CN100336835C - Carboxyl grafting method of polystyrene - Google Patents
Carboxyl grafting method of polystyrene Download PDFInfo
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- CN100336835C CN100336835C CNB2005100617708A CN200510061770A CN100336835C CN 100336835 C CN100336835 C CN 100336835C CN B2005100617708 A CNB2005100617708 A CN B2005100617708A CN 200510061770 A CN200510061770 A CN 200510061770A CN 100336835 C CN100336835 C CN 100336835C
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Abstract
The present invention relates to a carboxyl grafting method of polystyrene, which is characterized in that an alkylation reaction of the polystyrene and lactone or enoic acid is carried out under the action of an acid catalyst, and alkyl carboxylic acid containing 3 to 6 carbon atoms is grafted into the structure of the polystyrene to obtain modified polystyrene resin with cation exchange performance. The carboxyl grafting method of polystyrene comprises the following steps: the polystyrene and the acidic catalyst are mixed and stirred in a reaction solvent; a water bath with the temperature of 0 to 80 DEG C is carried out; the alkylation reaction is carried out by adding the lactone or the enoic acid, and the reaction lasts for 1 to 100 hours; the solid matter of the carboxyl grafting polystyrene is obtained through an after-treatment technology. The present invention has the characteristics of catalyst and solvent reuse, and low reaction temperature.
Description
Technical field
The present invention relates to a kind of method of polystyrene graft carboxyl, particularly utilize polystyrene under an acidic catalyst effect and lactone, olefin(e) acid generation alkylated reaction, polystyrene graft carboxyl preparation surface has the method for the Zeo-karb of carboxyl.
Background technology
Polystyrene after the functionalization can be widely used in fields such as biology, catalysis and analytical separation.The particularly rise of combinatorial chemistry in recent years, a kind of important carrier of crosslinked polystyrene Chang Zuowei compound library synthetic after the functionalization.As be usually used in solid-phase polypeptide synthetic Merrifield resin, it be chloromethylation crosslinked polystyrene (" combinatorial chemistry ", p167).Below be the example that a surface functional crosslinking polystyrene is used in combinatorial chemistry:
Other surface-functionalized as (Reactive ﹠amp such as Xu about crosslinked polystyrene; Functional Polymers; Preparation ofanion exchangers by reductive amination of acetylated crosslinked polystyrene; 1999; 42:235-242) carry out acylations earlier for crosslinked polystyrene; carry out reduction amination then, thereby prepare resin with ion-exchange performance.The synthetic route is as follows:
Li Juan and Li Hua-Ming (European Polymer Journal; Functionalization of syndiotactic polystyrenewith succinic anhydride in the presence of aluminum chloride; 2005; 41:823-829) disclose and a kind ofly a hydroxy-acid group is connected on the polystyrene molecule in the acylation reaction under the effect of aluminum trichloride (anhydrous) with Succinic anhydried and polystyrene, the grafted molar ratio is between 0.5-6%.Reaction equation is as follows:
This method utilization be the F-C acylation reaction, Succinic anhydried is as a kind of acylating reagent.Not only contain carboxyl in the product that obtains with this method, and also have the carbonyl that directly links to each other with phenyl ring, if directly as support of the catalyst or solid state reaction carrier, the existence of this carbonyl may have some side effects.Then need further to be reduced if eliminate the influence of this carbonyl, promptly need polystep reaction, preparation technology is comparatively complicated, and this method is because the singularity of reactant structure can only be applicable to the reactant that contains 4 carbon atoms.
