CN104479076A - Hydrophilic loofah - Google Patents
Hydrophilic loofah Download PDFInfo
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- CN104479076A CN104479076A CN201410740005.8A CN201410740005A CN104479076A CN 104479076 A CN104479076 A CN 104479076A CN 201410740005 A CN201410740005 A CN 201410740005A CN 104479076 A CN104479076 A CN 104479076A
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- luffa
- vegetable sponge
- sponge
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Abstract
The invention provides a hydrophilic loofah. The hydrophilic loofah is prepared by the following preparation method comprising the following steps: mixing loofah and an alkaline solution to obtain a pretreated loofah; and in the presence of an initiator, carrying out grafting reaction on a first monomer and the pretreated loofah to obtain the hydrophilic loofah, wherein the first monomer comprises one or more of acrylate and methacrylate; or mixing loofah and an alkaline solution to obtain a pretreated loofah; and in the presence of an initiator, carrying out grafting reaction on a second monomer and the pretreated loofah to obtain a modified loofah, wherein the second monomer comprises one or more of acrylamide, methacrylamide, acrylic acid and methacrylic acid; and reacting the modified loofah and an alkaline substance to obtain the hydrophilic loofah. The hydrophilic loofah provided by the invention comprises hydrophilic groups and has macroporous structures and fiber bundle structures so that the hydrophilic loofah has high water absorption rate.
Description
Technical field
The invention belongs to the technical field of Vegetable Sponge of Luffa, particularly relate to a kind of hydrophilic Vegetable Sponge of Luffa.
Background technology
Vegetable Sponge of Luffa has another name called chalina, is the vascular bundle of the dry mature fruit of cucurbitaceous plant sponge gourd.It has an abundant spongy capsule, by crisscross fibrous, it comprises Mierocrystalline cellulose and xylan (Xylan), may also contain mannosans (Mannan), Polygalactan (Galactan) and xylogen etc., Mierocrystalline cellulose accounts for 60%, hemicellulose account for 30% and xylogen account for 10% (Mao Jinhao, Shanghai University master Diplomarbeit, 2008).
Vegetable Sponge of Luffa is a kind of natural cellulose materials, and the research of Vegetable Sponge of Luffa concentrates on the third world countries such as South Asia, South Africa, South America.As Ghali (the ACS Symoposium Series in Tunisia, 385,337-354 (1989)), osmanli Seki (BioResources, 6,3836 – 3849 (2011)), Brazil Botaro (Journal of Applied Polymer Science, 123,2330-2337 (2012)) etc. people with the mechanical strength of Vegetable Sponge of Luffa reinforced polyester fiber, compare the microscopic appearance before and after synthesis, thermostability and crystal property simultaneously.The water-retaining capacity of natural fiber is not strong, be usually less than 10g/g, osmanli Demir uses 3-(trimethoxy is silica-based)-1-propylmercaptan, (3-aminopropyl) triethoxyl silane process Vegetable Sponge of Luffa surface respectively, then blended with the polypropylene (PP) through Maleic Anhydride Surface process, with the tensile strength of reinforced composite, and investigate the change at blended front and back water absorbing properties, surface microscopic topographic.Found that the water regain of untreated Vegetable Sponge of Luffa and PP blend is 2.7g/g, all occur declining through the Vegetable Sponge of Luffa of Maleic Anhydride Surface process and the water absorbent rate of PP blend through silane coupling agent surface-treated Vegetable Sponge of Luffa and PP blend and PP, drop to 1.7g/g, 1.6g/g, 1.9g/g (Composites:Part A:Applied scienceand manufacturing respectively, 37,447-456 (2006)).Therefore, the water absorbent rate to Vegetable Sponge of Luffa of prior art report is all lower.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of hydrophilic Vegetable Sponge of Luffa, hydrophilic Vegetable Sponge of Luffa provided by the invention has higher water absorbent rate.
The invention provides a kind of hydrophilic Vegetable Sponge of Luffa, obtained by following preparation method:
By Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa;
First monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa;
Described first monomer comprise in acrylate and methacrylate one or more.
The invention provides a kind of hydrophilic Vegetable Sponge of Luffa, obtained by following preparation method:
By Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa;
Second comonomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains modified loofah sponge;
Described second comonomer comprise in acrylamide, Methacrylamide, N hydroxymethyl acrylamide, vinylformic acid and methacrylic acid one or more;
Described modified loofah sponge and alkaline matter are reacted, obtains hydrophilic Vegetable Sponge of Luffa.
Preferably, described basic solution comprises one or more in sodium hydroxide solution, potassium hydroxide solution and aqua calcis;
The volumetric molar concentration of described basic solution is 0.001mol/L ~ 10mol/L.
Preferably, described graft reaction carries out under the existence of acidic aqueous solution;
Described acidic aqueous solution comprise in aqueous sulfuric acid, aqueous nitric acid, aqueous hydrochloric acid and phosphate aqueous solution one or more.
Preferably, described initiator comprises Oxidizing and Reducing Agents;
Described oxygenant comprise in Potassium Persulphate, manganese pyrophosphate, ceric ammonium nitrate, ammonium cerous sulfate and perchloric acid cerium one or more;
Described reductive agent is pre-treatment Vegetable Sponge of Luffa.
