CN110628313A - Method for preparing self-repairing aldehyde-removing polyurethane water-based paint from grape residues - Google Patents
Method for preparing self-repairing aldehyde-removing polyurethane water-based paint from grape residues Download PDFInfo
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- CN110628313A CN110628313A CN201910946426.9A CN201910946426A CN110628313A CN 110628313 A CN110628313 A CN 110628313A CN 201910946426 A CN201910946426 A CN 201910946426A CN 110628313 A CN110628313 A CN 110628313A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a self-repairing and aldehyde-removing waterborne polyurethane coating prepared from a nano composite material designed by utilizing wine grape residues. The reaction comprises the following steps: (1) extracting cellulose from grape residues, preparing cellulose nanocrystals by a eutectic solvent method, preparing a CNCs-based initiator (CNCs @ BiBB), and preparing a cellulose nanocrystal-based compound (CNCs @ PGMA) by using the CNCs @ BiBB; (2) the method comprises the steps of utilizing CNCs @ PGMA to carry out ring-opening reaction to prepare a cellulose nanocrystalline-based nano hybrid material (CNCs @ PGMA-TETA) with the aldehyde removing and self-repairing functions, and implanting the cellulose nanocrystalline-based nano hybrid material into an aqueous polyurethane coating to design and prepare the aqueous coating with the aldehyde removing and self-repairing functions.
Description
Technical Field
The invention relates to a method for preparing a self-repairing aldehyde-removing water-based paint by utilizing wine grape residues, in particular to a method for preparing a self-repairing aldehyde-removing water-based paint by implanting a cellulose nanocrystalline surface modification functional polymer extracted by a eutectic solvent into a water-based paint, belonging to the field of high polymer material synthesis.
Background
The formaldehyde resin is used as an important adhesive for wood and wood composite materials, and is widely applied to various furniture products and interior decoration materials. However, as one of the main indoor air pollutants, high concentration of formaldehyde can stimulate respiratory mucosa and eyes, damage respiratory system, nervous system and immune system, even cause carcinogenic hazard, and seriously affect human health. How to effectively and rapidly remove formaldehyde is always a social concern.
Currently, the main methods for removing formaldehyde are activated carbon adsorption and catalytic oxidation. For example, Lu et al evaluated the surface immobilization of nano TiO on Activated Carbon (AC) filter to improve the removal of indoor air pollutants2The result of the photocatalysis performance of the particles on formaldehyde (HCHO) removal shows that AC can adsorb pollutants in diluted air, so that high-concentration pollutants are generated on the surface of the catalyst, and the photocatalysis reaction rate is improved. Liu et al proposed a simple calcination-sol-gel process to convert g-C3N4、TiO2And spent zeolite catalyst (i.e., C)3N4-TiO2Waste zeolite) are combined together to prepare the different-structure adsorption-photocatalyst coating, and the photocatalytic treatment of industrial silicate waste is researched to enable the industrial silicate waste to become a high-efficiency photocatalytic coating which can be used for removing indoor formaldehyde。
The common aldehyde-removing coating always has the inevitable phenomena of cracks, damages, fractures and the like in the using process, and the long-term use of the coating is seriously influenced. The self-repairing coating is a coating with self-repairing capability after the coating is damaged to a certain degree, namely, under a rigid use environment, cracks are expanded to generate a self-repairing mechanism. The self-repairing coating is a novel intelligent coating and can realize automatic repair without any external interference. Typically, the self-healing coating is a nanocontainer or microcapsule encapsulating the inhibitor or healing agent.
Based on the above, the invention starts from the concept of recycling agricultural wastes, extracts and prepares the cellulose nanocrystals from the wine grape residues, introduces the functional aldehyde-removing polymer on the surface of the cellulose nanocrystals by using the latest ATRP technology, obtains the modified cellulose nanocrystals with the aldehyde-removing and emulsifying dual-functions, and prepares the water-based paint with the excellent aldehyde-removing function and the self-repairing function. The paint with excellent aldehyde removal function is prepared by utilizing a green process, high added value conversion of waste crops is realized, and the social and economic benefits are obvious.
