Water-based ceramic tile adhesive with high bonding strength as well as preparation method and application of water-based ceramic tile adhesive

Abstract

The invention relates to the technical field of water-based ceramic tile adhesives with high bonding strength, in particular to a water-based ceramic tile adhesive with high bonding strength as well as a preparation method and application thereof. The water-based ceramic tile adhesive contains an epoxy amine compound as shown in the following formula I, polyurethane as shown in the following formula II and carboxylated nanocellulose. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of water-based ceramic tile adhesives, and in particular to a water-based ceramic tile adhesive with high bonding strength, a preparation method and application thereof. Background Art

[0002] Ceramic tile adhesive is currently a commonly used adhesive for bonding ceramic tiles, clay bricks, cylinder bricks, slates, marble, and natural stones. Compared with cement mortar, it has better bonding strength, good durability, and convenient construction. It is used to stick various ceramic tiles and various stones on indoor and outdoor cement-based surfaces or walls and floors composed of various partition brick substrates. It has more and more applications in the field of engineering construction.

[0003] In the prior art, building adhesives are mainly polyvinyl formal adhesives, which contain a large amount of volatile and harmful organic substances, such as formaldehyde, which can cause great harm to the environment and human health. Summary of the invention

[0004] The purpose of the present invention is to provide a water-based ceramic tile adhesive with high bonding strength, a preparation method and application thereof, so as to solve the defects pointed out in the above background technology.

[0005] According to a first aspect of an embodiment of the present invention, a water-based ceramic tile adhesive with high bonding strength contains an epoxyamine compound having the following formula I, a polyurethane having the following formula II, and carboxylated nanocellulose:

[0006]

[0007] Wherein, n1 is 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 heterocyclyl group, or a substituted or unsubstituted 5-30 membered heteroaryl group;

[0011] R4 is

[0012] n2 and n3 are each independently 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 heterocyclyl 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 embodiment of the present invention, preferably, n1 is 1 to 10.

[0016] In one aspect of the embodiment of the present invention, preferably, n2 and n3 are each independently 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, a methyl group, an ethyl group or a propyl group.

[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 heterocyclyl group, or a substituted or unsubstituted 5-30 membered heteroaryl group.

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

[0022] In one aspect of the embodiments of the present invention, R1 and R2 are direct bonds; 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 an embodiment of the present invention, a water-based ceramic tile adhesive with high bonding strength comprises an epoxyamine compound having the following formula IA, a polyurethane having the following formula II-A, and carboxylated nanocellulose:

[0032]

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

[0034]

[0035] R4 is

[0036] R5 is any of the following groups:

[0037]

[0038] In one aspect of the embodiment 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 an embodiment of the present invention, the aqueous ceramic tile adhesive further contains at least one of talc, kaolin, calcium carbonate, silica sand, borax and glass powder.

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

[0041] According to a second aspect of an embodiment of the present invention, a method for preparing the aforementioned water-based ceramic tile adhesive with high bonding strength comprises the following steps:

[0042] Step 1: preparing an epoxyamine compound having the structure of the aforementioned formula I and a polyurethane having the structure of the aforementioned formula II;

[0043] 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);

[0044] 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).

[0045] In one aspect of the embodiments of the present invention, in step 1, the epoxyamine compound having the structure of formula I is prepared by the following steps:

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

[0047] 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;

[0048] Step 3-a: The product of step 2-a is kept warm for reaction for 1-3 hours, then heated to 75°C-85°C for reaction for 2-4 hours, and the epoxyamine compound having the structure of formula I is obtained after separation.

[0049] In one aspect of the embodiment of the present invention, in step 1, the polyurethane having the structure of formula II is prepared by the following steps:

[0050] 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;

[0051] 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.

