An aqueous ceramic tile adhesive with high bonding strength, its preparation method and application

Abstract

The present invention relates to the technical field of aqueous ceramic tile adhesives with high bonding strength, and particularly relates to an aqueous ceramic tile adhesive with high bonding strength, a preparation method thereof and an application; wherein, the aqueous ceramic tile adhesive contains an epoxyamine compound having the following formula I, a polyurethane having the following formula II, and carboxylated nanocellulose.

Description

Technical Field

[0001] The present invention relates to the technical field of aqueous ceramic tile adhesives, and particularly to an aqueous ceramic tile adhesive with high bonding strength, a preparation method thereof, and an application thereof. Background Art

[0002] Ceramic tile adhesives are currently a commonly used binder for bonding ceramic tiles, clay bricks, paving bricks, slate, marble, and natural stones. Compared with cement mortar, they are used to paste various ceramic tiles and various stones in interior and exterior cement-based surfaces or walls and floors composed of various partition tile substrates due to their better bonding strength, durability, and convenient construction. They have more and more applications in the field of engineering construction.

[0003] In the prior art, construction adhesives mainly rely on polyvinyl formal adhesives, which contain a large amount of volatile and harmful organic substances such as formaldehyde, causing great harm to the environment and human health. Summary of the Invention

[0004] The purpose of the present invention is to provide an aqueous ceramic tile adhesive with high bonding strength, a preparation method thereof, and an application thereof to solve the defects pointed out in the above background art.

[0005] According to the first aspect of the embodiments of the present invention, an aqueous ceramic tile adhesive with high bonding strength contains an epoxy amine compound having the following formula I, a polyurethane having the following formula II, and carboxylated nanocellulose:

[0006]

[0007] Wherein, n1 is from 1 to 100;

[0008] R1 and R2 are each independently a direct bond, a C1-C5 alkyl group, or a C2-C30 alkenyl group;

[0009] R3 is a C1-C5 alkyl group;

[0010] Ar1 is a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclic group, or a substituted or unsubstituted 5-30 membered heteroaryl group;

[0011] R4 is

[0012] n2 and n3 are each independently from 1 to 200;

[0013] R5 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclic group, or a substituted or unsubstituted 5-30 membered heteroaryl group;

[0014] R6 and R7 are each independently a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, or a substituted or unsubstituted C1-C30 alkoxy group.

[0015] In one aspect of the embodiments of the present invention, preferably, n1 is from 1 to 10.

[0016] In one aspect of the embodiments of the present invention, preferably, n2 and n3 are each independently from 5 to 20.

[0017] In one aspect of the embodiments of the present invention, R1 and R2 are each independently a direct bond or a C1-C5 alkyl group; preferably, R1 and R2 are each independently a direct bond or a C1-C3 alkyl group.

[0018] In one aspect of the embodiments of the present invention, specifically, R1 and R2 are each independently a direct bond, methyl, ethyl, or propyl.

[0019] In one aspect of the embodiments of the present invention, R3 is a C1-C5 alkyl group; preferably, R3 is a C1-C3 alkyl group.

[0020] In one aspect of the embodiments of the present invention, Ar1 is a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclic group, or a substituted or unsubstituted 5-30 membered heteroaryl group.

[0021] In one aspect of the embodiments of the present invention, preferably, Ar1 is a substituted or unsubstituted C5-12 cycloalkyl group, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted 5-12 membered heterocyclic group, or a substituted or unsubstituted 5-12 membered heteroaryl group, wherein the C5-12 cycloalkyl group, C6-C12 aryl group, 5-12 membered heterocyclic group, and 5-12 membered heteroaryl group are optionally substituted with one or more nitro groups, amino groups, carboxyl groups, C1-C5 alkyl groups, or C1-C5 alkoxy groups.

[0022] In one aspect of the embodiments of the present invention, R1 and R2 are a direct bond; and Ar1 is any one of the following groups:

[0023]

[0024] In one aspect of the embodiments of the present invention, R4 is:

[0025]

[0026] In one aspect of the embodiments of the present invention, R5 is any one of the following groups:

[0027]

[0028]

[0029] In one aspect of the embodiments of the present invention, R6 and R7 are the same group and are phenyl, methyl or ethyl.

[0030] In one aspect of the embodiments of the present invention, R3 is propyl.

