CN110437678B - Energy-saving environment-friendly water-based paint and preparation method thereof - Google Patents
Energy-saving environment-friendly water-based paint and preparation method thereof Download PDFInfo
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- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The coating comprises a water-based nitrocotton emulsion, wherein the water-based nitrocotton emulsion is an emulsion obtained by mixing polyurethane, epoxy modified water-based nitrocotton resin and water. The active group of the nitrocotton is utilized to carry out reaction, and hydrophilicity (comprising carboxyl, carboxylate group and ether bond) and a specific functional group (epoxy group) are introduced to the nitrocotton structure, so that the prepared nitrocotton resin can be stably dispersed in water; meanwhile, under the action of functional groups, a crosslinking reaction can be carried out during film formation to form three-dimensional molecules with infinite molecular weight, so that the flexibility and the water resistance after film formation are greatly improved; particularly, due to the action of the molecular skeleton of the nitrocotton, the degradation performance after film forming and curing is obviously improved compared with that of the common homozygous forming coating.
Description
Technical Field
The invention belongs to the field of functional coatings, and particularly relates to a natural environment-friendly coating for buildings and a preparation method thereof.
Background
The rapid development of the real estate industry in the last two decades is benefited, and the production and sales of the architectural coating in China also keep increasing rapidly. Meanwhile, China encourages low carbon, environmental protection, energy conservation and emission reduction for a long time, the building energy conservation standard is improved to 50 percent from the past 30 percent, and the requirements of parts of first-line cities such as Beijing, Shanghai and the like reach 65 percent. JG/T338-2011 building glass thermal insulation coating, JG/T402-2013 thermal reflection metal roof board, JG/T235-2014 building reflection thermal insulation coating, JGJ/T287-2014 building reflection thermal insulation coating energy-saving detection standard, GB/T31389-2015 building outer wall and roof thermal reflection material technical conditions and evaluation method, and JGJ/T359-2015 building reflection thermal insulation coating application technical regulation are established in the country, so that unprecedented opportunities are brought to the whole building coating energy-saving industry.
The building energy-saving coating can be divided into three types, namely a barrier type, a reflection type and a radiation type, according to different heat-preservation and energy-saving mechanisms. The base materials used by most of the current energy-saving coatings are solvent-based resins, and the defects are as follows: the high VOC content pollutes the environment and has great influence on the health of constructors. The use of aqueous resins as base materials has the disadvantage of insufficient water resistance.
Chinese patent 201810929529.X discloses a water-based heat-insulating and energy-saving silica aerogel and shell powder composite exterior wall coating, and a preparation method is provided, and the coating has the advantages of high adhesive force, heat insulation, energy consumption saving, aging resistance, stable property and the like. Chinese patent 201611132435.7 discloses a water-based heat-insulating coating and a preparation method thereof, wherein the preparation method comprises the steps of adding a mesoporous silica material, and compounding silica and polyurea cross-linked modified acrylate emulsion to obtain the high-performance transparent heat-insulating coating. Chinese patent 201810344715.7 discloses a water-based acrylic acid waterproof heat-insulating coating and a preparation method thereof, wherein the coating adopts acrylic ester emulsion as a base material, and hollow ceramic microspheres, nano far-infrared ceramic powder, hollow glass microspheres, white cement, calcium carbonate, quartz sand and titanium dioxide are added as fillers, and the coating is smooth and flat, and has the advantages of good hydrophobicity and self-cleaning performance, low heat conductivity coefficient and good reflective heat-insulating performance. And the three typical water-based reflective heat-insulating coating base materials are all synthetic materials and are not easy to degrade.
Object of the Invention
The invention aims to provide an energy-saving environment-friendly water-based paint and a preparation method thereof, and the energy-saving cooling environment-friendly paint with excellent water resistance, degradability and infrared reflection performance is obtained.