(J.Mao such as Mao Jianxin (Mao) and Okuhara, Y.Kamiya, T.Okuhara, Alkylation of 1,3,5-trimethylbenzenewith g-butyrolactone over heteropolyacid catalysts, Applied Catalysis A:General 2003,255 (2): 337-344; Okuhara and Nakajo, WO03/101925, Process for producing aromatic compounds by Friedel-crafts reaction), utilize the F-C alkylated reaction principles of chemistry, following reaction is disclosed:
Between the main explanation of this reaction and micromolecular aromatic hydrocarbons (1) and the gamma-butyrolactone F-C alkylated reaction can take place, thereby be mainly used in the alkyl acid that the little aromatic hydrocarbons of preparation molecular weight replaces: 4-(2,4, the 6-trimethylphenyl) butyric acid.This product is dissolved in reaction system, generally need obtain by method of extraction, therefore react under comparatively high temps (180 ℃) condition with solid acid catalyst (as heteropolyacid or Nafion-H) usually and obtain, the use of solid catalyst helps catalyzer and separates with reaction system, but the easy inactivation of solid catalyst, and temperature of reaction is higher.
Burzynski and Musial disclose about 4-phenylbutyric acid synthetic patent (US6,372,938,2002), they utilize gamma-butyrolactone and some small molecules aromatic hydrocarbons to synthesize the 4-phenylbutyric acid and the salt compounds thereof of a series of replacements under some Louis acid catalysis effects.Characteristics as reactant small molecules aromatic hydrocarbons are that they itself are liquid, therefore need not to add solvent in reaction system.The product that obtains like this---substituted aryl butyric acid and sodium salt thereof has the potential using value as the medicine aspect of some disease of treatment.The shortcoming of this class reaction system is that product and reactant and catalyzer are miscible, and catalyzer and small molecules product separating technique step are many, and catalyzer and solvent are difficult to reuse.
Summary of the invention
The present invention adopts the principles of chemistry of F-C alkylated reaction, utilize polystyrene under an acidic catalyst effect and lactone, olefin(e) acid generation alkylated reaction, purpose is that (the particularly surface of polystyrene material) connects an alkyl carboxylic acid that contains 3～6 carbon atoms in the polystyrene structure, make polystyrene surface be rich in alkyl carboxylic acid, become a kind of Zeo-karb material, this material can be applied in ion-exchange, chromatographic separation, support of the catalyst, solid phase synthesis or the biotechnology, has important use and is worth.
Polystyrene provided by the invention is under an acidic catalyst effect and lactone, olefin(e) acid generation alkylated reaction, connect an alkyl carboxylic acid that contains 3～6 carbon atoms in the polystyrene structure, what obtain is the modified polystyrene resin that the surface has cation exchange property.
During as reactant, chemical equation is as follows with lactone:
Wherein represent n=1～4 of carbon atom number.
If reactant is an olefin(e) acid, be example with vinylformic acid, chemical equation is as follows:
The steps include: polystyrene, an acidic catalyst, mix in the reaction solvent and stir, 0 ℃～80 ℃ water-baths (optimum temps is 15～45 ℃), add lactone or olefin(e) acid and carry out alkylated reaction, react 1～100 hour (Best Times is 4～10 hours), obtain the solid matter of the polystyrene of carboxyl grafting of the present invention through aftertreatment technology.Wherein consumption (weight) the proportionlity scope of polystyrene, an acidic catalyst, reaction solvent and lactone (or olefin(e) acid) four is 1: (0.1～10): (1～100): (0.01～10), optimum range is: 1: (1～5): (10～30): (0.5～3).
Polystyrene of the present invention is crosslinked polystyrene or uncrosslinked polystyrene.
An acidic catalyst of the present invention is aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, Zinc Chloride Anhydrous, anhydrous chlorides of rase gallium, anhydrous indium chloride.
Reaction solvent of the present invention is chlorobenzene, (adjacent, a position) dichlorobenzene, dithiocarbonic anhydride, oil of mirbane, Nitromethane 99Min..
Lactone of the present invention is the lactone of β, γ, δ, ε position, as beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi, 6-caprolactone.
