CN103374076A - Preparation method of oleophobic hydrophobic/hydrophilic functional self-conversion cellulose coating material - Google Patents
Preparation method of oleophobic hydrophobic/hydrophilic functional self-conversion cellulose coating material Download PDFInfo
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Abstract
The invention discloses a preparation method of an oleophobic hydrophobic/hydrophilic functional self-conversion cellulose coating material. The preparation method comprises the following steps of: adding 1-3 parts by weight of cellulose into 20-25 parts by weight of ionic liquid, dissolving, adding triphenylmethyl chloride and a pyrimidine catalyst, and reacting to obtain a reaction product I; adding methyl sodium chloroacetate into the reaction product I, and reacting to obtain a reaction product II; dispersing the reaction product II in an ethanol solution, dropping concentrated hydrochloric acid, and reacting to obtain a reaction product III; stirring 1, 1-2H-perfluoro alcohol and 4, 4-diphenylmethane diisocyanate to obtain a reaction product IV; adding the reaction product IV into the reaction product III to obtain a reaction product V; and grinding, placing into an acetone/water solution to prepare an emulsified solution, and coating on a PVC (polyvinyl chloride) thin film to obtain the oleophobic hydrophobic functional self-conversion cellulose coating material. According to the preparation method disclosed by the invention, a cellulose molecular chain stereoselective functional assembly method in the ionic liquid is introduced into the preparation of the amphipathic functional material, and the functional self-conversion of a coating can be further realized.
Description
Technical field
The present invention relates to a kind of functional cellulose coated material, particularly a kind of oleophobic hydrophobic/hydrophilic function is from changing cellulosic coating material preparation method.
Background technology
Along with the world economy fast development, oil, the colliery, increasingly exhausting and environmental pollution day by day serious of the Nonrenewable resources such as Sweet natural gas, cellulose-based agricultural-forestry biomass resources development and utilization becomes the focus of worldwide scientists study just gradually, be widely used at food, pulping and paper-making, the numerous areas such as functional composite material, many developed countries are with the development and utilization of the agricultural-forestry biomass resource consideration as national Major Strategic development, China also clearly with the agricultural-forestry biomass comprehensive exploitation with utilize as the field of giving priority in the national medium-to long-range program for scientific and technological development.Therefore, Efficient Development meets the needs of current science and technology guiding and socio-economic development with utilizing the agricultural-forestry biomass resource.
Cellulose molecular chain is with its special both sides chemical structure (C2, C3 ?OH and C6 ?OH), becomes the potential natural compounds of tool of preparation Amphoteric Materials.Therefore, how cellulose molecular chain is carried out molecular modification and functionalization assembling preparation both sexes functional materials, caused domestic and international scientist's extensive concern, become forward position and the hot issue of our times Mierocrystalline cellulose scientific research.For this reason, the researchist has carried out correlative study both at home and abroad, has obtained many important scientific payoffss.The foreign study personnel have also launched relevant research work, as Hwang etc. take dried shape Natvosol derivative as raw material in NaOH solution with toluenesulphonic acids poly fluoridation, the hydrophobic both sexes functional materials of preparation oleophobic.The method of the usefulness chemosynthesis such as Guittard is connected to hypromellose HPC with the perfluorooctane chloride chemistry and prepares both sexes and fluoridize cellulosic cpd.Cunha etc. are by the method for controlled heterogeneous modification, fluoridize bacteria cellulose with the penta fluoro benzene formyl chloride and prepare the super-hydrophobic cellulosic cpd material of fluoridizing, they also adopt 3 in toluene solution, 3,3 ?the trifluoropropyl acyl chlorides Mierocrystalline cellulose is carried out surface modification, it obtains preferably anti-water and anti-ester performance.