Preferably, the molar concentration rate of described oxygenant and monomer is (0.001 ~ 0.2): (0.2 ~ 10).
Preferably, the temperature of described graft reaction is 0 DEG C ~ 80 DEG C;
The time of described graft reaction is 2h ~ 72h.
Preferably, described alkaline matter comprises one or more in Strong oxdiative sodium water solution, potassium hydroxide aqueous solution and calcium hydroxide aqueous solution.
Preferably, the temperature that described modified loofah sponge and alkaline matter carry out reacting is 0 DEG C ~ 100 DEG C;
The time that described modified loofah sponge and alkaline matter carry out reacting is 1h ~ 36h.
Preferably, described hydrophilic Vegetable Sponge of Luffa comprises grafted cellulose and grafting hemicellulose;
The main chain of described grafted cellulose is Mierocrystalline cellulose, and the main chain of grafting hemicellulose is hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula I:
In formula I, described R is-H or-CH
3;
Described E is-ONa ,-OK ,-NH
2or-NH-CH
2oH.
The invention provides a kind of hydrophilic Vegetable Sponge of Luffa, obtained by following preparation method: by Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa; First monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa; Described first monomer comprise in acrylate and methacrylate one or more.Or by Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa; Second comonomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains modified loofah sponge; Described second comonomer comprise in acrylamide, Methacrylamide, vinylformic acid and methacrylic acid one or more; Described modified loofah sponge and alkaline matter are reacted, obtains hydrophilic Vegetable Sponge of Luffa.Grafting first monomer or second comonomer on hydrophilic Vegetable Sponge of Luffa provided by the invention, described first monomer or second comonomer are hydrophilic monomer, the hydrophilic Vegetable Sponge of Luffa prepared is made to comprise hydrophilic radical, and Vegetable Sponge of Luffa has macroporous structure and fiber Pipe bundle structure, hydrophilic Vegetable Sponge of Luffa is made to have higher water absorbent rate.Experimental result shows: the water absorbent rate of hydrophilic Vegetable Sponge of Luffa provided by the invention is 38.4g/g ~ 39.7g/g.
Embodiment
The invention provides a kind of hydrophilic Vegetable Sponge of Luffa, obtained by following preparation method:
By Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa;
First monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa;
Described first monomer comprise in acrylate and methacrylate one or more.
The present invention, by Vegetable Sponge of Luffa and basic solution mixing, obtains pre-treatment Vegetable Sponge of Luffa.The order by merging of the present invention to described Vegetable Sponge of Luffa and basic solution does not have special restriction, preferably Vegetable Sponge of Luffa is placed in basic solution.The present invention does not have special restriction to instrument used when described Vegetable Sponge of Luffa and basic solution mixing, adopts beaker well known to those skilled in the art.
The source of the present invention to described Vegetable Sponge of Luffa does not have special restriction, adopts Vegetable Sponge of Luffa well known to those skilled in the art, as adopted its commercial goods.
In the present invention, described basic solution preferably includes one or more in sodium hydroxide solution, potassium hydroxide solution and aqua calcis; The volumetric molar concentration of described basic solution is preferably 0.001mol/L ~ 10mol/L, is more preferably 0.01mol/L ~ 8mol/L, most preferably is 0.1mol/L ~ 7mol/L, is the most preferably 1mol/L ~ 3mol/L.In the present invention, described basic solution can remove the impurity on Vegetable Sponge of Luffa surface, and the hydroxyl in Vegetable Sponge of Luffa on Mierocrystalline cellulose and hemicellulose also can be made to come out.
In the present invention, in described basic solution, the amount of substance of solute and the mass ratio of Vegetable Sponge of Luffa are preferably (0.1 ~ 1) mol:(0.5 ~ 0.9) g, be more preferably (0.2 ~ 0.9) mol:(0.55 ~ 0.85) g, most preferably be (0.3 ~ 0.8) mol:(0.6 ~ 0.8) g.
In the present invention, the temperature of described Vegetable Sponge of Luffa and basic solution mixing is preferably 0 DEG C ~ 100 DEG C, is more preferably 10 DEG C ~ 90 DEG C, most preferably is 20 DEG C ~ 70 DEG C; The time of described Vegetable Sponge of Luffa and basic solution mixing is preferably 1h ~ 48h, is more preferably 4h ~ 40h, most preferably is 6h ~ 36h.
After completing the mixing of Vegetable Sponge of Luffa and basic solution, the Vegetable Sponge of Luffa after basic treatment preferably carries out washing and drying by the present invention successively, obtains pre-treatment Vegetable Sponge of Luffa.The method of the present invention to described washing does not have special restriction, adopts washing technology scheme well known to those skilled in the art.In the present invention, the solution of described washing preferably adopts distilled water.The present invention is preferably by extremely neutral for the Vegetable Sponge of Luffa washing after basic treatment.The method of the present invention to described drying does not have special restriction, adopts dry technology scheme well known to those skilled in the art.The present invention preferably adopts the mode of oven dry to carry out drying.In the present invention, the temperature of described oven dry is preferably 65 DEG C ~ 75 DEG C, is more preferably 68 DEG C ~ 72 DEG C, most preferably is 70 DEG C; The time of described oven dry is preferably 10h ~ 14h, is more preferably 11h ~ 13h, most preferably is 12h.Vegetable Sponge of Luffa after oven dry is preferably placed in moisture eliminator to constant weight by the present invention.