Disclosure of Invention
The invention aims to provide a method for preparing a self-repairing and aldehyde-removing water-based coating by using an ATRP surface modified cellulose nanocrystalline material.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
(1) the preparation of the cellulose nanocrystalline matrix composite material with the aldehyde removal and self-repairing functions comprises the following steps:
firstly, Cellulose Nanocrystals (CNCs) are extracted from wine grape residues, holocellulose is extracted from the wine grape residues according to a conventional process, taurine and choline chloride are taken according to a molar ratio of 1: 1 (namely a mass ratio of 9: 14) and react with the holocellulose, the mass ratio of the holocellulose to a eutectic solvent is 1: 100, the mixture is reacted after being mixed, dialysis is carried out after the reaction until the pH value is = 6.5 ~ 7,
the reaction temperature was 50 ~ 200 degrees celsius,
the time is 2 ~ 10 hours;
secondly, preparing a CNCs-based initiator (CNCs @ BiBB) by using the extracted CNCs,
dispersing cellulose nanocrystals in dimethylformamide, and sequentially dropwise adding triethylamine and 2-bromoisobutyryl bromide to prepare a cellulose nanocrystal-based macroinitiator (CNCs @ BiBB), wherein the mass ratio of triethylamine to 2-bromoisobutyryl bromide to a product in the cellulose nanocrystals is = 10 ~ 100: 10 ~ 100: 1 ~ 10,
the reaction temperature was 20 ~ 40 degrees celsius,
the reaction time was 8 ~ 24 hours;
secondly, preparing a cellulose nanocrystalline matrix composite (CNCs @ PGMA) by using CNCs @ BiBB,
preparing cellulose nanocrystal-based composites (CNCs @ PGMA) by grafting polyglycidyl methacrylate (GMA) onto Atom Transfer Radical (ATRP) with CNCs @ BiBB as an initiator, comprising: catalyst (CuBr)2) The method is characterized in that simple Atom Transfer Radical Polymerization (ATRP) can be carried out by taking the CNCs @ BiBB as an initiator to graft a polymer on the initiator, wherein the macroinitiator comprises Glycidyl Methacrylate (GMA), a reducing agent comprises ATRP initiator and a complexing agent comprises dimethylformamide = 1 ~ 10: 10 ~ 100: 0.1 ~ 1: 0.1 ~ 1: 0.1 ~ 1: 0.1 ~ 1: 10 ~ 100 according to mass ratio,
the reaction temperature is 10 ~ 100 degrees centigrade,
the reaction time was 1 ~ 12 hours;
finally, CNCs @ PGMA is utilized to carry out ring-opening reaction to prepare the cellulose nanocrystalline-based nano hybrid material (CNCs @ PGMA-TETA) with the functions of aldehyde removal and self-repairing,
dissolving triethylene tetramine (TETA) in a Dimethylformamide (DMF) three-neck flask, dropwise adding mixed CNCs @ PGMA and Dimethylformamide (DMF) dispersion liquid at room temperature (ultrasonic stirring), magnetically stirring at a certain temperature in a closed environment for reaction for 24 hours, washing with ethanol and water respectively after the reaction is finished, centrifuging, dialyzing, freeze-drying,
the temperature is 20 ~ 100 degrees celsius,
the time period was 10 minutes ~ 48 hours.