The environment-friendly water-based energy-saving coating provided by the invention comprises a water-based nitrocotton emulsion, wherein the water-based nitrocotton emulsion is an emulsion obtained by mixing polyurethane, epoxy modified water-based nitrocotton resin and water. The content of the water-based nitrocotton resin in the emulsion is 20-60%, and the water-based nitrocotton resin contains the following molecular chain segment structure:
and
wherein n is an integer greater than 0, each n is the same or different, R1、R2、R3Depending on the starting materials, R1And R2May be the same or different; r1、R2The remaining portion of the isocyanate species molecules after removal of the contained isocyanate groups; r3The rest of the hydrophilic group-containing double-end hydroxyl substance molecules after hydroxyl group removal.
Further, the hydroxyl-terminated substance containing hydrophilic groups is selected from polyethylene glycol substances, and is further selected from at least one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 3000 and polyethylene glycol 6000; or the hydrophilic group-containing double-end hydroxyl substance is selected from dihydroxy carboxylic acid substances, and is further selected from at least one of dimethylol propionic acid, dimethylol butyric acid, dihydroxy cyclobutane carboxylic acid and dihydroxy quinoline carboxylic acid.
Further, the isocyanate is selected from at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
For example, when dimethylolpropionic acid and dimethylolbutyric acid are selected as the hydrophilic group-containing double-end hydroxyl substances and isophorone diisocyanate is selected as the isocyanate, the structural schematic diagram of the corresponding typical molecular chain segment of the nitrocellulose resin is as follows:
and
the nitrocellulose resin is subjected to Fourier transform infrared spectroscopy analysis at 1107cm-1The peak of the absorption spectrum is 955cm-1The characteristic absorption peaks of carboxyl groups are shown at 1645, 837 and 1277cm-1The three characteristic absorption peaks indicate that the product molecules still contain more nitrocotton chain segments, as shown in figure 1.
The water-based nitrocotton emulsion is prepared by utilizing an active group of nitrocotton to react, and introducing hydrophilicity (including carboxyl, carboxylate group and ether bond) and a specific functional group (epoxy group) into a nitrocotton structure, so that the prepared novel nitrocotton can be stably dispersed in water; meanwhile, under the action of the functional groups, a crosslinking reaction can be carried out during film formation to form three-dimensional molecules with infinite molecular weight, so that the water resistance and the heat insulation property are greatly improved after film formation; particularly, due to the action of the molecular skeleton of the nitrocotton, the degradation performance of the coating after film forming and curing is improved (easy to degrade) compared with that of the common homozygous forming coating. In the presence of a curing agent, the first chain segment contains an epoxy group, and a film can be formed through a crosslinking reaction. The second chain segment has stronger hydrophilicity, does not generate crosslinking reaction per se, can promote the first chain segment to be dispersed in water, and improves the stability of the emulsion. After film formation, the second segment is dispersed in the cured film of the first segment.
Further, the content of the water-based nitrocotton resin in the emulsion is 20-60%.
Further, the paint also comprises functional pigment and filler, and further, the pigment and filler is selected from at least one of titanium dioxide, sericite powder, zinc oxide, precipitated barium sulfate and hollow glass beads.
Further, the coating also comprises at least one of an anti-settling agent, a defoaming agent, a dispersing agent, a thickening agent and a leveling and wetting agent.
Further, the coating comprises the following components in parts by weight: 25-60 parts of water-based nitrocotton emulsion, 20-45 parts of pigment and filler, 0.3-1.5 parts of anti-settling agent, 0.2-0.5 part of defoaming agent, 0.5-1 part of dispersing agent, 0.2-0.6 part of thickening agent, 0.1-1 part of leveling wetting agent and water.
Further, the anti-settling agent is one or two of a modified urea solution and a modified urea polyurethane solution.
Further, the defoaming agent is at least one of polyether modified polydimethylsiloxane, foam breaking polysiloxane and hydrophobic solid.
Further, the dispersant is one or two of a modified high molecular polymer solution containing high pigment affinity groups and a high molecular weight block copolymer solution with pigment affinity groups.
