CN115141547B

CN115141547B - Non-curing waterproof coating and preparation method thereof

Info

Publication number: CN115141547B
Application number: CN202210617016.1A
Authority: CN
Inventors: 于亮亮; 龚兴宇; 杨小育; 何淞坡; 陈思思
Original assignee: Keshun Waterproof Technology Co Ltd
Current assignee: Keshun Waterproof Technology Co Ltd
Priority date: 2022-06-01
Filing date: 2022-06-01
Publication date: 2023-04-11
Anticipated expiration: 2042-06-01
Also published as: CN115141547A

Abstract

The application discloses a non-curing waterproof coating and a preparation method thereof. The non-curable waterproof coating material in the present application comprises: 50 parts by weight of softening oil; 10-15 parts of modified wax powder; 13-20 parts by weight of thermoplastic elastomer; 5-15 parts of resin; 1-3 parts of silane coupling agent; 15-35 parts of filler; the modified wax powder is bifunctional group modified wax powder. The application provides a non-curing waterproof coating has overcome the not enough that current non-curing waterproof coating uses pitch, rubber to bring as the principal ingredients, can balance high low temperature performance betterly, and possesses good extensibility and environmental protection.

Description

Non-curing waterproof coating and preparation method thereof

Technical Field

The application belongs to the technical field of waterproof coatings, and particularly relates to a non-cured waterproof coating and a preparation method thereof.

Background

The non-curing waterproof coating has the characteristics of creep resistance, strong self-healing capability, excellent bonding property and the like, is widely applied to various waterproof projects, and becomes one of waterproof materials with faster development in the waterproof industry.

However, the traditional non-cured waterproof coating takes rubber and asphalt as main components, wherein the rubber components are easily decomposed at high temperature, the low-temperature performance and ductility of the non-cured waterproof coating per se are reduced, and even the waterproof effect is lost; secondly, the asphalt has the defects of low equivalent softening point, poor low temperature resistance and the like, and the asphalt easily volatilizes pungent odor at high temperature, seriously pollutes the environment and damages the body health of construction personnel. The existing non-curing waterproof coating also has a small amount of non-asphalt-based non-curing waterproof coating, but the existing non-curing waterproof coating cannot simultaneously achieve heat resistance, extensibility and environmental protection.

Disclosure of Invention

In view of this, the present application provides a non-curable waterproof coating and a preparation method thereof, aiming at solving the problems that the non-curable waterproof coating cannot balance high and low temperature performance, has poor extensibility and is poor in environmental protection.

The application provides in a first aspect a non-curable waterproof coating material, which comprises: softening oil, 50 parts by weight; 10-15 parts of modified wax powder; 13-20 parts of thermoplastic elastomer; 5-15 parts of resin; 1-3 parts of silane coupling agent; 15-35 parts of filler;

the modified wax powder is bifunctional group modified wax powder.

According to an embodiment of the first aspect of the present application, the monomers forming the bifunctional group comprise a first functional monomer and a second functional monomer;

the first functional monomer is selected from acrylamide compounds, (meth) acrylate compounds, multiolefin compounds, and combinations thereof;

the second functional monomer is selected from azo initiators comprising an ethylenically unsaturated group.

According to an embodiment of one aspect of the present application, the acrylamide-based compound is selected from one or more of N, N-methylenebisacrylamide, N-methylolacrylamide, and methacrylamide; and/or the presence of a gas in the gas,

the (methyl) acrylate compound is selected from one or more of ethylene glycol diacrylate, ethylene glycol methacrylate and ethylene glycol dimethacrylate; and/or the presence of a gas in the gas,

the multiolefin compound is selected from divinylbenzene and/or trivinylbenzene;

the azo-based initiator containing an ethylenically unsaturated group is an azo-based initiator containing a (meth) acrylate functional group.

According to an embodiment of one aspect of the present application, the softening oil is selected from one or more of naphthenic oil, minus line oil, paraffinic oil, white oil and aromatic oil; and/or the presence of a gas in the gas,

the viscosity of the softening oil at 130 ℃ is 400mPa.s-800mPa.s, the flash point is more than or equal to 210 ℃, the ash content is less than or equal to 2%, and the aniline point is less than or equal to 35 ℃.

According to an embodiment of one aspect of the present application, the thermoplastic elastomer is selected from hydrogenated styrenic thermoplastic elastomers and/or hydrogenated styrene-butadiene rubbers.

According to an embodiment of one aspect of the present application, the resin is selected from one or more of a cold-polymerized C5 hydrogenated petroleum resin, a cold-polymerized C9 hydrogenated petroleum resin, a C5/C9 copolymerized petroleum resin, and a cycloaliphatic resin.

According to an embodiment of one aspect of the present application, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.

According to an embodiment of one aspect of the present application, the filler is selected from one or more of desulfurized tire rubber powder, graphene, porous carbon nanotubes and porous carbon microspheres, wherein the particle size of the desulfurized tire rubber powder is 0.18-0.25mm.

In a second aspect, the present application provides a method for preparing a non-curable waterproof coating material, comprising:

heating the softening oil under stirring;

adding thermoplastic elastomer, resin, filler and silane coupling agent, heating and stirring;

stopping heating, providing and adding the modified wax powder, stirring and cooling to obtain the non-cured waterproof coating.