Then the method grafting Huan oxygen Bing Ji by atom transfer radical polymerization surface grafting and later stage modification ?methacrylic ester be the upper preparation in filter paper fibre element surface super-hydrophobic automatic cleaning fiber, then adopt the method for grafting poly diformazan silicon oxygen, perfluor molecular chain or alkyl to carry out surface treatment in the post-processed, the research surfacing has self-cleaning function.Above-mentioned research is to carry out the heterogeneous of cellulose molecular chain or homogeneous phase modification under conventional solvent (such as DMFc, NaOH/ urea, LiCl/DMAc) medium basically, with some functional group graftings at cellulose molecular chain C2, C3, on the C6, can't carry out the effective as selective modification, have both sexes functional materials or the compound of specific chemical structure with preparation.At present relevant research then is that the heterogeneous method petrochemical industry class organic polymer of employing is carrier, two kinds of different hydrophobic hydrophilic radical chemistry are connected, and the product yield that this preparation method obtains is low, and can have caused serious environmental pollution.
Summary of the invention
Purpose of the present invention is intended to overcome the problem that prior art exists, and provides a kind of in the situation that extraneous humidity changes, and can realize that oleophobic hydrophobic/hydrophilic function is from changing cellulosic coating material preparation method.
The present invention is by carrying out deep processing to the natural cellulose molecular chain, the oleophobic that 2 kinds of functions is different is hydrophobic, hydrophilic radical respectively chemistry be connected on the molecular chain, give molecular chain 2 different functions performances.The oleophobic functional group mainly be contain 1 ?the compound of 20 fluorine elements.The wetting ability functional group is to contain carboxylic group.The present invention utilizes cellulosic coating in the situation that extraneous humidity changes, cellulose molecular chain both sides oleophobic, hydrophilic radical cause the variation of coatingsurface tension force because of the variation of chemical space position, thereby the oleophobic hydrophobic/hydrophilic function that realizes the cellulosic coating material is changed function certainly.
The object of the invention is achieved through the following technical solutions:
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) in parts by weight, with 1 ?3 parts of Mierocrystalline celluloses join 20 ?in 25 parts of ionic liquids, 60 ?dissolve under 100 ℃ of temperature condition, add 6 ?10 parts of trityl chlorides and 9 ?15 parts of pyrimidine catalyzer, under the Ar atmospheric condition, be warming up to 70 ?100 ℃ keep 5 ?10h carry out C
6Upper trityl substitution reaction is cooled to room temperature, and reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, vacuum-drying obtains reaction product one; Described ionic liquid is 1 ?fourth base ?, 3 alkane imidazoles villaumites, 1 ?alkene the third basic ?3 alkane imidazoles villaumites or phosphorous acid hydrogen salt alkyl imidazole compound;
(2) methyl chloride with Mierocrystalline cellulose quality 5 ?8% adds in the dimethyl sulphoxide solution of reaction product one for sodium acetate, 60 ?100 ℃ of lower stirring reactions 20 ?72h, after finishing, reaction is down to room temperature, resulting solution is injected methanol solution, and with mass concentration be in 10 ?, 12% dilute acetic acid and after, adopt washing with alcohol, vacuum-drying obtains reaction product two again;
(3) in parts by weight, with 1 ?3 parts of reaction product two be scattered at ambient temperature in 15 parts of ethanolic solns, drip 1 ?5 parts of concentrated hydrochloric acids, react 20 ?behind the 30h, washing obtains reaction product three in lower vacuum-drying;
(4) with mol ratio be 1:1 ?1:1.8 1,1 ?2H ?perfluor alcohol and 4,4 ?the '-diphenylmethane diisocyanate coupling agent be dissolved in respectively in the dimethyl formamide reagent, and will dissolve 1,1 ?2H ?perfluor alcohol splash into 4,4 ?in the dimethyl formamide solution of '-diphenylmethane diisocyanate MDI, 50 ?70 ℃ lower stir 2 ?5h, under 90 ℃ of conditions of 60 ?, continue reaction 5 ?10h, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution; Be cooled to room temperature, obtain reaction product four; With described 1 ?3 parts of reaction product four join described 1 ?in 5 parts of reaction product three, 60 ?90 ℃ lower stir 6 ?20h, be cooled to room temperature, washing, drying gets reaction product five; 1,1 ?2H ?the structural formula of perfluor alcohol be CF
3(CF
2)
6CH
2OH;
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 ?15 parts of acetone/water solution, and 1500 rev/mins of high-speed stirring of 1350 ?are mixed the formation emulsified soln, prepare emulsion, and be uniformly coated on the PVC film, glue spread be 1 ?5g/cm
2, dry under vacuum condition, get the oleophobic hydrophobic function from changing the cellulosic coating material.