Further, the thickening agent is at least one of methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
Furthermore, the leveling wetting agent is at least one selected from aralkyl modified polymethylsiloxane, polyether modified polydimethylsiloxane and polyether modified polydimethylsiloxane.
Further, the titanium dioxide is rutile type titanium dioxide, wherein TiO is2The content is not less than 95 percent, and the content of rutile phase is not less than 99 percent. Preferably, the particle size of the titanium dioxide is 800-2000 meshes.
Furthermore, the particle size of the sericite powder is 800-1500 meshes.
Further, the particle size of the zinc oxide is 800-2000 meshes.
Furthermore, the particle size of the precipitated barium sulfate is 2000-4000 meshes.
Furthermore, the particle size of the hollow glass beads is one or a mixture of more of 40-110 um, 25-80 um and 25-70 um.
In the technical scheme of the invention, the aqueous nitrocotton emulsion is prepared by the following method:
the preparation method of the water-based nitrocotton emulsion provided by the invention comprises the following steps:
(1) introduction of hydrophilic groups
Reacting a double-end hydroxyl substance containing a hydrophilic group with isocyanate in a solvent dissolving environment at 65-85 ℃, preferably for 1-2 h, and feeding according to the ratio of the amount of hydroxyl to isocyanate substances of 1 (2-4);
(2) introduction of nitrocotton molecules and other functional groups
Reacting the reaction product obtained in the step (1) with polyethylene glycol, epoxy resin and nitrocotton at 70-90 ℃ under the condition of a catalyst, preferably for 2.5-4 h, and removing the solvent to obtain water-based nitrocotton resin;
(3) emulsification of resins
And (3) mixing the resin obtained by the reaction in the step (2) with water to obtain a water-based nitrocotton emulsion, which is also an emulsion for cellulose-based water-based paint.
Further, the hydrophilic group-containing double-end hydroxyl substance in the step (1) is selected from polyethylene glycol substances, such as at least one selected from polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 3000 and polyethylene glycol 6000, or selected from dihydroxy carboxylic acid substances, such as at least one selected from dimethylol propionic acid, dimethylol butyric acid, dimethylol cyclobutane carboxylic acid and dihydroxy quinoline carboxylic acid.
Further, the isocyanate in step (1) is selected from at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and Lysine Diisocyanate (LDI).
Further, the ratio of the content of isocyanate groups in the reaction product in the step (2) to the total content of hydroxyl groups in polyethylene glycol, nitrocellulose and epoxy resin is 1: 1.
Further, the ratio of the amount of the polyethylene glycol to the amount of the hydroxyl substances in the nitro-cotton and the epoxy resin in the step (2) is 0.05-0.2: 0.45-0.5: 0.45 to 0.3.
Further, the polyethylene glycol in the step (2) is at least one selected from polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000 and polyethylene glycol 6000.
Further, the epoxy resin in the step (2) is selected from at least one of E39, E42, E-44, E51 and E54.
Further, the nitrogen content of the nitrocotton in the step (2) is 10.8-12.2%.
Further, the epoxy resin in the step (2) is stirred and dissolved in advance, and a certain solvent is added to reduce the viscosity if necessary; the nitrocotton used is dissolved sufficiently in advance by a solvent.
Further, the solvent for dissolving the double-end hydroxyl raw material, the epoxy resin and the nitrocotton is selected from one or a mixture of more of acetone, butanone, xylene, ethyl acetate, butyl acetate, dimethylformamide and dimethylacetamide.
Further, the catalyst in the step (2) is at least one selected from organic tin such as dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate and triethyltin acetate, and commercial catalysts with similar functions can also be selected. Preferably, the catalyst is added in a proportion of 0.3% to 1.5% of the total mass of the reaction mass (excluding solvent).
Further, the mixing manner in step (3) is dropwise mixing, for example, distilled water or deionized water may be added dropwise to the solid under stirring; preferably, the time for dripping water is 20-25min, and stirring is continued for 30min after dripping; optionally, the stirring speed is increased to 700-800 r/min during the dropwise addition.