After obtaining pre-treatment Vegetable Sponge of Luffa, monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa by the present invention under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa.The order by merging of the present invention to the first monomer, initiator and pre-treatment Vegetable Sponge of Luffa does not have special restriction, preferably initiator and pre-treatment Vegetable Sponge of Luffa is first mixed, then adds the first monomer wherein.
In the present invention, described first monomer comprise in acrylate and methacrylate one or more, be more preferably sodium acrylate and/or sodium methacrylate.
In the present invention, described initiator preferably includes Oxidizing and Reducing Agents; Described oxygenant preferably include in Potassium Persulphate, manganese pyrophosphate, ceric ammonium nitrate, ammonium cerous sulfate and perchloric acid cerium one or more, more preferably comprise in Potassium Persulphate, ceric ammonium nitrate and ammonium cerous sulfate one or more; The molar concentration rate of described oxygenant and monomer is preferably (0.001 ~ 0.2): (0.2 ~ 10), be more preferably (0.01 ~ 0.18): (0.4 ~ 9), most preferably be (0.05 ~ 0.15): (1.0 ~ 8); The amount of substance of described oxygenant and monomer, than being preferably (0.01 ~ 0.08): 2mol, is more preferably (0.02 ~ 0.05): 2mol.
In the present invention, described reductive agent is pre-treatment Vegetable Sponge of Luffa; While the precursor of described pre-treatment Vegetable Sponge of Luffa as graft modification, also there is the effect of reduction, as the reductive agent in initiator, react as initiator initiation grafting together with described oxygenant.In an embodiment of the present invention, without the need to adding reductive agent in addition.In the present invention, described initiator is water soluble, redox system, causes the graft reaction of pre-treatment Vegetable Sponge of Luffa and monomer, makes the grafting efficiency of pre-treatment Vegetable Sponge of Luffa higher.
The present invention preferably carries out graft reaction under the existence of acidic aqueous solution.In the present invention, described acidic aqueous solution preferably includes one or more in aqueous sulfuric acid, aqueous nitric acid, aqueous hydrochloric acid and phosphate aqueous solution; The volumetric molar concentration of described acidic aqueous solution is preferably 0.001mol/L ~ 0.5mol/L, is more preferably 0.01mol/L ~ 0.4mol/L, most preferably is 0.1mol/L ~ 0.3mol/L; In described acidic aqueous solution, the amount of substance of solute and monomer is than being preferably 0.8 ~ 1.2:1000, is more preferably 0.9 ~ 1.1:1000.
The present invention preferably carries out graft reaction under sealed conditions.In the present invention, the temperature of described graft reaction is preferably 0 DEG C ~ 80 DEG C, is more preferably 5 DEG C ~ 75 DEG C, most preferably is 10 DEG C ~ 50 DEG C; The time of described graft reaction is preferably 2h ~ 72h, is more preferably 15h ~ 50h, most preferably is 36h ~ 48h.
After completing graft reaction, the graft reaction product obtained carries out washing and drying by the present invention, obtains hydrophilic Vegetable Sponge of Luffa.The present invention does not have special restriction to the method that grafting reaction product is washed, and adopts washing technology scheme well known to those skilled in the art.The present invention preferably adopts distilled water to wash grafting reaction product.The present invention is preferably extremely neutral by the washing of graft reaction product.After completing washing, the graft reaction product after washing is carried out drying by the present invention.The method of the present invention to the drying of the graft reaction product after washing does not have special restriction, adopts the technical scheme of drying well known to those skilled in the art.The present invention is preferably dried to constant weight to the graft reaction product after washing in vacuum drying oven.
The invention provides a kind of hydrophilic Vegetable Sponge of Luffa, obtained by following preparation method:
By Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa;
Second comonomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains modified loofah sponge;
Described second comonomer comprise in acrylamide, Methacrylamide, N hydroxymethyl acrylamide, vinylformic acid and methacrylic acid one or more;
Described modified loofah sponge and alkaline matter are reacted, obtains hydrophilic Vegetable Sponge of Luffa.
The present invention, by Vegetable Sponge of Luffa and basic solution mixing, obtains pre-treatment Vegetable Sponge of Luffa.
The source of the present invention to described Vegetable Sponge of Luffa does not have special restriction, adopts Vegetable Sponge of Luffa well known to those skilled in the art, as adopted its commercial goods.
In the present invention, described basic solution preferably includes one or more in sodium hydroxide solution, potassium hydroxide solution and aqua calcis; The volumetric molar concentration of described basic solution is preferably 0.001mol/L ~ 10mol/L, is more preferably 0.01mol/L ~ 8mol/L, most preferably is 0.1mol/L ~ 7mol/L, is the most preferably 1mol/L ~ 3mol/L.In the present invention, described basic solution can remove the impurity on Vegetable Sponge of Luffa surface, and the hydroxyl in Vegetable Sponge of Luffa on Mierocrystalline cellulose and hemicellulose also can be made to come out.