[0052] According to a third aspect of an embodiment of the present invention, there is provided an application of the aforementioned high-bonding-strength water-based ceramic tile adhesive, or a high-bonding-strength water-based ceramic tile adhesive obtained by the preparation method of the aforementioned high-bonding-strength water-based ceramic tile adhesive 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, the preparation method thereof is simple, and the raw materials used do not contain toxic or volatile organic substances; and the water-based ceramic tile adhesive with high bonding strength provided by the present invention has high bonding strength. The epoxyamine compound and the molecular skeleton of the polyurethane provided by the present invention both have flexible long chains, and have good flexibility and elasticity, and the combination of the two forms an interpenetrating and dense network structure, thereby giving it good bonding ability.

[0055] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention. DETAILED DESCRIPTION

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

[0057] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. The relevant embodiments described herein are illustrative and are used to provide a basic understanding of the present invention. The embodiments of the present invention should not be interpreted as limiting the present invention.

[0058] For simplicity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range. In addition, each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an unspecified range.

[0059] In this article, the terms "comprises", "comprising" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device that includes a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of more restrictions, an element defined by the sentence "comprising a ..." does not exclude the presence of other identical elements in the process, method, article or device that includes the element.

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

[0061] Unless otherwise specified, the terms used in the present invention have the commonly known meanings generally 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 using various measurement methods commonly used 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 illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a range of variation of less than or equal to ±10% of 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%. In addition, amounts, ratios, and other numerical values ​​are sometimes presented in this article in a range format. It should be understood that such a range format is for convenience and simplicity, and should be flexibly understood to include not only numerical values ​​explicitly designated as range limits, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0063] A list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, 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, 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 may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

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

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

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

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

[0068] In the context of the present invention, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system in which one or more of the ring atoms is an element other than carbon, such as nitrogen, oxygen or sulfur, either alone or in combination, preferably containing about 5 to about 6 ring atoms. The "heteroaryl" may be optionally substituted with one or more "ring system substituents", which may be the same or different, as defined herein. The prefix aza, oxa or thia before the heteroaryl root name indicates that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The nitrogen atom of the heteroaryl may be optionally oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl groups include pyridinyl, pyrazinyl, furanyl, thiophenyl, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-naphthyridinyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothiophenyl, quinolinyl, imidazolyl, thienopyridinyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridinyl, imidazopyridinyl, isoquinolinyl, benzazaindolyl, 1,2,4-triazinyl, benzothiazolyl, and the like.

[0069] In the context of the present invention, the term "amino" refers to a -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 be cyclized to form a cyclic amino group, such as a pyrrolidinyl or piperidinyl group. Such cyclic amino groups may incorporate other heteroatoms, for example to form piperazine or morpholine groups. Such cyclic amino groups may be optionally substituted, for example, by amino, hydroxyl or oxo groups.

[0070] In the context of the present invention, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to a straight chain, branched or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy and pentoxy. Alkoxy can optionally be substituted with one or more alkoxy substituents ("substituted alkoxy").

[0071] In the context of the present invention, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system, preferably a cycloalkyl ring containing about 5 to about 7 ring atoms. The cycloalkyl group may optionally be substituted with one or more "ring system substituents", which may be the same or different and are defined as 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 context of the present invention, the term "cycloalkoxy" refers to a group in which one or more carbons in a mono- or polycyclic ring system of a "cycloalkyl" are replaced with oxygen atoms.

[0072] In the context of the present invention, the term "heterocyclyl" refers to a non-aromatic saturated monocyclic or polycyclic ring system, wherein one or more of the ring atoms in the ring system is an element 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 preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxa or thia before the heterocyclyl root name indicates that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The heterocyclyl may be optionally substituted with one or more "ring system substituents", which are the same or different and are defined herein. The nitrogen or sulfur atom of the heterocyclyl may be optionally oxidized to the corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings include piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxacyclohexyl, tetrahydrofuranyl, tetrahydrophenylthio, tetrahydrothiopyranyl, and the like.