According to an embodiment of the second aspect of the present application, there is provided a modified wax powder comprising:

dissolving wax powder in a good solvent in an inert atmosphere, adding a chain transfer agent, the first functional monomer and a thermal initiator, uniformly stirring, and heating and refluxing to obtain a first product;

and dissolving the first product in a good solvent in an inert atmosphere, adding the second functional monomer and a photoinitiator, and carrying out photoinitiated polymerization grafting to obtain the modified wax powder.

According to an embodiment of another aspect of the application, the chain transfer agent is selected from one or more of 2- (dodecyltrithiocarbonate) -2-methylpropionic acid, s' -bis (α -Dimethylacetic Hydroxyethyl) trithiocarbonate, 4-cyano-4- (dodecylsulfonylthiocarbonyl) sulfovaleric acid and (4-cyanovaleric acid) trithioacetate.

According to an embodiment of another aspect of the present application, the thermal initiator is selected from azo-type initiators and/or organic peroxide initiators.

According to another aspect of the embodiment of the present application, the photoinitiator is selected from one or more of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, methyl 2-benzoylbenzoate and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone.

Compared with the prior art, the application has at least the following beneficial effects:

(1) The application provides a non-curing waterproof coating can balance high low temperature performance betterly, and possesses good extensibility and environmental protection performance.

The non-cured waterproof coating takes the softening oil as a main body, and a compact protective layer can be formed on the surface of the obtained non-cured waterproof coating by introducing the bifunctional modified wax powder and other components, so that the high-temperature resistance of a product is improved, the good extensibility of the product is kept, and the high-temperature and low-temperature performances of the product can be well balanced; in addition, the non-cured waterproof coating does not generate obvious pungent smell in the preparation and construction processes, accords with the concept of green environmental protection, has better advantages compared with the existing environment-friendly non-cured waterproof coating or non-asphalt non-cured waterproof coating, and does not have technical shortcuts in the application and construction aspects.

(2) The preparation method of the non-cured waterproof coating provided by the application is simple in process, short in time consumption, low in equipment requirement, well compatible with the existing process, and extremely high in large-scale application potential.

Detailed Description

In order to make the application purpose, technical solution and beneficial technical effects of the present application clearer, the present application is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present application and are not intended to limit the present application.

For the sake of brevity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.

In the description of the present application, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive of the present number, and "plural" of "one or more" means two or more.

The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.

The existing non-asphalt-based non-cured waterproof coating has the following disadvantages: (1) The non-asphalt-based non-cured waterproof coating cannot simultaneously take heat resistance and extensibility into consideration; (2) In order to maintain good heat resistance, a large amount of rubber powder is used as a filler, but pungent odor is generated at high temperature, which affects the environment and health of constructors.

Based on this, the inventors have made a great deal of research and have aimed to provide a non-curable waterproof coating material which can well balance high and low temperature performance and has good extensibility and environmental protection performance.

Non-curing waterproof coating

Embodiments of the first aspect of the present application provide a non-curable waterproof coating comprising: softening oil, 50 parts by weight; 10-15 parts of modified wax powder; 13-20 parts of thermoplastic elastomer; 5-15 parts of resin; 1-3 parts of silane coupling agent; 15-35 parts of filler;

the modified wax powder is bifunctional group modified wax powder.

According to the embodiment of the application, the non-cured waterproof coating takes the softening oil as a main body, and the obtained non-cured waterproof coating can form a compact protective layer by introducing the bifunctional modified wax powder and other components, so that the high temperature resistance of the non-cured waterproof coating is improved, the good extensibility is kept, and the high and low temperature performance of the product can be well balanced; in addition, the non-cured waterproof coating does not generate obvious pungent smell in the preparation and construction processes, and accords with the concept of environmental protection.

In some embodiments, the non-curable waterproof coating comprises: 50 parts by weight of softening oil; 12 parts of modified wax powder; 15 parts by weight of a thermoplastic elastomer; 8 parts of resin; 2 parts by weight of a silane coupling agent; 20 parts of filler.

In some embodiments, the modified wax powder is selected from one or more of a bifunctional group modified polyethylene wax powder, a bifunctional group modified polypropylene wax powder, and a bifunctional group modified polyimide wax powder.

In some embodiments, the modified wax powder may be a bifunctional group modified polyethylene wax powder, a bifunctional group modified polypropylene wax powder, a bifunctional group modified polyimide wax powder, or any mixture thereof.

According to the embodiment of the application, the modified wax powder has higher softening point and polarity, larger acid value and better compatibility with a system compared with the conventional wax powder.

In some embodiments, the monomers forming the bifunctional group comprise a first functional monomer and a second functional monomer; wherein the first functional monomer is an acrylamide compound, a (meth) acrylate compound, a polyene compound, and combinations thereof; the second functional monomer is selected from azo initiators comprising an ethylenically unsaturated group.