In the present invention, in described basic solution, the amount of substance of solute and the mass ratio of Vegetable Sponge of Luffa are preferably (0.1 ~ 1) mol:(0.5 ~ 0.9) g, be more preferably (0.2 ~ 0.9) mol:(0.55 ~ 0.85) g, most preferably be (0.3 ~ 0.8) mol:(0.6 ~ 0.8) g.
In the present invention, the temperature of described Vegetable Sponge of Luffa and basic solution mixing is preferably 0 DEG C ~ 100 DEG C, is more preferably 10 DEG C ~ 90 DEG C, most preferably is 20 DEG C ~ 70 DEG C; The time of described Vegetable Sponge of Luffa and basic solution mixing is preferably 1h ~ 48h, is more preferably 4h ~ 40h, most preferably is 6h ~ 36h.
After completing the mixing of Vegetable Sponge of Luffa and basic solution, the Vegetable Sponge of Luffa after basic treatment preferably carries out washing and drying by the present invention successively, obtains pre-treatment Vegetable Sponge of Luffa.The method of the present invention to described washing does not have special restriction, adopts washing technology scheme well known to those skilled in the art.In the present invention, the solution of described washing preferably adopts distilled water.The present invention is preferably by extremely neutral for the Vegetable Sponge of Luffa washing after basic treatment.The method of the present invention to described drying does not have special restriction, adopts dry technology scheme well known to those skilled in the art.The present invention preferably adopts the mode of oven dry to carry out drying.In the present invention, the temperature of described oven dry is preferably 65 DEG C ~ 75 DEG C, is more preferably 68 DEG C ~ 72 DEG C, most preferably is 70 DEG C; The time of described oven dry is preferably 10h ~ 14h, is more preferably 11h ~ 13h, most preferably is 12h.Vegetable Sponge of Luffa after oven dry is preferably placed in moisture eliminator to constant weight by the present invention.
After obtaining pre-treatment Vegetable Sponge of Luffa, monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa by the present invention under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa.The order by merging of the present invention to monomer, initiator and pre-treatment Vegetable Sponge of Luffa does not have special restriction, preferably initiator and pre-treatment Vegetable Sponge of Luffa is first mixed, then adds monomer wherein.
In the present invention, described second comonomer comprises one or more in acrylamide, Methacrylamide, N hydroxymethyl acrylamide, vinylformic acid and methacrylic acid.
In the present invention, described initiator preferably includes Oxidizing and Reducing Agents; Described oxygenant preferably include in Potassium Persulphate, manganese pyrophosphate, ceric ammonium nitrate, ammonium cerous sulfate and perchloric acid cerium one or more, more preferably comprise in Potassium Persulphate, ceric ammonium nitrate and ammonium cerous sulfate one or more; The molar concentration rate of described oxygenant and monomer is preferably (0.001 ~ 0.2): (0.2 ~ 10), be more preferably (0.01 ~ 0.18): (0.4 ~ 9), most preferably be (0.05 ~ 0.15): (1.0 ~ 8); The amount of substance of described oxygenant and monomer is than being preferably (0.01 ~ 0.08): 2, is more preferably (0.02 ~ 0.05): 2.
In the present invention, described reductive agent is pre-treatment Vegetable Sponge of Luffa; While the precursor of described pre-treatment Vegetable Sponge of Luffa as graft modification, also there is the effect of reduction, as the reductive agent in initiator, react as initiator initiation grafting together with described oxygenant.In an embodiment of the present invention, without the need to adding reductive agent in addition.In the present invention, described initiator is water soluble, redox system, causes the graft reaction of pre-treatment Vegetable Sponge of Luffa and monomer, makes the grafting efficiency of pre-treatment Vegetable Sponge of Luffa high.
The present invention preferably carries out graft reaction under the existence of acidic aqueous solution.In the present invention, described acidic aqueous solution preferably includes one or more in aqueous sulfuric acid, aqueous nitric acid, aqueous hydrochloric acid and phosphate aqueous solution; The volumetric molar concentration of described acidic aqueous solution is preferably 0.001mol/L ~ 0.5mol/L, is more preferably 0.01mol/L ~ 0.4mol/L, most preferably is 0.1mol/L ~ 0.3mol/L; In described acidic aqueous solution, the amount of substance of solute and monomer is than being preferably 0.8 ~ 1.2:1000, is more preferably 0.9 ~ 1.1:1000.
The present invention preferably carries out graft reaction under sealed conditions.In the present invention, the temperature of described graft reaction is preferably 0 DEG C ~ 80 DEG C, is more preferably 5 DEG C ~ 75 DEG C, most preferably is 10 DEG C ~ 50 DEG C; The time of described graft reaction is preferably 2h ~ 72h, is more preferably 15h ~ 50h, most preferably is 36h ~ 48h.
After completing graft reaction, the graft reaction product obtained carries out washing and drying by the present invention, obtains modified loofah sponge.The present invention does not have special restriction to the method that grafting reaction product is washed, and adopts washing technology scheme well known to those skilled in the art.The present invention preferably adopts distilled water to wash grafting reaction product.The present invention is preferably extremely neutral by the washing of graft reaction product.After completing washing, the graft reaction product after washing is carried out drying by the present invention.The method of the present invention to the drying of the graft reaction product after washing does not have special restriction, adopts the technical scheme of drying well known to those skilled in the art.The present invention is preferably dried to constant weight to the graft reaction product after washing in vacuum drying oven.
