CN102250258A - pH-/temperature dual-sensitive starch derivative and preparation method thereof - Google Patents
pH-/temperature dual-sensitive starch derivative and preparation method thereof Download PDFInfo
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- CN102250258A CN102250258A CN 201110162526 CN201110162526A CN102250258A CN 102250258 A CN102250258 A CN 102250258A CN 201110162526 CN201110162526 CN 201110162526 CN 201110162526 A CN201110162526 A CN 201110162526A CN 102250258 A CN102250258 A CN 102250258A
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Abstract
The invention relates to a pH-/temperature dual-sensitive starch derivative and a preparation method thereof, belonging to the field of functional high polymer materials. The preparation method of the pH-/temperature dual-sensitive nitrogen-containing starch derivative comprises the following three steps: firstly, introducing -CH2CHOHCH2O-(CH2CH2O)n-R1 gene through carrying out a reaction on the starch and alkyl glycidyl polyoxyethylene ether; further carrying out a reaction on an obtained product from the former step and epoxypropyltrialkyl ammonium chloride or (3-chlorine-2-hydroxy propyl)trialkyl ammonium chloride so as to introduce -CH2CHOHCH2-N<+>ER4R5R6Cl<->; and then carrying out a reaction on the product obtained in the former step and glycidyl dialkylamine or (3-chloride-hydroxy propyl)dialkylamine to introduce a group -E-NR2R3 so as to obtain the pH-/temperature dual-sensitive starch derivative. The pH-/temperature dual-sensitive glycan derivative integrates the advantages of the starch and a pH-/temperature dual-sensitive polymer material, namely, the derivative has the characteristics of good biocompatibility, low toxicity, good pH-/temperature dual sensitivities and the like, and is cheap and degradable.
Description
Technical field
The present invention relates to a kind of pH-/temperature Lazer sensitive starch derivative and preparation method thereof, belong to functional high polymer material field.This starch base intelligent material can be used for fields such as drug delivery, transmitter, biotechnology, emulsification, intelligent catalysis, separation engineering.
Background technology
The intelligent polymer material can be under the irritating of extraneous factor, corresponding sudden change takes place in some physics of himself and chemical property, the environment factor of irritating has temperature, pH, solution composition, ionic strength, light intensity, electric field, stress and magnetic field etc., is also referred to as and irritates response, irritates sensitivity, environment sensitive or dexterous polymer materials.Oneself shows extremely tempting potential application foreground to these materials in different field, as fields such as drug delivery, diagnostics, organizational project, biosensor, coating and weavings.In this base polymer, what be subjected to that people pay close attention to most is temperature and pH sensitive polymer, because temperature and pH are convenient to a kind of signal that irritates of operating easily again, and are one of important factors in physiology, the biological and chemical system.
At present, pH-/temperature Lazer sensitive polymeric material that one of the development trend in this field has good biodegradability properties and physiologically acceptable performance for preparation is to satisfy the biomedicine field application requiring better.Wherein, polysaccharide obtains people's extensive concern by it as feedstock production polysaccharide base pH-/temperature Lazer sensitive polymeric material owing to inexpensive, renewable, nontoxic, biodegradable, good biocompatibility.Present polysaccharide base pH-/temperature Lazer sensitive polymeric material main preparation methods is the temperature sensitive synthetic macromolecule of grafting on polysaccharide base skeleton (as poly-N one N-isopropylacrylamide family macromolecule) and pH-responsive synthetic macromolecule (as polyacrylic acid) (Prabaharan, M.; Mano, J.F.Macromol.Biosci.2006,6,991-1008).The pH-that makes like this/temperature Lazer sensitive polymeric material, though the biodegradable and physiologically acceptable of its skeleton polysaccharide, but the responsive synthetic macromolecule part of the temperature sensitive synthetic macromolecule of graft polymerization and pH-can not be degraded, and can only be the Lazer's sensitive polymeric material that can partly degrade.In addition, present polysaccharide base pH-/temperature Lazer its lower critical solution temperature of sensitive polymeric material (LCST) span of control is narrow, generally at 25-34 ℃ of (Prabaharan, M.; Mano, J.F.Macromol.Biosci.2006,6,991-1008), therefore, application is restricted.