Olefin(e) acid of the present invention comprises vinylformic acid, butenoic acid, pentenoic acid, hexenoic acid, and wherein the position of two keys can be at 2 to 4;
Aftertreatment technology of the present invention has two kinds: do not reclaim catalyzer and solvent 1.).Dope behind the alkylated reaction is poured into rapidly in hydrochloric acid-frozen water solution, fully stirs, and suction filtration, washing is to neutral, and drying is collected solid matter.2.) reclaim catalyzer and solvent.Dope behind the alkylated reaction, suction filtration under anhydrous state, with solid and liquid separation, the solution that will contain catalyzer and solvent after the separation reclaims, and is used for reacting next time; Separate the solid matter that obtains and then pour into rapidly in hydrochloric acid-frozen water solution, after fully stirring, suction filtration uses hot deionized water wash to neutral again, and drying is collected solid matter.
Product of the present invention be in surface or the structure grafting crosslinked polystyrene or the uncrosslinked polystyrene of 3-6 alkyl chain length carboxylic acid functional.
The technique effect that the present invention produces:
Crosslinked polystyrene of the present invention, it belongs to solid reactant, be in heterogeneous state with lactone, olefin(e) acid etc. in the liquid acid catalyst reaction of aluminum trichloride (anhydrous) etc., reaction finishes the back as long as can realize separating of product and catalyst system through simple suction filtration, make catalyzer and solvent to reuse, temperature of reaction lower (0 ℃-80 ℃).
The method of polystyrene graft carboxyl of the present invention, it is material modified to obtain new polystyrene surface, is applied in ion-exchange, chromatographic separation, support of the catalyst, solid phase synthesis or the biotechnology, has important use and is worth.
Concrete embodiment
Embodiment 1
Add uncrosslinked polystyrene 2.5g in the 100mL flask respectively, aluminum trichloride (anhydrous) 15g, orthodichlorobenzene 50ml, 2.5ml gamma-butyrolactone.Heating in water bath, temperature keeps 45 ℃, under agitation condition, reacted 5 hours, after reaction finishes, under agitation condition, pour into rapidly in 10% the hydrochloric acid ice aqueous solution, this moment, mixed solution became strongly-acid, and gained solution is grass green, wash the gained reaction mixture with saturated NaCl solution again, be washed till solution and be near neutral.Get the anhydrous CaCl of oil reservoir
2Drying, dried liquid are carried out underpressure distillation except that desolvating--orthodichlorobenzene, obtain thick liquid, and put into 100 ℃ of baking ovens and dry, obtain filemot solid 2g.Carboxyl is contained on the solid sample surface, and infrared spectra (FT-IR) analytical results confirms the (1705cm that exists of carboxyl in the sample
-1) consistent with the carbonyl peak of control sample 4-benzenebutanoic acid.
Embodiment 2.
Add crosslinked polystyrene 2.5g, orthodichlorobenzene 30mL, aluminum trichloride (anhydrous) 10g in the 50mL three-necked bottle, stir, the solution becomes yellowly, 20-32 ℃ of water-bath splashes into gamma-butyrolactone 2.5mL, stir and pour in hydrochloric acid-frozen water solution after 4 hours, crosslinked polystyrene still is solid-state in the system, and suction filtration (with a small amount of alcoholic solution washing) is extremely neutral with deionized water wash, collect solid matter, obtain solid sample 2.3 grams after the drying.
Embodiment 3.
Add crosslinked polystyrene 10g, orthodichlorobenzene 120mL, aluminum trichloride (anhydrous) 30g in the 250mL three-necked bottle, stir solution becomes yellowly, 20-32 ℃ of water-bath, splash into gamma-butyrolactone 10mL, continuously stirring, reaction soln becomes sorrel gradually, pour into after 4 hours in hydrochloric acid-frozen water solution, crosslinked polystyrene still is solid-state in the system, suction filtration (using the small amount of ethanol solution washing), extremely neutral with deionized water wash, collect solid matter, drying obtains solid sample 8.9 grams.Carboxyl is contained on the solid sample surface, and infrared spectra (FT-IR) analytical results confirms the (1705cm that exists of carboxyl in the sample
-1) consistent with the carbonyl peak of control sample 4-benzenebutanoic acid; The content of sample surfaces carboxyl can be determined H in this sample by the acid base titration volumetry in addition
+Ionic content (being the content of carboxyl) is 0.266mmol/g.