[0073] The present invention is further described below by way of specific examples. The various chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are all weight contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0074] Embodiment 1

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

[0076] A. Preparation of epoxyamine compounds with formula I structure:

[0077] At room temperature, 10 g of isophorone diamine (IPDA) was weighed and added to 250 mL of acetone, and magnetic stirring was continued (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 mixture to the above acetone solution, continue magnetic stirring after addition, keep warm for 2.5 hours, then heat to 80 ° C for 3 hours, after the reaction is completed, rotary evaporation is performed to obtain the white solid epoxyamine compound I-1 of Example 1.

[0079]

[0080] Among them, R4 is

[0081] B. Preparation of polyurethane with formula II structure:

[0082] At room temperature, 3 g of polyethyleneimine with an average degree of polymerization of 100 was dissolved in 100 mL of N-methylpyrrolidone and stirred continuously. Then, 12 g of isophorone diisocyanate was added. After magnetic stirring for 45 min, the mixture was dried to obtain the polyurethane II-1 of Example 1.

[0083]

[0084] Among them, R5 is

[0085] C. Preparation of 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 epoxy amine compound and 0.5 g of 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 and 1 g of glass powder, stir mechanically for 30 min, heat the mixture to 45°C after stirring to evaporate part of the water, stop heating when the mixture is in a gel state, and obtain the water-based ceramic tile adhesive of Example 1.

[0087] Embodiment 2

[0088] The preparation method of the water-based ceramic tile adhesive comprises the following steps:

[0089] A. Preparation of epoxyamine compounds with formula I structure:

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

[0091] 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 mixture to the aforementioned ethanol solution, continue magnetic stirring after addition, keep warm for 2.5 hours, then heat to 80°C for 3 hours, and after the reaction is completed, obtain the epoxyamine compound I-2 of Example 2 as a white solid by rotary evaporation.

[0092]

[0093] Among them, R4 is

[0094] B. Preparation of polyurethane with formula II structure:

[0095] At room temperature, 3 g of polyethyleneimine with an average degree of polymerization of 100 was dissolved in 100 mL of N-methylpyrrolidone and stirred continuously. Then, 12 g of isophorone diisocyanate was added. After magnetic stirring for 45 minutes, the mixture was dried to obtain the polyurethane II-1 of Example 2.

[0096]

[0097] Among them, R5 is

[0098] C. Preparation of water-based 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 epoxy amine compound and 0.5 g of 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 and 1 g of glass powder, stir mechanically for 30 min, heat the mixture to 45°C after stirring to evaporate part of the water, stop heating when the mixture is in a gel state, and obtain the water-based ceramic tile adhesive of Example 2.

[0100] Embodiment 3

[0101] The preparation method of the water-based ceramic tile adhesive comprises the following steps:

[0102] A. Preparation of epoxyamine compounds with formula I structure:

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

[0104] 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 mixture to the aforementioned acetone solution, continue magnetic stirring after addition, keep warm for 2.5 hours, then heat to 80°C for 3 hours, and after the reaction is completed, obtain the epoxyamine compound I-3 of Example 3 as a white solid by rotary evaporation.

[0105]

[0106] Among them, R4 is

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

[0108] At room temperature, 3 g of polyethyleneimine with an average degree of polymerization of 100 was dissolved in 100 mL of N-methylpyrrolidone and stirred continuously. Then, 12 g of isophorone diisocyanate was added. After magnetic stirring for 45 min, the mixture was dried to obtain the polyurethane II-1 of Example 3.

[0109]

[0110] Among them, R5 is

[0111] C. Preparation of water-based 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, and stir magnetically for 1.5 h. Then add 3 g of the prepared epoxy amine compound and 0.5 g of aqueous acrylic dispersion, and 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 and 1 g of glass powder, and stir mechanically for 30 min. After stirring, heat the mixture to 45°C to evaporate part of the water. Stop heating when the mixture is in a gel state to obtain the water-based ceramic tile adhesive of Example 3.

