CN103788264B - A kind of grafting amido hydroximic acid polymkeric substance and preparation method thereof - Google Patents
A kind of grafting amido hydroximic acid polymkeric substance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of grafting amido hydroximic acid polymkeric substance and preparation method thereof, this polymkeric substance is prepared through substitution reaction by polyacrylic acid or chloromethylated polystyrene and N-kharophen alkyl hydroximic acid, wherein, N-kharophen alkyl hydroximic acid is by lactan and Acetyl Chloride 98Min. by N-amidate action, then under weak basic condition, carries out ring-opening reaction with azanol and obtain; Preparation method's process of the present invention is simple, reaction conditions is gentle, yield is high, in obtained amido hydroximic acid polymkeric substance, the percentage of grafting of hydroximic acid is up to more than 97%, to the iron in solution, copper, cobalt, nickel, lanthanum, cerium, yttrium, praseodymium, neodymium etc., there is good ligancy, flocculation agent can be used as, or precipitation by metallic ion agent, or ion exchange resin.
Description
Technical field
The present invention relates to a kind of grafting amido hydroximic acid polymkeric substance and preparation method thereof, belong to polymkeric substance preparation field.
Background technology
The coordination structure that hydroximic acid compound is unique because itself and metal ion are formed and excellent ligancy and be widely used in the fields such as the flotation in burning ore deposit, solvent extraction, chemical analysis, medicine and waste water control.Hydroximic acid resin is also applied to the field such as separation, enrichment of the metal ions such as iron, copper, rare earth.
At present, the synthesis of hydroximic acid polymkeric substance is that the method for carrying out polymer modification for skeleton with polystyrene, polyacrylic ester, polyacrylonitrile, polyacrylamide, starch and their multipolymer etc. prepares mostly.Patent CN1872885A discloses a kind of method preparing the water-soluble polymers containing hydroxamic acid group of amount of polymers, the water-soluble acrylic polymer powder of amount of polymers is dispersed in polar organic solvent by this method, carry out heterogeneous esterification with alkylating reagent and hydroxylamine solution respectively and hydroxamic acid compounds reacts, generate the water-soluble polymers containing hydroxamic acid group of amount of polymers.Wang Bi etc. have studied polyacrylamide and prepare with azanol reaction in the basic conditions containing hydroximic acid side group polymers collecting agent, (king is green by force for the chelating ability of this collecting agent and lead ion, Xu Guili, Hu Xingqi. chemical research and application .2008,20 (5): 561-564).Kumar etc. have studied polyacrylamide base hydroxamic acid resin to the adsorption and enrichment of the rare earth elements such as La, Ce, Pr in seawater, enrichment factor can reach more than 100, and not by the interference (KumarSA of Na (I), Mg (II), PandeySP, ShenoyNS, etal.Desalination, 2011,281:49-54).Lee etc. take ethyl propenoate as monomer, divinylbenzene is linking agent, trimethylpentane is pore-creating agent, adopt the method for suspension polymerization to prepare polyethyl acrylate and be cross-linked divinylbenzene spheroid, again this resin and oxammonium hydrochloride are reacted obtained hydroximic acid resin (T.S.Lee, D.W.Jeon, J.K.Kim in the basic conditions, etal.FibersandPolymers.2001,2 (1): 13 ~ 17.).Hydroxyl efficiency of oximation reaction due to polymkeric substance is subject to the restriction of polymer backbone, and reaction efficiency is lower.Patent CN103304713A discloses a kind of preparation method of poly-N-hexyl hydroximic acid acrylamide polymer, with acrylic acid polymer and 6-Aminohexyl hydroximic acid for raw material, at the temperature of 100 ~ 160 DEG C, react synthesis in 1 ~ 4 hour obtain poly-N-hexyl hydroximic acid acrylamide polymer.The method utilizes the amino of the carboxyl of acrylic acid polymer and 6-Aminohexyl hydroximic acid to carry out the grafting that substitution reaction realizes superpolymer, significantly improve reaction efficiency, but the temperature of reaction of this method is still higher, easily there is rearrangement reaction under hydroximic acid high temperature, decompose.