After obtaining modified loofah sponge, described modified loofah sponge and alkaline matter react by the present invention, obtain hydrophilic Vegetable Sponge of Luffa.The order by merging of the present invention to described alkaline matter and modified loofah sponge does not have special restriction, is preferably joined in modified loofah sponge by alkaline matter.In the present invention, when described second comonomer is acrylamide, Methacrylamide or N hydroxymethyl acrylamide, the modified loofah sponge obtained and alkaline matter are hydrolyzed and salt-forming reaction; When described second comonomer is acrylic or methacrylic acid, the modified loofah sponge obtained and alkaline matter carry out salt-forming reaction.
In the present invention, described alkaline matter preferably includes one or more in Strong oxdiative sodium water solution, potassium hydroxide aqueous solution and calcium hydroxide aqueous solution; In described alkaline matter, the volumetric molar concentration of solute is preferably 0.001mol/L ~ 10mol/L, is more preferably 0.1mol/L ~ 8mol/L, most preferably is 0.5mol/L ~ 5mol/L.
In the present invention, the amount of substance of described alkaline matter and the mass ratio of modified loofah sponge are preferably (0.0006 ~ 6) mol:0.55g, be more preferably (0.006 ~ 5) mol:0.55g, most preferably be (0.06 ~ 4) mol:0.55g.
In the present invention, the temperature that described modified loofah sponge and alkaline matter carry out reacting is preferably 0 DEG C ~ 100 DEG C, is more preferably 5 DEG C ~ 80 DEG C, most preferably is 10 DEG C ~ 50 DEG C; The time that described modified loofah sponge and alkaline matter carry out reacting is preferably 1h ~ 36h, is more preferably 2h ~ 30h, most preferably is 3h ~ 12h.
When the present invention obtains hydrophilic Vegetable Sponge of Luffa, the first monomer or second comonomer are grafted on Mierocrystalline cellulose in Vegetable Sponge of Luffa and hemicellulose, described hydrophilic Vegetable Sponge of Luffa comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula I:
In formula I, described R is-H or-CH
3;
Described E is-ONa ,-OK ,-NH
2or-NH-CH
2oH.
In the present invention, in hydrophilic Vegetable Sponge of Luffa, the side chain of grafted cellulose and grafting hemicellulose is grafted to by the first monomer or second comonomer and pre-treatment Vegetable Sponge of Luffa described in technique scheme is formed, the quality of described pre-treatment Vegetable Sponge of Luffa and the amount of substance of the first monomer are than being preferably (0.1 ~ 1.0) g:(0.01 ~ 0.4) mol, be more preferably (0.5 ~ 0.8) g:(0.1 ~ 0.3) mol; The quality of described pre-treatment Vegetable Sponge of Luffa and the amount of substance of second comonomer are than being preferably (0.2 ~ 1.0) g:(0.02 ~ 0.4) mol, be more preferably (0.4 ~ 0.7) g:(0.2 ~ 0.3) mol; The amount of substance of described alkaline matter and the mass ratio of modified loofah sponge are preferably (0.0006 ~ 6) mol:0.55g, are more preferably (0.006 ~ 5) mol:0.55g, most preferably are (0.06 ~ 4) mol:0.55g.
Concrete, shown in described formula I, the repeating unit of structure is specially:
The present invention carries out water absorbing properties test to obtained hydrophilic Vegetable Sponge of Luffa, and test process is as follows:
Be that the hydrophilic Vegetable Sponge of Luffa of A is put into distilled water and soaked 10min by quality, take out, be placed on 30s on filter screen, the water on elimination surface, and weigh and be designated as quality B, obtain the water absorbent rate of hydrophilic Vegetable Sponge of Luffa according to formula (1), in triplicate, the mean value of measurement is as water absorbent rate for this process:
Water absorbent rate (g/g)=(the B-A)/A (1) of hydrophilic Vegetable Sponge of Luffa
Wherein, A is the initial mass of hydrophilic Vegetable Sponge of Luffa, g;
B is the quality of the hydrophilic Vegetable Sponge of Luffa after soaking in distilled water, g.
