CN117946395A - Epoxy rock plate adhesive for splicing rock plates and preparation method and application thereof - Google Patents
Epoxy rock plate adhesive for splicing rock plates and preparation method and application thereof Download PDFInfo
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- CN117946395A CN117946395A CN202410121123.4A CN202410121123A CN117946395A CN 117946395 A CN117946395 A CN 117946395A CN 202410121123 A CN202410121123 A CN 202410121123A CN 117946395 A CN117946395 A CN 117946395A
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- 239000011435 rock Substances 0.000 title claims abstract description 94
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 56
- 239000000853 adhesive Substances 0.000 title claims abstract description 54
- 239000004593 Epoxy Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920006295 polythiol Polymers 0.000 claims abstract description 156
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
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- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 238000009736 wetting Methods 0.000 claims abstract description 16
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000005376 alkyl siloxane group Chemical group 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 2
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- 150000002466 imines Chemical class 0.000 claims description 2
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- 239000004408 titanium dioxide Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
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- 230000000052 comparative effect Effects 0.000 description 12
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012790 adhesive layer Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 5
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 5
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
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- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
Abstract
The invention relates to an epoxy rock plate adhesive for rock plate splicing, and a preparation method and application thereof, wherein the epoxy rock plate adhesive for rock plate splicing comprises a component A and a component B, and the epoxy rock plate adhesive comprises the following components in parts by weight: the component A comprises 100 parts of liquid epoxy resin, 1-5 parts of epoxy silane coupling agent, 1-20 parts of reactive diluent, 10-70 parts of pigment and filler, 0.1-1 part of first defoamer and 0.1-1 part of first wetting dispersant; the component B comprises 60-115 parts of polythiol curing agent, 1-5 parts of mercapto coupling agent, 1-20 parts of diluent, 40-100 parts of pigment and filler, 0.1-1 part of second defoamer and 0.1-1 part of second wetting dispersant; the polythiol curing agent comprises 1-5 weight percent: 1 and a second polythiol; the first polythiol is a linear structure polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups. The epoxy rock plate adhesive for splicing the rock plates has the advantages of high bonding strength after solidification, good weather resistance, better water resistance, quick initial setting, high positioning efficiency, high post-solidification crosslinking density and capability of meeting higher mechanical requirements more quickly.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an epoxy rock plate adhesive for splicing rock plates, and a preparation method and application thereof.
Background
The rock plate is made of natural raw materials through firing by a special process, and mainly comprises various raw materials such as quartz, feldspar, oxides providing colors and the like, after being pressed by 400 bars of high pressure, the rock plate is fired at a high temperature of more than 1200 ℃, and can withstand the processing procedures of cutting, drilling, polishing and the like.
Most of rock plate products are subjected to processes of splicing, fixing, polishing and the like in a stone processing factory, and the adhesive to be spliced has relatively quick initial setting time (2-5 min) in the process of splicing the rock plates, so that the coating of the rock plates and the penetration of the adhesive are facilitated, and in addition, after the rock plate adhesive is coated, the time for curing the rock plate adhesive to reach the Shore D hardness of more than or equal to 80D is as short as possible, so that the movement of the bonded stone and the polishing treatment of the adhesive layer are realized.
Because the rock plate has high density and smooth surface, the bonding effect of the adhesive such as marble adhesive, dry coating adhesive and the like on the rock plate is poor. The rock plate adhesive on the market mainly comprises three types of unsaturated resin rock plate adhesive, acrylic ester rock plate adhesive and epoxy resin rock plate adhesive. The unsaturated resin rock plate adhesive has the advantages of high curing speed, suitability for stone processing factory splicing technology, highest market occupation rate, high shrinkage rate during curing, low bonding strength, poor bonding in a humid environment, short storage period, and long-term contact of monomers containing stimulative odor such as styrene, and is unfavorable for health; the acrylic acid ester rock plate adhesive has obvious pungent smell, the surface of the adhesive layer is sticky after curing, the shock resistance is poor, and the acrylic acid ester rock plate adhesive contains a certain amount of reducing agent and is easy to turn yellow; the epoxy resin rock plate adhesive has longer curing time, long curing period and brittle cured product.
