characterized in that it comprises following components by weight portions:
By 100 parts of the concentrated natural latexes of dried glue;
0.1～60 part of maleic anhydride acylation chitosan salt.
2. maleic anhydride acylation chitosan salt/nature rubber graft copolymer according to claim 1 also can add stablizer, activator and one or both initiators of following weight part when it is characterized in that preparing:
1.0～5.0 parts of stablizers;
0.01～0.8 part of initiator;
0.01～0.3 part in activator.
3. the preparation method of maleic anhydride acylation chitosan salt/nature rubber graft copolymer according to claim 1 and 2 is characterised in that it is to comprise the following steps:
In concentrated natural latex, add stablizer nonionogenic tenside peregal " O ", make latex keep stable, heat up; Regulate maleic anhydride acylation chitosan salts solution pH value between the 8-12, it is joined in the above-mentioned natural rubber latex then, and add initiator benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, sulphur, hydrogen phosphide cumene, Potassium Persulphate, N, in the N-methylene-bisacrylamide one or both were parked 24 hours; Adding the activator tetraethylenepentamine, continue to heat up, is under 60 ℃～125 ℃ in temperature, reacts 2-24 hour, makes lactous maleic anhydride acylation chitosan salt/nature rubber graft copolymer.
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Cited By (8)
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| CN102010530A (en) * | 2010-11-11 | 2011-04-13 | 中国热带农业科学院农产品加工研究所 | Chitosan derivative/epoxidized natural rubber composite material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007186510A (en) * | 2005-12-28 | 2007-07-26 | Sunstar Inc | Denture stabilizer composition |
| CN101314631A (en) * | 2008-07-16 | 2008-12-03 | 太原理工大学 | Preparation process for nano-scale chitosan and latex graft copolymer |
-
2010
- 2010-06-03 CN CN2010101920351A patent/CN101864051B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007186510A (en) * | 2005-12-28 | 2007-07-26 | Sunstar Inc | Denture stabilizer composition |
| CN101314631A (en) * | 2008-07-16 | 2008-12-03 | 太原理工大学 | Preparation process for nano-scale chitosan and latex graft copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 《Fibers and Polymers》 20091231 Jobish Johns, et al. Mechanical Properties of MA Compatibilised NR/CS Blends 761-767 1 第10卷, 第6期 2 * |
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| CN102010530B (en) * | 2010-11-11 | 2012-11-21 | 中国热带农业科学院农产品加工研究所 | Chitosan derivative/epoxidized natural rubber composite material and preparation method thereof |
| CN102260763A (en) * | 2011-06-23 | 2011-11-30 | 陕西科技大学 | Modified chitosan amphoteric polymer retanning agent and preparation method thereof |
| CN102260763B (en) * | 2011-06-23 | 2013-09-25 | 陕西科技大学 | Modified chitosan amphoteric polymer retanning agent and preparation method thereof |
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| CN104448453B (en) * | 2013-09-18 | 2016-04-06 | 中国石油天然气股份有限公司 | The preparation method of the low cigarette of a kind of halogen acidylate, fire-retardant powder styrene butadiene rubber |
| CN105884930A (en) * | 2014-05-16 | 2016-08-24 | 中国热带农业科学院农产品加工研究所 | Preparation method of nano-chitosan for preparing antibacterial natural rubber composite material |
| CN106089155A (en) * | 2016-06-08 | 2016-11-09 | 刘家容 | A kind of geothermal well mixing water intaking well drilling technology |
| CN109320017A (en) * | 2018-11-02 | 2019-02-12 | 浙江海洋大学 | A kind of processing method of landfill leachate |
| CN109320017B (en) * | 2018-11-02 | 2021-09-17 | 浙江海洋大学 | Method for treating landfill leachate |
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