Summary of the invention
The object of the invention is the amido hydroximic acid polymkeric substance being to provide a kind of high percentage of grafting, this polymkeric substance has good ligancy to the iron in solution, copper, cobalt, nickel, lanthanum, cerium, yttrium, praseodymium, neodymium etc., can flocculation agent be used as, or precipitation by metallic ion agent, or ion exchange resin.
Another object of the present invention is the method being to provide a kind of process is simple, reaction conditions is gentle, yield is high preparation described amido hydroximic acid polymkeric substance.
A kind of grafting amido hydroximic acid polymkeric substance of the present invention, this grafting amido hydroximic acid polymkeric substance is prepared through substitution reaction by polyacrylic acid or chloromethylated polystyrene and the N-kharophen alkyl hydroximic acid with formula I structure, has formula II structural unit:
Wherein,
N is 3 ~ 5, R
or
group;
The percentage of grafting of N-kharophen alkyl hydroximic acid on polyacrylic acid or chloromethylated polystyrene is not less than 97%.
It is 200 ~ 6 × 10 that described polyacrylic acid comprises molecular weight
6linear polyacrylic acid or degree of crosslinking be the CP of 2% ~ 12%, described chloromethylated polystyrene degree of crosslinking is 2% ~ 12%.
Described N-kharophen alkyl hydroximic acid is prepared by following methods: by C
4~ C
6lactan and Acetyl Chloride 98Min. join in reactor with mol ratio 1:1.0 ~ 1.5, stir at 0 ~ 50 DEG C, carry out N-amidate action, simultaneously, the alkaline compound of described lactan 1.0 ~ 3.0 times of molar weights is slowly joined in described reactor, in and N-amidate action generate acid; After N-amidate action completes, in described reactor, add the azanol of described lactan 1 ~ 1.2 times of molar weight and the alkaline compound of described lactan 1 ~ 3 times of molar weight, carry out ring-opening reaction, after ring-opening reaction completes, in reactor, add acid be adjusted to pH value for acid, to obtain final product.
The described preferred temperature of reaction of N-acylation reaction is 15 ~ 40 DEG C; Most preferably be 25 ~ 35 DEG C.
The described N-acylation reaction time is 1 ~ 4h.
The described ring-opening reaction time is 1 ~ 4h.
Described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate, Quilonum Retard, calcium oxide, tertiary butyl sodium alkoxide or tertiary butyl potassium alcoholate.
The process that described alkaline compound slowly adds is that alkaline compound is divided into some parts, is added in batches in reaction solution by gained some parts of alkali.
The solvent that described N-acylation reaction adopts is methylene dichloride, chloroform or tetrahydrofuran (THF), and described solvent load is 2 ~ 5 times of lactan quality.
Described ring-opening reaction also adds water and/or methyl alcohol as solvent.
Described adjust ph is acid, and being preferably adjust ph is 4 ~ 6.
Described azanol adds with hydroxylammonium salt form, and described hydroxylammonium salt is oxammonium hydrochloride, oxammonium sulfate or carbonic acid azanol.
Present invention also offers a kind of preparation method of described grafting amido hydroximic acid polymkeric substance, this preparation method be by described N-kharophen alkyl hydroximic acid and polyacrylic acid or chloromethylated polystyrene under alkaline compound and condensing agent existence condition, carry out substitution reaction in 20 ~ 80 DEG C, to obtain final product; Wherein, the carboxyl in polyacrylic acid or the chloromethyl in chloromethylated polystyrene: the kharophen in N-kharophen hydroximic acid: alkaline compound: the mol ratio of condensing agent is 1:1 ~ 2:1.5 ~ 4:0.5 ~ 1.
Described condensing agent is N, N-carbonyl dimidazoles (CDI), benzotriazole-N, N, N, N-tetramethyl-urea phosphofluoric acid ester (HBTU), O-(7-nitrogen benzotriazole)-N, N, N, N-tetramethyl-urea phosphofluoric acid ester (HATU), N, N-dicyclohexylcarbodiimide (HOBt), N, N-DIC (DIC) or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus (PyBOP).
