CN102603976B - Preparation method of quaternary phosphonium cation starch microspheres - Google Patents
Preparation method of quaternary phosphonium cation starch microspheres Download PDFInfo
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Abstract
The invention discloses a preparation method of quaternary phosphonium cation starch microspheres. The method comprises the steps that: (1) starch, cation monomers, and acrylamide are weighed; (2) the starch is prepared into a paste by using water; the cation monomers and acrylamide are delivered into the paste; N,N'-methylenebisacrylamide is added to the mixture; an oxidizing agent is added to the mixture; the mixture is uniformly mixed, such that a dispersed phase is formed; (3) a disperse medium is adopted; an inverse suspending dispersing agent is added to the disperse medium; the mixture is heated, such that the dispersing agent is dissolved; (4) the dispersed phase is added to the disperse medium, and the mixture is uniformly mixed by stirring, such that a water-in-oil suspension liquid is formed; nitrogen is delivered in for removing oxygen; or a reducing agent can be added, and a reaction is carried out for 0.5-5h under a temperature of 0-60 DEG C; (5) when the reaction is finished, the temperature is reduced, oil and water phases are separated; and the material is washed, such that the cation starch microspheres are obtained. The technology provided by the invention is simple, and is suitable for industrial productions. The cation starch microspheres provided by the invention is advantaged in high absorbency and good thermal stability.
Description
Technical field
The present invention relates to the spherex preparation, a kind of preparation method of quaternary phosphine type cationic starch microballoon specifically, the cationic starch microballoon that adopts this technology to produce can be applied to that absorption and/or the control to anionic compound discharges in the industry such as chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry and the field.
Background technology
Crosslinked starch microspheres with natural polymer as carrier, have the advantages such as degradability, controlled capability, biocompatibility, absorption and embedding, raw material sources are abundant, have broad application prospects in the industries such as chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry and field as carrier, sorbent material, embedding medium etc., especially in medicine carrying and isolation of purified field.
Crosslinked starch microspheres has anionic starch microballoon, cationic starch microballoon and neutral starch microballoon three classes.The adsorption group of neutral starch microballoon is single, mainly depends on physical action and bigger serface and finishes absorption to target compound, a little less than the adsorption strength, has limited the widespread use of crosslinked starch microspheres.The ionic starch microballoon is to introduce negatively charged ion or cation group in the spherex molecular structure, changes absorption property, improves adsorption strength, realizes selective adsorption.Introduce cation group in the molecular structure of cationic starch microballoon, improved the ability that spherex adsorbs those electronegative property small molecules or ion.
The report of relevant cationic starch microballoon preparation aspect seldom.
CN1070116A discloses a kind of manufacture method of ion type starch microballs, and the method is to form with the alkaline solution of 5～40% cationic starches or anionic starch or ative starch and epoxy chloropropane or phosphorus oxychloride cross-link.Above-mentioned other microballoon can also suspend with the phosphorus oxychloride secondary crosslinking again and form.Prepared microballoon can adsorb charged will going, and the medicine that adsorbs is played saturation, reaches simultaneously the purpose of control release amount of medicine by regulating degree of crosslinking, need to be applicable to injection or the tablet medicine of slowly release.
The careful grade of Li Zhong prepared N with inverse suspension method, N '-methylene-bisacrylamide crosslinked starch microspheres, and the cationic starch microballoon for preparing with the crosslinked starch microspheres reaction take the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride as etherifying agent.The rounding form that the cationic starch microballoon has kept, but particle diameter slightly increases, and dispersing property is better.(Li Zhongjin, Zhao Xinfa. the cation modifying research of crosslinked starch microspheres. Shaanxi energy Vocationl Technical College journal, 2009,3(11), 21-24; Xiao Haojiang, Ning Qingju, Li Zhongjin, Zhao Xinfa, Zhu Lei. Cationic Starch Microspheres Synthesized By Inverse Suspension Method. Shaanxi Tech Univ's journal, 2007,25 (4), 32-36).
Summary of the invention
The purpose of this invention is to provide the method that a kind of " single stage method " prepares quaternary phosphine type cationic starch microballoon, namely adopted inverse suspension polymerization technique, when cationic monomer being grafted on the starch skeleton, carried out crosslinkedly, obtained the cationic starch microballoon.
The objective of the invention is to be achieved through the following technical solutions: the preparation method of quaternary phosphine type cationic starch microballoon of the present invention may further comprise the steps:
(1) take by weighing starch, cationic monomer, acrylamide, mass percent is 100/ 1～60/1～60; Described starch comprises any one in W-Gum, potato starch, sweet potato starch, tapioca (flour), sweet potato starch, wheat kind of starch, green starch, Rhizoma Nelumbinis starch, the water caltrop starch, or multiple.