[0031] In one aspect of the embodiments of the present invention, a water-based ceramic tile adhesive with high bonding strength contains an epoxyamine compound having the following formula I-A, a polyurethane having the following formula II-A, and carboxylated nanocellulose:

[0032]

[0033] Wherein, n1 is from 1 to 100; n2 and n3 are each independently from 1 to 200; Ar1 is any one of the following groups:

[0034]

[0035] R4 is

[0036] R5 is any one of the following groups:

[0037]

[0038] In one aspect of the embodiments of the present invention, the water-based ceramic tile adhesive further contains at least one curing agent. Specifically, the curing agent can be a water-based acrylic dispersion, but is not limited thereto.

[0039] In one aspect of the embodiments of the present invention, the water-based ceramic tile adhesive further contains at least one of talc powder, kaolin, calcium carbonate, silica sand, borax and glass powder.

[0040] In one aspect of the embodiments of the present invention, based on the total mass of the water-based ceramic tile adhesive, the mass percentage of at least one of talc powder, calcium carbonate, silica sand, borax and glass powder is 5%-75%.

[0041] According to the second aspect of the embodiments of the present invention, a preparation method of the aforementioned water-based ceramic tile adhesive with high bonding strength includes the following steps:

[0042] Step 1: Prepare an epoxy amine compound having the aforementioned structure of Formula I and the aforementioned polyurethane having the structure of Formula II;

[0043] Step 2: Add the polyurethane having the structure of Formula II and carboxylated nanocellulose to water and stir for 1 - 3 h to obtain the product of Step 2; wherein, the mass ratio of the carboxylated nanocellulose, the polyurethane having the structure of Formula II, and water is (1 - 10):100:(300 - 500);

[0044] Step 3: Add the epoxy amine compound having the structure of Formula I to the product of Step 2, stir for 0.2 - 1 h, then add a curing agent, and continue to stir for 1.5 - 3 h to obtain the water-based ceramic tile adhesive; wherein, the mass ratio of the curing agent, the polyurethane having the structure of Formula II, and the epoxy amine compound having the structure of Formula I is (5 - 15):100:(50 - 80).

[0045] In one aspect of the embodiments of the present invention, in Step 1, the epoxy amine compound having the structure of Formula I is prepared through the following steps:

[0046] Step 1-a: Weigh a diamine compound containing an Ar1 group and add the diamine compound containing the Ar1 group to a first solvent;

[0047] Step 2-a: Mix polyethylene glycol diglycidyl ether with one of epoxy resin E44 or epoxy resin E51 to obtain a mixture of Step 2-a, and then add the mixture of Step 2-a to the first solvent to obtain the product of Step 2-a;

[0048] Step 3-a: Keep the product of Step 2-a at a constant temperature for reaction for 1 - 3 h, then heat it to 75°C - 85°C for reaction for 2 - 4 h, and after separation, obtain the epoxy amine compound having the structure of Formula I.

[0049] In one aspect of the embodiments of the present invention, in Step 1, the polyurethane having the structure of Formula II is prepared through the following steps:

[0050] Step 1-b: Add a polymer containing a secondary amine group and an R6 group to a second solvent to obtain the product of Step 1-b;

[0051] Step 2-b: Add an isocyanate compound to the product of Step 1-b and stir for 0.5 - 1.5 h, and after separation, obtain the polyurethane having the structure of Formula II.

[0052] According to the third aspect of the embodiments of the present invention, there is provided an application of the aforementioned water-based ceramic tile adhesive with high bonding strength, or a water-based ceramic tile adhesive with high bonding strength obtained by the preparation method of the aforementioned water-based ceramic tile adhesive with high bonding strength, in building materials.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] The present invention provides a water-based ceramic tile adhesive with high bonding strength. Its preparation method is simple, and the raw materials used do not contain toxic or volatile organic substances; moreover, the water-based ceramic tile adhesive with high bonding strength provided by the present invention has a relatively high bonding strength. Flexible long chains exist in the molecular skeletons of the epoxyamine compound and polyurethane provided by the present invention, which have good flexibility and elasticity. The combination of the two forms an interpenetrating and dense network structure, thereby endowing it with good adhesion ability.

[0055] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present invention. Detailed Description of the Invention

[0056] Here, the exemplary embodiments will be described in detail. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. On the contrary, they are only examples of devices and methods consistent with some aspects of the present invention as detailed in the appended claims.

[0057] To make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of the present invention. The embodiments of the present invention should not be construed as limiting the present invention.

[0058] For the sake of simplicity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, each individually disclosed point or single numerical value itself can be used as a lower limit or an upper limit and combined with any other point or single numerical value or combined with other lower limits or upper limits to form a range not explicitly recited.