[0113] Embodiment 4

[0114] The steps of Example 4 are basically the same as those of Example 3, except that when preparing a polyurethane having a structure of Formula II, 12 g of isophorone diisocyanate is replaced with 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 that R5 is); wherein R5 is

[0115] Embodiment 5

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

[0117] Embodiment 6

[0118] The steps of Example 6 are basically the same as those of Example 3, except that when preparing the polyurethane having the structure of Formula II, 12 g of isophorone diisocyanate is replaced with 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 that R5 is); wherein R5 is

[0119] Comparative Example 1

[0120] The preparation method of the water-based ceramic tile adhesive comprises the following steps:

[0121] A. Preparation of epoxyamine compounds with formula I structure:

[0122] At room temperature, 10 g of isophorone diamine (IPDA) was weighed and added to 250 mL of acetone, and magnetic stirring was continued (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 mixture to the above acetone solution, continue magnetic stirring after addition, keep warm for 2.5 hours, then heat to 80 ° C for 3 hours, after the reaction is completed, rotary evaporation is performed to obtain the white solid epoxyamine compound I-1 of comparative example 1.

[0124]

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

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

[0127] Comparative Example 2

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

[0129] A. Preparation of polyurethane having formula II structure:

[0130] At room temperature, 3 g of polyethyleneimine with an average degree of polymerization of 100 was dissolved in 100 mL of N-methylpyrrolidone, and the mixture was stirred continuously. Then, 12 g of isophorone diisocyanate was added, and the mixture was stirred magnetically for 45 min. The mixture was dried to obtain polyurethane II-1 of Comparative Example 2:

[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, 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 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 and 1 g of glass powder, stir mechanically for 30 min, heat the mixture to 45 ° C after stirring to evaporate part of the water, stop heating when the mixture is in a gel state, and obtain the water-based ceramic tile adhesive of 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 epoxyamine compounds with formula I structure:

[0138] At room temperature, weigh 10 g of pyridine-3,5-diamine, add pyridine-3,5-diamine to 250 mL of ethanol, and continue 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 mixture to the above acetone solution, continue magnetic stirring after addition, keep warm for 2.5 hours, then heat to 80 ° C for 3 hours, after the reaction is completed, rotary evaporation is performed to obtain the white solid epoxyamine compound I-3 of comparative example 3.

[0140]

[0141] Among them, R4 is

[0142] B. Preparation of 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, stir magnetically for 1.5 h, then add 3 g of the prepared epoxy amine compound and 0.5 g of 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 and 1 g of glass powder, stir mechanically for 30 min, heat the mixture to 45 ° C after stirring to evaporate part of the water, stop heating when the mixture is in a gel state, and obtain the water-based ceramic tile adhesive of comparative example three.

[0144] Comparative Example 4

[0145] The steps of Comparative Example 4 are the same as those of Comparative Example 2, except that the polyurethane II-2 prepared in Example 4 is used in Comparative Example 4 instead of 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 epoxyamine compounds with formula I structure:

[0149] At room temperature, 10 g of isophorone diamine (IPDA) was weighed and added to 250 mL of acetone, and magnetic stirring was continued (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 mixture to the above acetone solution, continue magnetic stirring after addition, keep warm for 2.5 hours, then heat to 80°C for 3 hours. After the reaction is completed, rotary evaporation is performed to obtain the white solid epoxyamine compound I-1 of comparative example 5.

[0151]

[0152] Among them, R4 is

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

[0154] At room temperature, 5 g of polyaniline with an average degree of polymerization of 10 was dissolved in 100 mL of N-methylpyrrolidone and stirred continuously. Then, 12 g of isophorone diisocyanate was added and magnetic stirring was performed for 45 min. After drying, polyurethane II-5 of comparative example 5 was obtained.