According to an embodiment of the present application, the functional monomers modifying the wax powder include a first functional monomer and a second functional monomer. The wax powder grafted with the first functional monomer contains one or more of ketocarbonyl, hydroxyl and carbon-carbon double bonds; the second functional monomer can be further grafted on the wax powder grafted with the first functional monomer, so as to obtain modified wax powder, wherein the modified wax powder contains R-N bonds (R is alkyl) capable of continuously initiating polymerization.

In some embodiments, the acrylamide-based compound is selected from one or more of N, N-methylenebisacrylamide, N-methylolacrylamide, and methacrylamide.

In some embodiments, the (meth) acrylate compound is selected from one or more of ethylene glycol diacrylate, ethylene glycol methacrylate, and ethylene glycol dimethacrylate.

In some embodiments, the multiolefin compound is selected from divinylbenzene and/or trivinylbenzene.

In some embodiments, the azo-based initiator comprising an ethylenically unsaturated group is an azo-based initiator comprising a (meth) acrylate functional group.

According to the examples of the present application, the acrylamide compound, the (meth) acrylate compound and the multiolefin compound each contain an unsaturated double bond, and the double bond in the monomer molecule of the above compounds is opened and grafted with the wax powder segment by the thermal initiator to be bonded to at least a part of the surface of the wax powder matrix.

According to the embodiment of the application, the azo initiator containing the (meth) acrylate functional group contains a graftable unsaturated double bond and a functional group capable of initiating a crosslinking reaction, so that the azo initiator containing the (meth) acrylate functional group can be grafted on the first monomer modified wax powder under the action of the photoinitiator, and a good foundation is laid for initiating the crosslinking reaction among the components in the product by the subsequent modified wax powder.

In some embodiments, the azo-based initiator comprising a (meth) acrylate functional group is selected from 4,4 '-azobis (4-cyanovaleric acid) esterified with 2-hydroxyethyl acrylate, and/or 4,4' -azobis (4-cyanovaleric acid) esterified with 2-hydroxypropyl acrylate.

In some embodiments, the modified wax powder has a viscosity of 400 to 600mPa.s at 130 ℃, a softening point of 125 to 165 ℃, an acid number of 10 to 30, a molecular mass distribution of 4 to 7, and a molecular weight of 2000 to 4500g/mol.

According to the embodiment of the application, the wax powder subjected to bifunctional modification has a moderate softening point, which plays an important role in improving the high-temperature resistance of the non-cured waterproof coating. In addition, the modified wax powder can react with other components containing unsaturated double bonds by utilizing the groups on the modified wax powder, so that the compatibility of the modified wax powder in a system is improved. Meanwhile, the second functional monomer grafted on the modified wax powder by chain forging can continue to perform a crosslinking reaction, and finally a compact protective layer is formed on the surface of the coating, so that the high-temperature resistance of the product is improved, the good extensibility is kept, and the high-temperature and low-temperature performance of the product is well balanced.

In some embodiments, the softening oil is selected from one or more of naphthenic, minus-line, paraffinic, white, and aromatic oils. For example, the softening oil may be a naphthenic oil, a paraffinic oil, an aromatic oil, or a combination of a paraffinic oil and a white oil. The softening oil can also be a composition of any one or more of the softening oils.

Wherein the viscosity of the softening oil at 130 ℃ is 400mPa.s-800mPa.s, the flash point is more than or equal to 210 ℃, the ash content is less than or equal to 2%, the aniline point is less than or equal to 35 ℃, and no obvious layering phenomenon exists after standing for 7 days at room temperature.

According to the embodiment of the application, the softening oil is used as a good solvent, so that the viscosity of a system can be reduced, the low-temperature performance of the non-cured waterproof coating is improved, the flash point of the softening oil is higher, the phenomenon of flash combustion or explosion cannot occur during high-temperature construction, the construction environment can be greatly improved, and the construction safety can be ensured.

In some embodiments, the thermoplastic elastomer is selected from hydrogenated styrenic thermoplastic elastomers and/or hydrogenated styrene-butadiene rubbers.

In some embodiments, the thermoplastic elastomer is selected from one or more of a hydrogenated styrene-butadiene-styrene block copolymer, a hydrogenated styrene-isoprene-styrene block copolymer, and a hydrogenated styrene-butadiene rubber. Wherein the volatile content of the thermoplastic elastomer is less than or equal to 0.8 percent, the melt flow rate is 2-8g/10min, and the tensile strength is more than or equal to 7.0MPa;

according to the embodiment of the application, the hydrogenation treatment can saturate the unstable double bond structure on the chain forging of the original copolymer, reduce the content of active hydrogen, improve the stability and aging resistance of the copolymer, ensure that the thermoplastic elastomer can still keep good modification effect in the later aging process, and provide certain strength and extensibility for the waterproof coating.

In some embodiments, the resin is selected from one or more of a cold-polymerized C5 hydrogenated petroleum resin, a cold-polymerized C9 hydrogenated petroleum resin, a C5/C9 copolymerized petroleum resin, and a cycloaliphatic resin. Wherein the molecular weight of the resin is 2000-5000g/mol, the relative density is 0.95-1.08, and the softening point is 80-140 ℃.