Described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate, Quilonum Retard, calcium oxide, tertiary butyl sodium alkoxide or tertiary butyl potassium alcoholate.
Described substitution reaction temperature of reaction is preferably 40 ~ 60 DEG C; Most preferably be 50 DEG C.
The described substitution reaction time is 1 ~ 4h.
The solvent that described substitution reaction adopts is acetone or toluene.
The linear grafting amido hydroximic acid polymkeric substance obtained for raw material with linear polypropylene acid polymer in the present invention can be used as flocculation agent or precipitation by metallic ion agent; Ion exchange resin can be used as with the hydroximic acid resin that CP or crosslinked chloromethylated polystyrene resin obtain for raw material.
Beneficial effect of the present invention: first the present invention obtains N-kharophen alkyl hydroximic acid by simple method, then N-kharophen alkyl hydroximic acid is grafted on grafting amido hydroximic acid polymkeric substance polyacrylic acid or chloromethylated polystyrene resin obtaining high percentage of grafting.The present invention is by strictly controlling temperature of reaction, and in conjunction with the use of weak base compound, farthest reduce decomposition and the rearrangement reaction of N-kharophen alkyl hydroximic acid in grafting substitution reaction process, can make polymkeric substance while obtaining higher yields, keep the hydroxyl oximate rate of superelevation, the grafting amido hydroximic acid polymkeric substance that the present invention obtains has good ligancy to the iron in solution, copper, cobalt, nickel, lanthanum, cerium, yttrium, praseodymium, neodymium etc., flocculation agent can be used as, or precipitation by metallic ion agent, or ion exchange resin; The preparation process of this polymkeric substance is simple, and reaction conditions is gentle, and product yield is high.
Accompanying drawing explanation
[Fig. 1] linearly gathers the infrared spectrogram of 4-(N-acetylacrylamide)-butyl hydroximic acid polymkeric substance.
[Fig. 2] linearly gathers the infrared spectrogram of 6-(N-acetylacrylamide)-hexyl hydroximic acid polymkeric substance.
[Fig. 3] gathers the infrared spectrogram of 4-(N-acetylacrylamide)-butyl hydroximic acid resin.
[Fig. 4] gathers the infrared spectrogram of 4-[(N-ethanoyl)-4-polyethylene benzamido group]-butyl hydroximic acid resin.
[Fig. 5] gathers the infrared spectrogram of 6-(N-acetylacrylamide)-hexyl hydroximic acid resin.
[Fig. 6] gathers the infrared spectrogram of 6-[(N-ethanoyl)-4-polyethylene benzamido group]-hexyl hydroximic acid resin.
Embodiment
Following examples are further illustrating content of the present invention, instead of limit the scope of the invention.
In embodiment, unless otherwise specified all numbers and percentage ratio all refer to quality.
Embodiment 1
The preparation of linear poly-4-(N-acetylacrylamide)-butyl hydroximic acid polymkeric substance
(1) controlling temperature of reactor is 30 DEG C, by 17.02 parts of purity be 99% 2-Pyrrolidone and 16.48 parts of purity be that 99% Acetyl Chloride 98Min. adds in reactor, add 45.28 parts of methylene dichloride and make solvent, under agitation 12.72 parts of sodium carbonate are divided and multiple batches ofly add reactor, react after 3 hours; And then 13.90 parts of oxammonium hydrochlorides and 42.40 parts of sodium carbonate are added in above-mentioned reactor, and add 47.40 parts of methanol as solvent, reaction 3 hours further; Then being adjusted to pH value with 1mol/L sulfuric acid is that 6 precipitation organic phases are 4-kharophen butyl hydroximic acid.
(2) by 4-kharophen butyl hydroximic acid obtained for 32 parts of steps 1,7.20 parts of molecular-weight average be 3000 linear polyacrylic acid and 16 parts of CDI add in reactor; add 92 parts of toluene and make solvent; under agitation add 32.4 parts of sodium carbonate; be heated to 50 DEG C; react 4 hours, filter, linearly gathered 4-(N-acetylacrylamide)-butyl hydroximic acid solid; product yield is 97.8%, and calculating polyacrylic hydroxyl oximate rate according to results of elemental analyses is 97.6%.The infrared spectra of product is shown in Fig. 1, wherein 3201cm
-1for N-H and O-H stretching vibration; 2912cm
-1and 2845cm
-1for saturated C-H stretching vibration; 1637cm
-1for C=O stretching vibration, 1569cm
-1for the stretching vibration of acid amides.
Embodiment 2
The preparation of linear poly-6-(N-acetylacrylamide)-hexyl hydroximic acid polymkeric substance
(1) according to the method for embodiment 1 step (1), it is the hexanolactam of 99% that the 2-Pyrrolidone being 99% by 17.02 parts of purity used changes 22.64 parts of purity into, and controlling temperature of reactor is 25 DEG C, and other condition is constant, obtained 6-kharophen hexyl hydroximic acid.
(2) the 6-kharophen hexyl hydroximic acid 37.6 parts of steps 1 obtained, 7.20 parts of molecular-weight average are 2 × 10
6polyacrylic acid and 16 parts of CDI add in reactor; add 58 parts of acetone as solvent; under agitation add 31.8 parts of sodium carbonate; be heated to 40 DEG C; react 4 hours, filter, obtain poly-6-(N-acetylacrylamide)-hexyl hydroximic acid solid; product yield is 96.1%, and calculating polyacrylic hydroxyl oximate rate according to results of elemental analyses is 98.9%.The infrared spectra of product is shown in Fig. 2, wherein 3156cm
-1for N-H and O-H stretching vibration; 2934cm
-1and 2856cm
-1for saturated C-H stretching vibration; 1644cm
-1for C=O stretching vibration, 1582cm
-1for the stretching vibration of acid amides.
Embodiment 3
The preparation of poly-4-(N-acetylacrylamide)-butyl hydroximic acid resin
The preparation process of 4-kharophen butyl hydroximic acid is identical with embodiment 1 step (1), just temperature of reaction is adjusted to 25 DEG C.32 parts of 4-kharophen butyl hydroximic acids, 8.62 parts of macropore polyacrylic resin D113 and 16 part CDI are added in reactor; add 58 parts of acetone as solvent; under agitation add 32.4 parts of sodium carbonate; be heated to 60 DEG C; react 4 hours, filter, obtain poly-4-(N-acetylacrylamide)-butyl hydroximic acid resin; product yield is 96.4%, and the hydroxyl oximate rate calculating polyacrylic resin according to results of elemental analyses is 97.9%.The infrared spectrogram of product is shown in Fig. 3, wherein 3429cm
-1for N-H and O-H stretching vibration; 2960cm
-1and 2927cm
-1for saturated C-H stretching vibration; 1734cm
-1for C=O stretching vibration, 1635cm
-1for the stretching vibration of acid amides.
Embodiment 4
The preparation of poly-4-[(N-ethanoyl)-4-polyethylene benzamido group]-butyl hydroximic acid resin
The preparation process of 4-kharophen butyl hydroximic acid is identical with embodiment 1 step (1), just temperature of reaction is adjusted to 25 DEG C.32 parts of 4-kharophen butyl hydroximic acids and 18.11 parts of chloromethylated styrene resins (cl content is 19.6%) are added in reactor with 10 parts of CDI; add 92 parts of toluene and make solvent; under agitation add 25.2 parts of sodium bicarbonates; be heated to 50 DEG C; react 4 hours; filter; obtain poly-4-[(N-ethanoyl)-4-polyethylene benzamido group]-butyl hydroximic acid resin; product yield is 98.1%, and the hydroxyl oximate rate calculating chloromethylated styrene resin according to results of elemental analyses is 98.7%.Product infrared spectrogram is shown in Fig. 4, wherein 3441cm
-1for N-H and O-H stretching vibration; 3023cm
-1and 2924cm
-1for saturated C-H stretching vibration; 1627cm
-1for the stretching vibration of amino.