The modified loofah sponge of the present invention to preparation carries out water absorbing properties test, and detailed process is as follows:
Be that the modified loofah sponge of C is put into distilled water and soaked 10min by quality, taking-up is placed on filter screen and weighs after 30s, is designated as quality D, calculates the water absorbent rate of modified loofah sponge according to formula (2), in triplicate, the mean value of measurement is as water absorbent rate for this process:
Water absorbent rate (g/g)=(the D-C)/C (2) of modified loofah sponge
Test result shows: the water absorbent rate of modified loofah sponge prepared by the present invention is 9.0g/g ~ 9.3g/g; The water absorbent rate of hydrophilic Vegetable Sponge of Luffa provided by the invention is 38.4g/g ~ 39.7g/g.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of hydrophilic Vegetable Sponge of Luffa provided by the invention being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
In 1000mL beaker, add 600mL 1.5mol/L sodium hydroxide solution and the fresh Vegetable Sponge of Luffa of 0.7g, temperature, at 70 DEG C, stirs 6h, neutrality is washed till with distilled water, after sample is dried 12 hours at 70 DEG C, put into moisture eliminator to constant weight, obtain pre-treatment Vegetable Sponge of Luffa;
100mL 0.02mol/L dilute nitric acid solution and 0.5g pre-treatment Vegetable Sponge of Luffa, 0.02mol ceric ammonium nitrate and 2mol acrylamide is added in 250mL two mouthfuls of flasks, sealing, graft reaction 48h is carried out in 30 DEG C, after reaction terminates, graft reaction product distilled water is washed till neutrality, then the graft reaction product after washing is dried to constant weight in vacuum drying oven, obtains the modified loofah sponge of Polyacrylamide Grafted;
In 1000mL beaker, add the mixing solutions of 600mL 2mol/L sodium hydroxide and calcium hydroxide and the modified loofah sponge of 0.55g Polyacrylamide Grafted, at 50 DEG C, stir, reaction 10h, washes 5 times by reaction product distilled water, each 600mL; Reaction product after washing is dried to constant weight in vacuum drying oven, obtains hydrophilic Vegetable Sponge of Luffa.
Hydrophilic Vegetable Sponge of Luffa prepared by the present invention comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula 101 and formula 102.
The present invention gets 0.1g modified loofah sponge and 0.1g hydrophilic Vegetable Sponge of Luffa respectively, and measure its water absorbent rate to distilled water according to the method described above, test result is: its water absorbent rate reaches 9.3g/g and 39.7g/g respectively.
Embodiment 2
600mL 0.5mol/L sodium hydroxide and potassium hydroxide mixed solution and the fresh Vegetable Sponge of Luffa of 0.7g is added in 1000mL beaker, when temperature maintains 35 DEG C, stir 36h, be washed till neutrality with distilled water, after sample is dried 12 hours at 70 DEG C, put into moisture eliminator to constant weight;
100mL 0.01mol/L sulphuric acid soln, 0.5g pre-treatment Vegetable Sponge of Luffa, 0.05mol Potassium Persulphate and 2mol Methacrylamide is added in 250mL two mouthfuls of flasks, sealing, in 10 DEG C of reaction 60h, after reaction terminates, take out reaction product, reaction product distilled water is washed till neutrality, in vacuum drying oven, is dried to constant weight, obtain the Vegetable Sponge of Luffa of PMAm graft modification;
The Vegetable Sponge of Luffa after 600mL 4mol/L sodium hydroxide solution and the graft modification of 0.55g PMAm is added in 1000mL beaker, temperature is at 10 DEG C, stir 12h, 5 times are washed with distilled water, each 600mL, in vacuum drying oven, be dried to constant weight, obtain the hydrophilic Vegetable Sponge of Luffa being hydrolyzed rear PMAm graft modification.
Hydrophilic Vegetable Sponge of Luffa prepared by the present invention comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula 103 and/or formula 104.
The present invention gets 0.1g modified loofah sponge and 0.1g hydrophilic Vegetable Sponge of Luffa, measures its water absorbent rate to distilled water according to the method described above, reaches 9.2g/g and 39.5g/g respectively.
Embodiment 3
In 1000mL beaker, add 600mL 1.25mol/L aqua calcis and the fresh Vegetable Sponge of Luffa of 0.7g, temperature, at 40 DEG C, stirs 24h, neutrality is washed till with distilled water, after sample is dried 12 hours at 70 DEG C, put into moisture eliminator to constant weight, obtain pre-treatment Vegetable Sponge of Luffa;
100mL 0.02mol/L sulphuric acid soln and the rear material of 0.5g alkalization is added in 250mL two mouthfuls of flasks, 0.02mol/L ammonium cerous sulfate, 1.5mol Methacrylamide, sealing, at 30 DEG C, carry out graft reaction 48h, after reaction terminates, graft reaction product distilled water is washed till neutrality, graft reaction product after washing is dried to constant weight in vacuum drying oven, obtains the modified loofah sponge of PMAm grafting;
The Vegetable Sponge of Luffa after 600mL 0.5mol/L potassium hydroxide solution and the graft modification of 0.55g PMAm is added in 1000mL beaker, at temperature maintains 25 DEG C, stir, reaction 3h, reaction product distilled water is washed 5 times, each 600mL, is then dried to constant weight by the reaction product after washing, obtains hydrophilic Vegetable Sponge of Luffa in vacuum drying oven.
Hydrophilic Vegetable Sponge of Luffa prepared by the present invention comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula 103 and/or formula 104.
Get 0.1g modified loofah sponge and 0.1g hydrophilic Vegetable Sponge of Luffa, measure its water absorbent rate to distilled water according to the method described above, reach 9.3g/g and 38.9g/g respectively.