The starch that belongs to polysaccharide is the abundant natural high moleculer eompound of occurring in nature content, as cheap, be easy to get, nontoxic, biodegradable, reproducible biomass resource, its development and application is subjected to people's extensive attention.Prepare intelligent material if it is carried out chemical modification, and be applied in fields such as pharmaceutical carrier, transmitter, biotechnology, intelligent catalysis, separation engineering, will have bigger advantage.But at present, by starch is that feedstock production pH-/temperature Lazer sense material report is less, be detected in CN101830992A, but the pH-of its report/temperature Lazer sensitive starch derivative is carboxylic anionic pH-/temperature Lazer sensitive starch derivative, is restricted when the biomass of decoupled band negative charge such as the protein in the aqueous solution etc.
Summary of the invention
One of purpose of the present invention provides a kind of pH-/temperature Lazer and feels nitrogenous starch derivative and make each method; Two of purpose provides a kind of pH-/temperature Lazer sensitive starch derivative temperature sensitive and the responsive synthetic macromolecule of pH-that do not contain; Three of purpose just provide a kind of lower critical solution temperature can be in 10～85 ℃ of scopes the pH-/temperature Lazer sensitive starch derivative of accuracy controlling; Three of purpose just provides a kind of cationic pH-/temperature Lazer sensitive starch derivative.
As everyone knows, accurately control hydrophilic and can give water-soluble polymer temperature sensitive performance, further introduce weak ionogen and can give the pH-sensitive property.Therefore, we can utilize starch to have the characteristics of very high reactive behavior (three hydroxyls that can be used for reacting are arranged on each glucose unit), introduce specific hydrophobic group and light current from group, the hydrophilic of accurately regulating starch derivative can prepare pH-/temperature Lazer sensitive starch derivative.
Concrete technical scheme of the present invention is: it is hydrogen partial quilt-CH in the starch hydroxyl that nitrogenous starch derivative is felt by a kind of pH-/temperature Lazer
2CHOHCH
2O-(CH
2CH
2O)
n-R
1,-E-NR
2R
3Group and-CH
2CHOHCH
2-N
+R
4R
5R
6Cl
-The group replacement obtains, and it has following general structure:
PS-(A)
x(B)
y(C)
z (1)
(1) in the formula: PS is a starch, is selected from any in corn, potato, Ipomoea batatas, tapioca (flour) and the acid degradation starch thereof;
A is-CH
2CHOHCH
2O-(CH
2CH
2O)
n-R
1, n=0～5 wherein, R
1=C
3-8The straight or branched alkyl;
B is-CH
2CHOHCH
2-N
+R
4R
5R
6Cl
-, R
3, R
4And R
5=methyl or ethyl, R
3, R
4And R
5Identical or different;
C is-E-NR
2R
3, E=-CH wherein
2CH
2-or-CH
2CHOHCH
2-; R
2And R
3=C
2-5Alkyl, R
2And R
3Identical or different or R
2And R
3Common and nitrogen-atoms makeup ring;
X, y, z are substitution value, wherein 0.1＜x＜2,0.05＜y＜0.5,0.05＜z＜1.
It is to regulate pH-/temperature dual-sensitivity that the hydrophilic-lipophilic balance of starch derivative obtains by the substitution value of control group A, B, C that nitrogenous starch derivative is felt by described pH-/temperature Lazer, its lower critical solution temperature is 10～75 ℃ of range, by regulating its lower critical solution temperature of pH also 15～85 ℃ of range.
Preparation method's the step that nitrogenous starch derivative is felt by described a kind of pH-/temperature Lazer is as follows:
(1) at first with starch, account for starch weigh 10%～40% sodium hydroxide and with the starch quality ratio be that 1: 5～10 solvent joins in the middle of the reactor, 20～60 ℃ of stirring reactions 1 hour; By alkyl Polyethylene Glycol Bisglycidyl Ether and starch mol ratio is 0.15～4: 1, drips the alkyl Polyethylene Glycol Bisglycidyl Ether, at 60～80 ℃ of stirring reaction 5-8 hours; Hydrochloric acid neutralization, acetone is separated out, and filters, and is 60～90% aqueous acetone solution washing with weight percentage to the starch derivative of A group that do not had chlorion, dry acquisition grafting, and be used for next step;
(2) with the first step starch derivative, account for starch derivative weigh 2%～30% sodium hydroxide and with the starch quality ratio be that 1: 5～10 solvent joins in the middle of the reactor, 20～60 ℃ of stirring reactions 1 hour; By epoxypropyl tri alkyl ammomium chloride or (3-chloro-2-hydroxypropyl) tri alkyl ammomium chloride and starch mol ratio is 0.05～2: 1, add epoxypropyl tri alkyl ammomium chloride or (3-chloro-2-hydroxypropyl) tri alkyl ammomium chloride, at 40～80 ℃ of stirring reaction 5-8 hours, be neutralized to neutrality with hydrochloric acid, product with the aqueous methanol washing for several times, the starch derivative of dry A that obtained grafting and B group, and be used for next step;
(3) with the second step starch derivative, account for starch derivative weigh 2%～20% sodium hydroxide and with the starch quality ratio be that 1: 5～10 solvent joins in the middle of the reactor, 20～60 ℃ of stirring reactions 1 hour; By epoxypropyl dialkylamine or (3-chloro-2-hydroxypropyl) dialkylamine and starch mol ratio is 0.15～2: 1, add epoxypropyl dialkylamine or (3-chloro-2-hydroxypropyl) dialkylamine, at 40～80 ℃ of stirring reaction 5-8 hours, be neutralized to neutrality with hydrochloric acid, product with aqueous methanol washing for several times, the pH-/temperature Lazer sensitive starch derivative of dry obtained grafting A, B and three groups of C.