(2) The CNCs @ PGMA-TETA is used for preparing the water paint with the functions of removing aldehyde and self-repairingNAdding methyl-2-pyrrolidone, polyurethane 2000, dibutyltin dilaurate and dimethylolpropionic acid into a reaction kettle, adding dibutyltin dilaurate, heating to 85 ~ 90 ℃ for 15 minutes until the reaction mixture is uniform, cooling the reaction mixture to 54 ~ 60 ℃, adding 4, 4-diisocyanate dicyclohexylmethane and neopentyl glycol, raising the mixed reaction temperature to 70 ~ 75 ℃, keeping the temperature for 15 minutes until the mixture is uniformly mixed, then adding deionized water, a mixture of dimethylethanolamine, ethylenediamine and CNCs @ PGMA-TETA at the temperature of 85 ~ 90 ℃ for dispersing, keeping the dispersion temperature at 70 ~ 75 ℃ for 30 minutes, and cooling to 30 ~ 35 ℃, wherein the mass ratio of CNCs @ PGMA-TETA:Nmethyl-2-pyrrolidone, polyurethane 2000, dibutyltin dilaurate, dimethylolpropionic acid, 4-diisocyanate dicyclohexylmethane, neopentyl glycol, deionized water, dimethylethanolamine, ethylenediamine = 0.1 ~ 10: 350 ~ 432: 230 ~ 315: 227 ~ 257: 89 ~ 129: 516 ~ 573: 3.6 ~ 6.5.5: 1800 ~ 2348: 68 ~ 82.3.3: 28 ~ 43.7.7.
Detailed Description
(1) The first embodiment is as follows: extraction of cellulose nanocrystals from wine grape residue
Crushing grape residues, extracting in a benzene alcohol (300 ml of toluene: 150 ml of ethanol) solution for 6 hours, drying at 60 ℃, dissolving in water in a three-neck flask, adjusting the pH value with 2 ml of acetic acid, adding 18 g of sodium chlorite, reacting at 78 ℃ after ultrasonic dissolution, adding half of the amount of the acetic acid and the sodium chlorite after reacting for 1 hour, continuing to react for 1 hour, standing, centrifugally washing with ethanol, drying at 60 ℃ for 16 hours, reacting with sodium hydroxide (5%) at 60 ℃ for 4 hours, and centrifugally washing with distilled water to obtain cellulose; weighing 0.5g of holocellulose and 23.68 g of taurine, 26.32 g of choline chloride, mixing, reacting at 100 ℃ for 4 hours, and dialyzing until the pH is = 7.
(2) The second embodiment is as follows: preparation of CNCs-based initiators (CNCs @ BiBB) Using extracted CNCs
350 mg of CNCs were sonicated in 30 ml of dimethylformamide (molecular sieve removed water) for 20 min. Then the mixed solution is transferred into a three-neck flask from a beaker, and 5.5 ml of triethylamine and 5.5 ml of 2-bromoisobutyryl bromide are sequentially dripped into the three-neck flask by a constant pressure dropping funnel under magnetic stirring. After 8h reaction at room temperature, the solution is reddish brown with a little precipitate, washed three times by ultracentrifugation with ethanol and distilled water in sequence, and freeze-dried when the supernatant is clear.
(3) The third concrete embodiment: preparation of cellulose nanocrystal-based composites (CNCs @ PGMA) from CNCs @ BiBB
CNCs @ BiBB (30 mg), CuBr2(6.8 mg), EBiB (7.8. mu.L), GMA (1 ml), PMDETA (6.3. mu.L), dimethylformamide (1 ml) and ascorbic acid (10 mg) were added to an ammonia cylinder and dispersed by sonication for 20 minutes. After 10 minutes of nitrogen charge, the reaction was carried out in an oil bath at 85 ℃ for 2 hours. After the reaction was completed, the solid-liquid separation was carried out by ultracentrifugation (supernatant was precipitated in methanol, and the lower layer solid was washed three times with ethanol and then freeze-dried).
(4) The specific implementation case four: preparation of cellulose nanocrystalline-based nano hybrid material (CNCs @ PGMA-TETA) with aldehyde removal and self-repair functions by using CNCs @ PGMA to carry out ring-opening reaction
5 ml of diethylenetetramine (TETA) was dissolved in a 10 ml Dimethylformamide (DMF) three-neck flask, and 10 ml of a Dimethylformamide (DMF) dispersion with 50 mg of CNCs @ PGMA mixed (stirred ultrasonically for 30 minutes) was added dropwise at room temperature, and the addition was completed within 30 minutes. Reacting at 50 deg.C under magnetic stirring for 24 hr (sealing), washing with ethanol and water respectively, centrifuging, dialyzing for 7 days, and freeze drying.