According to the embodiment of the application, the resin has the advantages of low melting point, strong water resistance, good compatibility with other components in a system, moderate relative molecular mass and free monomer content, and capabilities of improving initial viscosity and peel strength of the waterproof coating, improving high-temperature performance of a product and improving anti-aging performance of the resin by carrying out hydrogenation treatment. Unlike the resins prepared by thermal polymerization, the resins prepared by cold polymerization, i.e., resins prepared by using a catalyst, produce lighter color, better quality, and less volatile matter.

In some embodiments, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (beta-methoxyethoxy) silane.

According to the embodiment of the application, the silane coupling agent can reduce the viscosity and the interface performance of a system, improve the compatibility of the filler and the system, avoid the agglomeration of the filler and improve the dispersion degree of the filler; on the other hand, the polymer can react with a polymer modifier in the system to play a role of bridging, thereby avoiding the segregation phenomenon between two phases.

In some embodiments, the filler is selected from one or more of desulfurized tire rubber powder, graphene, porous carbon nanotubes and porous carbon microspheres, wherein the particle size of the desulfurized tire rubber powder is 0.18-0.25mm.

For example, the filler may be desulfurized tire rubber powder, or may be porous carbon nanotubes, or may be porous carbon microspheres, or may be a mixture of desulfurized tire rubber powder and graphene. The filler may also be a combination of any one or more of the above.

According to the embodiment of the application, the filler can improve the heat resistance and viscosity of the system and accelerate the melting speed of other components in the system, and the selected filler is stable at high temperature, does not generate obvious pungent odor in the production process, and is safe and environment-friendly.

Preparation method of non-cured waterproof coating

The application also provides a preparation method of the non-cured waterproof coating, which comprises the following steps:

s10, heating softening oil under a stirring state;

s20, adding a thermoplastic elastomer, resin, a filler and a silane coupling agent, heating and stirring;

and S30, stopping heating, providing and adding the modified wax powder, stirring and cooling to obtain the non-cured waterproof coating.

In some embodiments, the step S10 further includes:

s100, adding softening oil into a reactor, stirring and heating the softening oil to 150-160 ℃;

in some embodiments, the step S20 further includes:

s200, adding a thermoplastic elastomer and resin into a reactor, stirring and heating to 170-175 ℃, and stirring for 2-2.5 hours at 172-176 ℃ after complete dispersion and no obvious particle agglomeration;

s210, adding a filler, and stirring for 0.2-0.4h;

s220, adding a silane coupling agent, and stirring for 1-1.5 hours at 170-175 ℃ to uniformly disperse;

in some embodiments, the step S30 further includes:

and S300, stopping heating, adding the modified wax powder, stirring for 1-1.5h, cooling to 120-130 ℃, and collecting the non-cured waterproof coating.

According to the embodiment of the application, the softening oil is heated to 150-160 ℃, so that the fluidity of the softening oil can be enhanced, and the dispersion of other components is facilitated.

According to the examples of the application, the thermoplastic elastomer and the resin are added, stirred and heated to 170-175 ℃, and after complete dispersion and no obvious particle agglomeration, the mixture is stirred for 2-2.5 hours at 172-176 ℃, wherein the temperature is the melting temperature of the thermoplastic elastomer and the resin, so that the thermoplastic elastomer and the resin can be fully melted in the softening oil.

According to the embodiment of the application, the heat resistance can be improved and the viscosity of the system can be increased by adding the filler and continuously stirring for 0.2-0.4 h. Adding silane coupling agent, stirring for 1-1.5h at 170-175 deg.C to make it uniformly disperse, and making one end of the coupling agent and filler in the system produce chemical reaction at the above-mentioned temp. to reduce surface energy of filler and make the filler be better dispersed, and making another end of the coupling agent react with high-molecular modifying agent in the system to obtain the action of bridging so as to prevent segregation phenomenon between two phases. And after the heating is stopped, adding the modified wax powder, stirring for 1-1.5h, wherein the temperature of the reaction kettle after the heating is stopped is enough to melt and fully react the modified wax powder, and the temperature is basically reduced to 120-130 ℃ after the reaction is finished, and discharging.

In some embodiments, the providing of the modified wax powder in step S30 includes:

s310, dissolving wax powder in a good solvent in an inert atmosphere, adding a chain transfer agent, a first functional monomer and a thermal initiator, uniformly stirring, and heating and refluxing;

s320, adding absolute ethyl alcohol and a good solvent for washing, repeating for 2-3 times, and drying the product to obtain a first product;

s330, dissolving the first product in a good solvent in an inert atmosphere, adding a second functional monomer and a photoinitiator, stirring at room temperature until the second functional monomer and the photoinitiator are uniformly dispersed, and initiating a polymerization reaction by using ultraviolet light;

s340, adding absolute ethyl alcohol and a good solvent for washing, repeating for 2-3 times, and drying the product to obtain the modified wax powder.

In some embodiments, the good solvent may be selected from one or more of n-hexane, xylene, and petroleum ether.

According to the examples of the present application, the wax powder and the first product have good dispersibility and compatibility in the above-mentioned good solvent.

