阅读说明：本技术 一种聚烯丙基苯甲酰胺-石墨烯水凝胶及其制法 (A kind of polyallyl benzamide-graphene hydrogel and its preparation method ) 是由 张贵勇 于 2019-08-16 设计创作，主要内容包括：本发明涉及石墨烯水凝胶技术领域,且公开了一种聚烯丙基苯甲酰胺-石墨烯水凝胶及其制法,包括以下原料：苯甲酰氯、丙烯基胺、缩合催化剂、聚合引发剂、石墨烯、无氧超纯水、四甲基乙二胺。该聚烯丙基苯甲酰胺-石墨烯水凝胶及其制法,通过使用聚烯丙基苯甲酰胺作为水凝胶基体,聚烯丙基苯甲酰胺中含有大量高活性基团<Image he="114" wi="213" file="DDA0002170133260000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其结构具有亚氨基容易和水通过氢键形成氢链网络结构,因此聚烯丙基苯甲酰胺具有很强的亲水性,提高了水凝胶的吸水性和保水性,同时聚烯丙基苯甲酰胺化学稳定性较好,聚烯丙基苯甲酰胺基水凝胶其化学性能稳定,热稳定性好,在高温下不易分解的优点,提高了水凝胶的耐久性和适用性。(The present invention relates to graphene technical field of hydrogel, and disclose a kind of polyallyl benzamide-graphene hydrogel and its preparation method, including following raw material: chlorobenzoyl chloride, acrylic amine, condensation catalyst, polymerization initiator, graphene, anaerobic ultrapure water, tetramethylethylenediamine.Polyallyl benzamide-graphene the hydrogel and its preparation method contain a large amount of high activity groups by using polyallyl benzamide as hydrogel matrix in polyallyl benzamide There is its structure imino group to be easy to pass through hydrogen bond formation hydrogen chain network structure with water, therefore polyallyl benzamide has very strong hydrophily, improve the water absorbency and water retentivity of hydrogel, polyallyl benzamide chemical stability is preferable simultaneously, its stable chemical performance of polyallyl benzamide based aquagel, the advantages of thermal stability is good, is not easily decomposed at high temperature improves the durability and applicability of hydrogel.)

1. a kind of polyallyl benzamide-graphene hydrogel and its preparation method, the raw material including following parts by weight proportion, Be characterized in that: 12-18 parts of chlorobenzoyl chlorides, 10-15 parts of acrylic amine, 0.4-0.7 parts of condensation catalysts, 0.5-2 parts of polymerizations cause Agent, 4-7 parts of graphenes, 57-73 parts of anaerobic ultrapure waters, 0.1-0.3 parts of tetramethylethylenediamines.

2. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The chlorobenzoyl chloride molecular formula is C₆H₅COCl, structural formula areIts mass fraction is 97.5-98.6%.

3. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The acrylic amine structure skeleton symbol is CH₂=CHCH₂-NH₂, mass fraction 96.2-98.1%.

4. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The condensation catalyst is 4-dimethylaminopyridine (DMAP), molecular formula C₇H₁₀N₂, structural formula isIts quality point Number is 95.6-97.7%.

5. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The polyethyleneglycol modified amination graphene of the graphene, structural formula are

6. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The anaerobic ultrapure water is finally to be passed through N by applying distillation, deionization, reverse osmosis technology₂Remove oxygen in water preparation It obtains.

7. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The polymerization initiator is benzoyl peroxide, and structural formula isIts mass fraction is 96.8- 98.1%.

8. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: The tetramethylethylenediamine skeleton symbol is (CH₃)₂N-CH₂CH₂-N(CH₃)₂, mass fraction 94.6-97.2%.

9. a kind of polyallyl benzamide-graphene hydrogel and its preparation method according to claim 1, it is characterised in that: A kind of polyallyl benzamide-graphene hydrogel, preparation method the following steps are included:

(1) it prepares allyl benzene formamide: being passed through N into 1000mL three-necked bottle₂Or Ar inert gas removes air, then to three The anhydrous n,N-Dimethylformamide of 400mL (DMF) is added in neck bottle, then successively weighs 12-18 parts of chlorobenzoyl chlorides, 10-15 part third Alkenyl amine, 0.4-0.7 parts of condensation catalyst 4-dimethylaminopyridine are added in three-necked bottle, and three-necked bottle is placed in thermostatical oil bath In, it is heated to 130-135 DEG C, 12-15h is at the uniform velocity stirred under magnetic stirring apparatus, reaction is observed by TLC thin layer chromatography After fully reacting, the solution in three-necked bottle is transferred in 2000mL separatory funnel for reaction result, be added 500mL distilled water and The extraction of 800mL ethyl acetate, takes ethyl acetate organic layer, and add 500mL distilled water and be extracted twice, obtaining ethyl acetate has Machine layer is simultaneously evaporated under reduced pressure by Rotary Evaporators and removes ethyl acetate, then will concentration mixture carried out by silica gel column chromatography it is thin Layer chromatography separation, eluant, eluent is petroleum ether: ethyl acetate=5:1, isolated product is enriched with, and pass through Rotary Evaporators Vacuum distillation and oil pump suction filtration, which be concentrated under reduced pressure, removes eluant, eluent, obtains product allyl benzene formamide, reaction equation is such as Under:

(2) it prepares polyallyl benzamide: 400mL ethylene glycol being added into 1000mL beaker, sequentially adds above-mentioned steps (1) allyl benzene formamide made from and 0.5-2 parts of polymerization initiators simultaneously stir evenly, and solution in beaker is transferred into high pressure water In thermal response kettle, and reaction kettle is placed in reaction kettle heater, is heated to 110-115 DEG C, 8-10h is reacted, after fully reacting It is cooled to room temperature, and material in reaction kettle is filtered by Buchner funnel, obtain canescence floccule, then use 3000- 3500mL distills water washing canescence floccule, finally the floccule of washes clean is placed in baking oven be heated to 70-75 DEG C it is dry Dry 6-8h obtains pale solid polyallyl benzamide

(2) it prepares polyallyl benzamide-graphene hydrogel: being passed through N into 1000mL three-necked bottle₂Or Ar inert gas removes Air is removed, polyallyl benzamide made from above-mentioned steps (2) and 57-73 parts of anaerobic ultrapure waters, 4-7 parts are sequentially added Graphene, 0.1-0.3 part tetramethylethylenediamine, three-necked bottle are placed in ultrasonication instrument, supersonic frequency 25-30KHz, ultrasound Power is 1800W, carries out ultrasonic disperse and handles 3-4h, and after fully reacting, gel semi-finished product are passed through 2000-2500mL distilled water Washing surface injects sealing moulding in mold after to be dried, obtains polyallyl benzamide-graphene hydrogel.

Technical field

The present invention relates to graphene technical field of hydrogel, specially a kind of polyallyl benzamide-graphene water-setting Glue and its preparation method.

Background technique

Hydrogel is the gel using water as decentralized medium, and one is introduced in the water soluble polymer with cross-linked network Divide hydrophobic grouping and hydrophilic residue, hydrophilic residue and water molecules, hydrone is connected to netted inside, and hydrophobic residue is met Water swellable cross-linked polymer is a kind of macromolecule network system, and property is soft, is able to maintain certain shape, can be absorbed a large amount of Water, as a kind of high water-keeping material of high water absorption, hydrogel is widely used in multiple fields, such as the drought resisting of arid area, makeup Facial mask, defervescence plaster used, pain easing plaster, agricultural film in product, the moisture condensation preventing agent in building, conditioning agent, the water blockoff in petrochemical industry It adjusts, the dehydration of crude oil or product oil, the dust suppressant in mining industry, antistaling agent, thickener in food, the drug in medical treatment carries Body etc., it is notable that different application fields should select different macromolecule raw materials, to meet the needs of different.

But hydrogel product mechanical performance currently on the market is poor, toughness is insufficient, and mechanical strength is lower, cause its When practical application, durability is not high, and the chemical stability of hydrogel and thermal stability are poor, has to temperature high sensitive Property, at high temperature, matrix, which is easy to decompose, causes hydrogel to lose performance, reduces the practicability and applicability of hydrogel.

Summary of the invention

(1) the technical issues of solving

In view of the deficiencies of the prior art, the present invention provides a kind of polyallyl benzamide-graphene hydrogel and its Preparation method, it is poor to solve existing gel products mechanical performance, and toughness is insufficient, the not high problem of durability, while solving water again The chemical stability and thermal stability of gel are poor, have hypersensitivity to temperature, and matrix, which is easy to decompose, at high temperature leads to water Gel loses the problem of performance.

(2) technical solution

To achieve the above object, the invention provides the following technical scheme: a kind of polyallyl benzamide-graphene water-setting Glue and its preparation method, the raw material including following parts by weight proportion: 12-18 parts of chlorobenzoyl chlorides, 10-15 parts of acrylic amine, 0.4-0.7 Part condensation catalyst, 0.5-2 parts of polymerization initiators, 4-7 parts of graphenes, 57-73 parts of anaerobic ultrapure waters, 0.1-0.3 parts of tetramethyls Ethylenediamine.

Preferably, the chlorobenzoyl chloride molecular formula is C₆H₅COCl, structural formula areIts mass fraction is 97.5- 98.6%.

Preferably, the acrylic amine structure skeleton symbol is CH₂=CHCH₂-NH₂, mass fraction 96.2-98.1%.