(5) The concrete implementation case five: water-based paint with aldehyde removal and self-repairing functions prepared by CNCs @ PGMA-TETA
432.2 grams of N-methyl-2-pyrrolidone, 315.0 grams of polyurethane 2000, 257 grams of dibutyltin dilaurate, 129.0 grams of dimethylolpropionic acid were added to the reaction kettle, 257 grams of dibutyltin dilaurate were added, heated to 85 ~ degrees celsius, held for 15 minutes until the reaction mixture was homogeneous, then the reaction mixture was cooled to 54 ~ degrees celsius, 573.0 grams of 4, 4-diisocyanate dicyclohexylmethane, 6.5 grams of neopentyl glycol were added, the mixing reaction temperature was raised to 70 ~ degrees celsius, held for 15 minutes until homogeneous mixing, a mixture of 2348 grams of deionized water, 82.3 grams of dimethylethanolamine, 43.7 grams of ethylenediamine, 0.5 grams of cncs @ PGMA-TETA was added at 85 degrees celsius, the dispersion temperature was maintained at 70 ~ degrees celsius, 75 degrees celsius, stirred for 30 minutes, and cooled to 30 ~ degrees celsius.
Claims (2)
1. The invention provides a method for preparing a self-repairing aldehyde-removing water-based paint by using wine grape residues, which is characterized by comprising the following two steps of:
(1) the preparation of the cellulose nanocrystalline matrix composite material with the aldehyde removal and self-repairing functions comprises the following steps:
firstly, Cellulose Nanocrystals (CNCs) are extracted from wine grape residues, holocellulose is extracted from the wine grape residues according to a conventional process, taurine and choline chloride are taken according to a molar ratio of 1: 1 (namely a mass ratio of 9: 14) and react with the holocellulose, the mass ratio of the holocellulose to a eutectic solvent is 1: 100, the mixture is reacted after being mixed, dialysis is carried out after the reaction until the pH value is = 6.5 ~ 7,
the reaction temperature was 50 ~ 200 degrees celsius,
the time is 2 ~ 10 hours;
secondly, preparing a CNCs-based initiator (CNCs @ BiBB) by using the extracted CNCs,
dispersing cellulose nanocrystals in dimethylformamide, and sequentially dropwise adding triethylamine and 2-bromoisobutyryl bromide to prepare a cellulose nanocrystal-based macroinitiator (CNCs @ BiBB), wherein the mass ratio of triethylamine to 2-bromoisobutyryl bromide to a product in the cellulose nanocrystals is = 10 ~ 100: 10 ~ 100: 1 ~ 10,
the reaction temperature was 20 ~ 40 degrees celsius,
the reaction time was 8 ~ 24 hours;
secondly, preparing a cellulose nanocrystalline matrix composite (CNCs @ PGMA) by using CNCs @ BiBB,
preparing cellulose nanocrystal-based composites (CNCs @ PGMA) by grafting polyglycidyl methacrylate (GMA) onto Atom Transfer Radical (ATRP) with CNCs @ BiBB as an initiator, comprising: catalyst (CuBr)2) The method is characterized in that simple Atom Transfer Radical Polymerization (ATRP) can be carried out by taking the CNCs @ BiBB as an initiator to graft a polymer on the initiator, wherein the macroinitiator comprises Glycidyl Methacrylate (GMA), a reducing agent comprises ATRP initiator and a complexing agent comprises dimethylformamide = 1 ~ 10: 10 ~ 100: 0.1 ~ 1: 0.1 ~ 1: 0.1 ~ 1: 0.1 ~ 1: 10 ~ 100 according to mass ratio,
the reaction temperature is 10 ~ 100 degrees centigrade,
the reaction time was 1 ~ 12 hours;
finally, CNCs @ PGMA is utilized to carry out ring-opening reaction to prepare the cellulose nanocrystalline-based nano hybrid material (CNCs @ PGMA-TETA) with the functions of aldehyde removal and self-repairing,