According to the embodiment of the application, under the high-temperature condition, the thermal initiator is decomposed to generate free radicals, the free radicals initiate polymerization of the wax powder and the first functional monomer, grafting of the first functional monomer polymerization chain segment to the wax powder is achieved, and meanwhile, the wax powder-first functional monomer chain segment free radicals are generated and react with the chain transfer agent to form dormant intermediates. The dormant intermediate has poor stability, can be cracked by itself, releases new active free radicals from corresponding sulfur atoms, and the active free radicals can reinitiate the wax powder and the first functional monomer to be polymerized so as to repeat the grafting process, thereby finally obtaining the first product.

Under the irradiation of ultraviolet light, the photoinitiator is decomposed to generate free radicals, the free radicals can activate a chain transfer agent dormant body at the tail end of the chain segment of the first product and generate new active free radicals, and the active free radicals initiate the polymerization of the first product and the second functional monomer so as to generate a polymerization chain segment of the second functional monomer on the basis of the polymerization chain segment of the first functional monomer and complete the grafting of the second functional monomer. In step S330, no additional chain transfer agent must be added, since the chain transfer agent attached to the end of the first functional monomer segment in the reaction of S310 may still be activated in S330 and continue to participate in the reaction.

According to the embodiment of the present application, in order to prevent oxygen from generating inhibition and affecting the grafting rate of the monomer, the oxygen in the reactor needs to be discharged before the reaction.

In some embodiments, the chain transfer agent is selected from one or more of 2- (dodecyltrithiocarbonate) -2-methylpropionic acid, s' -bis (α -dimethylethyl acetate) trithiocarbonate, 4-cyano-4- (dodecylsulfonylthiocarbonyl) sulfovaleric acid, and (4-cyanovaleric acid) trithioacetate.

According to the examples of the present application, the addition of the chain transfer agent does not have a great influence on the reaction speed, but serves to control the length of the chain, that is, the degree of polymerization of the polymer, or the viscosity of the polymer.

In some embodiments, the thermal initiator is selected from azo-type initiators and/or organic peroxide initiators.

In some embodiments, the photoinitiator is selected from one or more of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenone, methyl 2-benzoylbenzoate, and 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone.

For example, the photoinitiator may be 2-hydroxy-2-methyl propiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, or a mixture of 2-hydroxy-2-methyl propiophenone and 1-hydroxycyclohexyl phenyl ketone. The photoinitiator may also be a combination of any one or more of the above.

The preparation method of the non-cured waterproof coating provided by the application is simple in process, short in time consumption, low in equipment requirement, well compatible with the existing process, and extremely high in large-scale application potential.

The non-cured waterproof agent provided by the application can well balance high and low temperature performance, and has good extensibility and environmental protection performance. Therefore, the non-cured waterproof coating can be applied to indoor and outdoor cement concrete structures, wall surfaces and ground surfaces of mortar and masonry structures and the like.

Examples

The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.

Example 1

The non-curing waterproof coating comprises, by weight, 48 parts of naphthenic oil, 10 parts of polyethylene wax powder modified by grafting N, N-methylene bisacrylamide and ACVA-HEA, 13 parts of hydrogenated styrene-butadiene-styrene block copolymer, 7 parts of cold polymerized C9 hydrogenated petroleum resin, 2 parts of gamma-aminopropyltriethoxysilane and desulfurized tire rubber powder: and 20 parts of filler with the graphene mass ratio = 7:3.

Providing a modified wax powder comprising: dissolving polyethylene wax powder in xylene in an inert atmosphere, adding 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, N-methylene bisacrylamide and azobisisobutyronitrile, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and xylene for washing, removing unreacted monomers and impurities, filtering and drying to obtain a first product; under the action of 2-hydroxy-2-methyl propiophenone, the first product and ACVA-HEA react fully, 5-7 times of ethanol solution and xylene are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtering, drying and grafting.

Example 2

A non-curable waterproof coating material, wherein each component comprises paraffin oil: 50 parts of softening oil with the reduced linear oil mass ratio =4:6, 11 parts of polyethylene wax powder graft-modified by N-methylolacrylamide and ACVA-HEA, 13 parts of hydrogenated styrene-isoprene-styrene block copolymer, 8.5 parts of alicyclic resin, 2.5 parts of vinyl triethoxysilane, and desulfurized tire rubber powder: 15 parts of filler with the mass ratio of the porous carbon nano-tubes = 7:3.

Providing a modified wax powder comprising: dissolving polyethylene wax powder in xylene under inert atmosphere, adding s, s' -di (alpha-dimethyl hydroxyethyl acetate) trithiocarbonate, N-hydroxymethyl acrylamide and azobisisobutyronitrile, heating and refluxing for 5h at 120 ℃, adding 5-7 times of ethanol solution and xylene for washing to remove unreacted monomers and impurities, and filtering and drying to obtain a first product; under the action of 2-benzoyl methyl benzoate, the first product and ACVA-HEA react fully, 5-7 times of ethanol solution and xylene are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtration, drying and grafting.

Example 3

A non-curable waterproof coating material, wherein each component comprises paraffin oil: 50 parts of softening oil with aromatic oil mass ratio =3:7, 11 parts of polyimide wax powder graft-modified by ethylene glycol diacrylate and ACVA-HEA, 15 parts of hydrogenated styrene-isoprene-styrene block copolymer, 6 parts of C9 hydrogenated petroleum resin, 2 parts of vinyl trimethoxy silane, desulfurized tire rubber powder: 16 parts of filler with the mass ratio of the porous carbon microspheres = 5:5.