The massfraction that described solvent is selected from methanol aqueous solution, the water of water, 80-95% is that the massfraction of the aqueous ethanolic solution of 80-95%, water is isopropanol water solution any of 80-95%.
It is by control group A that nitrogenous starch derivative is felt by above-mentioned pH-/temperature Lazer, B, the substitution value of C is regulated pH-/temperature dual-sensitivity that the hydrophilic-lipophilic balance of starch derivative obtains, its lower critical solution temperature can be 10～75 ℃ of range, can also be 10～75 ℃ of range by regulating its lower critical solution temperature of pH.Such novel starch derivative because existing light current has hydrophobic grouping again from group on the starch chain, also has good surfactivity and rheologic behavio(u)r except having pH-/temperature dual-sensitivity energy.
The invention has the beneficial effects as follows: this pH-/temperature Lazer sensitive starch derivative combines starch and high molecular advantage is felt by pH-/temperature Lazer, excellent performance, compare inexpensive, good biocompatibility with present polysaccharide Ji Wenmin pH-/temperature Lazer sense polymer, toxicity is little, degradation property is outstanding, for fields such as medicine controlled releasing/slowly-releasing, bioseparation provide a kind of safer temperature sensitive polymer, and its LCST can regulate and control from the substitution value of group and hydrophobic grouping easily by light current on the adjusting starch chain.PH-/temperature Lazer the sensitive starch derivative of this method preparation can be applicable to pharmacy field, can be used as pharmaceutical carrier, has temperature sensitive controlled delayed release function, also can be used on the other biological field of medicaments.Can be used as the separation of coloured glaze water-based guest molecule in the separation engineering field.In the chemical reaction field, can be used as temperature control phase transfer reaction carrier.Because of its surface of good activity and rheologic behavio(u)r, this temperature sensitive starch also has thickening, emulsification, dispersive function, can be widely used in the daily-use chemical industry industry.
Embodiment
Embodiment 1
At first with 5 gram tapioca (flour)s, 1 gram sodium hydroxide, 20 ml waters join in 100 milliliters of there-necked flasks, heated and stirred to 40 ℃ reaction 1 hour, drip sec.-propyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) 4.35 grams then, be warming up to 60 ℃ of stirring reactions 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 20 ℃ of stirring reactions added epoxypropyl trimethylammonium chloride ammonium 0.29 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 0.24 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 2
At first with 5 gram tapioca (flour)s, 1 gram sodium hydroxide, 30 ml waters join in 100 milliliters of there-necked flasks, heated and stirred to 40 ℃ reaction 1 hour, drip sec.-propyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) 5.67 grams then, be warming up to 60 ℃ of stirring reactions 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 20 ℃ of stirring reactions added epoxypropyl trimethylammonium chloride ammonium 1.3 grams after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.5 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 2.58 grams after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 3
At first with 5 gram yam starchs, 1 gram sodium hydroxide, 30 ml waters join in 100 milliliters of there-necked flasks, heated and stirred to 40 ℃ reaction 1 hour, drip allyl polyglycol glycidyl ether (polymerization degree n=0) 3.85 grams then, be warming up to 70 ℃ of stirring reactions 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 35 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl trimethylammonium chloride ammonium 0.29 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 35 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 0.24 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 4
At first with 5 gram sweet potato starch, 1 gram sodium hydroxide, 30 ml waters join in 100 milliliters of there-necked flasks, heated and stirred to 40 ℃ reaction 1 hour, drip allyl polyglycol glycidyl ether (polymerization degree n=0) 6.59 grams then, be warming up to 70 ℃ of stirring reactions 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 35 ml waters, solid sodium hydroxide 1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl trimethylammonium chloride ammonium 0.65 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 35 ml waters, solid sodium hydroxide 0.5 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 5.16 grams after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 5
At first with 5 gram W-Gums, 1 restrains sodium hydroxide, and 25 ml waters join in 100 milliliters of there-necked flasks, and heated and stirred to 50 ℃ reaction 1 hour drips amyl group Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=3) 8.28 grams then, is warming up to 80 ℃ of stirring reactions 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl dimethyl ethyl ammonium chloride 0.36 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 35 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added N-epoxypropyl Pyrrolidine 0.27 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 6