Embodiment 5
The preparation of poly-6-(N-acetylacrylamide)-hexyl hydroximic acid resin
The preparation process of 6-kharophen hexyl hydroximic acid is identical with embodiment 2 step (1), just temperature of reaction is adjusted to 35 DEG C.37.6 parts of 6-kharophen hexyl hydroximic acids and 8.62 parts of macropore polyacrylic resin D113 and 16 part CDI are added in reactor; add 58 parts of acetone as solvent; under agitation add 42.4 parts of sodium carbonate; be heated to 50 DEG C; react 4 hours, filter, obtain poly-6-(N-acetylacrylamide)-hexyl hydroximic acid resin; product yield is 97.7%, and the hydroxyl oximate rate calculating polyacrylic resin according to results of elemental analyses is 97.2%.The infrared spectrogram of product is shown in Fig. 5, wherein 3426cm
-1for N-H and O-H stretching vibration; 2988cm
-1and 2927cm
-1for saturated C-H stretching vibration; 1727cm
-1for C=O stretching vibration, 1645cm
-1for the stretching vibration of acid amides.
Embodiment 6
The preparation of poly-6-[(N-ethanoyl)-4-polyethylene benzamido group]-hexyl hydroximic acid resin
The preparation process of 6-kharophen hexyl hydroximic acid is identical with embodiment 2 step (1), just temperature of reaction is adjusted to 25 DEG C.37.6 parts of 6-kharophen hexyl hydroximic acids and 18.11 parts of chloromethylated styrene resins (cl content is 19.6%) are added in reactor with 12 parts of DIC; add 92 parts of toluene and make solvent; under agitation add 42.4 parts of sodium carbonate; be heated to 40 DEG C; react 4 hours, filter, obtain poly-6-[(N-ethanoyl)-4-polyethylene benzamido group]-hexyl hydroximic acid resin; product yield is 97.9%, and the hydroxyl oximate rate calculating polyacrylic resin according to results of elemental analyses is 97.6%.The infrared spectrogram of product is shown in Fig. 6, wherein 3448cm
-1for N-H and O-H stretching vibration; 3025cm
-1and 2925cm
-1for saturated C-H stretching vibration; 1627cm
-1for the stretching vibration of amino.
Embodiment 7
Linear gathers the sedimentation function of 4-(N-acetylacrylamide)-butyl hydroximic acid
Get the Co (II) that 100 parts of concentration are 10mmol/L respectively, Cu (II), Fe (III) metal ion solution, be 5.5 by sulfuric acid adjust ph, respectively add 1 part and linearly gather 4-(N-acetylacrylamide)-butyl hydroximic acid as precipitation agent, stir 30 minutes at 25 DEG C, filtering separation filtrate and precipitation, measure the concentration of metal ion in filtrate, calculate Co in solution (II), Cu (II), the clearance of Fe (III) is respectively 89.22%, 95.30% and 90.85%, illustrate that linear poly-4-(N-acetylacrylamide)-butyl hydroximic acid is to Co (II), Cu (II), Fe (III) has good precipitation removal ability.
Embodiment 8
The flocculating settling characteristics of linear poly-6-(N-acetylacrylamide)-hexyl hydroximic acid
After 6-(N-acetylacrylamide)-hexyl hydroximic acid sodium hydroxide saponification will be gathered; joining solid content is in the alumina laterite slurry of 25%; poly-6-(N-acetylacrylamide)-hexyl hydroximic acid consumption is 5mg/L; within 15 minutes, substantially complete settling process; red mud height of deposition is 22.8% of the former height of ore pulp, illustrates that poly-6-(N-acetylacrylamide)-hexyl hydroximic acid has good settling property to red mud.