Preferably, the drying of described step (2), step (3) and step (4) be 55 ?65 ℃ of lower vacuum-dryings.Acetone and water equal-volume in the described acetone/water solution; In parts by weight, acetone/water solution is 10 parts.Described Mierocrystalline cellulose is bleached pulp Mierocrystalline cellulose, Microcrystalline Cellulose, pure cellulose or dissolving pulp Mierocrystalline cellulose.Described coated material preparation method adopts the coating preparation.Described concentrated hydrochloric acid mass concentration is 38%.The described drying of step (4) be through 40 ?45 ℃ of vacuum-drying 20-24h.Step (3) and (4) described washing are for using the methyl alcohol repetitive scrubbing.
With respect to prior art, the present invention has following advantage:
The present invention adopts homogeneous phase and the heterogeneous method that mutually combines, and oleophobic is hydrophobic, both sides that hydrophilic radical is connected to cellulose molecular chain reach efficient and the modification of the degree of depth first, prepares oleophobic, hydrophile function from the cellulosic coating material of conversion; The present invention utilizes cellulosic coating in the situation that extraneous humidity changes, and cellulose molecular chain both sides oleophobic, hydrophilic radical be because of surface tension variations, and causes the locus of chemical group to change, the certainly conversion of practical function.
Embodiment
For understanding better the present invention, the invention will be further described below in conjunction with embodiment, but embodiments of the present invention are not limit so.
Embodiment 1
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) in weight fraction, with 1 part of cellulosic material join 20 part 1 ?Ding Ji ?100 ℃ of 3 alkane imidazoles villaumite ionic liquids carry out CL, add 8 parts of trityl chlorides and 9 parts of pyrimidine catalyzer, under the Ar atmospheric condition, be warming up to 80 ℃ and keep 8h to carry out C
6Upper trityl substitution reaction is cooled to room temperature, and reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, vacuum-drying obtains reaction product one; This step has mainly been utilized C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior.
(2) with the methyl chloride of Mierocrystalline cellulose quality 5% for sodium acetate (ClCH
2COONa) add in the DMSO solution of reaction product one, at 80 ℃ of lower stirring reaction 30h, after finishing, reaction is down to room temperature, resulting solution is injected methanol solution, and with mass concentration be in 10% dilute acetic acid and after, adopting volumetric concentration is 80% washing with alcohol 3 times again, and obtains reaction product two 60 ℃ of lower vacuum-dryings;
(3) in weight fraction, 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, drip 2 parts of mass concentrations and be 38% concentrated hydrochloric acid, behind the reaction 20h, the product methanol wash obtains reaction product three 60 ℃ of lower vacuum-dryings;
(4) with 1,1 ?2H ?perfluor alcohol and 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively take molar ratio as 1:1 in the 200ml dimethyl formamide DMF reagent, and will dissolve 1,1 ?2H ?perfluor alcohol dropwise splash into 4,4 ?in the '-diphenylmethane diisocyanate MDI/ dimethyl formamide DMF solution, at 55 ℃ of lower 3h that stir, under 70 ℃ of conditions, continue reaction 5h, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution; Be cooled to room temperature, obtain reaction product four; Described 2 parts of reaction product four are slowly joined in described 2 parts of reaction product three, at 60 ℃ of lower 8h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, get reaction product five; 1,1 ?2H ?the structural formula of perfluor alcohol be CF
3(CF
2)
6CH
2OH;
(5) in weight fraction, 1 part of reaction product five is ground to meal, puts into the acetone/water solution that 10 parts of equal-volume ratios form, and high-speed stirring (350 rev/mins) is mixed the formation emulsified soln, prepare emulsion, and evenly coating (glue spread is 1g/cm with the PVC film
2) on, under vacuum condition, with 60 ℃ of dryings, get the oleophobic hydrophobic function from changing the cellulosic coating material.