Providing a modified wax powder comprising: dissolving polyimide wax powder in xylene under inert atmosphere, adding s, s' -di (alpha-dimethyl hydroxyethyl acetate) trithiocarbonate, ethylene glycol diacrylate and azobisisobutyronitrile, heating and refluxing for 5h at 120 ℃, adding 5-7 times of ethanol solution and xylene for washing, removing unreacted monomers and impurities, filtering and drying to obtain a first product; under the action of 2-benzoyl methyl benzoate, the first product and ACVA-HEA react fully, 5-7 times of ethanol solution and xylene are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtration, drying and grafting.

Example 4

A non-curable waterproof coating material, wherein each component comprises naphthenic oil: 46 parts of softening oil with aromatic oil mass ratio =5:5, 10 parts of polypropylene wax powder graft-modified by N, N-methylene bisacrylamide and ACVA-HPA, hydrogenated styrene-butadiene-styrene block copolymer: 12 parts of hydrogenated styrene-isoprene-styrene block copolymer, 12 parts of thermoplastic polyolefin with the mass ratio of =5:5, 13 parts of C5/C9 copolymer resin, 3 parts of vinyl trimethoxy silane and 16 parts of desulfurized tire rubber powder.

Providing a modified wax powder comprising: dissolving polypropylene wax powder in xylene under inert atmosphere, adding 4-cyano-4- (dodecyl sulfonyl thiocarbonyl) sulfovaleric acid, N-methylene bisacrylamide and azobisisobutyronitrile, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and xylene, washing to remove unreacted monomers and impurities, filtering, and drying to obtain a first product; under the action of 2-benzoyl methyl benzoate, the first product and ACVA-HPA react fully, 5-7 times of ethanol solution and xylene are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtration, drying and grafting.

Example 5

A non-curable waterproof coating material, wherein each component comprises paraffin oil: 47 parts of softening oil with aromatic oil mass ratio =3:7, 11 parts of polyimide wax powder graft-modified by ethylene glycol dimethacrylate and ACVA-HEA, 17 parts of styrene-isoprene-styrene block copolymer, 3.5 parts of C9 hydrogenated petroleum resin, 1.5 parts of gamma- (2,3-glycidoxy) propyl trimethoxy silane and 20 parts of porous carbon microspheres.

Providing a modified wax powder comprising: dissolving polyimide wax powder in xylene in an inert atmosphere, adding 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, ethylene glycol dimethacrylate and benzoyl peroxide, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and xylene, washing to remove unreacted monomers and impurities, filtering and drying to obtain a first product; under the action of 1-hydroxycyclohexyl phenyl ketone, the first product and ACVA-HEA are fully reacted, 5-7 times of ethanol solution and xylene are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtration, drying and grafting.

Example 6

The non-cured waterproof coating comprises, by weight, 52 parts of aromatic oil, 13 parts of polypropylene wax powder grafted and modified by ethylene glycol diacrylate and ACVA-HPA, 16 parts of hydrogenated styrene-isoprene-styrene block copolymer, 7.5 parts of C5 hydrogenated petroleum resin, 1.5 parts of gamma-methacryloxypropyl trimethoxy silane and 10 parts of porous carbon nano tube.

Providing a modified wax powder comprising: dissolving polypropylene wax powder in n-hexane in an inert atmosphere, adding 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, ethylene glycol diacrylate and benzoyl peroxide, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and n-hexane, washing to remove unreacted monomers and impurities, filtering and drying to obtain a first product; under the action of 1-hydroxycyclohexyl phenyl ketone, the first product fully reacts with ACVA-HPA, 5-7 times of ethanol solution and n-hexane are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained by filtering, drying and grafting.

Example 7

A non-cured waterproof coating, wherein the components comprise, by weight: 52 parts of softening oil with white oil mass ratio =8:2, 14 parts of polypropylene wax powder graft-modified by N-hydroxymethyl acrylamide and ACVA-HEA, 13 parts of hydrogenated styrene-butadiene rubber block copolymer, 5 parts of C9 hydrogenated petroleum resin, 2 parts of N- [3- (trimethoxysilyl) propyl ] ethylenediamine and 14 parts of porous carbon nanotube.

Providing a modified wax powder comprising: dissolving polypropylene wax powder in petroleum ether under inert atmosphere, adding (4-cyanovaleric acid) trithioacetate, N-hydroxymethyl acrylamide and benzoyl peroxide into the petroleum ether, heating and refluxing the mixture for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and petroleum ether into the mixture, washing the mixture to remove unreacted monomers and impurities, and filtering and drying the mixture to obtain a first product; under the action of 2-hydroxy-2-methyl propiophenone, the first product and ACVA-HEA react fully, 5-7 times of ethanol solution and petroleum ether are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtering, drying and grafting.