Embodiment 4
In 1000mL beaker, add 600mL 1.5mol/L sodium hydroxide solution and the fresh Vegetable Sponge of Luffa of 0.7g, temperature 20 DEG C, stir 48h, be washed till neutrality with distilled water, after sample is dried 12 hours at 70 DEG C, put into moisture eliminator to constant weight, obtain pre-treatment Vegetable Sponge of Luffa;
100mL 0.02mol/L salpeter solution, 0.5g pre-treatment Vegetable Sponge of Luffa, 0.002mol/L ammonium cerous sulfate and Potassium Persulphate mixed solution and 2mol acrylamide is added in 250mL two mouthfuls of flasks, sealing, in 50 DEG C of reaction 36h, sample is washed till neutrality with distilled water after taking out, in vacuum drying oven, be dried to constant weight, obtain the modified loofah sponge of Polyacrylamide Grafted;
In 1000mL beaker, add the modified loofah sponge after 600mL 5mol/L potassium hydroxide and calcium hydroxide mixing solutions, 0.55g Polyacrylamide Grafted, at 10 DEG C, stir, reaction 36h, after reaction terminates, reaction product distilled water is washed 5 times, each 600mL; Then the reaction product after washing is dried to constant weight in vacuum drying oven, obtains hydrophilic Vegetable Sponge of Luffa.
Hydrophilic Vegetable Sponge of Luffa prepared by the present invention comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula 101 and/or formula 102.
Get 0.1g modified loofah sponge and hydrophilic Vegetable Sponge of Luffa, measure its water absorbent rate to distilled water according to the method described above, reach 9.0g/g and 39.6g/g respectively.
Embodiment 5
In 1000mL beaker, add 600mL 1.5mol/L potassium hydroxide solution and the fresh Vegetable Sponge of Luffa of 0.7g, temperature, at 70 DEG C, stirs 6h, neutrality is washed till with distilled water, after sample is dried 12 hours at 70 DEG C, put into moisture eliminator to constant weight, obtain pre-treatment Vegetable Sponge of Luffa;
100mL 0.02mol/L dilute nitric acid solution and the rear Vegetable Sponge of Luffa material of 0.5g alkalization is added in 250mL two mouthfuls of flasks, 0.02mol Potassium Persulphate, add 2mol sodium acrylate again, sealing, at 30 DEG C, react 48h, after reaction terminates, reaction product distilled water is washed till neutrality, reaction product after washing is dried to constant weight in 70 DEG C of vacuum drying ovens, obtains hydrophilic Vegetable Sponge of Luffa.
Hydrophilic Vegetable Sponge of Luffa prepared by the present invention comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula 101.
The present invention gets 0.1g hydrophilic Vegetable Sponge of Luffa, and measure its water absorbent rate to distilled water according to the method described above, test result is: the water absorbent rate of the hydrophilic Vegetable Sponge of Luffa that the present embodiment 5 is obtained can reach 38.9g/g.
Embodiment 6
600mL 1.5mol/L aqua calcis and the fresh Vegetable Sponge of Luffa of 0.7g is added in 1000mL beaker, temperature is at 70 DEG C, stir, reaction 6h, after reaction terminates, reaction product distilled water is washed till neutrality, the reaction product after washing is dried 12 hours at 70 DEG C, put into moisture eliminator to constant weight, obtain pre-treatment Vegetable Sponge of Luffa;
100mL 0.02mol/L dilute nitric acid solution and the rear Vegetable Sponge of Luffa material of 0.5g alkalization is added in 250mL two mouthfuls of flasks, 0.02mol ammonium cerous sulfate, add 2mol sodium methacrylate again, sealing, in 30 DEG C of reaction 48h, sample is washed till neutrality with distilled water after taking out, and is dried to constant weight, obtains hydrophilic Vegetable Sponge of Luffa in 70 DEG C of vacuum drying ovens.
Hydrophilic Vegetable Sponge of Luffa prepared by the present invention comprises grafted cellulose and grafting hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula 103.
The present invention gets 0.1g hydrophilic Vegetable Sponge of Luffa, and measure its water absorbent rate to distilled water according to the method described above, test result is: the water absorbent rate of the hydrophilic Vegetable Sponge of Luffa that the present embodiment 6 is obtained can reach 38.4g/g.
As seen from the above embodiment, the invention provides a kind of hydrophilic Vegetable Sponge of Luffa, obtained by following preparation method: by Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa; First monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa; Described first monomer comprise in acrylate and methacrylate one or more.Or by Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa; Second comonomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains modified loofah sponge; Described second comonomer comprise acrylamide, Methacrylamide, in one or more; Described modified loofah sponge and alkaline matter are reacted, obtains hydrophilic Vegetable Sponge of Luffa.Grafting first monomer or second comonomer on hydrophilic Vegetable Sponge of Luffa provided by the invention, described first monomer or second comonomer are hydrophilic monomer, the hydrophilic Vegetable Sponge of Luffa prepared is made to comprise hydrophilic radical, and Vegetable Sponge of Luffa has macroporous structure and fiber Pipe bundle structure, hydrophilic Vegetable Sponge of Luffa is made to have higher water absorbent rate.Experimental result shows: the water absorbent rate of hydrophilic Vegetable Sponge of Luffa provided by the invention is 38.4g/g ~ 39.7g/g.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a hydrophilic Vegetable Sponge of Luffa, is obtained by following preparation method:
By Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa;
First monomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains hydrophilic Vegetable Sponge of Luffa;
Described first monomer comprise in acrylate and methacrylate one or more.