Detect through the test of sound attitude surface contact angle, the functional fiber element that present embodiment obtains from transition material have good oleophobic property, have hydrophobic to hydrophilic from conversion performance, the contact angle that oil phase begins on the PVC top coat is 146 °, and water is reduced to 35 ° from 152 ° at the contact angle on the fabric in 45min.
Can find out from present embodiment, the oleophobic hydrophobic/hydrophilic function of present embodiment preparation obtains better oleophobic, hydrophilic from conversion performance from changing cellulosic coating material preparation method, and the chemical addition is not high, has good application prospect, the fields such as petrochemical complex parting material, air conditioner used in kitchen be can be widely used in, oil, moisture are used for from engineering.
Embodiment 2
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) in parts by weight, with 1 part of cellulosic material join 20 part 1 ?Xi Bing Ji ?100 ℃ of 3 alkane imidazoles villaumite ionic liquids carry out CL, after 8 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 85 ℃ and keep 8h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 7% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 80 ℃ of lower stirring reaction 54h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) in parts by weight, 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol and 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively take molar ratio as 1:1.2 in the 200ml dimethyl formamide DMF reagent, and will dissolve 1,1 ?2H ?perfluor alcohol dropwise splash into 4,4 ?in the '-diphenylmethane diisocyanate MDI/ dimethyl formamide DMF solution, at 60 ℃ of lower 4h that stir, under 70 ℃ of conditions, continue reaction 8h, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution; Be cooled to room temperature, obtain reaction product four; Described 3 parts of reaction product four are slowly joined in described 5 parts of reaction product three, at 75 ℃ of lower 12h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, get reaction product five; 1,1 ?2H ?the structural formula of perfluor alcohol be CF
3(CF
2)
6CH
2OH.
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts of acetone/water solution that formed by the equal-volume ratio, and high-speed stirring (speed is 1400 rev/mins) is mixed the formation emulsified soln, prepare emulsion, and (the amount 1.5g/m of coating on even coating and the PVC film
2), under vacuum condition with 60 ℃ of dryings.
After testing, the functional fiber element that adopts this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 131 °, and water is reduced to 45 ° from 144 ° at the contact angle on the fabric in 45min.
Embodiment 3
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6The difference of ?OH reactive behavior: 1 part of cellulosic material is joined 60 ℃ of 20 parts of room temperature phosphorous acid hydrogen salt alkyl imidazole compound ions liquid carry out CL, after 9 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 90 ℃ and keep 8h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 8% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 70 ℃ of lower stirring reaction 72h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively in the dimethyl formamide DMF reagent take molar ratio as the 1:1.8 ratio, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash into 4,4 ?in the '-diphenylmethane diisocyanate MDI/ dimethyl formamide DMF solution, under 55 ℃, stir 2h, and reaction solution is continued reaction 9h under 78 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.3 parts of reaction product four of above-mentioned preparation are slowly joined in 4 parts of reaction product three solution of above-mentioned preparation, at 90 ℃ of lower 20h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and (glue spread is 4g/m on even coating and the PVC film
2), under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 155 °, and water is reduced to 42 ° from 147 ° at the contact angle on the fabric in 45min.
Embodiment 4
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carries out CL, after 7 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 75 ℃ and keep 9h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 5% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 90 ℃ of lower stirring reaction 60h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively in the dimethyl formamide DMF reagent with the equimolar ratio example, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash in '-diphenylmethane diisocyanate MDI/ dimethyl formamide DMF solution, under 60 ℃, stir 2h, and reaction solution is continued reaction 7h under 80 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.3 parts of reaction product four of above-mentioned preparation are slowly joined in 2 parts of reaction product three solution of above-mentioned preparation, at 60 ℃ of lower 10h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, with evenly coating and PVC film (the amount 1.2g/m of coating of emulsion
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 131 °, and water is reduced to 45 ° from 138 ° at the contact angle on the fabric in 45min.