Further, the solvent removal mode in the step (2) adopts the steps of heating the reaction product and distilling the organic solvent under reduced pressure; preferably, the temperature is increased to 85-95 ℃, and the pressure is reduced to-0.03 to-0.1 MPa.
Further, when the emulsion is prepared, if reduced pressure distillation is adopted in the step (2), the temperature is reduced to 30-50 ℃ after distillation, and then the emulsion is mixed with water.
The preparation method of the coating provided by the invention specifically comprises the following steps:
according to the proportion of the coating, distilled water, 1/2 defoamer, leveling wetting agent, dispersant and anti-settling agent are uniformly mixed, then the mixture is uniformly mixed with pigment and filler to obtain pigment and filler slurry, and the slurry is uniformly mixed with the aqueous nitrocellulose emulsion, the thickener and the rest defoamer in proportion in the formula to obtain the coating.
Further, the mixing mode is ball milling mixing.
Further, the distilled water, the 1/2 defoaming agent, the leveling agent, the wetting agent, the dispersing agent and the anti-settling agent are mixed and dispersed for 5-10 minutes at the rotating speed of 350-550 revolutions per minute.
Further, the pigment and the filler are mixed and dispersed for 30 to 50 minutes at the rotating speed of 400 to 600 revolutions per minute.
Further, the nitrocellulose emulsion, the thickener and the rest of the defoamer are mixed and dispersed for 20-40 minutes at the rotating speed of 350-600 revolutions per minute.
The invention has the following beneficial effects:
1. the coating disclosed by the invention takes the water-based nitrocotton emulsion as a base material, has the advantages of nature, environmental protection, safety, no toxicity, environmental friendliness and the like, does not cause physical harm to constructors, does not cause pollution to the atmospheric environment, and has the VOC content of less than 50 g/L.
2. The paint is compounded by a plurality of functional pigments and fillers, has a high near-infrared reflection effect, has a near-infrared band reflectivity ratio of not less than 0.8, and has high infrared reflectivity, so that the paint has good cooling and energy-saving effects. The energy-saving coating is coated on the outer surface of a building, and can efficiently reflect infrared rays with obvious thermal effect in sunlight (and artificial light sources), so that the temperature rise of the surface and the interior of the building is reduced. The power consumption of refrigeration equipment such as air conditioners, fans, refrigerators and the like in summer can be effectively saved when the energy-saving refrigerator is used for electric appliances.
3. As the coating of the invention adopts the water-based nitrocotton emulsion as the base material, compared with the existing homozygous forming water-based coating (such as water-based acrylic acid, water-based polyurethane and the like), the coating is easier to degrade, and the time required for achieving the same degradation condition is greatly shortened compared with that of an acrylate coating; and the paint has more excellent water resistance, and the paint film appearance has no obvious change after 240h soaking at 40 +/-1 ℃ in a water resistance test.
4. The impact resistance of the coating is not less than 50cm, and the coating has good flexibility.
Drawings
FIG. 1 is an infrared analysis spectrum of the aqueous nitrocotton in the example.
Detailed Description
The present invention is further illustrated by the following specific embodiments. The following description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims and their equivalents, as well as any equivalents thereof, which may be directly or indirectly applied to other related arts.
In the following examples, the degradation performance of the coatings was tested according to the accelerated degradation method published in the literature with slight modification, as follows: respectively weighing and recording the cured coating and the acrylic ester coating film, then respectively placing the films into a 50m L hydrothermal reaction kettle, adding 25m L distilled water (p H is 7), sealing the reaction kettle, placing the reaction kettle into a 150-DEG C oven, respectively reacting for 1h, 2h, 3h and 4h, cooling to normal temperature, taking out the films, drying at 70 ℃, weighing the mass of the films again, and reflecting the degradation degree of the coating film according to the ratio of the residual mass after the coating film is degraded to the initial mass.