Described cationic monomer has general formula:
Wherein, R
1, R
2, R
3, R
5, R
6, R
7The organic group of H, monovalence independently of one another; R
4Be the organic group of divalence, M is N or P, and X is Cl or Br.
Described cationic monomer can be one or more monomers, and selected monomer can Shi quaternary alkylphosphonium salt monomer Huo quaternary alkylphosphonium salt and quaternary ammonium salt.With the dissimilar monomer-grafted different qualities that can bring into play two kinds of chain links to the starch polymer.For example a kind of quaternary ammonium salt and a kind of quaternary alkylphosphonium salt are grafted to formed cationic starch microballoon on the starch skeleton together, its performance depends on quaternary ammonium salt on the one hand with the total amount of quaternary alkylphosphonium salt, it is the positively charged ion total amount, on the other hand because the atomic radius of P is greater than the cationic heat-resistant stability of quaternary phosphine of N and the sucting strength of electronegativity group all is better than quaternary ammonium cation, the ratio of quaternary alkylphosphonium salt so the performance of cationic starch microballoon also depends on quaternary ammonium salt.With the change of quaternary alkylphosphonium salt ratio, cationic starch microballoon performance such as absorption property, sustained release performance etc. can corresponding changes along with quaternary ammonium salt.
The preferred dimethyl diallyl ammonium chloride of described cationic monomer, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride or brometo de amonio, methylacryoyloxyethyl dimethyl octyl group brometo de amonio, allyl group trimethyl ammonium chloride or brometo de amonio, allyl group triphenyl ammonium chloride or brometo de amonio, 3-Methacrylamide oxypropyl trimethyl ammonium chloride, vinyl benzyl tributyl phosphonium chloride, vinyl benzyl triphenyl phosphonium chloride, allyl group triphenyl phosphonium chloride.
(2) water with starch pasting after, add cationic monomer, acrylamide, add the N that accounts for cationic monomer and acrylamide gross weight 1～10%, N '-methylene-bisacrylamide, adding accounts for cationic monomer, acrylamide and N, the oxygenant of N '-methylene-bisacrylamide gross weight 0.1～3%, and mix, form disperse phase, the amount of oxygenant preferred 0.1～1%.
Acrylamide is used for improving the grafting efficiency of cationic ethylenic polymer monomer on starch polymer as copolymerization monomer.
N, N '-methylene-bisacrylamide are used to form crosslinking structure and improve the grafting efficiency of cationic ethylenic polymer monomer on starch polymer as linking agent.Owing to the intensity difference of starch, limited to a great extent the range of application of starch granules.By making starch crosslinked, can improve the intensity of spherex, slow down the degradation speed of starch, also can reduce to a certain extent the ability of absorption electronegativity group.The amount of linking agent must be suitably, and too high meeting becomes fragile spherex, and the amount of absorption electronegativity group can descend; The intensity of crossing low then spherex is little, does not have and puies forward high-intensity purpose.
(3) get the dispersion medium of 2～10 times of disperse phase quality, add the inverse suspending agent of disperse phase quality 0.1～2% in the dispersion medium, heating makes the dispersion agent dissolving;
Described dispersion medium is mutual exclusive nonpolar or the organic solvent that polarity is little of any and water, preferred fat hydrocarbon and/or aromatic hydrocarbon are specially one or more combinations in toluene, dimethylbenzene, hexane, hexanaphthene, normal heptane, isomery paraffin, isoparaffin, gasoline, kerosene, vegetables oil, the chloroform.
The HLB value of described inverse suspending agent can be a kind of dispersion agent less than 8, also can be the mixture of multiple dispersion agent.Can be Span80, Span60 specifically, or the mixture of Span80, Span60 and Tween60.
(4) disperse phase is joined in the dispersion medium, stir, form water-in-oil-type suspension, then letting nitrogen in and deoxidizing; Take by weighing and account for cationic monomer, acrylamide and N, the reductive agent of N '-methylene-bisacrylamide gross weight 0～3% is dissolved in a small amount of water, and slowly is added in the dispersion system.Under 0～60 ℃ of temperature, reacted 0.5～5 hour.
Under the help of dispersion agent, water is scattered in the oil phase, under the vigorous stirring, form suspension, then initiation grafting copolymerization and crosslinked.Can be without reductive agent, and only just can the initiation grafting reaction with oxygenant.Preferred hydrogen peroxide, persulphate, tetravalent cerium salt.Again initiator system of ammonium persulfate, Sodium Persulfate, ceric ammonium nitrate.