Embodiment 5
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carries out CL, after 9 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 80 ℃ and keep 9h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 6% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 100 ℃ of lower stirring reaction 50h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively in the dimethyl formamide DMF reagent take molar ratio as the 1:1.2 ratio, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash in 4,4 ?'-diphenylmethane diisocyanate MDI solution, under 70 ℃, stir 2h, and reaction solution is continued reaction 8h under 90 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.2 parts of reaction product four of above-mentioned preparation are slowly joined in 2 parts of reaction product three solution of above-mentioned preparation, at 80 ℃ of lower 20h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and evenly coating and PVC film (the amount 4.5g/m of coating
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 143 °, and water is reduced to 41 ° from 149 ° at the contact angle on the fabric in 45min.
Embodiment 6
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carries out CL, after 8 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 80 ℃ and keep 10h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 6% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 80 ℃ of lower stirring reaction 50h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively in the dimethyl formamide DMF reagent with the equimolar ratio example, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash into 4,4 ?in the '-diphenylmethane diisocyanate MDI/ dimethyl formamide DMF solution, under 60 ℃, stir 2h, and reaction solution is continued reaction 9h under 90 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.3 parts of reaction product four of above-mentioned preparation are slowly joined in 5 parts of reaction product three solution of above-mentioned preparation, at 90 ℃ of lower 15h that stir, be cooled to room temperature, spend the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and evenly coating and PVC film (the amount 2.5g/m of coating
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 138 °, and water is reduced to 42 ° from 145 ° at the contact angle on the fabric in 45min.
Embodiment 7
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carries out CL, after 9 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 65 ℃ and keep 6h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 5% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 90 ℃ of lower stirring reaction 65h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively in the dimethyl formamide DMF reagent with the equimolar ratio example, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash into 4,4 ?in the '-diphenylmethane diisocyanate MDI/ dimethyl formamide DMF solution, under 70 ℃, stir 2h, and reaction solution is continued reaction 10h under 90 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.2 parts of reaction product four of above-mentioned preparation are slowly joined in 4 parts of reaction product three solution of above-mentioned preparation, at 80 ℃ of lower 10h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and evenly coating and PVC film (the amount 3.5g/m of coating
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 136 °, and water is reduced to 45 ° from 140 ° at the contact angle on the fabric in 45min.
Embodiment 8
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carries out CL, after 6 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 80 ℃ and keep 10h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 7% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 80 ℃ of lower stirring reaction 70h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) in parts by weight, 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?the ratio of '-diphenylmethane diisocyanate MDI coupling agent take molar ratio as 1:1 be dissolved in respectively in the dimethyl formamide DMF reagent, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash into 4,4 ?among '-diphenylmethane diisocyanate MDI solution/dimethyl formamide DMF, under 60 ℃, stir 2h, and reaction solution is continued reaction 10h under 80 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.3 parts of reaction product four of above-mentioned preparation are slowly joined in 5 parts of reaction product three solution of above-mentioned preparation, at 80 ℃ of lower 12h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) 1 part of reaction product five is ground to meal, puts into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and evenly coating and PVC film (the amount 2.5g/m of coating
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 140 °, and water is reduced to 39 ° from 154 ° at the contact angle on the fabric in 45min.
Embodiment 9
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: in parts by weight, 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carry out CL, after 8 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 80 ℃ and keep 10h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 5% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in the DMSO solution of reaction product one, at 60 ℃ of lower stirring reaction 20h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) in parts by weight, 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively take molar ratio as the 1:1.2 ratio in dimethyl formamide (DMF) reagent, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash into 4,4 ?in the dimethyl formamide solution of '-diphenylmethane diisocyanate MDI, under 50 ℃, stir 2h, and reaction solution is continued reaction 7h under 80 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.2 parts of reaction product four of above-mentioned preparation are slowly joined in 2 parts of reaction product three solution of above-mentioned preparation, at 75 ℃ of lower 10h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5) 1 part of reaction product five is ground to meal, puts into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and evenly coating and PVC film (the amount 1.5g/m of coating
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 122 °, and water is reduced to 44 ° from 132 ° at the contact angle on the fabric in 45min.