Embodiment 4.
Other conditions are with embodiment 3, and only changing the solvent orthodichlorobenzene is oil of mirbane.Obtain solid sample 8.5 grams at last.H in the sample
+Ionic content (being the content of carboxyl) is 0.245mmol/g.
Embodiment 5.
Add crosslinked polystyrene 10g in the 250mL three-necked bottle, orthodichlorobenzene 120mL, anhydrous indium chloride 30g stirs, the solution becomes yellowly, 32 ℃ of water-baths splash into gamma-butyrolactone 10mL, ceaselessly stir, react after 6 hours, get exsiccant suction filtration container and carry out suction filtration,, collect liquid to the exsiccant containers for future use with solid in the reaction system and liquid separation.Solid is then poured into rapidly in hydrochloric acid-frozen water solution, fully stirs, and suction filtration is extremely neutral with the deionized water wash of heat again, collects solid matter, and drying obtains solid sample 9.2 grams.Determine H in this sample by the acid base titration volumetry
+Ionic content (being the content of carboxyl) is 0.518mmol/g.
Embodiment 6.
Other conditions are with embodiment 5, and only changing the reactant gamma-butyrolactone is 6-caprolactone.Obtain solid sample 16 grams at last.Carboxyl is contained on the solid sample surface, and infrared spectra (FT-IR) analytical results confirms the (1705cm that exists of carboxyl in the sample
-1) consistent with the carbonyl peak of control sample 4-benzenebutanoic acid; H in the sample
+Ionic content (being the content of carboxyl) is 0.188mmol/g.
Embodiment 7.
Add crosslinked polystyrene 10g in the 250mL three-necked bottle, orthodichlorobenzene 120mL, aluminum trichloride (anhydrous) 30g stirs, the solution becomes yellowly, 25 ℃ of water-baths splash into vinylformic acid 10mL, ceaselessly stir, react after 6 hours, get exsiccant suction filtration container and carry out suction filtration,, collect liquid to the exsiccant containers for future use with solid in the reaction system and liquid separation.Solid is then poured into rapidly in hydrochloric acid-frozen water solution, fully stirs, and suction filtration is extremely neutral with the deionized water wash of heat again, collects solid matter, and drying obtains solid sample 8.8 grams.Carboxyl is contained on the solid sample surface, and infrared spectra (FT-IR) analytical results confirms the (1705cm that exists of carboxyl in the sample
-1) consistent with the carbonyl peak of control sample 4-benzenebutanoic acid; Determine H in this sample by the acid base titration volumetry
+Ionic content (being the content of carboxyl) is 0.147mmol/g.
Embodiment 8.
Add crosslinked polystyrene 10g, orthodichlorobenzene 120mL, Zinc Chloride Anhydrous 30g in the 250mL three-necked bottle, stir, the solution becomes yellowly, 40 ℃ of water-baths splash into 2-butylene acid 10mL, stir and pour in hydrochloric acid-frozen water solution after 4 hours, solid matter is arranged in the system, suction filtration (with a small amount of alcoholic solution washing), extremely neutral with deionized water wash, collect solid matter, obtain solid sample 9.0 grams after the drying.Determine H in this sample by the acid base titration volumetry
+Ionic content is 0.210mmol/g.
Claims (7)
1, a kind of method of polystyrene graft carboxyl, it is characterized in that polystyrene is under an acidic catalyst effect and lactone or olefin(e) acid generation alkylated reaction, in the polystyrene structure, connect an alkyl carboxylic acid that contains 3～6 carbon atoms, obtain having the modified polystyrene resin of cation exchange property, the steps include: polystyrene, an acidic catalyst, reaction solvent mixes, stir, 0～80 ℃ of water-bath, add lactone or olefin(e) acid and carry out alkylated reaction, reacted 1～100 hour, obtain the solid matter of the polystyrene of carboxyl grafting through aftertreatment technology, polystyrene wherein, an acidic catalyst, the consumption part by weight relation extents of reaction solvent and lactone or olefin(e) acid is 1: 0.1～10: 1～100: 0.01～10, and described an acidic catalyst is an aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, Zinc Chloride Anhydrous, the anhydrous chlorides of rase gallium, anhydrous indium chloride a kind of; Described lactone is the lactone of β, γ, δ, ε position; Described olefin(e) acid is a kind of of vinylformic acid, butenoic acid, pentenoic acid, hexenoic acid; Described reaction solvent is a kind of of chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, dithiocarbonic anhydride, oil of mirbane, Nitromethane 99Min..