Example 8

A non-cured waterproof coating, wherein each component comprises aromatic oil: 50 parts of softening oil with white oil mass ratio =8:2, 13 parts of polyethylene wax powder modified by ethylene glycol diacrylate and ACVA-HEA grafting, 15 parts of hydrogenated styrene-butadiene-styrene block copolymer, 10 parts of C5/C9 copolymer resin, 2 parts of N- [3- (trimethoxysilyl) propyl ] ethylenediamine, and the mass ratio of porous carbon nanotube: 10 parts of filler with the mass ratio of the porous carbon microspheres = 5:5.

Providing a modified wax powder comprising: dissolving polyethylene wax powder in n-hexane in an inert atmosphere, adding (4-cyanovaleric acid) trithioacetate, ethylene glycol diacrylate and azodiisobutyronitrile, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and n-hexane, washing to remove unreacted monomers and impurities, filtering and drying to obtain a first product; under the action of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, the first product and ACVA-HEA are fully reacted, 5-7 times of ethanol solution and n-hexane are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtering, drying and grafting.

Example 9

A non-cured waterproof coating, wherein each component comprises aromatic oil: 46 parts of softening oil with the weight ratio of minus line oil =4:6, 10 parts of polypropylene wax powder modified by grafting N, N-methylene bisacrylamide and ACVA-HEA, 13 parts of hydrogenated styrene-isoprene-styrene block copolymer, 8 parts of C9 hydrogenated petroleum resin, 3 parts of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, and desulfurized tire rubber powder: and 20 parts of filler with the graphene mass ratio = 8:2.

Providing a modified wax powder comprising: dissolving polypropylene wax powder in petroleum ether under inert atmosphere, adding (4-cyanovaleric acid) trithioacetate, N-methylene bisacrylamide and azobisisobutyronitrile, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and petroleum ether, washing to remove unreacted monomers and impurities, filtering and drying to obtain a first product; under the action of 2-hydroxy-2-methyl propiophenone, the first product and ACVA-HEA react fully, 5-7 times of ethanol solution and petroleum ether are added for washing to remove unreacted monomers and impurities, and the modified wax powder is obtained through filtering, drying and grafting.

Comparative example

Comparative example 1

The non-curing waterproof coating comprises, by weight, 48 parts of naphthenic oil, 10 parts of polyethylene wax powder, 13 parts of hydrogenated styrene-butadiene-styrene block copolymer, 7 parts of cold polymerized C9 hydrogenated petroleum resin, 2 parts of gamma-aminopropyltriethoxysilane, and desulfurized tire rubber powder: and 20 parts of filler with the graphene mass ratio = 7:3.

Comparative example 2

The non-cured waterproof coating comprises, by weight, 48 parts of naphthenic oil, 10 parts of oxidized polyethylene wax powder, 13 parts of hydrogenated styrene-butadiene-styrene block copolymer, 7 parts of cold poly C9 hydrogenated petroleum resin, 2 parts of gamma-aminopropyltriethoxysilane, and desulfurized tire rubber powder: 20 parts of filler with graphene mass ratio = 7:3.

The oxidized polyethylene wax powder provided comprises: the raw material is high-pressure polyethylene, the oxidant is air, the reaction temperature is 165 ℃, the reaction pressure is 0.8MPa, and the reaction time is 8 hours.

Comparative example 3

The non-curing waterproof coating comprises, by weight, 48 parts of naphthenic oil, 10 parts of polyethylene wax powder modified by N, N-methylene bisacrylamide grafting, 13 parts of hydrogenated styrene-butadiene-styrene block copolymer, 7 parts of cold polymerized C9 hydrogenated petroleum resin, 2 parts of gamma-aminopropyltriethoxysilane, and desulfurized tire rubber powder: and 20 parts of filler with the graphene mass ratio = 7:3.

Providing a modified wax powder comprising: dissolving polyethylene wax powder in N-hexane, adding (4-cyanovaleric acid) trithioacetate, N-methylene bisacrylamide and azobisisobutyronitrile, heating and refluxing for 5 hours at 120 ℃, adding 5-7 times of ethanol solution and N-hexane, washing to remove unreacted monomers and impurities, filtering, and drying to obtain the modified wax powder.

Comparative example 4

The non-curing waterproof coating comprises, by weight, 48 parts of naphthenic oil, 10 parts of polyethylene wax powder modified by ACVA-HEA grafting, 13 parts of hydrogenated styrene-butadiene-styrene block copolymer, 7 parts of cold polymerized C9 hydrogenated petroleum resin, 2 parts of gamma-aminopropyltriethoxysilane and desulfurized tire rubber powder: and 20 parts of filler with the graphene mass ratio = 7:3.

Providing a modified wax powder comprising: dissolving polyethylene wax in xylene, adding (4-cyanovaleric acid) trithioacetate, reacting the polyethylene wax powder with ACVA-HEA under the action of 2-hydroxy-2-methyl propiophenone, adding 5-7 times of ethanol solution and xylene, washing to remove unreacted monomers and impurities, filtering, drying, and grafting to obtain modified wax powder.