In the prior art, patent document CN114958280A discloses a bi-component rock plate adhesive, a preparation method and application thereof, wherein a traditional polyurethane system is adopted, and the cured products of the two systems are elastic bodies, are not matched with stone with higher hardness, such as rock plates, and have lower bonding strength and hardness after curing and poorer water resistance. Patent document CN 112961612a discloses a high-strength high-weather-resistance rock plate adhesive and a preparation method, wherein an acrylic ester curing system is adopted, so that most acrylic ester adhesives have the defects of common diseases, obvious pungent smell, sticky adhesive layer surface after curing, poor impact resistance, a certain amount of reducing agent, easy yellowing and the like. Patent document CN115948140A discloses an epoxy bi-component adhesive, a preparation method and application, adopts a curing system of epoxy resin and modified alicyclic amine, and has the defects of long curing time, long curing period, brittle cured product and the like. Patent document CN115584229a discloses a two-component epoxy rock plate adhesive, a preparation method and application thereof, which adopts a curing system of epoxy resin and modified alicyclic amine, wherein the epoxy resin uses partial polyurethane grafted modified epoxy resin to improve the flexibility of a cured product, and the curing agent uses partial thiourea-polyamine condensation curing agent to improve the curing speed of the system, but the thiourea-polyamine condensation curing agent, the modified alicyclic amine curing agent has larger curing speed difference, the adhesive property of the thiourea-polyamine condensation curing agent and the epoxy resin after primary curing is poor, the overall viscosity of the system is increased, and the subsequent curing of the modified alicyclic amine and epoxy is hindered, so that the whole curing time is longer, and the 45-degree angle splicing process of the rock plate in a processing plant is not facilitated.
There is also fast-curing adhesive of epoxy resin-polythiol in the market, but in order to realize the effect of fast curing, a certain amount of tertiary amine accelerator is usually added into the common polythiol, so that the polythiol can realize early curing, but has high bonding strength in a short time after curing, and can achieve strong bonding performance only by needing one-day curing time.
Disclosure of Invention
The invention provides an epoxy rock plate adhesive for splicing rock plates, and a preparation method and application thereof, and aims to solve the problem that the existing epoxy resin-polythiol is difficult to have high adhesive strength in a short time after being cured.
The technical scheme provided by the invention is as follows:
In a first aspect, the present invention provides a polythiol having the formula:
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
In some preferred embodiments of the invention, n is 1-5 and m is 1-5.
In some more preferred embodiments of the invention, n is 1-3 and m is 1-3.
In some more preferred embodiments of the present invention,
R1 represents: -CH 2-CH2-CH2 -SH;
R2 represents:
In a second aspect, the present invention provides a process for preparing the polythiol described above, comprising: under the catalysis of concentrated hydrochloric acid, (R3O) 3Si(CH2)n SH and (R3O) 3Si(CH2)mN(CH3)2 with the molar ratio of 1:0.8-1.2 are reacted in an alcohol solvent at 75-95 ℃ to obtain the polythiol by purifying the product;
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
r2 represents- (CH 2)mN(CH3)2, m is 1-10);
R3 represents methyl or ethyl.
In a third aspect, the invention provides a polythiol curing agent comprising, by weight, 1-5:1 and a second polythiol; the first polythiol is linear polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups.
In some embodiments of the invention, the first polythiol has the formula:
The second polythiol has the following structural formula:
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
In a fourth aspect, the invention provides an epoxy rock board adhesive for splicing rock boards, which comprises a component A and a component B, wherein the epoxy rock board adhesive comprises the following components in parts by weight:
The component A comprises 100 parts of liquid epoxy resin, 1-5 parts of epoxy silane coupling agent, 1-20 parts of reactive diluent, 10-70 parts of pigment and filler, 0.1-1 part of first defoamer and 0.1-1 part of first wetting dispersant;
The component B comprises 60-115 parts of polythiol curing agent, 1-5 parts of mercapto coupling agent, 1-20 parts of diluent, 40-100 parts of pigment and filler, 0.1-1 part of second defoamer and 0.1-1 part of second wetting dispersant;
the polythiol curing agent comprises the following components in percentage by weight: 1 and a second polythiol; the first polythiol is linear polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups.
In some embodiments of the invention, the first polythiol has the formula:
The second polythiol has the following structural formula:
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
In some embodiments of the invention, the liquid epoxy is one or more of E44, E51; the epoxy silane coupling agent is one or more of 3- (2, 3-glycidoxy) propyl trimethoxy silane and 3- (2, 3-glycidoxy) propyl methyl diethoxy silane; the sulfhydryl coupling agent is one or more of 3-mercaptopropyl triethoxysilane and 3-mercaptopropyl trimethoxysilane; the reactive diluent is one or more of 1,4 butanediol diglycidyl ether and trimethylolpropane triglycidyl ether; the diluent is one or more of benzyl alcohol and diethylene glycol; the pigment filler is one or more of whisker silicon, titanium dioxide and hydrophobic fumed silica; the first defoamer is one or more of a foam breaking polymer solution and a polyether modified methane-based siloxane copolymer solution which do not contain organic silicon; the second defoaming agent is one or more of solution of foam breaking polymer and polysiloxane and polymethyl alkyl siloxane; the first wetting dispersant is an alkyl ammonium salt of a high molecular weight copolymer; the second wetting dispersant is a polyglycol-polyester modified polyolefin imine.