At first with 5 gram W-Gums, 0.5 restrains sodium hydroxide, and 20 ml waters join in 100 milliliters of there-necked flasks, and stirring at room reaction 1 hour drips butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) 1.8 grams then, is warming up to 70 ℃ of stirring reactions 4 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, stirring at room reaction added epoxypropyl trimethylammonium chloride ammonium 0.29 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 0.24 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 7
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) add-on is 2.4 grams, and other steps are with embodiment 7.
Embodiment 8
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) add-on is 3 grams, and other steps are with embodiment 7.
Embodiment 9
At first with 5 gram W-Gums, 0.5 restrains sodium hydroxide, and 20 ml waters join in 100 milliliters of there-necked flasks, and stirring at room reaction 1 hour drips butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) 1.8 grams then, is warming up to 70 ℃ of stirring reactions 4 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.8 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, stirring at room reaction added epoxypropyl trimethylammonium chloride ammonium 2.4 grams after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.5 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 0.85 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 10
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=0) add-on is 2.4 grams, and other steps are with embodiment 10.
Embodiment 11
At first with 5 gram W-Gums, 1 restrains sodium hydroxide, and 20 ml waters join in 100 milliliters of there-necked flasks, and stirring at room reaction 1 hour drips butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) 4.3 grams then, is warming up to 70 ℃ of stirring reactions 4 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, stirring at room reaction added epoxypropyl trimethylammonium chloride ammonium 0.29 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 0.24 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 12
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) add-on is 4.8 grams, and other steps are with embodiment 12.
Embodiment 13
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) add-on is 5.4 grams, and other steps are with embodiment 12.
Embodiment 14
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) add-on is 6.6 grams, and other steps are with embodiment 12.
Embodiment 15
At first with 5 gram W-Gums, 2 gram sodium hydroxide, weight percentage is that 50 milliliters of 80% aqueous ethanolic solutions join in 100 milliliters of there-necked flasks, heated and stirred to 60 ℃ reaction 1 hour, drip butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) 6.7 grams then, be warming up to 70 ℃ of stirring reactions 8 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.In 100 milliliters of there-necked flasks, add 55 milliliters of weight percentage and be the starch derivative of 80% aqueous ethanolic solution, solid sodium hydroxide 1 gram, above-mentioned preparation, heated and stirred to 60 ℃ reaction 1 hour, add epoxypropyl dimethyl ethyl ammonium chloride 2.14 grams, be heated to 70 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and with methanol wash for several times, drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.5 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 3.87 grams after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 16
At first with 5 gram tapioca (flour)s, 1.5 gram sodium hydroxide, weight percentage is that 50 milliliters of 95% aqueous ethanolic solutions join in 100 milliliters of there-necked flasks, heated and stirred to 60 ℃ reaction 1 hour, drip butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) 5.2 grams then, be warming up to 70 ℃ of stirring reactions 8 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.In 100 milliliters of there-necked flasks, add 55 milliliters of weight percentage and be the starch derivative of 95% aqueous ethanolic solution, solid sodium hydroxide 0.1 gram, above-mentioned preparation, heated and stirred to 60 ℃ reaction 1 hour, add (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride 1.59 grams, be heated to 70 ℃ of reactions 7 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.100 milliliters of 55 milliliters of weight percentage is the starch derivative of 95% aqueous ethanolic solution, solid sodium hydroxide 0.1 gram, above-mentioned preparation, and 40 ℃ of stirring reactions added (2-chloroethyl) diethylamide 2.7 grams after 1 hour, were heated to 70 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 17
At first with 5 gram tapioca (flour)s, 2 restrain sodium hydroxide, and 40 ml waters join in 100 milliliters of there-necked flasks, and heated and stirred to 40 ℃ reaction 1 hour drips butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=2) 5.67 grams then, is warming up to 60 ℃ of stirring reactions 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 20 ℃ of stirring reactions added epoxypropyl trimethylammonium chloride ammonium 0.29 gram after 1 hour, were heated to 70 ℃ of reactions 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 30 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 0.24 gram after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 18
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=2) add-on is 6.7 grams, and other steps are with embodiment 12.