[0059] In this text, the terms "comprising", "including" or any other variant thereof are intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or device. Without further limitation, an element qualified by the statement "comprising an..." does not exclude the presence of additional identical elements in the process, method, article or device comprising said element.

[0060] In the description herein, unless otherwise specified, "above" and "below" include the number itself.

[0061] Unless otherwise specified, the terms used in the present invention have the well-known meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values of the various parameters mentioned in the present invention can be measured by various common measurement methods in the art (for example, they can be tested according to the methods given in the embodiments of the present invention).

[0062] The term "about" is used to describe and account for small variations. When used in connection with an event or circumstance, the term can refer to instances where the event or circumstance occurs precisely as well as instances where it occurs very nearly. For example, when used in connection with a numerical value, the term can refer to a range of variation of ±10% less than or equal to the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, sometimes quantities, ratios and other numerical values are presented in range format in this text. It should be understood that such range formats are for convenience and brevity and should be interpreted flexibly to include not only the explicitly specified numerical values as range limits but also all individual numerical values or sub-ranges subsumed within the said range as if each numerical value and sub-range were explicitly specified.

[0063] A list of items connected by the terms "at least one of", "at least one kind of" or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B and C. Item A can include a single component or multiple components. Item B can include a single component or multiple components. Item C can include a single component or multiple components.

[0064] In the present disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which may be straight-chain or branched. Branched means one or more lower alkyl groups attached to a linear alkyl chain, such as methyl, ethyl or propyl. "Lower alkyl" refers to a group containing from about 1 to about 6 carbon atoms in the chain, which may be straight-chain or branched.

[0065] In the present disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group which contains at least one carbon-carbon double bond and which may be straight-chain or branched. Branched means one or more lower alkyl groups attached to a linear alkenyl chain, such as methyl, ethyl or propyl. "Lower alkenyl" refers to a group containing from about 2 to about 6 carbon atoms in the chain, which may be straight-chain or branched.

[0066] In the present disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group which contains at least one carbon-carbon triple bond and which may be straight-chain or branched. Branched means one or more lower alkyl groups attached to a linear alkynyl chain, such as methyl, ethyl or propyl. "Lower alkynyl" refers to a group containing from about 2 to about 6 carbon atoms in the chain, which may be straight-chain or branched. Non-limiting examples of alkynyl include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl and decynyl.

[0067] In the present disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. The aryl may optionally be substituted by one or more "ring system substituents", which may be the same or different, as defined herein. Non-limiting examples of suitable aryl include phenyl and naphthyl.

[0068] In the present disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system in which one or more ring atoms are elements other than carbon, such as nitrogen, oxygen or sulfur, either individually or in combination, and preferably the heteroaryl contains from about 5 to about 6 ring atoms. The "heteroaryl" may optionally be substituted by one or more "ring system substituents", which may be the same or different, as defined herein. The prefixes aza, oxa or thia before the heteroaryl root name indicate that at least one nitrogen, oxygen or sulfur atom is present as a ring atom, respectively. The nitrogen atom of the heteroaryl may optionally be oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl include pyridyl, pyrazinyl, furyl, phenylthio, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, phthalazinyl, imidazo[1,2-a]pyridyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothienyl, quinolinyl, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzazaindolyl, 1,2,4-triazinyl, benzothiazolyl, etc.

[0069] In the present disclosure, the term "amino" refers to an -NR′R″ group. The amino group may be optionally substituted. In an unsubstituted amino group, R′ and R″ are hydrogen. In a substituted amino group, R′ and R″ may each independently be, but are not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkanoyl, aryl, arylalkyl, or heteroaryl, provided that R′ and R″ are not both hydrogen. In a substituted amino group, R′ and R″ may cyclize to form a cyclic amino group, such as pyrrolidinyl or piperidinyl. Such cyclic amino groups may incorporate other heteroatoms, such as to form piperazine or morpholine groups. Such cyclic amino groups may be optionally substituted, for example, by amino, hydroxy, or oxo groups.

[0070] In the present disclosure, the term "alkoxy" refers to -O-alkyl. An alkoxy group may refer to a straight-chain, branched-chain, or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, and pentyloxy. An alkoxy group may be optionally substituted by one or more alkoxy substituents ("substituted alkoxy").

[0071] In the present disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system, preferably a cycloalkyl ring containing from about 5 to about 7 ring atoms. A cycloalkyl may be optionally substituted by one or more "ring system substituents", which may be the same or different and are as defined above. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Non-limiting examples of suitable polycyclic cycloalkyls include 1-decalinyl, norbornyl, adamantyl, etc. In the present disclosure, the term "cycloalkoxy" refers to a group in which one or more carbons in the mono- or polycyclic ring system of "cycloalkyl" are replaced by oxygen atoms.