The preparation methods of the non-curable waterproof coatings of the above examples 1 to 9 and comparative examples 1 to 4 were:

adding the softening oil into a reactor, stirring and heating the softening oil to 155 ℃;

adding thermoplastic elastomer and resin into a reactor, stirring and heating to 170 ℃, and stirring for 2.5 hours at 175 ℃ after complete dispersion and no obvious particle agglomeration;

adding a filler, and stirring for 0.3h; adding a silane coupling agent, and stirring for 1.5 hours at 175 ℃ to uniformly disperse;

stopping heating, adding the modified wax powder, stirring for 1.5h, cooling to 120 ℃, and collecting the non-cured waterproof coating.

Test section

The non-curable waterproof coatings of examples 1 to 9 and comparative examples 1 to 4 described above were subjected to the relevant performance tests with reference to standard J/CT 2428-2017, wherein the aging treatment means aging the non-curable waterproof coatings at 70 ℃ for 7 days. The test results of examples 1 to 9 and comparative examples 1 to 4 are shown in table 1 below.

TABLE 1 results of performance test of non-curable waterproofing paints for examples 1 to 9 and comparative examples 1 to 4

From the test results, the non-cured waterproof coatings prepared in the embodiments 1 to 9 have excellent high and low temperature performance, and can still maintain good extensibility at-15 ℃, which is far beyond the requirement of JC/T2428-2017, when the modified wax powder in the application is not used in the comparative examples 1 to 4, the high and low temperature performance and the extensibility are poorer than those of the non-cured waterproof coatings prepared in the embodiments 1 to 9, and in addition, the non-cured waterproof coatings prepared in the embodiments 1 to 9 have no obvious pungent odor in the preparation process, and are safe and environment-friendly.

In summary, the modified wax powder in the non-curable waterproof coating can utilize the grafting group thereon to react with other components containing unsaturated double bonds, so as to improve the compatibility of the modified wax powder in the system, and meanwhile, the second functional monomer grafted on the modified wax powder chain forging can continue to initiate a crosslinking reaction, so as to finally form a compact protective layer on the surface of the coating, improve the high temperature resistance of the non-curable waterproof coating, keep good extensibility and balance the high and low temperature performance of the product.

While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A non-curable waterproof coating material, comprising:

50 parts by weight of softening oil;

10-15 parts of modified wax powder;

13-20 parts by weight of thermoplastic elastomer;

5-15 parts of resin;

1-3 parts of silane coupling agent;

15-35 parts of filler;

the modified wax powder is bifunctional group modified wax powder, and the monomers for forming the bifunctional group comprise a first functional monomer and a second functional monomer;

the first functional monomer is selected from the group consisting of acrylamide compounds, (meth) acrylate compounds, multiolefin compounds, and combinations thereof;

the second functional monomer is selected from azo initiators containing (meth) acrylate functional groups.

2. The non-curable waterproof coating material according to claim 1, characterized in that the acrylamide compound is selected from one or more of N, N-methylenebisacrylamide, N-methylolacrylamide, and methacrylamide; and/or the presence of a gas in the atmosphere,

the (meth) acrylate compound is selected from one or more of ethylene glycol diacrylate, ethylene glycol methacrylate and ethylene glycol dimethacrylate; and/or the presence of a gas in the gas,

the multiolefin compound is selected from divinylbenzene and/or trivinylbenzene.

3. The non-curable waterproof coating material according to claim 1, wherein the softening oil is selected from one or more of naphthenic oil, minus line oil, paraffinic oil, white oil and aromatic oil; and/or the presence of a gas in the gas,

4. The non-curable waterproof coating material according to claim 1, wherein the thermoplastic elastomer is selected from hydrogenated styrene-based thermoplastic elastomer and/or hydrogenated styrene-butadiene rubber; and/or the presence of a gas in the gas,

the resin is selected from one or more of a poly-C5 hydrogenated petroleum resin, a poly-C9 hydrogenated petroleum resin, a C5/C9 copolymerized petroleum resin and a cycloaliphatic resin.

5. The non-curable waterproof coating material according to claim 1, wherein the silane coupling agent is one or more selected from the group consisting of γ -aminopropyltriethoxysilane, γ - (2,3-glycidoxy) propyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (β -methoxyethoxy) silane.

6. The non-cured waterproof coating material of claim 1, wherein the filler is selected from one or more of desulfurized tire rubber powder, graphene, porous carbon nanotubes and porous carbon microspheres,

wherein the particle size of the desulfurized tire rubber powder is 0.18-0.25mm.

7. A process for preparing the non-curable waterproof coating material according to any one of claims 1 to 6, characterized by comprising:

heating the softening oil under stirring;

adding the thermoplastic elastomer, the resin, the filler and the silane coupling agent, heating and stirring;

stopping heating, providing and adding the modified wax powder, stirring and cooling to obtain the non-cured waterproof coating;

the providing of the modified wax powder comprises:

8. The process of claim 7 wherein the chain transfer agent is selected from one or more of 2- (dodecyl trithiocarbonate) -2-methylpropionic acid, s' -bis (α -Dimethylacetic Hydroxyethyl) trithiocarbonate, 4-cyano-4- (dodecylsulfonylthiocarbonyl) sulfovaleric acid, and (4-cyanovaleric acid) trithioacetate; and/or

The thermal initiator is selected from azo initiators and/or organic peroxide initiators; and/or

The photoinitiator is selected from one or more of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzoyl methyl benzoate and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone.