CN112812668B - Coating containing modified waste rubber powder and preparation method thereof - Google Patents
Coating containing modified waste rubber powder and preparation method thereof Download PDFInfo
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- CN112812668B CN112812668B CN202011623313.4A CN202011623313A CN112812668B CN 112812668 B CN112812668 B CN 112812668B CN 202011623313 A CN202011623313 A CN 202011623313A CN 112812668 B CN112812668 B CN 112812668B
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/46—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a coating containing modified waste rubber powder and a preparation method thereof. The coating comprises the following components in percentage by weight: 25-40 parts by mass of resin; 10-30 parts by mass of modified waste rubber powder; 5-20 parts by mass of a filler; 0.1-0.3 parts by mass of a wetting dispersant; 0.05-0.25 parts by mass of a film-forming assistant; 0.05-0.15 parts by mass of a defoaming agent; 0.05-0.1 parts by mass of a thickener; 30-50 parts by mass of a solvent; the modified waste rubber powder is prepared by sequentially carrying out urea formaldehyde pre-modification and coupling agent grafting modification on waste rubber powder. Compared with the traditional coating containing unmodified waste rubber powder, the coating containing the modified waste rubber powder has the advantages of excellent appearance, adhesive force, wear resistance, water resistance and higher hardness.
Description
Technical Field
The invention relates to a coating containing modified waste rubber powder and a preparation method thereof, belonging to the technical field of coatings.
Background
Waste rubber is one of the main solid pollutants in the world, and causes problems in the aspects of environment, society, economy and the like. The traditional waste rubber treatment method is simple landfill and incineration, and is easy to cause greater environmental pollution. The recycling is an effective way for treating the waste rubber, and the current specific method comprises the following steps: renewing rubber products, manufacturing regenerated rubber, pyrolyzing and recycling useful substances, incinerating at high temperature to utilize heat energy, producing rubber powder and the like. The application of the waste rubber powder to the composite material is a feasible, economic and effective waste rubber recycling method, the material cost can be obviously reduced, and the performance of plastics and rubber can be obviously improved through proper waste rubber powder modification/functionalization.
The surface of the crumb rubber is generally non-polar and has few functional groups, and direct incorporation into the polymer matrix results in poor interfacial bonding. In response to this problem, various methods of modifying waste rubber powders have been developed, including in particular: mechanochemical modification, regenerative desulfurization degradation modification, core-shell modification, gas modification, radiation modification, sulfonation, chlorination modification and the like.
At present, the modified waste rubber powder is mostly applied to the following aspects: for example, patent CN201910240098.0 grafts alkane long chain on the surface of waste rubber powder for asphalt modification; patent CN200710029124.2 utilizes sol-gel method to prepare nano SiO2The modified waste rubber powder is used for producing regenerated rubber; the patent CN201510514544.4 modifies the surface of waste rubber powder step by step through a mechanochemical method and a modifier, and is used for rubber and thermosetting resin matrixes; in patent CN200610125315.4, an alkenyl monomer or an acetylene monomer is used for grafting or a functional group reaction to obtain modified rubber powder which is used for materials such as plastics, rubber and the like with different properties. However, the research and application of the waste rubber powder in the coating aspect are less.
As is well known, the unmodified waste rubber powder has poor compatibility in a coating system, so that the performance of a paint film is deteriorated, and the problems of layering and sedimentation phenomena, uneven particle size, uneven coating surface and the like exist at the same time. How to solve the application of the waste rubber powder with inert surface in the coating field is a technical problem to be solved urgently.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a coating material containing modified waste rubber powder and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
a coating containing modified waste rubber powder comprises the following components in parts by weight:
resin: 25-40 parts by mass;
modified waste rubber powder: 10-30 parts by mass;
filling: 5-20 parts by mass;
wetting and dispersing agent: 0.1 to 0.3 parts by mass;
film-forming auxiliary agent: 0.05-0.25 parts by mass;
defoaming agent: 0.05-0.15 parts by mass;
thickening agent: 0.05-0.1 parts by mass;
solvent: 30-50 parts by mass;
the modified waste rubber powder is prepared by sequentially carrying out urea formaldehyde pre-modification and coupling agent grafting modification on waste rubber powder.
In one embodiment, the resin is an aqueous emulsion, preferably of the polyurethane, polyacrylate, epoxy type.
In one embodiment, the filler is one or more of titanium dioxide, mica powder, carbon black, silica micropowder, barium sulfate and zinc chloride.
In one embodiment, the wetting and dispersing agent is one or more of an ionic, nonionic, and electroneutral wetting and dispersing agent compatible with the resin.
In one embodiment, the coalescing agent is one or more of alcohols, alcohol esters, alcohol ethers, alcohol ether esters.
In one embodiment, the defoamer is one or more of an organosiloxane, polyether, amine, imine, or amide.
In one embodiment, the thickener is one or more of a cellulosic, polyacrylate, associative polyurethane thickener.
In one embodiment, the solvent is deionized water.
One embodiment, the modified waste rubber powder is prepared by fully swelling waste rubber powder in a mixed aqueous solution of urea and aldehyde, and performing urea formaldehyde pre-modification through an addition-polycondensation reaction to obtain urea formaldehyde pre-modified waste rubber powder; and then, carrying out coupling agent grafting modification on the urea formaldehyde pre-modified waste rubber powder by adopting a coupling agent, and washing and drying the obtained product to obtain the modified waste rubber powder.
A preferable scheme is that the preparation of the modified waste rubber powder specifically comprises the following steps:
a) fully swelling waste rubber powder in a mixed aqueous solution of urea and aldehyde; then adding a dispersing agent, and stirring to uniformly mix; then adjusting the pH value to 8-9, and stirring and reacting for 1-3 hours at 50-75 ℃; then adjusting the pH value to 2-5, and stirring and reacting for 3-8 hours at 50-75 ℃; carrying out reduced pressure suction filtration, collecting a solid product, washing and drying to obtain urea formaldehyde pre-modified waste rubber powder;
b) dispersing the urea formaldehyde pre-modified waste rubber powder obtained in the step a) in an alcohol solvent, then slowly adding a coupling agent and deionized water in sequence, adjusting the pH value to be 8-9, stirring and reacting for 3-12 hours at room temperature, then aging for 8-24 hours, carrying out vacuum filtration, collecting a solid product, washing, and drying to obtain the modified waste rubber powder.
In the preparation process of the modified waste rubber powder, the dosage ratio of each raw material is as follows:
waste rubber powder: 5-25 parts by mass;
mixed aqueous solution of urea and aldehyde: 40-75 parts by mass;
dispersing agent: 0.05-0.2 parts by mass;
coupling agent: 0.05-3 parts by mass;
alcohol solvent: 15-50 parts by mass;
deionized water: 2 to 8 parts by mass.
According to a preferable scheme, in the preparation process of the modified waste rubber powder, the dosage ratio of each raw material is as follows:
waste rubber powder: 10-20 parts by mass;
mixed aqueous solution of urea and aldehyde: 45-65 parts by mass;
dispersing agent: 0.05-0.15 parts by mass;
coupling agent: 0.1-2 parts by mass;
alcohol solvent: 20-35 parts by mass;
deionized water: 4 to 6 parts by mass.
In a preferable scheme, in the step a), the waste rubber powder is fully stirred and swelled in a mixed aqueous solution of urea and aldehyde until the swelling index reaches 0.7-1.2.
In a preferable scheme, in the step a), the particle size of the waste rubber powder is 100-1000 meshes, and is preferably 300-1000 meshes.
In a preferable scheme, in the step a), the mixed aqueous solution of urea and aldehyde is prepared by uniformly mixing urea, deionized water and 35-45 wt% of aldehyde aqueous solution, wherein the molar ratio of aldehyde to urea is (1.4-2.0): 1.
in a preferred embodiment, the aldehyde is at least one selected from formaldehyde, glyoxal, succinaldehyde, glutaraldehyde and furfural, and further preferably, the formaldehyde is used in combination with one or more other aldehydes, and the molar ratio of the formaldehyde to the other aldehydes is (2.5-4.6): 1.
in a preferable scheme, in the preparation process of the modified waste rubber powder, an alkaline pH regulator is used for regulating the pH to 8-9, and an acidic pH regulator is used for regulating the pH to 2-5, wherein the alkaline pH regulator includes but is not limited to sodium hydroxide, triethanolamine and ammonia water, preferably triethanolamine, and the acidic pH regulator includes but is not limited to hydrochloric acid, formic acid and acetic acid, preferably hydrochloric acid.
In a preferable scheme, the dispersant is any one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
In a preferable embodiment, the coupling agent is at least one selected from silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, borate coupling agent, chromium complex and other coupling agents of higher fatty acid, alcohol and ester, preferably any one selected from silane coupling agent and titanate coupling agent.
Further, the silane coupling agent has a structural general formula of Y-R-Si-X3The terminal group Y of the organosilane coupling agent of (1) can undergo a physical entanglement/chemical bonding reaction with the resin, wherein:
y is selected from-CI, -OH, -SH, -NH2、-OCO-CMe＝CH2、-OCH2-CHCH2、
-NCO、-HN-Ph、-HNCONH2、-NHCH2CH2NH2、-N3、-NR2Any one of R' Cl;
x is selected from Cl, OMe, OEt, OAC, OCH2CH2OCH3Any one of the above;
r is selected from- (CH)2)m- (m 1 or 3), -C6H4Any one of them.
Further, the silane coupling agent is at least one selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane (KH560), gamma-aminopropyltriethoxysilane (KH550), gamma-methacryloxypropyltrimethoxysilane (KH-570), bis- (gamma-triethoxysilylpropyl) tetrasulfide (KH-845-4), vinyltriethoxysilane (A151) and vinyltrimethoxysilane (A171).
In a preferable scheme, the alcohol solvent is an alcohol solvent matched with the coupling agent, and is specifically selected from any one of methanol, ethanol, propanol and butanol; when the coupling agent is of the structural general formula Y-R-Si-X3The alcohol solvent is an alcohol solvent which matches the hydrolyzable functional group X on the organosilane coupling agent, for example, the organosilane coupling agent having a methoxy group is preferably methanol, and the organosilane coupling agent having an ethoxy group is preferably ethanol.
A method for preparing the coating containing the modified waste rubber powder comprises the following steps:
uniformly mixing a solvent, a wetting dispersant and a defoaming agent in proportion; then adding the modified waste rubber powder and the filler in proportion, and stirring and mixing uniformly; then adding the resin and the film forming aid in proportion, and stirring and mixing uniformly; and then adding a thickening agent in a proportion amount, and stirring and mixing uniformly to obtain the coating containing the modified waste rubber powder.
Compared with the prior art, the invention has the following remarkable beneficial effects:
1. the surface modification of the waste rubber powder is to perform urea formaldehyde pre-modification on the waste rubber powder, and then perform coupling agent grafting modification on the waste rubber powder subjected to urea formaldehyde pre-modification, compared with the traditional simple grafting modification, the surface modification method can adopt a urea formaldehyde transition layer as an inert rubber powder surface to anchor active points, provide conditions for subsequent grafting of active groups, and effectively overcome the problem of poor interface compatibility of the waste rubber powder and a coating substrate;
2. the modified waste rubber powder particles are not easy to agglomerate and bond, the granularity and the distribution thereof are controllable, the waste rubber powder can be used as a filler to be applied to the coating, and the problem of uneven coating surface caused by uneven grain diameter can be effectively avoided; in addition, active groups on the surface of the modified waste rubber powder can generate physical and chemical actions with resin, so that the comprehensive properties of the coating in the aspects of adhesive force, wear resistance, water resistance, hardness and the like can be effectively improved;
3. the invention effectively expands the application range of the waste rubber powder, improves the economic added value of the waste rubber powder, is beneficial to reducing the coating cost and realizing the recycling of the waste rubber, and has environmental protection significance.
Drawings
FIG. 1 shows the surface topography of waste rubber powder (FIG. 1a), urea formaldehyde pre-modified waste rubber powder (FIG. 1b) and KH550 modified waste rubber powder (FIG. 1c) in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the waste rubber powder, urea formaldehyde pre-modified waste rubber powder and KH550 modified waste rubber powder in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining the embodiment.
Example 1
Firstly, preparing modified waste rubber powder:
a) soaking 10g of waste rubber powder (100 meshes) in a mixed aqueous solution of 2.66g of urea, 35.5g of deionized water, 3.72g of formaldehyde (37 wt%) and 3.13g of glyoxal (30 wt%), and fully stirring for swelling until the swelling index reaches 0.7; then 0.05g of sodium dodecyl benzene sulfonate is added and stirred to be uniformly mixed; then regulating the pH value to 8 by using triethanolamine, and stirring and reacting for 3 hours at 50 ℃; then adjusting the pH value to 5 by using hydrochloric acid, and stirring and reacting for 3 hours at 50 ℃; carrying out reduced pressure suction filtration, collecting a solid product, repeatedly washing with deionized water and ethanol respectively, and drying to obtain urea formaldehyde pre-modified waste rubber powder;
b) dispersing the obtained urea formaldehyde pre-modified waste rubber powder in 20g of ethanol, then sequentially and slowly adding 0.1g of silane coupling agent KH550, slowly dropwise adding 4g of deionized water, adjusting the pH value to 8 by using ammonia water, stirring at normal temperature for reaction for 3 hours, then aging for 24 hours, carrying out vacuum filtration, collecting a solid product, sequentially and repeatedly washing with ethanol and deionized water, and drying to obtain the KH550 modified waste rubber powder.
Fig. 1 is a surface topography diagram of the waste rubber powder, the urea formaldehyde pre-modified waste rubber powder and the KH550 modified waste rubber powder in the embodiment, and it can be seen that: the waste rubber powder (1a) is black irregular granular, and the urea formaldehyde pre-modified waste rubber powder (1b) is attached to a white urea formaldehyde shell on the surface of the KH550 modified waste rubber powder (1c) granules, so that the waste rubber powder is in an adhesion and dispersion state.
Fig. 2 is an infrared spectrum of the waste rubber powder, the urea formaldehyde pre-modified waste rubber powder, and the KH550 modified waste rubber powder in this embodiment, which shows that: the urea formaldehyde pre-modified waste rubber powder is 3500-3000 cm-1A broad and strong hydroxyl absorption peak appears; the KH550 modified waste rubber powder is 3500-3000 cm-1The absorption peak of hydroxyl group at (C) is reduced, and 1000cm-1About the peak of the Si-O-Si group, 783cm-1Display CH2The peak of ether bond between-O-Si, indicating that the waste rubber powder was successfully modified with KH 550.
Secondly, preparing the coating containing the modified waste rubber powder:
uniformly mixing 30g of deionized water, 0.1g of wetting dispersant (BYK-161) and 0.05g of polysiloxane antifoaming agent (BYK-066); then adding the waste rubber powder (shown in the table 1), 2g of titanium dioxide, 1g of mica powder and 2g of carbon black in proportion, and stirring and mixing uniformly; then 25g of epoxy resin(s) are added
331 tao shi chemical) and 0.05g of alcohol ester film-forming assistant (dodecanol ester), and stirring and mixing uniformly; adding 0.02g cellulose thickening agent (carboxymethyl cellulose), stirring and mixing uniformly; preparing the aqueous epoxy coating containing the KH550 modified waste rubber powder.
The basic properties of the paint film were measured and the results are shown in Table 1:
TABLE 1 paint film Properties of epoxy paints containing waste rubber powders
As can be seen from table 1: the waterborne epoxy coating containing the modified waste rubber powder provided by the invention has excellent appearance (smooth and flat), adhesive force, wear resistance and water resistance, and higher hardness, and all physical properties of the waterborne epoxy coating meet or are even better than the national standards for waterborne epoxy coatings.
Example 2
Firstly, preparing modified waste rubber powder:
a) soaking 15g of waste rubber powder (1000 meshes) in a mixed aqueous solution of 4.00g of urea, 39g of deionized water, 7.51g of formaldehyde (37 wt%) and 4.47g of succinaldehyde (40 wt%), and fully stirring for swelling until the swelling index reaches 1.2; then 0.1g of sodium dodecyl sulfate is added and stirred to be uniformly mixed; then, the pH was adjusted to 9 with sodium hydroxide, and the reaction was stirred at 75 ℃ for 1 hour; then adjusting the pH to 5 by using acetic acid, and stirring and reacting for 5 hours at 75 ℃; carrying out reduced pressure suction filtration, collecting a solid product, repeatedly washing with deionized water and ethanol respectively, and drying to obtain urea formaldehyde pre-modified waste rubber powder;
b) dispersing the obtained urea formaldehyde pre-modified waste rubber powder in 35g of ethanol, then sequentially and slowly adding 2g of silane coupling agent KH560, slowly dropwise adding 6g of deionized water, adjusting the pH value to 9 by using ammonia water, stirring at normal temperature for reaction for 12 hours, then aging for 8 hours, carrying out vacuum filtration, collecting a solid product, sequentially and repeatedly washing with ethanol and deionized water, and drying to obtain the KH560 modified waste rubber powder.
Secondly, preparing the coating containing the modified waste rubber powder:
an aqueous polyurethane coating containing KH560 modified waste rubber powder was prepared according to the method described in example 1, wherein in the coating: 40g of deionized water, 0.2g of non-ionic wetting dispersant (TEGO Wet 500), 0.1g of defoaming agent (BYK-024), a proportioning amount of waste rubber powder (shown in Table 2), 5g of silica powder, 2.5g of zinc chloride, 5g of carbon black, 35g of waterborne polyurethane emulsion, 0.15g of alcohol ether film-forming assistant (propylene glycol methyl ether) and 0.06g of associative polyurethane thickener (U.S. Volts, R-288).
The basic properties of the paint film were measured and the results are shown in Table 2.
TABLE 2 paint film properties of waterborne polyurethane paints containing waste rubber powder
As can be seen from table 2: the waterborne polyurethane coating containing the modified waste rubber powder provided by the invention has excellent appearance (smooth and flat), adhesive force, wear resistance and water resistance, and higher hardness, and all physical properties of the waterborne polyurethane coating meet or are even better than the national standards for waterborne polyurethane coatings.
Example 3
Firstly, preparing modified waste rubber powder:
a) soaking 30g of waste rubber powder (600 meshes) in a mixed aqueous solution of 5.00g of urea, 42.10g of deionized water, 11.30g of formaldehyde (37 wt%) and 5.81g of succinaldehyde (40 wt%) and fully stirring for swelling until the swelling index reaches 1.0; then 0.15g of sodium dodecyl benzene sulfonate is added and stirred to be uniformly mixed, and the stirring speed is 250 rpm; then, the pH was adjusted to 8.6 with sodium hydroxide, and the reaction was stirred at 65 ℃ for 3 hours; then adjusting the pH value to 3.6 by using hydrochloric acid, and stirring and reacting for 8 hours at 65 ℃; carrying out reduced pressure suction filtration, collecting a solid product, repeatedly washing with deionized water and ethanol respectively, and drying to obtain urea formaldehyde pre-modified waste rubber powder;
b) dispersing the obtained urea formaldehyde pre-modified waste rubber powder in 30g of ethanol, then sequentially and slowly adding 1.8g of silane coupling agent KH570, slowly dropwise adding 5.5g of deionized water, adjusting the pH value to 8.6 by using ammonia water, stirring at normal temperature for reaction for 9 hours, then aging for 16 hours, carrying out vacuum filtration, collecting a solid product, sequentially and repeatedly washing with ethanol and deionized water, and drying to obtain the KH570 modified waste rubber powder.
Secondly, preparing the coating containing the modified waste rubber powder:
an aqueous acrylic coating containing KH 570-modified waste rubber powder was prepared according to the method shown in example 1, wherein in the coating: 50g of deionized water, 0.3g of wetting dispersant (TEGO 270), 0.15g of defoaming agent (TEGO Foamex 1488, TEGO901W), proportioning waste rubber powder (shown in Table 3), 4g of zinc chloride, 4g of mica powder, 12g of barium sulfate, 40g of aqueous acrylic emulsion, 0.25g of film-forming additive (dipropylene glycol butyl ether: isopropanol: 2: 1, mass ratio) and 0.1g of thickening agent (PUR 42: PVA 1788: 3:1, mass ratio).
The basic properties of the paint film were measured and the results are shown in Table 3.
TABLE 3 film Properties of aqueous acrylic paint containing waste rubber powder
As can be seen from table 3: the water-based acrylic coating containing the modified waste rubber powder provided by the invention has excellent appearance (smooth and flat), adhesive force, wear resistance and water resistance, and higher hardness, and all physical properties of the water-based acrylic coating meet or are even better than the national standards for water-based acrylic coatings.
In summary, the following steps: the waste rubber powder particles subjected to urea formaldehyde pre-modification and coupling agent grafting modification are not easy to agglomerate and bond, the granularity and the distribution thereof are controllable, the interface compatibility with a coating substrate is good, and the waste rubber powder can be used as a filler to be applied to a coating; thereby effectively enlarging the application range of the waste rubber powder, improving the economic added value of the waste rubber powder, being beneficial to reducing the coating cost and realizing the recycling of the waste rubber, and having the significance of environmental protection.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.