2, the method for polystyrene graft carboxyl according to claim 1 is characterized in that the consumption part by weight relation extents 1: 1～5: 10～30: 0.5～3 of described polystyrene, an acidic catalyst, reaction solvent and lactone or olefin(e) acid.
3, the method for polystyrene graft carboxyl according to claim 1 is characterized in that described bath temperature scope is 15～45 ℃, alkylated reaction 4～10 hours.
4, the method for polystyrene graft carboxyl according to claim 1 is characterized in that described polystyrene is a crosslinked polystyrene.
5, the method for polystyrene graft carboxyl according to claim 1 is characterized in that described lactone is a kind of of beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi, 6-caprolactone.
6, the method for polystyrene graft carboxyl according to claim 1 is characterized in that described aftertreatment technology: the dope behind the alkylated reaction is poured into rapidly in hydrochloric acid-frozen water solution, fully stir, and suction filtration, washing is to neutral, and drying is collected solid matter; Or the dope behind the alkylated reaction, suction filtration under anhydrous state, with solid and liquid separation, the solution that will contain catalyzer and solvent after the separation reclaims, and is used for reacting next time; Separate the solid matter that obtains and then pour into rapidly in hydrochloric acid-frozen water solution, after fully stirring, suction filtration uses hot deionized water wash to neutral again, and drying is collected solid matter.
7, the method product of polystyrene graft carboxyl according to claim 1, the crosslinked polystyrene or the uncrosslinked polystyrene of 3-6 alkyl chain length carboxylic acid functional that it is characterized in that in surface or the structure grafting.
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| CN100336835C true CN100336835C (en) | 2007-09-12 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277441A (en) * | 2003-03-19 | 2003-10-02 | Asahi Denka Kogyo Kk | Polystyrene-type graft polymer and method for producing the same |
| CN1462758A (en) * | 2003-06-03 | 2003-12-24 | 南京师范大学 | Method for synthesizing resin with high water absorption by using polystyrene |
| CN1467235A (en) * | 2003-04-04 | 2004-01-14 | 湘潭大学 | Method for preparing polar monomer graft syndiotactic polystyrene copolymer |
| US20040132908A1 (en) * | 2003-01-07 | 2004-07-08 | Tsiang Raymond Chien-Chao | Graft copolymers of syndiotactic polystyrene with polar functional group containing grafting arms and processes for their preparations |
| CN1591005A (en) * | 2003-09-02 | 2005-03-09 | 浙江大学 | Linkage type cation chromatographic column and its preparation method |
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- 2005-12-02 CN CNB2005100617708A patent/CN100336835C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040132908A1 (en) * | 2003-01-07 | 2004-07-08 | Tsiang Raymond Chien-Chao | Graft copolymers of syndiotactic polystyrene with polar functional group containing grafting arms and processes for their preparations |
| JP2003277441A (en) * | 2003-03-19 | 2003-10-02 | Asahi Denka Kogyo Kk | Polystyrene-type graft polymer and method for producing the same |
| CN1467235A (en) * | 2003-04-04 | 2004-01-14 | 湘潭大学 | Method for preparing polar monomer graft syndiotactic polystyrene copolymer |
| CN1462758A (en) * | 2003-06-03 | 2003-12-24 | 南京师范大学 | Method for synthesizing resin with high water absorption by using polystyrene |
| CN1591005A (en) * | 2003-09-02 | 2005-03-09 | 浙江大学 | Linkage type cation chromatographic column and its preparation method |
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