The VOC content is tested according to GB1581, the water resistance is tested according to GB/T1733, the impact resistance is tested according to GB/T1731, and the near-infrared band reflectivity and the ultraviolet visible near-infrared spectrophotometer are used for testing.
Example 1
Preparing water-based nitrocotton emulsion:
(1) adding 12g of isophorone diisocyanate (IPDI), 8.64g of polyethylene glycol 400 and 15g of acetone into a three-neck flask provided with a stirrer and a reflux condenser, and continuously stirring for reacting for 2 hours at 70 ℃;
(2) adding 12.96g of polyethylene glycol 4000 and 19.44g of epoxy resin E-42 into the product obtained in the step (1), adding 14.74g of nitrocotton dissolved in butanone and 1g of dioctyltin dilaurate into the system, heating to 80 ℃, and carrying out heat preservation reaction for 1 h; then heating to 85 ℃ and reacting for 3 hours at constant temperature;
(3) and (3) distilling the organic solvent from the reaction liquid obtained in the step (2) under reduced pressure, cooling to 50 ℃, dropwise adding 150mL of distilled water or deionized water within 20min, simultaneously rapidly stirring for 700-800 r/mi, and emulsifying to obtain the cellulose-based high-stability emulsion for the water-based environment-friendly coating.
Example 2
(1) 12g of Toluene Diisocyanate (TDI) was charged in a three-necked flask equipped with a stirrer and a reflux condenser,
6.9g of polyethylene glycol 200 and 15g of acetone, and continuously stirring and reacting for 1h at 65 ℃;
(2) adding 13.8g of polyethylene glycol 2000 and 23.39g of epoxy resin E-39 into the product obtained in the step (1), adding 10.35g of nitrocotton dissolved by acetone and 0.7g of dibutyltin dilaurate into the system, heating to 70 ℃, and carrying out heat preservation reaction for 1 h; then raising the temperature to 90 ℃ and reacting for 2h at constant temperature.
(3) And (3) distilling the product in the step (2) under reduced pressure to remove the organic solvent. And cooling to 50 ℃, dropwise adding 150mL of distilled water or deionized water within 20min, and simultaneously rapidly stirring for 700-800 r/min for emulsification to obtain the cellulose-based high-stability emulsion for the water-based environment-friendly coating.
Example 3
(1) Adding 12g of diphenylmethane diisocyanate (MDI), 9.6g of polyethylene glycol 600 and 20g of xylene into a three-neck flask provided with a stirrer and a reflux condenser, and continuously stirring and reacting for 2 hours at the temperature of 80 ℃;
(2) adding 9.6g of PEG6000 and 29.09g of epoxy resin E-44 into the product obtained in the step (1), adding 12.36g of nitrocotton dissolved in butanone and 1g of triethyl tin acetate into the system, heating to 85 ℃, and carrying out heat preservation reaction for 1 h; then raising the temperature to 90 ℃ and reacting for 2.5h at constant temperature.
(3) And (3) distilling the product in the step (2) under reduced pressure to remove the organic solvent. And cooling to 50 ℃, dropwise adding 150mL of distilled water or deionized water within 20min, and simultaneously rapidly stirring for 700-800 r/min and emulsifying to obtain the cellulose-based high-stability resin for the water-based environment-friendly coating.
In the following examples, pigments and fillers, anti-settling agents, defoaming agents, dispersing agents, thickeners, leveling agents and wetting agents are all commercially available.