Embodiment 19
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) add-on is 8.5 grams, and other steps are with embodiment 12.
Embodiment 20
Butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=1) add-on is 10 grams, and other steps are with embodiment 12.
Embodiment 21
At first with 5 gram tapioca (flour)s, 2 gram sodium hydroxide, 50 milliliters of weight percentage are that 80% methanol aqueous solution joins in 100 milliliters of there-necked flasks heated and stirred to 40 ℃ reaction 1 hour, drip butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=2) 10.9 grams then, back flow reaction 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.In 100 milliliters of there-necked flasks, add 50 milliliters of weight percentage and be the starch derivative of 80% methanol aqueous solution, solid sodium hydroxide 0.5 gram, above-mentioned preparation, 50 ℃ of stirring reactions are after 1 hour, add epoxypropyl trimethylammonium chloride ammonium 1.94 grams, back flow reaction 7 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 80% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 50 ml waters, solid sodium hydroxide 0.5 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 4 grams after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 22
At first with 5 gram tapioca (flour)s, 2 gram sodium hydroxide, 50 milliliters of weight percentage are that 90% methanol aqueous solution joins in 100 milliliters of there-necked flasks heated and stirred to 40 ℃ reaction 1 hour, drip butyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=2) 16 grams then, back flow reaction 5 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.In 100 milliliters of there-necked flasks, add 50 milliliters of weight percentage and be the starch derivative of 90% methanol aqueous solution, solid sodium hydroxide 1 gram, above-mentioned preparation, 50 ℃ of stirring reactions are after 1 hour, add epoxypropyl trimethylammonium chloride ammonium 3.2 grams, back flow reaction 7 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 90% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 50 ml waters, solid sodium hydroxide 1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added epoxypropyl diethylamide 6.5 grams after 1 hour, were heated to 50 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 23
At first with 5 gram yam starchs, 2 gram sodium hydroxide, 50 milliliters of weight percentage are that 90% isopropanol water solution joins in 100 milliliters of there-necked flasks heated and stirred to 60 ℃ reaction 1 hour, drip hexyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=4) 10 grams then, back flow reaction 8 hours.Reaction finishes, and is neutralized to neutrality with hydrochloric acid, and operating weight percentage ratio is 90% aqueous acetone solution cleaning product, and drying is used for next step reaction.In 100 milliliters of there-necked flasks, add 50 milliliters of weight percentage and be the starch derivative of 90% isopropanol water solution, solid sodium hydroxide 0.1 gram, above-mentioned preparation, 50 ℃ of stirring reactions are after 1 hour, add epoxypropyl dimethyl ethyl ammonium chloride 0.36 gram, back flow reaction 7 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, and the product weight percentage is 90% methanol aqueous solution washing several, and drying is used for next step reaction.The starch derivative that adds 50 ml waters, solid sodium hydroxide 0.1 gram, above-mentioned preparation in 100 milliliters of there-necked flasks, 40 ℃ of stirring reactions added N-epoxypropyl hexahydropyridine 0.31 gram after 1 hour, were heated to 80 ℃ of reactions 6 hours.Reaction finishes, and is cooled to room temperature, is neutralized to neutrality with glacial acetic acid, product with aqueous methanol washing for several times, drying, grafting the pH-/temperature Lazer of A, B and three groups of C feel nitrogenous starch derivative.
Embodiment 24
Iso-octyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=5) substitutes hexyl Polyethylene Glycol Bisglycidyl Ether (polymerization degree n=4), and add-on is 12 grams, and other steps are with embodiment 23.
The lower critical solution temperature (LCST) of the above-mentioned preparation sample that records by light transmittance ratio method changes as shown in the table with pH.
The LCST under condition of different pH of embodiment sample
Claims (4)
1. pH-/temperature Lazer sensitive starch derivative, it is characterized in that: this starch derivative is the hydrogen partial quilt-CH in the starch hydroxyl
2CHOHCH
2O-(CH
2CH
2O)
n-R
1,-E-NR
2R
3Group and-CH
2CHOHCH
2-N
+R
4R
5R
6Cl
-The group replacement obtains, and it has following general structure:
PS-(A)
x(B)
y(C)
z (1)
(1) in the formula: PS is a starch, is selected from any in corn, potato, Ipomoea batatas, tapioca (flour) and the acid degradation starch thereof;
A is-CH
2CHOHCH
2O-(CH
2CH
2O)
n-R
1, n=0～5 wherein, R
1=C
3-8The straight or branched alkyl;
B is-CH
2CHOHCH
2-N
+R
4R
5R
6Cl
-, R
3, R
4And R
5=methyl or ethyl, R
3, R
4And R
5Identical or different;
C is-E-NR
2R
3, E=-CH wherein
2CH
2-or-CH
2CHOHCH
2-; R
2And R
3=C
2-5Alkyl, R
2And R
3Identical or different or R
2And R
3Common and nitrogen-atoms makeup ring;
X, y, z are substitution value, wherein 0.1＜x＜2,0.05＜y＜0.5,0.05＜z＜1.
2. a kind of pH-according to claim 1/temperature Lazer sensitive starch derivative, it is characterized in that: described pH-/temperature Lazer sensitive starch derivative is to regulate pH-/temperature dual-sensitivity that the hydrophilic-lipophilic balance of starch derivative obtains by the substitution value of control group A, B, C, its lower critical solution temperature is 10～75 ℃ of range, by regulating its lower critical solution temperature of pH 15～85 ℃ of range.
3. the preparation method of a kind of pH-according to claim 1/temperature Lazer sensitive starch derivative is characterized in that: this preparation method's step is as follows:
(1) at first with starch, account for starch weigh 10%～40% sodium hydroxide and with the starch quality ratio be that 1: 5～10 solvent joins in the middle of the reactor, 20～60 ℃ of stirring reactions 1 hour; By alkyl Polyethylene Glycol Bisglycidyl Ether and starch mol ratio is 0.15～4: 1, drips the alkyl Polyethylene Glycol Bisglycidyl Ether, at 60～80 ℃ of stirring reaction 5-8 hours; Hydrochloric acid neutralization, acetone is separated out, and filters, and is 60～90% aqueous acetone solution washing with weight percentage to the starch derivative of A group that do not had chlorion, dry acquisition grafting, and be used for next step;
(2) with the first step starch derivative, account for starch derivative weigh 2%～30% sodium hydroxide and with the starch quality ratio be that 1: 5～10 solvent joins in the middle of the reactor, 20～60 ℃ of stirring reactions 1 hour; By epoxypropyl tri alkyl ammomium chloride or (3-chloro-2-hydroxypropyl) tri alkyl ammomium chloride and starch mol ratio is 0.05～2: 1, add epoxypropyl tri alkyl ammomium chloride or (3-chloro-2-hydroxypropyl) tri alkyl ammomium chloride, at 40～80 ℃ of stirring reaction 5-8 hours, be neutralized to neutrality with hydrochloric acid, product with the aqueous methanol washing for several times, the starch derivative of dry A that obtained grafting and B group, and be used for next step;
(3) with the second step starch derivative, account for starch derivative weigh 2%～20% sodium hydroxide and with the starch quality ratio be that 1: 5～10 solvent joins in the middle of the reactor, 20～60 ℃ of stirring reactions 1 hour; By epoxypropyl dialkylamine or (3-chloro-2-hydroxypropyl) dialkylamine and starch mol ratio is 0.15～2: 1, add epoxypropyl dialkylamine or (3-chloro-2-hydroxypropyl) dialkylamine, at 40～80 ℃ of stirring reaction 5-8 hours, be neutralized to neutrality with hydrochloric acid, product with aqueous methanol washing for several times, the pH-/temperature Lazer sensitive starch derivative of dry obtained grafting A, B and three groups of C.
4. the preparation method of a kind of pH-according to claim 3/temperature Lazer sensitive starch derivative is characterized in that: the massfraction that described solvent is selected from methanol aqueous solution, the water of water, 80-95% is that the massfraction of the aqueous ethanolic solution of 80-95%, water is isopropanol water solution any of 80-95%.
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| CN101700922A (en) * | 2009-11-20 | 2010-05-05 | 大连理工大学 | cationic starch flocculant |
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