Embodiment 10
A kind of oleophobic hydrophobic/hydrophilic function may further comprise the steps from changing cellulosic coating material preparation method:
(1) utilizes C on the cellulose molecular chain
2, C
3And C
6?the difference of OH reactive behavior: 1 part of cellulosic material is joined 100 ℃ of 20 parts of ionic liquid at room temperature carries out CL, after 9 parts of trityl chlorides and 9 parts of pyrimidine catalyzer are joined in the above-mentioned reaction mixture, be warming up to 95 ℃ and keep 6h to carry out C
6Upper trityl substitution reaction (under the Ar atmospheric condition) is cooled to room temperature subsequently; Reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, last vacuum-drying obtains required reaction product one.
(2) be that 5% methyl chloride is for sodium acetate (ClCH with relative concentration
2COONa) add in reaction product one/DMSO solution, at 68 ℃ of lower stirring reaction 65h, after finishing, reaction is down to room temperature, resulting solution is put into 300ml80%(v/v) methyl alcohol and with dilute acetic acid and after, adopt again 80%(v/v) washing with alcohol 3 times and obtain reaction product two 60 ℃ of lower vacuum-dryings.
(3) in parts by weight, 1 part of reaction product two is scattered in 15 parts of ethanolic solns at ambient temperature, and concentrated hydrochloric acid is dripped gradually as in the above-mentioned solution, use methanol wash behind the reaction 20h, obtain reaction product three 60 ℃ of lower vacuum-dryings.
(4) with 1,1 ?2H ?perfluor alcohol [(CF
3(CF
2)
nCH
2OH); N=2,6] with 4,4 ?'-diphenylmethane diisocyanate MDI coupling agent be dissolved in respectively in the dimethyl formamide DMF reagent with the equimolar ratio example, and will dissolve 1,1 ?2H ?the pure [(CF of perfluor
3(CF
2)
nCH
2OH) dropwise splash in 4,4 ?'-diphenylmethane diisocyanate MDI solution, under 65 ℃, stir 2h, and reaction solution is continued reaction 8h under 78 ℃ of conditions, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution.React the complete room temperature that is cooled to and obtain reaction product four.3 parts of reaction product four of above-mentioned preparation are slowly joined in 4 parts of reaction product three solution of above-mentioned preparation, at 90 ℃ of lower 18h that stir, be cooled to room temperature, use the methyl alcohol repetitive scrubbing, through 60 ℃ of vacuum-drying 24h, obtain reaction product five.
(5)) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 parts acetone/water solution, and high-speed stirring mixing formation emulsified soln, prepare emulsion, and evenly coating and PVC film (the amount 3.5g/m of coating
2) on, under vacuum condition with 60 ℃ of dryings.In the acetone/water solution, acetone and water equal-volume.
After testing, the functional fiber element that adopts the described method of this example to obtain has good oleophobic hydrophobic/hydrophilic from conversion performance from transition material, the contact angle that oil phase begins on the PVC top coat is 145 °, and water is reduced to 38 ° from 147 ° at the contact angle on the fabric in 45min.
Can better implement the present invention as mentioned above.
Claims (8)
1. an oleophobic hydrophobic/hydrophilic function is characterized in that may further comprise the steps from changing cellulosic coating material preparation method:
(1) in parts by weight, with 1 ?3 parts of Mierocrystalline celluloses join 20 ?in 25 parts of ionic liquids, 60 ?dissolve under 100 ℃ of temperature condition, add 6 ?10 parts of trityl chlorides and 9 ?15 parts of pyrimidine catalyzer, under the Ar atmospheric condition, be warming up to 70 ?100 ℃ keep 5 ?10h carry out C
6Upper trityl substitution reaction is cooled to room temperature, and reaction mixture is injected methanol solution, and by using methyl alcohol repetitive scrubbing and filtration, vacuum-drying obtains reaction product one; Described ionic liquid is 1 ?fourth base ?, 3 alkane imidazoles villaumites, 1 ?alkene the third basic ?3 alkane imidazoles villaumites or phosphorous acid hydrogen salt alkyl imidazole compound;