Example 4
The formulation composition is shown in the following table:
(1) grinding and preparing pigment and filler slurry:
adding distilled water (self-made), 1/2 polyether modified polydimethylsiloxane defoaming agent, aralkyl modified polymethylsiloxane leveling wetting agent, modified high polymer solution dispersing agent containing high pigment affinity group and modified urea solution anti-settling agent into a ball milling tank, dispersing for 5 minutes at the rotating speed of 350 r/min, and then adding pigment and filler, wherein rutile type titanium dioxide TiO295 percent of the pigment filler, 99 percent of rutile phase, 800 meshes of average grain diameter and 800 meshes of average grain diameter of zinc oxide, and the pigment filler is obtained by dispersing and grinding for 30 minutes at the rotating speed of 400 r/min
(2) Adding the water-based nitrocellulose emulsion, the thickening agent methylcellulose and the rest of the defoamer polyether modified polydimethylsiloxane metered in the formula into a ball milling tank, and dispersing for 40 minutes at the rotating speed of 400 revolutions per minute to prepare the water-based energy-saving coating.
The product is easily degraded, and the time required for the product to reach the same degradation condition is about 2/3 of that of acrylic resin;
the VOC content of the coating is about 45 g/L;
the appearance of a paint film does not have obvious change after 240h soaking at 40 +/-1 ℃ in a water resistance test;
impact resistance is not less than 50 cm;
the reflection ratio of the near-infrared band is 0.83;
has higher infrared reflection performance, better environmental protection performance (easy degradation and low VOC content), impact resistance, water resistance and cooling and energy-saving effects.
Example 5
The formulation composition is shown in the following table:
(1) grinding and preparing pigment and filler slurry:
adding distilled water (self-made), 1/2 foam breaking polysiloxane and hydrophobic solid mixture defoamer, polyether modified polydimethylsiloxane leveling wetting agent, high molecular weight block copolymer solution dispersant with pigment affinity group and modified urea polyurethane solution anti-settling agent into a ball milling tank, dispersing for 5 minutes at the rotating speed of 350 r/min, and adding pigment and filler, wherein rutile type titanium dioxide TiO 2297 percent of the pigment filler slurry, 99.3 percent of rutile phase, 1000 meshes of average particle size, 800 meshes of average particle size of sericite powder and 1000 meshes of average particle size of zinc oxide, and dispersing and grinding for 50 minutes at the rotating speed of 400 r/min to obtain the pigment filler slurry.
(2) And adding the mixture of the aqueous nitrocellulose emulsion, the thickening agent hydroxymethyl cellulose, the rest defoaming agent foam breaking polysiloxane and the hydrophobic solid which are metered in the formula into a ball milling tank, and dispersing for 40 minutes at the rotating speed of 450 revolutions per minute to prepare the aqueous energy-saving coating.
The product is easy to degrade, and the time required for the product to reach the same degradation condition is about half of that of acrylic resin; the coating VOC content is about 42 g/L; the appearance of a paint film does not have obvious change after 240h soaking at 40 +/-1 ℃ in a water resistance test; the impact resistance is not lower than 50cm, and the near-infrared band reflectance is 0.85; the hemispherical emissivity is 0.85, and the infrared reflection paint has high infrared reflection performance, good environmental protection performance (easy degradation and low VOC content), good impact resistance, good water resistance and good cooling and energy-saving effects.
Example 6
The formulation composition is shown in the following table:
(1) grinding and preparing pigment and filler slurry:
adding distilled water (self-made), 1/2 foam breaking polysiloxane and hydrophobic solid mixture defoamer, polyether modified polydimethylsiloxane leveling wetting agent, high molecular weight block copolymer solution dispersant with pigment affinity group and modified urea polyurethane solution anti-settling agent into a ball milling tank, dispersing for 5 minutes at the rotating speed of 350 r/min, and adding pigment and filler, wherein rutile type titanium dioxide TiO 2298 percent of the content, 99.5 percent of rutile phase, 1200 meshes of average grain diameter of zinc oxide, 2000 meshes of average grain diameter of precipitated barium sulfate, and dispersing and grinding for 50 minutes at the rotating speed of 430 revolutions per minute to obtain pigment and filler slurry.
The particle size of the water-based nitrocellulose emulsion and the hollow glass beads metered in the formula is 40-110 um, the mixture of the thickening agent hydroxypropyl methyl cellulose, the rest defoaming agent foam-breaking polysiloxane and the hydrophobic solid is added into a ball milling tank, and the mixture is dispersed for 40 minutes at the rotating speed of 400 revolutions per minute, so that the water-based energy-saving coating is prepared.