[0072] In the present disclosure, the term "heterocyclic group" refers to a non-aromatic saturated monocyclic or polycyclic ring system in which one or more ring atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur, either alone or in combination. There are no adjacent oxygen and / or sulfur atoms in the ring system, and preferably the heterocycle contains from about 5 to about 6 ring atoms. The prefixes aza, oxa, or thia before the heterocyclic group root name indicate that at least one nitrogen, oxygen, or sulfur atom, respectively, is present as a ring atom. The heterocyclic group may be optionally substituted by one or more "ring system substituents", which may be the same or different and are as defined herein. The nitrogen or sulfur atoms of the heterocyclic group may be optionally oxidized to the corresponding N-oxides, S-oxides, or S,S-dioxides. Non-limiting examples of suitable monocyclic heterocyclic group rings include piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl, tetrahydrofuranyl, tetrahydrobenzothienyl, tetrahydrothiopyranyl, etc.

[0073] The content of the present invention will be further described by way of specific embodiments. All kinds of chemical reagents used in the embodiments of the content of the present invention are obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are mass contents. Unless otherwise specified, it is understood to be carried out at room temperature.

[0074] Example 1

[0075] The preparation method of the water-based ceramic tile adhesive comprises the following steps:

[0076] A. Preparation of an epoxyamine compound having the structure of Formula I:

[0077] At room temperature, weigh 10 g of isophorone diamine (IPDA), add the isophorone diamine to 250 mL of acetone, and continuously carry out magnetic stirring (300 r / min);

[0078] Weigh 8 g of polyethylene glycol diglycidyl ether and 6.5 g of epoxy resin E44, mix the two and dissolve them in 100 mL of acetone, slowly add the mixed solution to the aforementioned acetone solution, continuously carry out magnetic stirring after adding, keep the temperature for reaction for 2.5 h, then heat to 80 °C and react for 3 h. After the reaction is completed, the epoxyamine compound I-1 in the form of a white solid in Example 1 is obtained through rotary evaporation.

[0079]

[0080] Among them, R4 is

[0081] B. Preparation of a polyurethane having the structure of Formula II:

[0082] At room temperature, dissolve 3 g of polyethyleneimine with an average degree of polymerization of 100 in 100 mL of N-methylpyrrolidone, continuously stir, then add 12 g of isophorone diisocyanate, and after magnetic stirring for 45 min, the polyurethane II-1 in Example 1 is obtained after drying.

[0083]

[0084] Among them, R5 is

[0085] C. Preparation of the water-based ceramic tile adhesive:

[0086] Weigh 5 g of the prepared polyurethane and 0.25 g of carboxylated nanocellulose, add them to 400 mL of water, stir magnetically for 1.5 h, then add 3 g of the prepared epoxyamine compound and 0.5 g of the aqueous acrylic dispersion, stir magnetically for 1 h, then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, stir mechanically for 30 min. After the stirring is completed, heat the mixture to 45 °C to evaporate some water, and stop heating when the mixture becomes gel-like to obtain the aqueous ceramic tile adhesive of Example 1.

[0087] Example 2

[0088] The preparation method of the aqueous ceramic tile adhesive comprises the following steps:

[0089] A. Preparation of the epoxyamine compound having the structure of Formula I:

[0090] At room temperature, weigh 10 g of 3,5-diaminobenzoic acid, add 3,5-diaminobenzoic acid to 250 mL of ethanol, and continuously stir magnetically (300 r / min);

[0091] Weigh 8 g of polyethylene glycol diglycidyl ether and 6.5 g of epoxy resin E44, mix and dissolve them in 100 mL of acetone, slowly add the mixed solution to the aforementioned ethanol solution, and continuously stir magnetically after adding, keep the reaction at a constant temperature for 2.5 h, then heat to 80 °C and react for 3 h. After the reaction is completed, obtain the white solid epoxyamine compound I-2 of Example 2 through rotary evaporation.

[0092]

[0093] Among them, R4 is

[0094] B. Preparation of the polyurethane having the structure of Formula II:

[0095] At room temperature, dissolve 3 g of polyethyleneimine with an average degree of polymerization of 100 in 100 mL of N-methylpyrrolidone, continuously stir, then add 12 g of isophorone diisocyanate, stir magnetically for 45 min, and then obtain the polyurethane II-1 of Example 2 after drying.

[0096]

[0097] Among them, R5 is

[0098] C. Preparation of the aqueous ceramic tile adhesive:

[0099] Weigh 5 g of the prepared polyurethane and 0.25 g of carboxylated nanocellulose, add them to 400 mL of water, stir magnetically for 1.5 h, then add 3 g of the prepared epoxyamine compound and 0.5 g of the aqueous acrylic dispersion, stir magnetically for 1 h, then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, stir mechanically for 30 min. After the stirring is completed, heat the mixture to 45 °C to evaporate some water, and stop heating when the mixture becomes gel-like to obtain the aqueous ceramic tile adhesive of Example 2.

[0100] Example 3

[0101] The preparation method of the aqueous ceramic tile adhesive comprises the following steps:

[0102] A. Preparation of the epoxyamine compound with the structure of Formula I:

[0103] At room temperature, weigh 10 g of pyridine-3,5-diamine, add pyridine-3,5-diamine to 250 mL of ethanol, and continuously stir magnetically (300 r / min);

[0104] Weigh 8 g of polyethylene glycol diglycidyl ether and 6.5 g of epoxy resin E44, dissolve the two in 100 mL of acetone, slowly add the mixed solution to the aforementioned acetone solution, continuously stir magnetically after adding, keep the reaction at a constant temperature for 2.5 h, then heat to 80 °C and react for 3 h. After the reaction is completed, obtain the white solid epoxyamine compound I-3 of Example 3 through rotary evaporation.

[0105]

[0106] Among them, R4 is

[0107] B. Preparation of the polyurethane with the structure of Formula II:

[0108] At room temperature, dissolve 3 g of polyethyleneimine with an average degree of polymerization of 100 in 100 mL of N-methylpyrrolidone, continuously stir, then add 12 g of isophorone diisocyanate, stir magnetically for 45 min, and then obtain the polyurethane II-1 of Example 3 after drying.

[0109]

[0110] Among them, R5 is

[0111] C. Preparation of the aqueous ceramic tile adhesive:

[0112] Weigh 5 g of the prepared polyurethane and 0.25 g of carboxylated nanocellulose, add them to 400 mL of water, stir magnetically for 1.5 h, then add 3 g of the prepared epoxyamine compound and 0.5 g of the aqueous acrylic dispersion, stir magnetically for 1 h, then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, stir mechanically for 30 min. After stirring, heat the mixture to 45 °C to evaporate some water, and stop heating when the mixture becomes gel-like to obtain the aqueous ceramic tile adhesive of Example 3.

[0113] Example 4

[0114] The steps of Example 4 are basically the same as those of Example 3, except that when preparing the polyurethane with the structure of Formula II, 12 g of isophorone diisocyanate is replaced by 14 g of dimethylbiphenyl diisocyanate to obtain polyurethane II-2 (the structural formula is the same as that of the aforementioned polyurethane II-1, except for R5); wherein, R5 is

[0115] Example 5

[0116] The steps of Example 5 are basically the same as those of Example 3, except that when preparing the polyurethane with the structure of Formula II, 12 g of isophorone diisocyanate is replaced by 13 g of 4,4'-diisocyanatodicyclohexylmethane to obtain polyurethane II-3 (the structural formula is the same as that of the aforementioned polyurethane II-1, except for R5); wherein, R5 is

[0117] Example 6

[0118] The steps of Example 6 are basically the same as those of Example 3, except that when preparing the polyurethane with the structure of Formula II, 12 g of isophorone diisocyanate is replaced by 14 g of diphenylmethane diisocyanate to obtain polyurethane II-4 (the structural formula is the same as that of the aforementioned polyurethane II-1, except for R5); wherein, R5 is

[0119] Comparative Example 1

[0120] The preparation method of the aqueous ceramic tile adhesive comprises the following steps:

[0121] A. Preparation of the epoxyamine compound with the structure of Formula I:

[0122] At room temperature, weigh 10 g of isophorone diamine (IPDA), add isophorone diamine to 250 mL of acetone, and continuously stir magnetically (300 r / min);

[0123] Weigh 8 g of polyethylene glycol diglycidyl ether and 6.5 g of epoxy resin E44, mix the two and dissolve them in 100 mL of acetone. Slowly add the mixed solution to the aforementioned acetone solution, and continue magnetic stirring after addition. Keep the temperature for reaction for 2.5 h, then heat to 80 °C and react for 3 h. After the reaction is completed, obtain the epoxy amine compound I-1 in the form of a white solid in Comparative Example 1 through rotary evaporation.

[0124]

[0125] B. Preparation of water-based ceramic tile adhesive:

[0126] Weigh 0.25 g of carboxylated nanocellulose and add it to 400 mL of water. Stir magnetically for 1.5 h, then add 3 g of the epoxy amine compound I-1, stir magnetically for 1 h, then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, and stir mechanically for 30 min. After the stirring is completed, heat the mixture to 45 °C to evaporate part of the water, and stop heating when the mixture becomes gel-like to obtain the water-based ceramic tile adhesive in Comparative Example 1.

[0127] Comparative Example 2

[0128] The preparation method of the water-based ceramic tile adhesive includes the following steps:

[0129] A. Preparation of polyurethane with the structure of Formula II:

[0130] At room temperature, dissolve 3 g of polyethyleneimine with an average degree of polymerization of 100 in 100 mL of N-methylpyrrolidone, continue stirring, then add 12 g of isophorone diisocyanate, and after magnetic stirring for 45 min, obtain polyurethane II-1 in Comparative Example 2 after drying:

[0131]

[0132] Among them, R5 is

[0133] B. Preparation of water-based ceramic tile adhesive:

[0134] Weigh 5 g of the prepared polyurethane and 0.25 g of carboxylated nanocellulose and add them to 400 mL of water. Stir magnetically for 1.5 h, then add 3 g of the prepared epoxy amine compound and 0.5 g of water-based acrylic dispersion, stir magnetically for 1 h, then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, and stir mechanically for 30 min. After the stirring is completed, heat the mixture to 45 °C to evaporate part of the water, and stop heating when the mixture becomes gel-like to obtain the water-based ceramic tile adhesive in Comparative Example 2.

[0135] Comparative Example 3

[0136] The preparation method of the water-based ceramic tile adhesive comprises the following steps:

[0137] A. Preparation of an epoxyamine compound having the structure of formula I:

[0138] At room temperature, weigh 10 g of pyridine-3,5-diamine, add pyridine-3,5-diamine to 250 mL of ethanol, and continuously carry out magnetic stirring (300 r / min);

[0139] Weigh 8 g of polyethylene glycol diglycidyl ether and 6.5 g of epoxy resin E44, mix the two and dissolve them in 100 mL of acetone. Slowly add the mixed solution to the aforementioned acetone solution, and continuously carry out magnetic stirring after adding. Keep the reaction at a constant temperature for 2.5 h, then heat to 80 °C and react for 3 h. After the reaction is completed, obtain the white solid epoxyamine compound I-3 of Comparative Example 3 through rotary evaporation.

[0140]

[0141] Among them, R4 is

[0142] B. Preparation of the water-based ceramic tile adhesive:

[0143] Weigh 5 g of the prepared polyurethane and 0.25 g of carboxylated nanocellulose, add them to 400 mL of water, carry out magnetic stirring for 1.5 h, then add 3 g of the prepared epoxyamine compound and 0.5 g of the water-based acrylic dispersion, carry out magnetic stirring for 1 h, and then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, and carry out mechanical stirring for 30 min. After the stirring is completed, heat the mixture to 45 °C to evaporate part of the water, and stop heating when the mixture becomes gel-like to obtain the water-based ceramic tile adhesive of Comparative Example 3.

[0144] Comparative Example 4

[0145] The steps of Comparative Example 4 are the same as those of Comparative Example 2, except that Comparative Example 4 uses the polyurethane II-2 prepared in Example 4 to replace the polyurethane II-1 used in Comparative Example 2.

[0146] Comparative Example 5

[0147] The preparation method of the water-based ceramic tile adhesive comprises the following steps:

[0148] A. Preparation of an epoxyamine compound having the structure of formula I:

[0149] At room temperature, weigh 10 g of isophorone diamine (IPDA), add isophorone diamine to 250 mL of acetone, and continuously carry out magnetic stirring (300 r / min);

[0150] Weigh 8 g of polyethylene glycol diglycidyl ether and 6.5 g of epoxy resin E44, mix the two and dissolve them in 100 mL of acetone. Slowly add the mixed solution to the aforementioned acetone solution, and continuously carry out magnetic stirring after adding. Keep the reaction at a certain temperature for 2.5 h, then heat to 80 °C and react for 3 h. After the reaction is completed, obtain the epoxy amine compound I-1 in the form of a white solid of Comparative Example 5 through rotary evaporation.

[0151]

[0152] Among them, R4 is

[0153] B. Preparation of polyurethane with the structure of formula II:

[0154] At room temperature, dissolve 5 g of polyaniline with an average degree of polymerization of 10 in 100 mL of N-methylpyrrolidone, continuously stir, then add 12 g of isophorone diisocyanate, and carry out magnetic stirring for 45 min. After drying, obtain the polyurethane II-5 of Comparative Example 5.

[0155]

[0156] Among them, R5 is

[0157] C. Preparation of water-based ceramic tile adhesive:

[0158] Weigh 5 g of the prepared polyurethane and 0.25 g of carboxylated nanocellulose, add them to 400 mL of water, carry out magnetic stirring for 1.5 h, then add 3 g of the prepared epoxy amine compound and 0.5 g of water-based acrylic dispersion, carry out magnetic stirring for 1 h, and then add 0.3 g of borax, 0.4 g of silica sand, 1 g of calcium carbonate, 0.2 g of talc powder and 1 g of glass powder, and carry out mechanical stirring for 30 min. After the stirring is completed, heat the mixture to 45 °C to evaporate part of the water, and stop heating when the mixture becomes gel-like to obtain the water-based ceramic tile adhesive of Comparative Example 5.

[0159] Peel strength and tensile strength test:

[0160] Peel strength test: Use ceramic tiles with a length of 8 cm, a width of 3 mm, and a thickness of 0.5 cm as test pieces. Coat the samples of Examples 1 to 6 and Comparative Examples 1 to 5 on the entire width of the test pieces, and test the peel strength according to the standard of GB / T2790—1995.

[0161] Tensile strength test: Use ceramic tiles with a length of 8 cm, a width of 3 mm, and a thickness of 0.5 cm as test pieces. Coat the samples of Examples 1 to 6 and Comparative Examples 1 to 5 on the entire width of the test pieces. The length of the glue application is 4 cm, and the thickness of the glue application is controlled at about 0.5 mm. After bonding the glue-applied parts of the two test pieces, then apply uniform pressure to the entire bonding surface, and then heat and cure at 60 °C for 3 h. Then install the above test pieces on a tensile testing machine, set the test speed to 50 ± 5 mm / min and start the test, gradually increase the tensile force until fracture, and record the maximum tensile stress as F m , and the obtained tensile strength R = F m / S1, where S1 is the area of the glue-applied part. The values of the obtained peel strength and tensile strength are shown in the following table.

[0162] Peeling strength (N / cm) Tensile strength (mPa) Example 1 57 7.47 Example 2 47 7.15 Example 3 60 7.92 Example 4 67 8.54 Example 5 61 7.98 Example 6 68 8.49 Comparative Example 1 27 4.12 Comparative Example 2 41 6.15 Comparative Example 3 26 4.03 Comparative Example 4 38 5.77 Comparative Example 5 45 6.32

[0163] From the test results of Comparative Examples 1 to 4, it can be seen that since the epoxyamine compound plays a role in improving the crystallinity of polyurethane and enhancing the intermolecular interaction of the polyurethane system, using only the epoxyamine compound having the structure of Formula I provided by the present invention or using only the polyurethane having the structure of Formula II provided by the present invention, their peel strength and tensile strength as water-based ceramic tile adhesives are not as good as those of Examples 1 to 6 using both the epoxyamine compound having the structure of Formula I and the polyurethane having the structure of Formula II provided by the present invention. Both the epoxyamine compound and the polyurethane provided by the present invention have flexible long chains in their molecular skeletons, with good flexibility and elasticity. The combination of the two forms an interpenetrating and dense network structure, thereby endowing it with good bonding ability.

[0164] Comparing the test results of Comparative Example 1 and Example 3, it can be seen that when an aromatic ring is introduced into the epoxyamine compound segment, its peel strength and tensile strength can be improved. This is because when the epoxyamine compound has both a rigid aromatic ring and a flexible long chain, the interpenetrating network structure formed with polyurethane is more difficult to separate. The flexible long chain and the polyurethane segment are intertwined to form a network structure, and the pyridine rings at both ends play a fixing role. Similarly, comparing Example 3, 5 with Example 4, 6, it can be seen that the polyurethane segments are connected by amide bonds formed with isocyanate. When the isocyanate contains an aromatic ring, its peel strength and tensile strength can be improved. Also because the polyurethane segments at both ends of the benzene ring and the long chain on the epoxyamine compound are intertwined to form a network structure, and the benzene ring in the middle plays a fixing role. From the test results of Comparative Example 5, it can be seen that although the peel strength and tensile strength can be improved when the isocyanate contains an aromatic ring; however, when an aromatic ring is introduced into the polyurethane segment in Comparative Example 5, its peel strength and tensile strength decrease rapidly. This is because when an aromatic ring is introduced into the polyurethane segment, the steric hindrance is relatively large, which is not conducive to the formation of an interpenetrating network structure with the epoxyamine compound segment; at the same time, from the test results of Comparative Examples 1 to 4, it can also be seen that when using the epoxyamine compound with the structure of Formula I provided by the present invention alone or using the polyurethane with the structure of Formula II provided by the present invention alone, when there is an aromatic ring in both of their structures, their peel strength and tensile strength are not stronger than the case where there is no aromatic ring in the structure.

[0165] Other embodiments of the present invention will be readily apparent to those skilled in the art upon consideration of the specification and practice disclosed herein. The present invention is intended to cover any variations, uses, or adaptations of the present invention that follow the general principles of the present invention and include known common knowledge or conventional technical means in the technical field not disclosed by the present invention.

Claims

1. A water-based ceramic tile adhesive with high bonding strength, characterized in that: The aqueous ceramic tile adhesive contains an epoxyamine compound having the following formula I, a polyurethane having the following formula II, and carboxylated nanocellulose: Wherein, n1 is 1 to 100; R1 and R2 are each independently a direct bond, a C1-C5 alkyl group or a C2-C30 alkenyl group; R3 is a C1-C5 alkyl group; Ar1 is a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclyl group, or a substituted or unsubstituted 5-30 membered heteroaryl group; R4 is n2 and n3 are each independently 1 to 200; R5 is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclyl group, or a substituted or unsubstituted 5-30 membered heteroaryl group; R6 and R7 are each independently a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, or a substituted or unsubstituted C1-C30 alkoxy group.

2. The water-based ceramic tile adhesive with high bonding strength according to claim 1, characterized in that: R1 and R2 are direct bonds; and Ar1 is any one of the following groups:

3. The water-based ceramic tile adhesive with high bonding strength according to claim 1, characterized in that: R4 is 4. The water-based ceramic tile adhesive with high bonding strength according to claim 1, characterized in that: R5 is any one of the following groups:

5. The water-based ceramic tile adhesive with high bonding strength according to claim 1, characterized in that: R6 and R7 are the same group and are phenyl, methyl or ethyl.

6. The water-based ceramic tile adhesive with high bonding strength according to claim 5, characterized in that: R3 is propyl.

7. The water-based ceramic tile adhesive with high bonding strength according to claim 1, characterized in that: The aqueous ceramic tile adhesive also contains at least one curing agent.

8. A method for preparing the water-based ceramic tile adhesive with high bonding strength according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1: preparing an epoxyamine compound having a structure of formula I and a polyurethane having a structure of formula II; Step 2: adding the polyurethane having the structure of formula II and the carboxylated nanocellulose to water, stirring for 1-3 hours, to obtain the product of step 2; wherein the mass ratio of the carboxylated nanocellulose, the polyurethane having the structure of formula II and water is (1-10):100:(300-500); Step 3: Add an epoxy amine compound having a structure of formula I to the product of step 2, add a curing agent after stirring for 0.2-1h, and continue stirring for 1.5-3h to obtain the water-based ceramic tile adhesive; wherein the mass ratio of the curing agent, the polyurethane having a structure of formula II and the epoxy amine compound having a structure of formula I is (5-15):100:(50-80).

9. The method for preparing the water-based ceramic tile adhesive with high bonding strength according to claim 8, characterized in that: In step 1, the epoxyamine compound having the structure of formula I is prepared by the following steps: Step 1-a: weighing a diamine compound containing an Ar1 group, and adding the diamine compound containing an Ar1 group to a first solvent; Step 2-a: mixing polyethylene glycol diglycidyl ether with one of epoxy resin E44 or epoxy resin E51 to obtain a mixture of step 2-a, and then adding the mixture of step 2-a to the first solvent to obtain a product of step 2-a; Step 3-a: keeping the product of step 2-a warm for 1-3 hours, then heating to 75°C-85°C for 2-4 hours, and separating to obtain the epoxyamine compound having the structure of formula I; In step 1, the polyurethane having the structure of formula II is prepared by the following steps: Step 1-b: adding a polymer containing a secondary amine group and an R6 group to a second solvent to obtain a product of step 1-b; Step 2-b: adding an isocyanate compound to the product of step 1-b, stirring for 0.5-1.5 hours, and obtaining the polyurethane having the structure of formula II after separation.

10. Use of the high-bonding-strength water-based ceramic tile adhesive according to any one of claims 1 to 7, or the high-bonding-strength water-based ceramic tile adhesive obtained by the preparation method of the high-bonding-strength water-based ceramic tile adhesive according to claim 8 or 9 in building materials.

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