(2) methyl chloride with Mierocrystalline cellulose quality 5 ?8% adds in the dimethyl sulphoxide solution of reaction product one for sodium acetate, 60 ?100 ℃ of lower stirring reactions 20 ?72h, after finishing, reaction is down to room temperature, resulting solution is injected methanol solution, and with mass concentration be in 10 ?, 12% dilute acetic acid and after, adopt washing with alcohol, vacuum-drying obtains reaction product two again;
(3) in parts by weight, with 1 ?3 parts of reaction product two be scattered at ambient temperature in 15 parts of ethanolic solns, drip 1 ?5 parts of concentrated hydrochloric acids, react 20 ?behind the 30h, washing obtains reaction product three in lower vacuum-drying;
(4) with mol ratio be 1:1 ?1:1.8 1,1 ?2H ?perfluor alcohol and 4,4 ?the '-diphenylmethane diisocyanate coupling agent be dissolved in respectively in the dimethyl formamide reagent, and will dissolve 1,1 ?2H ?perfluor alcohol splash into 4,4 ?in the dimethyl formamide solution of '-diphenylmethane diisocyanate MDI, 50 ?70 ℃ lower stir 2 ?5h, under 90 ℃ of conditions of 60 ?, continue reaction 5 ?10h, until with till not having ?OH group to exist in the infrared spectra FTIR discovery reaction solution; Be cooled to room temperature, obtain reaction product four; With described 1 ?3 parts of reaction product four join described 1 ?in 5 parts of reaction product three, 60 ?90 ℃ lower stir 6 ?20h, be cooled to room temperature, washing, drying gets reaction product five; 1,1 ?2H ?the structural formula of perfluor alcohol be CF
3(CF
2)
6CH
2OH;
(5) in parts by weight, 1 part of reaction product five is ground to meal, put into 10 ?15 parts of acetone/water solution, and 1500 rev/mins of high-speed stirring of 1350 ?are mixed the formation emulsified soln, prepare emulsion, and be uniformly coated on the PVC film, glue spread be 1 ?5g/cm
2, dry under vacuum condition, get the oleophobic hydrophobic function from changing the cellulosic coating material.
2. oleophobic hydrophobic function according to claim 1 is from changing cellulosic coating material preparation method, and it is characterized in that: the drying of described step (2), step (3) and step (4) is in 65 ℃ of lower vacuum-dryings of 55 ?.
3. oleophobic hydrophobic function according to claim 1 is characterized in that: acetone and water equal-volume in the described acetone/water solution from changing cellulosic coating material preparation method; In parts by weight, acetone/water solution is 10 parts.
4. oleophobic hydrophobic function according to claim 1 is from changing cellulosic coating material preparation method, and it is characterized in that: described Mierocrystalline cellulose is bleached pulp Mierocrystalline cellulose, Microcrystalline Cellulose, pure cellulose or dissolving pulp Mierocrystalline cellulose.
5. oleophobic hydrophobic function according to claim 1 is characterized in that from changing cellulosic coating material preparation method: described coated material preparation method adopts the coating preparation.
6. oleophobic hydrophobic function according to claim 1 is from changing cellulosic coating material preparation method, and it is characterized in that: described concentrated hydrochloric acid mass concentration is 38%.
7. oleophobic hydrophobic function according to claim 1 is characterized in that from changing cellulosic coating material preparation method: the described drying of step (4) is through 45 ℃ of vacuum-drying 20-24h of 40 ?.
8. oleophobic hydrophobic function according to claim 1 is characterized in that from changing cellulosic coating material preparation method: step (3) and (4) described washing are for using the methyl alcohol repetitive scrubbing.
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| CN105935502A (en) * | 2016-05-10 | 2016-09-14 | 上海澍澎新材料科技有限公司 | Super hydrophilic and underwater super oleophobic oil-water separation screen film and production method thereof |
| CN106944328B (en) * | 2017-02-14 | 2018-02-02 | 南京林业大学 | A kind of preparation method of nano-cellulose aerogel microballoon coating filter paper |
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| CN105935502B (en) * | 2016-05-10 | 2018-04-03 | 上海澍澎新材料科技有限公司 | A kind of super hydrophilic and underwater superoleophobic oil-water separation mesh film and preparation method thereof |
| CN106944328B (en) * | 2017-02-14 | 2018-02-02 | 南京林业大学 | A kind of preparation method of nano-cellulose aerogel microballoon coating filter paper |
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