The product is easy to degrade, and the time required for the product to reach the same degradation condition is about half of that of acrylic resin; the VOC content of the coating is about 48 g/L; the appearance of a paint film does not have obvious change after 240h soaking at 40 +/-1 ℃ in a water resistance test; the impact resistance is not lower than 50 cm; the near-infrared band reflectance is 0.89, and the coating has high infrared reflection performance, good environmental protection performance (easy degradation and low VOC content), good impact resistance, good water resistance and good cooling and energy-saving effects.
Example 7
The formulation composition is shown in the following table:
(1) grinding and preparing pigment and filler slurry:
adding distilled water (self-made), 1/2 polyether modified polydimethylsiloxane defoaming agent, polyether modified polydimethylsiloxane leveling wetting agent, modified high polymer solution dispersing agent containing high pigment affinity group, modified urea polyurethane solution and modified urea solution anti-settling agent into a ball milling tank, dispersing for 10 minutes at the rotating speed of 350 r/min, and adding pigment and filler, wherein the rutile type titanium dioxide TiO is prepared by298 percent of the pigment filler slurry, 99.5 percent of rutile phase, 1250 meshes of average grain size of sericite, 1250 meshes of average grain size of zinc oxide, 2000 meshes of average grain size of precipitated barium sulfate, and dispersing and grinding for 50 minutes at the rotating speed of 450 revolutions per minute to obtain the pigment filler slurry.
(2) The particle size of the water-based nitrocellulose emulsion and the hollow glass beads measured according to the formula is 25-70 um, the thickening agent hydroxyethyl cellulose and the rest of the defoaming agent polyether modified polydimethylsiloxane are added into a ball milling tank, and are dispersed for 50 minutes at the rotating speed of 400 revolutions per minute, so that the water-based energy-saving coating is prepared.
The product is easily degraded, and the time required for the product to reach the same degradation condition is about 3/4 of that of acrylic resin; the VOC content of the coating is about 50 g/L; the appearance of a paint film does not have obvious change after 240h soaking at 40 +/-1 ℃ in a water resistance test; the impact resistance is not less than 50cm, the near-infrared band reflectance is 0.87, the infrared reflection performance is higher, and the environment-friendly performance (easy degradation and low VOC content), the impact resistance, the water resistance and the cooling and energy-saving effects are better.
Claims (8)
1. The energy-saving environment-friendly water-based paint is characterized by comprising the following components in parts by weight: 25-60 parts of water-based nitrocotton emulsion, 20-45 parts of pigment and filler, 0.3-1.5 parts of anti-settling agent, 0.2-0.5 part of defoaming agent, 0.5-1 part of dispersing agent, 0.2-0.6 part of thickening agent, 0.1-1 part of leveling wetting agent and distilled water;
the content of the water-based nitrocotton resin in the emulsion is 20% -60%;
the pigment and filler is selected from at least one of titanium dioxide, sericite powder, zinc oxide, precipitated barium sulfate and hollow glass beads;
the preparation method of the water-based nitrocotton emulsion comprises the following steps:
(1) introduction of hydrophilic groups
Reacting a double-end hydroxyl substance containing a hydrophilic group with isocyanate in a solvent dissolving environment at 65-85 ℃ for 1-2 h, and feeding according to the ratio of the amount of hydroxyl to isocyanate substances of 1: 2-4;
(2) introduction of nitrocotton molecules and other functional groups
Reacting the reaction product obtained in the step (1) with polyethylene glycol, epoxy resin and nitrocotton at 70-90 ℃ under the condition of a catalyst for 2.5-4 h, and removing the solvent to obtain water-based nitrocotton resin;
(3) emulsification of resins
Mixing the resin obtained by the reaction in the step (2) with water to obtain a water-based nitrocotton emulsion;
the isocyanate is at least one selected from toluene diisocyanate, isophorone diisocyanate , diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
2. The coating as claimed in claim 1, wherein the hydrophilic group-containing double-terminal hydroxyl substance is selected from polyethylene glycol substances, and is at least one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 3000 and polyethylene glycol 6000; or the hydrophilic group-containing double-end hydroxyl substance is selected from dihydroxy carboxylic acid substances.
3. The coating according to claim 2, wherein the dihydroxy carboxylic acids are at least one selected from the group consisting of dimethylol propionic acid, dimethylol butyric acid, dimethylol cyclobutane carboxylic acid, and dihydroxy quinoline carboxylic acid.
4. The coating of claim 1, wherein the anti-settling agent is a modified urea solution and/or a modified urea polyurethane solution; the defoaming agent is at least one of polyether modified polydimethylsiloxane, foam breaking polysiloxane and hydrophobic solid.
5. The coating of claim 1, wherein the dispersant is one or both of a modified high molecular weight polymer solution containing a high pigment affinity group and a high molecular weight block copolymer solution having a pigment affinity group; the thickener is at least one of methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
6. The coating of claim 1, wherein the leveling wetting agents are each selected from at least one of aralkyl modified polymethylsiloxanes and polyether modified polydimethylsiloxanes.
7. The coating of claim 1, wherein the titanium dioxide is rutile titanium dioxide, wherein the TiO is2The content is not less than 95 percent, and the content of rutile phase is not less than 99 percent; titanium white powderThe particle size is 800-2000 meshes, the particle size of sericite powder is 800-1500 meshes, the particle size of zinc oxide is 800-2000 meshes, the particle size of precipitated barium sulfate is 2000-4000 meshes, and the particle size of hollow glass beads is one or a mixture of 40-110 microns, 25-80 microns and 25-70 microns.
8. The preparation method of the coating of any one of claims 1 to 7, characterized in that, according to the composition proportion of the coating, distilled water, 1/2 defoamer, leveling wetting agent, dispersant and anti-settling agent are uniformly mixed, then the mixture is uniformly mixed with pigment and filler to obtain pigment and filler slurry, and the slurry is uniformly mixed with the aqueous nitrocellulose emulsion, thickener and the rest defoamer in proportion in the formula to obtain the coating.
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| JPS4825099A (en) * | 1971-07-30 | 1973-04-02 | ||
| CN1504490A (en) * | 2002-12-03 | 2004-06-16 | 日本聚氨酯工业株式会社 | Polyisocyanates solution , adhesive and paint using the same |
| CN107245139A (en) * | 2017-04-12 | 2017-10-13 | 立邦工业涂料(上海)有限公司 | A kind of nitrocotton is polymer-modified, preparation method and applications |
| CN109575697A (en) * | 2018-11-19 | 2019-04-05 | 西华大学 | A kind of starch-based aqueous coating composition and preparation method thereof |
| CN109942770A (en) * | 2019-03-28 | 2019-06-28 | 西华大学 | A kind of water paint emulsion compositions and preparation method thereof |
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| EP3387062A2 (en) * | 2015-12-07 | 2018-10-17 | Acetate International LLC | Cellulose acetate film forming compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS4825099A (en) * | 1971-07-30 | 1973-04-02 | ||
| CN1504490A (en) * | 2002-12-03 | 2004-06-16 | 日本聚氨酯工业株式会社 | Polyisocyanates solution , adhesive and paint using the same |
| CN107245139A (en) * | 2017-04-12 | 2017-10-13 | 立邦工业涂料(上海)有限公司 | A kind of nitrocotton is polymer-modified, preparation method and applications |
| CN109575697A (en) * | 2018-11-19 | 2019-04-05 | 西华大学 | A kind of starch-based aqueous coating composition and preparation method thereof |
| CN109942770A (en) * | 2019-03-28 | 2019-06-28 | 西华大学 | A kind of water paint emulsion compositions and preparation method thereof |
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