[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, stir magnetically for 1.5 h, then add 3 g of the prepared epoxy amine compound and 0.5 g of 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 and 1 g of glass powder, stir mechanically for 30 min, heat the mixture to 45 ° C after stirring to evaporate part of the water, stop heating when the mixture is in a gel state, and obtain the water-based ceramic tile adhesive of comparative example five.

[0159] Peel strength and tensile strength test:

[0160] Peel strength test: A ceramic tile with a length of 8 cm, a width of 3 mm, and a thickness of 0.5 cm was used as a test piece. The samples of Examples 1 to 6 and Comparative Examples 1 to 5 were respectively coated on the entire width of the test piece, and the peel strength was tested according to GB / T2790-1995 standard.

[0161] Tensile strength test: A ceramic tile with a length of 8 cm, a width of 3 mm, and a thickness of 0.5 cm was used as a test piece. The samples of Examples 1 to 6 and Comparative Examples 1 to 5 were coated on the entire width of the test piece, respectively. The coating length was 4 cm, and the coating thickness was controlled at about 0.5 mm. After the two test pieces were glued together, pressure was evenly applied to the entire bonding surface, and then heated and cured at 60°C for 3 hours. Then, the above test piece was installed on a tensile testing machine, and the test speed was set to 50±5 mm / min and then the test was started. The tensile force was gradually increased until it broke, and the maximum tensile stress was recorded as F. m , the tensile strength R = F m / S1, where S1 is the area of ​​the glue coating. The peel strength and tensile strength values ​​obtained are shown in the following table.

[0162] Peel strength (N / cm) Tensile strength(mPa) Embodiment 1 57 7.47 Embodiment 2 47 7.15 Embodiment 3 60 7.92 Embodiment 4 67 8.54 Embodiment 5 61 7.98 Embodiment 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 compounds play a role in improving the crystallinity of polyurethane and enhancing the interaction between the molecules of the polyurethane system, the peel strength and tensile strength of the epoxyamine compounds with the structure of formula I provided by the present invention alone or the polyurethane with the structure of formula II provided by the present invention alone as a water-based ceramic tile adhesive are not as good as those of Examples 1 to 6 in which the epoxyamine compounds with the structure of formula I and the polyurethane with the structure of formula II provided by the present invention are used simultaneously. The molecular skeletons of the epoxyamine compounds and polyurethanes provided by the present invention both have flexible long chains, good flexibility and elasticity, and the combination of the two forms an interpenetrating and dense network structure, thereby giving it good bonding ability.

[0164] It can be seen from the test results of Example 1 and Example 3 that when an aromatic ring is introduced into the epoxyamine compound chain segment, its peel strength and tensile strength can be improved. This is because when the epoxyamine compound has both an aromatic ring of a rigid structure and a flexible long chain, the interpenetrating network structure formed by it and the polyurethane is more difficult to separate, and the flexible long chain and the polyurethane chain segment are interwoven to form a network structure, and the pyridine rings at both ends play a fixing role. Similarly, it can be seen from the comparison of Examples 3, 5 and 4, 6 that the polyurethane chain segments are connected by an amide bond formed with isocyanate, and when the isocyanate contains an aromatic ring, its peel strength and tensile strength can be improved, also because the polyurethane chain segments at both ends of the benzene ring and the long chain on the epoxyamine compound are interwoven 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 of isocyanate can be improved when it contains an aromatic ring; however, when the aromatic ring is introduced into the polyurethane segment in Comparative Example 5, the peel strength and tensile strength are rapidly reduced. This is because when the aromatic ring is introduced into the polyurethane segment, its 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 the epoxyamine compound having the structure of Formula I provided by the present invention is used alone or the polyurethane having the structure of Formula II provided by the present invention is used alone, when the aromatic ring exists in both structures, the peel strength and tensile strength are not stronger than the case where the aromatic ring does not exist in the structure.

[0165] Those skilled in the art will readily appreciate other embodiments of the present invention after considering the specification and practicing the disclosure 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 common knowledge or customary technical means in the art that are 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.

Images