Claims (9)
1. The coating containing the modified waste rubber powder is characterized by comprising the following components in parts by weight:
resin: 25-40 parts by mass;
modified waste rubber powder: 10-30 parts by mass;
filling: 5-20 parts by mass;
wetting and dispersing agent: 0.1 to 0.3 parts by mass;
film-forming auxiliary agent: 0.05-0.25 parts by mass;
defoaming agent: 0.05-0.15 parts by mass;
thickening agent: 0.05-0.1 parts by mass;
solvent: 30-50 parts by mass;
the preparation of the modified waste rubber powder comprises the steps of fully swelling the waste rubber powder in a mixed aqueous solution of urea and aldehyde, and carrying out urea formaldehyde pre-modification through an addition-polycondensation reaction to obtain urea formaldehyde pre-modified waste rubber powder; and then, carrying out coupling agent grafting modification on the urea formaldehyde pre-modified waste rubber powder by adopting a coupling agent, and washing and drying the obtained product to obtain the modified waste rubber powder.
2. The modified waste rubber powder-containing coating material according to claim 1, wherein: the resin is an aqueous emulsion.
3. The modified waste rubber powder-containing coating material according to claim 1, wherein: the filler is one or more of titanium dioxide, mica powder, carbon black, silica micropowder, barium sulfate and zinc chloride; the wetting dispersant is one or more of ionic, nonionic and electric neutral wetting dispersants matched with resin; the film-forming auxiliary agent is one or more of alcohols, alcohol esters, alcohol ethers and alcohol ether esters; the defoaming agent is one or more of organic siloxane, polyether, amine, imine and amide; the thickening agent is one or more of cellulose, polyacrylate and associated polyurethane thickening agent; the solvent is deionized water.
4. The modified waste rubber powder-containing coating material according to claim 1, wherein: the preparation method of the modified waste rubber powder specifically comprises the following steps:
a) fully swelling waste rubber powder in a mixed aqueous solution of urea and aldehyde; then adding a dispersing agent, and stirring to uniformly mix; then adjusting the pH value to 8-9, and stirring and reacting for 1-3 hours at 50-75 ℃; then adjusting the pH value to 2-5, and stirring and reacting for 3-8 hours at 50-75 ℃; finally, carrying out vacuum filtration, collecting a solid product, washing and drying to obtain urea formaldehyde pre-modified waste rubber powder;
b) dispersing the urea formaldehyde pre-modified waste rubber powder obtained in the step a) in an alcohol solvent, then slowly adding a coupling agent and deionized water in sequence, adjusting the pH value to be 8-9, stirring and reacting for 3-12 hours at room temperature, then aging for 8-24 hours, carrying out vacuum filtration, collecting a solid product, washing, and drying to obtain the modified waste rubber powder.
5. The coating containing the modified waste rubber powder as claimed in claim 4, wherein the modified waste rubber powder is prepared from the following raw materials in proportion:
waste rubber powder: 5-25 parts by mass;
mixed aqueous solution of urea and aldehyde: 40-75 parts by mass;
dispersing agent: 0.05-0.2 parts by mass;
coupling agent: 0.05-3 parts by mass;
alcohol solvent: 15-50 parts by mass;
deionized water: 2 to 8 parts by mass.
6. The modified waste rubber powder-containing coating material according to claim 4, wherein: in the step a), the particle size of the waste rubber powder is 100-1000 meshes.
7. The modified waste rubber powder-containing coating material according to claim 4, wherein: in the step a), the waste rubber powder is fully stirred and swelled in a mixed aqueous solution of urea and aldehyde until the swelling index reaches 0.7-1.2, the mixed aqueous solution of urea and aldehyde is prepared by uniformly mixing urea, deionized water and 35-45 wt% of aldehyde aqueous solution, wherein the molar ratio of aldehyde to urea is (1.4-2.0): 1.
8. the modified waste rubber powder-containing coating material according to claim 4, wherein: the coupling agent is selected from at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, borate coupling agent, chromium complex and other coupling agents of higher fatty acid, alcohol and ester.
9. A method for preparing a coating material containing modified waste rubber powder according to claim 1, comprising the steps of: uniformly mixing a solvent, a wetting dispersant and a defoaming agent in proportion; then adding the modified waste rubber powder and the filler in proportion, and stirring and mixing uniformly; then adding the resin and the film forming aid in proportion, and stirring and mixing uniformly; and then adding a thickening agent in a proportion amount, and stirring and mixing uniformly to obtain the coating containing the modified waste rubber powder.
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| CN114958099A (en) * | 2022-05-27 | 2022-08-30 | 临沂嘉莱乐装饰材料有限公司 | High-elasticity waterproof coating based on functional modified rubber and preparation method and application thereof |
| CN115449251B (en) * | 2022-09-26 | 2023-09-08 | 上海工程技术大学 | Heat insulation coating capable of blocking ultraviolet and near infrared and preparation method thereof |
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