Preferably, the condensation catalyst is 4-dimethylaminopyridine (DMAP), molecular formula C₇H₁₀N₂, structural formula isIts mass fraction is 95.6-97.7%.

Preferably, the polyethyleneglycol modified amination graphene of the graphene, structural formula are

Preferably, the anaerobic ultrapure water is finally to be passed through N by applying distillation, deionization, reverse osmosis technology₂It removes Oxygen in water is gone to be prepared.

Preferably, the polymerization initiator is benzoyl peroxide, and structural formula isIts quality Score is 96.8-98.1%.

Preferably, the tetramethylethylenediamine skeleton symbol is (CH₃)₂N-CH₂CH₂-N(CH₃)₂, mass fraction is 94.6-97.2%.

Preferably, a kind of polyallyl benzamide-graphene hydrogel, preparation method the following steps are included:

(1) it prepares allyl benzene formamide: being passed through N into 1000mL three-necked bottle₂Or Ar inert gas removes air, then The anhydrous n,N-Dimethylformamide of 400mL (DMF) is added into three-necked bottle, then successively weighs 12-18 parts of chlorobenzoyl chlorides, 10-15 Part acrylic amine, 0.4-0.7 parts of condensation catalyst 4-dimethylaminopyridine are added in three-necked bottles, and three-necked bottle is placed in constant temperature oil bath In pot, it is heated to 130-135 DEG C, 12-15h is at the uniform velocity stirred under magnetic stirring apparatus, reaction is seen by TLC thin layer chromatography Reaction result is surveyed, after fully reacting, the solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water is added It is extracted with 800mL ethyl acetate, takes ethyl acetate organic layer, and add 500mL distilled water and be extracted twice, obtain ethyl acetate Organic layer is simultaneously evaporated under reduced pressure removing ethyl acetate by Rotary Evaporators, and concentration mixture is then passed through silica gel column chromatography and is carried out TLC separation, eluant, eluent are petroleum ether: ethyl acetate=5:1, isolated product are enriched with, and pass through rotary evaporation Instrument vacuum distillation and oil pump suction filtration, which be concentrated under reduced pressure, removes eluant, eluent, obtains product allyl benzene formamide, reaction equation It is as follows:

(2) it prepares polyallyl benzamide: 400mL ethylene glycol being added into 1000mL beaker, sequentially adds above-mentioned Allyl benzene formamide made from step (1) and 0.5-2 parts of polymerization initiators simultaneously stir evenly, and solution in beaker is transferred into height It presses in hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heater, be heated to 110-115 DEG C, react 8-10h, reacted It is cooled to room temperature after complete, and material in reaction kettle is filtered by Buchner funnel, obtained canescence floccule, then use 3000-3500mL distills water washing canescence floccule, and finally the floccule of washes clean is placed in baking oven and is heated to 70-75 DEG C dry 6-8h, obtains pale solid polyallyl benzamide

(3) it prepares polyallyl benzamide-graphene hydrogel: being passed through N into 1000mL three-necked bottle₂Or Ar indifferent gas Body removes air, sequentially adds polyallyl benzamide made from above-mentioned steps (2) and 57-73 parts of anaerobic ultrapure waters, 4- 7 parts of graphenes, 0.1-0.3 parts of tetramethylethylenediamines, three-necked bottle are placed in ultrasonication instrument, supersonic frequency 25-30KHz, Ultrasonic power is 1800W, carries out ultrasonic disperse and handles 3-4h, and after fully reacting, gel semi-finished product are steamed by 2000-2500mL Distilled water washing surface injects sealing moulding in mold after to be dried, obtains polyallyl benzamide-graphene hydrogel.

(3) beneficial technical effect

Compared with prior art, the present invention has following beneficial technical effect:

1, the polyallyl benzamide-graphene hydrogel and its preparation method are made by using polyallyl benzamide For hydrogel matrix, contain a large amount of high activity groups in polyallyl benzamide, structure has that imino group is easy and water is logical It crosses hydrogen bond and forms hydrogen chain network structure, therefore polyallyl benzamide has very strong hydrophily, improves the suction of hydrogel Aqueous and water-retaining property, while polyallyl benzamide chemical stability is preferable, compared with traditional polyacrylamide hydrogel, gathers Its stable chemical performance of allyl benzene formamido hydrogel, thermal stability is good, the advantages of being not easily decomposed at high temperature, improves The durability and applicability of hydrogel.

2, the polyallyl benzamide-graphene hydrogel and its preparation method, by the way that amination graphene modified water is added Gel, graphene have intensity high, good toughness, the excellent advantage of heat-conductive characteristic, improve graphene-hydrogel intensity and The mechanical performances such as toughness enhance the durability of hydrogel in practical applications, while graphene strengthens the heat biography of hydrogel Performance is led, improves the high temperature resistance of hydrogel, also, graphene is polyethyleneglycol modified amination graphene, tool There is electron donating property-NH₂Group is easy that graphene uniform is made to be attached to polyallyl benzamide surface, and polyethyleneglycol modified The excellent dispersion performance that has of amination graphene, improve the polyallyl benzamide-dispersion of graphene in water Performance, the hydrogel product dispersibility prepared is more preferable, and finely dispersed hydrogel has good tensile strength and fracture strong Degree, improves the durability in hydrogel mechanical performance and practical application.