dissolving triethylene tetramine (TETA) in a Dimethylformamide (DMF) three-neck flask, dropwise adding mixed CNCs @ PGMA and Dimethylformamide (DMF) dispersion liquid at room temperature (ultrasonic stirring), magnetically stirring at a certain temperature in a closed environment for reaction for 24 hours, washing with ethanol and water respectively after the reaction is finished, centrifuging, dialyzing, freeze-drying,
the temperature is 20 ~ 100 degrees celsius,
the time is 10 minutes ~ 48 hours;
(2) the CNCs @ PGMA-TETA is used for preparing the water paint with the functions of removing aldehyde and self-repairingNAdding methyl-2-pyrrolidone, polyurethane 2000, dibutyltin dilaurate and dimethylolpropionic acid into a reaction kettle, adding dibutyltin dilaurate, heating to 85 ~ 90 ℃ for 15 minutes until the reaction mixture is uniform, cooling the reaction mixture to 54 ~ 60 ℃, adding 4, 4-diisocyanate dicyclohexylmethane and neopentyl glycol, raising the mixed reaction temperature to 70 ~ 75 ℃, keeping the temperature for 15 minutes until the mixture is uniformly mixed, then adding deionized water, a mixture of dimethylethanolamine, ethylenediamine and CNCs @ PGMA-TETA at the temperature of 85 ~ 90 ℃ for dispersing, keeping the dispersion temperature at 70 ~ 75 ℃ for 30 minutes, and cooling to 30 ~ 35 ℃, wherein the mass ratio of CNCs @ PGMA-TETA:Nmethyl-2-pyrrolidone, polyurethane 2000, dibutyltin dilaurate, dimethylolpropionic acid, 4-diisocyanate dicyclohexylmethane, neopentyl glycol, deionized water, dimethylethanolamine, ethylenediamine = 0.1 ~ 10: 350 ~ 432: 230 ~ 315: 227 ~ 257: 89 ~ 129: 516 ~ 573: 3.6 ~ 6.5.5: 1800 ~ 2348: 68 ~ 82.3.3: 28 ~ 43.7.7.
2. The self-repairing and aldehyde-removing waterborne polyurethane coating prepared by using the ATRP surface-modified cellulose nanocrystal material obtained by extracting cellulose nanocrystals from wine grape residues according to claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643374A (en) * | 2012-04-26 | 2012-08-22 | 北京化工大学 | High-performance cationic gene vectors with PGMA (polyglycidyl methacrylate) serving as framework constructed by ATRP (atom transfer radical polymerization) method |
| CN104387563A (en) * | 2014-11-19 | 2015-03-04 | 中山大学 | Hyperbranched polyurethane having self-repairing function in seawater as well as preparation method and application thereof |
| CN106867388A (en) * | 2017-01-18 | 2017-06-20 | 华南理工大学 | A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof |
| CN109810605A (en) * | 2019-01-25 | 2019-05-28 | 鲁东大学 | A kind of selfreparing removes the preparation method of aldehyde Water-borne Coatings Emulsion |
| CN110028781A (en) * | 2019-04-29 | 2019-07-19 | 中国科学院长春应用化学研究所 | A kind of selfreparing aqueous polyurethane/Cellulose nanocrystal composite material and preparation method |
-
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- 2019-10-05 CN CN201910946426.9A patent/CN110628313A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643374A (en) * | 2012-04-26 | 2012-08-22 | 北京化工大学 | High-performance cationic gene vectors with PGMA (polyglycidyl methacrylate) serving as framework constructed by ATRP (atom transfer radical polymerization) method |
| CN104387563A (en) * | 2014-11-19 | 2015-03-04 | 中山大学 | Hyperbranched polyurethane having self-repairing function in seawater as well as preparation method and application thereof |
| CN106867388A (en) * | 2017-01-18 | 2017-06-20 | 华南理工大学 | A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof |
| CN109810605A (en) * | 2019-01-25 | 2019-05-28 | 鲁东大学 | A kind of selfreparing removes the preparation method of aldehyde Water-borne Coatings Emulsion |
| CN110028781A (en) * | 2019-04-29 | 2019-07-19 | 中国科学院长春应用化学研究所 | A kind of selfreparing aqueous polyurethane/Cellulose nanocrystal composite material and preparation method |
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