2. a hydrophilic Vegetable Sponge of Luffa, is obtained by following preparation method:
By Vegetable Sponge of Luffa and basic solution mixing, obtain pre-treatment Vegetable Sponge of Luffa;
Second comonomer is carried out graft reaction with described pre-treatment Vegetable Sponge of Luffa under the existence of initiator, obtains modified loofah sponge;
Described second comonomer comprise in acrylamide, Methacrylamide, N hydroxymethyl acrylamide, vinylformic acid and methacrylic acid one or more;
Described modified loofah sponge and alkaline matter are reacted, obtains hydrophilic Vegetable Sponge of Luffa.
3. hydrophilic Vegetable Sponge of Luffa according to claim 1 and 2, is characterized in that, described basic solution comprise in sodium hydroxide solution, potassium hydroxide solution and aqua calcis one or more;
The volumetric molar concentration of described basic solution is 0.001mol/L ~ 10mol/L.
4. hydrophilic Vegetable Sponge of Luffa according to claim 1 and 2, is characterized in that, described graft reaction carries out under the existence of acidic aqueous solution;
Described acidic aqueous solution comprise in aqueous sulfuric acid, aqueous nitric acid, aqueous hydrochloric acid and phosphate aqueous solution one or more.
5. hydrophilic Vegetable Sponge of Luffa according to claim 1 and 2, is characterized in that, described initiator comprises Oxidizing and Reducing Agents;
Described oxygenant comprise in Potassium Persulphate, manganese pyrophosphate, ceric ammonium nitrate, ammonium cerous sulfate and perchloric acid cerium one or more;
Described reductive agent is pre-treatment Vegetable Sponge of Luffa.
6. hydrophilic Vegetable Sponge of Luffa according to claim 6, is characterized in that, the molar concentration rate of described oxygenant and monomer is (0.001 ~ 0.2): (0.2 ~ 10).
7. hydrophilic Vegetable Sponge of Luffa according to claim 1 and 2, is characterized in that, the temperature of described graft reaction is 0 DEG C ~ 80 DEG C;
The time of described graft reaction is 2h ~ 72h.
8. hydrophilic Vegetable Sponge of Luffa according to claim 2, is characterized in that, described alkaline matter comprise in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution and calcium hydroxide aqueous solution one or more.
9. hydrophilic Vegetable Sponge of Luffa according to claim 2, is characterized in that, the temperature that described modified loofah sponge and alkaline matter carry out reacting is 0 DEG C ~ 100 DEG C;
The time that described modified loofah sponge and alkaline matter carry out reacting is 1h ~ 36h.
10. hydrophilic Vegetable Sponge of Luffa according to claim 1 and 2, is characterized in that, described hydrophilic Vegetable Sponge of Luffa comprises grafted cellulose and grafting hemicellulose;
The main chain of described grafted cellulose is Mierocrystalline cellulose, and grafting hemicellulose backbone is hemicellulose;
The side chain of described grafted cellulose and grafting hemicellulose is made up of the repeating unit of structure shown in formula I:
In formula I, described R is-H or-CH
3;
Described E is-ONa ,-OK ,-NH
2or-NH-CH
2oH.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105217781A (en) * | 2015-10-10 | 2016-01-06 | 浙江省环境保护科学设计研究院 | A kind of natural polymer subbase material for water treatment and preparation method thereof |
| CN105670844A (en) * | 2016-03-15 | 2016-06-15 | 湖北工业大学 | Disposable loofah sponge energy-saving soap and preparation method thereof |
| CN107176881A (en) * | 2017-06-28 | 2017-09-19 | 常州麒通国际贸易有限公司 | A kind of Water-retaining slow-release fertilizer and preparation method thereof |
| CN112625476A (en) * | 2020-12-29 | 2021-04-09 | 成都芙涵麟涂料科技有限公司 | Preparation method of diatom ooze coating |
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| CN102600813B (en) * | 2012-04-06 | 2013-11-20 | 济南大学 | Preparation method and application of surface artemisinin molecule imprinting adsorbing material of vegetable sponge |
| CN102614852B (en) * | 2012-04-16 | 2013-11-20 | 武汉理工大学 | Preparation method for spongy ion exchange fiber |
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| VINOD KUMAR GUPTA, ET AL.: "Acrylic acid grafted cellulosic Luffa cylindrical fiber for the removal of dye and metal ions", 《CARBOHYDRATE POLYMERS》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217781A (en) * | 2015-10-10 | 2016-01-06 | 浙江省环境保护科学设计研究院 | A kind of natural polymer subbase material for water treatment and preparation method thereof |
| CN105217781B (en) * | 2015-10-10 | 2017-11-24 | 浙江省环境保护科学设计研究院 | A kind of natural polymer subbase material for water treatment and preparation method thereof |
| CN105670844A (en) * | 2016-03-15 | 2016-06-15 | 湖北工业大学 | Disposable loofah sponge energy-saving soap and preparation method thereof |
| CN105670844B (en) * | 2016-03-15 | 2018-09-25 | 湖北工业大学 | Disposable luffa energy-saving soap and preparation method thereof |
| CN107176881A (en) * | 2017-06-28 | 2017-09-19 | 常州麒通国际贸易有限公司 | A kind of Water-retaining slow-release fertilizer and preparation method thereof |
| CN112625476A (en) * | 2020-12-29 | 2021-04-09 | 成都芙涵麟涂料科技有限公司 | Preparation method of diatom ooze coating |
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