Embodiment 9
Polyamidoamines hydroximic acid resin is to metal biosorption performance
Compound concentration is the Fe (III) of 1g/L respectively, Cu (II), Ni (II), La (III), Y (III) metal ion solution, respectively add by the consumption of 4g/L poly-4-(N-acetylacrylamide)-butyl hydroximic acid resin that embodiment 3 ~ 6 prepares respectively, poly-6-(N-acetylacrylamide)-hexyl hydroximic acid resin, poly-4-[(N-ethanoyl)-4-polyethylene benzamido group]-butyl hydroximic acid resin and poly-6-[(N-ethanoyl)-4-polyethylene benzamido group]-hexyl hydroximic acid resin, controlling adsorption temp is 25 DEG C, adsorption time is 3 hours, the loading capacity recording resin is as shown in table 1.
Table 1 polyamidoamines hydroximic acid resin is to metal biosorption capacity (unit: mmol/g)
Claims (8)
1. the preparation method of a grafting amido hydroximic acid polymkeric substance, it is characterized in that, by the N-kharophen alkyl hydroximic acid of formula 1 structure and polyacrylic acid or chloromethylated polystyrene under alkaline compound and condensing agent existence condition, carry out substitution reaction in 20 ~ 80 DEG C, the grafting amido hydroximic acid polymkeric substance of formula II structural unit must be had; Wherein, the carboxyl in polyacrylic acid or the chloromethyl in chloromethylated polystyrene: the kharophen in N-kharophen hydroximic acid: alkaline compound: the mol ratio of condensing agent is 1:1 ~ 2:1.5 ~ 4:0.5 ~ 1;
Wherein,
N is 3 ~ 5, R
group;
The percentage of grafting of N-kharophen alkyl hydroximic acid on polyacrylic acid or chloromethylated polystyrene is not less than 97%.
2. preparation method as claimed in claim 1, it is characterized in that, it is 200 ~ 6 × 10 that described polyacrylic acid comprises molecular weight
6linear polyacrylic acid or degree of crosslinking be the CP of 2% ~ 12%, described chloromethylated polystyrene degree of crosslinking is 2% ~ 12%.
3. preparation method as claimed in claim 1, it is characterized in that, described N-kharophen alkyl hydroximic acid is prepared by following methods: by C
4~ C
6lactan and Acetyl Chloride 98Min. join in reactor with mol ratio 1:1.0 ~ 1.5, stir at 0 ~ 50 DEG C, carry out N-amidate action, simultaneously, the alkaline compound of described lactan 1.0 ~ 3.0 times of molar weights is slowly joined in described reactor, in and N-amidate action generate acid; After N-amidate action completes, in described reactor, add the azanol of described lactan 1 ~ 1.2 times of molar weight and the alkaline compound of described lactan 1 ~ 3 times of molar weight, carry out ring-opening reaction, after ring-opening reaction completes, in reactor, add acid be adjusted to pH value for acid, to obtain final product.
4. preparation method as claimed in claim 3, it is characterized in that, the described N-acylation reaction time is 1 ~ 4h.
5. preparation method as claimed in claim 3, it is characterized in that, the described ring-opening reaction time is 1 ~ 4h.
6. preparation method as claimed in claim 1, it is characterized in that, described condensing agent is N, N-carbonyl dimidazoles, benzotriazole-N, N, N, N-tetramethyl-urea phosphofluoric acid ester, O-(7-nitrogen benzotriazole)-N, N, N, N-tetramethyl-urea phosphofluoric acid ester, N, N-dicyclohexylcarbodiimide, N, N-DIC or phosphofluoric acid benzotriazole-1-base-oxygen base tripyrrole alkyl phosphorus.
7. preparation method as claimed in claim 1, it is characterized in that, described alkaline compound is sodium bicarbonate, saleratus, Calcium hydrogen carbonate, sodium carbonate, salt of wormwood, calcium carbonate or Quilonum Retard.
8. preparation method as claimed in claim 1, it is characterized in that, the described substitution reaction time is 1 ~ 4h.
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| CN109530094B (en) * | 2019-01-17 | 2021-05-28 | 湖南中医药大学 | Amido hydroxy carboxylic acid/hydroximic acid compound and application thereof in mineral flotation |
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