Also described Oxidizing and Reducing Agents can be formed oxidation-reduction trigger system.Described oxidation-reduction trigger system can be hydrogen peroxide-ferrous salt, persulphate-ferrous salt, persulphate-sulphite, tetravalent cerium salt-alcohol or amine or mercaptan.Described reductive agent comprises that ferrous sulfate, iron protochloride, S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite, ammonium sulphite, ammonium bisulfite, alcohol, amine are a kind of, or multiple.Preferred persulphate-the sulphite of described oxidation-reduction trigger system.
(5) reaction cools the temperature to normal temperature after finishing, and profit is separated, and washing obtains the cationic starch microballoon.
The present invention adopts conventional inverse suspension polymerization technique, preparation quaternary phosphine salt type cationic starch microballoon, and technique is simple, is easy to suitability for industrialized production.Quaternary alkylphosphonium salt is compared with quaternary ammonium salt, and is thermally-stabilised good, and it is high about 100 times that anti-microbial property is wanted, strong with the binding ability of gegenion or group.Therefore, compare the Heat stability is good of the prepared De quaternary phosphine of the present invention type cationic starch microballoon, high adsorption capacity with existing quaternary ammonium cation starch microballoon.Quaternary alkylphosphonium salt monomer and quaternary ammonium salt monomer are grafted on the starch together, can reduce on the one hand the material cost of cationic starch microballoon, can change on the other hand the ratio of two kinds of cationic monomers, thereby regulate the absorption property of cationic starch microballoon.
Embodiment
The present invention is described further below in conjunction with embodiment, but is not restriction the present invention.
Embodiment 1
Measure 100 milliliters of toluene and 40 milliliters of Viscotrol C, place 250 milliliters of three-necked bottles, add 0.8 gram Span80, be heated to 50 ℃, stir, be made into oil phase.Extracting corn starch 6 grams are 85 ℃ of gelatinizations 30 minutes, cold really to room temperature with 50 ml distilled waters in addition.Add 1 gram N under stirring in starch paste, N '-methylene-bisacrylamide, 2 gram acrylamides, 3 gram allyl group trimethyl ammonium chlorides, 1 restrain allyl group three phenyl phosphonium bromides and 0.1 gram ammonium persulphate, stir, and obtain water.Water is slowly joined in the oil phase, and 600 rev/mins of control stirring velocitys place microscopically to observe every sampling in 2 minutes, and after the liquid pearl was uniformly dispersed, slowly adding was dissolved with a small amount of aqueous solution of 0.02 gram sodium bisulfite in advance, reacts 3 hours.Then, filter, use first the ethyl acetate cleaning, use again acetone, ethanol repetitive scrubbing.50 ℃ of vacuum-dryings obtain the white powder spherex.With 20 starch granuless of optics microscopic, asking its median size is 506 microns.
Embodiment 2
Measure 120 milliliters of hexanaphthenes, place 250 milliliters of three-necked bottles, add 0.6 gram Span80 and 0.4 gram Tween60, be heated to 50 ℃, stir, be made into oil phase.Other gets solubility W-Gum 2.0 grams, carries out gelatinization 30 minutes with 20 ml distilled waters at 80 ℃, is cooled to room temperature.Add 0.3 gram N under stirring in starch paste, N '-methylene-bisacrylamide, 2.0 gram acrylamides, 0.5 gram vinyl benzyl tributyl phosphonium chloride and 0.03 restrain ceric ammonium nitrate, stir, and are adjusted to slant acidity with nitric acid, obtain water.Water is slowly joined in the oil phase, place microscopically to observe every sampling in 2 minutes, after the liquid pearl is uniformly dispersed, be warming up to 40 ℃, reacted 4 hours.Then, leave standstill, high speed centrifugation separates, and divides and goes upper oil phase.With the polymer phase cleaning of ethyl acetate with lower floor, use acetone, ethanol repetitive scrubbing first, 50 ℃ of vacuum-dryings obtain the white powder spherex again.With 20 starch granuless of optics microscopic, asking its median size is 108 microns.
Embodiment 3
Measure 80 milliliters of hexanaphthenes and 20 milliliters of chloroforms, place 250 milliliters of three-necked bottles, by adding 0.9 gram Span60 and 0.1 gram Tween60, be heated to 50 ℃, stir, be made into oil phase.Other gets 2 gram tapioca (flour)s, with 30 ml distilled waters 85 ℃ of gelatinizations 30 minutes, be cooled to room temperature, continue to add 0.4 gram N, N '-methylene-bisacrylamide, 0.6 gram acrylamide, 0.5 gram vinyl benzyl tributyl ammonium chloride, 1.5 gram vinyl benzyl tributyl phosphonium chlorides and 0.2 gram Sodium Persulfate, stir, obtain water.Water is slowly joined in the oil phase, and 1500 rev/mins of control stirring velocitys place microscopically to observe every sampling in 2 minutes, until the liquid pearl is uniformly dispersed, fill the nitrogen deoxygenation 15 minutes.Be warming up to subsequently 65 ℃, add the aqueous solution that is dissolved with in advance 0.15 gram sodium bisulfite, reacted 2 hours.Then, leave standstill, high speed centrifugation separates, and divides and goes upper oil phase.With the polymer phase cleaning of ethyl acetate with lower floor, use acetone, ethanol repetitive scrubbing first, 50 ℃ of vacuum-dryings obtain the white powder spherex again.With 20 starch granuless of optics microscopic, asking its median size is 223 microns.