Specific embodiment

To achieve the above object, the invention provides the following technical scheme: a kind of polyallyl benzamide-graphene water-setting Glue and its preparation method, the raw material including following parts by weight proportion: 12-18 parts of chlorobenzoyl chlorides, 10-15 parts of acrylic amine, 0.4-0.7 Part condensation catalyst, 0.5-2 parts of polymerization initiators, 4-7 parts of graphenes, 57-73 parts of anaerobic ultrapure waters, 0.1-0.3 parts of tetramethyls Ethylenediamine, chlorobenzoyl chloride molecular formula are C₆H₅COCl, structural formula areIts mass fraction is 97.5-98.6%, propylene Base amine structure skeleton symbol is CH₂=CHCH₂-NH₂, mass fraction 96.2-98.1%, condensation catalyst is 4- dimethylamino pyrrole Pyridine (DMAP), molecular formula C₇H₁₀N₂, structural formula isIts mass fraction is 95.6-97.7%.

Preferably, the polyethyleneglycol modified amination graphene of the graphene, structural formula areAnaerobic ultrapure water is finally passed through by applying distillation, deionization, reverse osmosis technology N₂It removes oxygen in water to be prepared, polymerization initiator is benzoyl peroxide, and structural formula isIts Mass fraction is 96.8-98.1%, and tetramethylethylenediamine skeleton symbol is (CH₃)₂N-CH₂CH₂-N(CH₃)₂, mass fraction is 94.6-97.2%, a kind of polyallyl benzamide-graphene hydrogel, preparation method the following steps are included:

(1) it prepares allyl benzene formamide: being passed through N into 1000mL three-necked bottle₂Or Ar inert gas removes air, then The anhydrous n,N-Dimethylformamide of 400mL (DMF) is added into three-necked bottle, then successively weighs 12-18 parts of chlorobenzoyl chlorides, 10-15 Part acrylic amine, 0.4-0.7 parts of condensation catalyst 4-dimethylaminopyridine are added in three-necked bottles, and three-necked bottle is placed in constant temperature oil bath In pot, it is heated to 130-135 DEG C, 12-15h is at the uniform velocity stirred under magnetic stirring apparatus, reaction is seen by TLC thin layer chromatography Reaction result is surveyed, after fully reacting, the solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water is added It is extracted with 800mL ethyl acetate, takes ethyl acetate organic layer, and add 500mL distilled water and be extracted twice, obtain ethyl acetate Organic layer is simultaneously evaporated under reduced pressure removing ethyl acetate by Rotary Evaporators, and concentration mixture is then passed through silica gel column chromatography and is carried out TLC separation, eluant, eluent are petroleum ether: ethyl acetate=5:1, isolated product are enriched with, and pass through rotary evaporation Instrument vacuum distillation and oil pump suction filtration, which be concentrated under reduced pressure, removes eluant, eluent, obtains product allyl benzene formamide, reaction equation It is as follows:

(2) it prepares polyallyl benzamide: 400mL ethylene glycol being added into 1000mL beaker, sequentially adds above-mentioned Allyl benzene formamide made from step (1) and 0.5-2 parts of polymerization initiators simultaneously stir evenly, and solution in beaker is transferred into height It presses in hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heater, be heated to 110-115 DEG C, react 8-10h, reacted It is cooled to room temperature after complete, and material in reaction kettle is filtered by Buchner funnel, obtained canescence floccule, then use 3000-3500mL distills water washing canescence floccule, and finally the floccule of washes clean is placed in baking oven and is heated to 70-75 DEG C dry 6-8h, obtains pale solid polyallyl benzamide

(3) it prepares polyallyl benzamide-graphene hydrogel: being passed through N into 1000mL three-necked bottle₂Or Ar indifferent gas Body removes air, sequentially adds polyallyl benzamide made from above-mentioned steps (2) and 57-73 parts of anaerobic ultrapure waters, 4- 7 parts of graphenes, 0.1-0.3 parts of tetramethylethylenediamines, three-necked bottle are placed in ultrasonication instrument, supersonic frequency 25-30KHz, Ultrasonic power is 1800W, carries out ultrasonic disperse and handles 3-4h, and after fully reacting, gel semi-finished product are steamed by 2000-2500mL Distilled water washing surface injects sealing moulding in mold after to be dried, obtains polyallyl benzamide-graphene hydrogel.