Claims (10)
1. the preparation method of a quaternary phosphine type cationic starch microballoon is characterized in that: may further comprise the steps:
(1) take by weighing starch, cationic monomer, acrylamide, three's proportion by weight is 100/ 1～60/1～60;
(2) water with starch pasting after, add cationic monomer, acrylamide, add the N that accounts for cationic monomer and acrylamide gross weight 1～10%, N '-methylene-bisacrylamide, add and account for cationic monomer, acrylamide and N, the oxygenant of N '-methylene-bisacrylamide gross weight 0.1～3%, and mix, disperse phase formed;
(3) get the dispersion medium of 2～10 times of disperse phase quality, add the inverse suspending agent of disperse phase quality 0.1～2% in the dispersion medium, heating makes the dispersion agent dissolving;
(4) disperse phase is joined in the dispersion medium, stir, form water-in-oil-type suspension, then letting nitrogen in and deoxidizing; Take by weighing and account for cationic monomer, acrylamide and N, the reductive agent of N '-methylene-bisacrylamide gross weight 0～3% is dissolved in a small amount of water, and slowly is added in the dispersion system, under 0～60 ℃ of temperature, reacts 0.5～5 hour;
(5) reaction cools the temperature to normal temperature after finishing, and profit is separated, and washing obtains the cationic starch microballoon.
2. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 1, it is characterized in that: cationic monomer is a kind of monomer or various of monomer.
3. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 1 and 2 is characterized in that: described cationic monomer Wei quaternary alkylphosphonium salt monomer, or quaternary alkylphosphonium salt and two kinds of monomers of quaternary ammonium salt and usefulness, and described cationic monomer has general formula:
Wherein, R
1, R
2, R
3, R
5, R
6, R
7The organic group of H, monovalence independently of one another; R
4Be the organic group of divalence, M is N or P, and X is Cl or Br.
4. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 3 is characterized in that two kinds of monomers of: Zai quaternary alkylphosphonium salt and quaternary ammonium salt and time spent, and both weight ratios are 1:0～30.
5. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 1, it is characterized in that: described starch is any one in W-Gum, potato starch, sweet potato starch, tapioca (flour), sweet potato starch, wheat kind of starch, green starch, Rhizoma Nelumbinis starch, the water caltrop starch, or multiple.
6. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 1 is characterized in that: described dispersion medium is immiscible nonpolar of any and water or organic solvent that polarity is little, and described dispersion medium is aliphatic hydrocarbon and/or aromatic hydrocarbon.
7. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 6, it is characterized in that: described organic solvent is one or more combinations in toluene, dimethylbenzene, hexane, hexanaphthene, normal heptane, isomery paraffin, isoparaffin, gasoline, kerosene, vegetables oil, the chloroform.
8. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 1, it is characterized in that: the HLB value of described inverse suspending agent can be a kind of dispersion agent less than 8, also can be composite dispersing agent.
9. according to claim 1 or the preparation method of 8 described quaternary phosphine type cationic starch microballoons, it is characterized in that: described inverse suspending agent is Span80, Span60, or the mixture of Span80, Span60 and Tween60.
10. the preparation method of quaternary phosphine type cationic starch microballoon according to claim 1, it is characterized in that: described oxygenant forms initiator system as initiator or Oxidizing and Reducing Agents, described oxygenant is persulphate, ceric ammonium nitrate, and it is persulphate-sulphite that described Oxidizing and Reducing Agents forms initiator system.
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| CN104250347B (en) * | 2013-06-28 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of acrylamide based copolymer and its preparation method and application |
| CN104004134B (en) * | 2014-05-30 | 2016-06-29 | 西华大学 | A kind of preparation method of the monodispersity arch nanospheres of size tunable |
| CN104479149B (en) * | 2014-12-14 | 2018-01-19 | 桂林理工大学 | Self-crosslinking AM/AA grafting is esterified the preparation method of Hydroxypropyl Tapioca Starch microballoon and its to Pb2+Absorption |
| CN109420469B (en) * | 2017-08-22 | 2021-01-05 | 中国石油化工股份有限公司 | Cationic doped starch microsphere material and preparation method and application thereof |
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