In a fifth aspect, the invention provides a method for preparing epoxy rock board glue for splicing rock boards, comprising the following steps:
preparation of component A: uniformly mixing liquid epoxy resin, a reactive diluent and a first defoamer under a negative pressure condition to obtain a first component premix; uniformly mixing the component A premix, the epoxy silane coupling agent and the pigment and filler under the negative pressure condition to obtain a component A;
Preparation of component B: uniformly mixing a polythiol curing agent, a diluent and a second defoamer under a negative pressure condition to obtain a component B premix; uniformly mixing the component B premix, the mercapto-terminated coupling agent, the pigment and filler and the wetting dispersant under the negative pressure condition to obtain the component B;
And packaging the component A and the component B respectively.
In a sixth aspect, the invention provides a method for using epoxy rock board glue for splicing rock boards, comprising the following steps:
the weight ratio is 0.8-1.2: and 1, uniformly mixing the component A and the component B at room temperature, rapidly coating the mixture on a spliced seam of a rock plate, and pressing and curing for 2-5min.
Compared with the prior art, the invention has the following advantages:
1. Compared with the existing rock plate adhesive, the epoxy rock plate adhesive for splicing the rock plates adopts an epoxy resin-mercaptan quick-curing system, and has the advantages of high bonding strength after curing, good weather resistance and better water resistance.
2. The epoxy rock plate adhesive for rock plate splicing provided by the invention has the advantages of wide application environment, high activity of thiol by adopting polyfunctional thiol, quick initial setting, high positioning efficiency, high post-curing crosslinking density, capability of reaching higher mechanical requirements more quickly, suitability for rock plate processing technology of stone processing factories, and efficiency improvement.
3. The first polythiol has more mercapto groups structurally, has high reactivity and multiple crosslinking points, and the second polythiol has a bodily form structure and a tertiary amine structure structurally, wherein the bodily form structure can improve the hardness of a cured product, and the tertiary amine structure can enable the polythiol to be rapidly cured, so that the problems of short storage period, easy color change, large smell and easy skinning on the surface caused by adding the tertiary amine accelerator are solved.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides polythiol which has the following structural formula:
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
The polythiol has a body type structure, and simultaneously contains four thiol structure branched chains and four tertiary amine structure branched chains, and because the introduction of the tertiary amine structure can play a role in promoting the curing of epoxy resin, no tertiary amine accelerator is needed to be added, the problems of short storage period, easy color change, large smell, easy skinning on the surface and the like caused by adding the tertiary amine accelerator into the polythiol are completely eradicated, and meanwhile, the body type structure can play a good role in increasing the surface hardness of a cured product, and because the polythiol contains more Si-O-Si bonds, the epoxy resin has better toughness and water resistance.
The invention also provides a method for preparing the polythiol, which adopts 3-mercaptopropyl triethoxysilane and (N, N-dimethyl-3-aminopropyl) trimethoxysilane to synthesize the polythiol, and comprises the following steps: under the catalysis of concentrated hydrochloric acid, (R3O) 3Si(CH2)n SH and (R3O) 3Si(CH2)mN(CH3)2 with the molar ratio of 1:0.8-1.2 are reacted in an alcohol solvent at 75-95 ℃ to obtain the polythiol by purifying the product;
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
R3 represents methyl or ethyl.
The invention also provides a polythiol curing agent, which comprises the following components in percentage by weight: 1 and a second polythiol; the first polythiol is linear polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups.
The polythiol curing agent is prepared by compounding two polythiols, wherein the first polythiol has a linear structure, the hardness is lower in a short time after curing, a tertiary amine accelerator is needed to be added in the prior art to realize quick curing, but the viscosity of the first polythiol is lower, and the operation is easy; the second polythiol contains a bulk structure which can well exert an effect of increasing the surface hardness of the cured product, and a plurality of tertiary amine structures which can promote curing, but the second polythiol has a large viscosity and cures too quickly. The invention combines the first polythiol and the second polythiol, can control the operable time within a certain range, and improves the early hardness.
In some embodiments of the invention, the first polythiol has the formula:
The second polythiol has the following structural formula:
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
In this embodiment, the first polythiol has more thiol groups, higher activity, lower molecular weight, lower viscosity, and easier use, and the thiol groups are in branched positions, and the odor is lower; the second polythiol has larger molecular weight, larger viscosity and too fast curing, and needs to be compounded with the first polythiol for use.
The invention also provides an epoxy rock plate adhesive for splicing rock plates, which comprises a component A and a component B, wherein the epoxy rock plate adhesive comprises the following components in parts by weight:
The component A comprises 100 parts of liquid epoxy resin, 1-5 parts of epoxy silane coupling agent, 1-20 parts of reactive diluent, 10-70 parts of pigment and filler, 0.1-1 part of first defoamer and 0.1-1 part of first wetting dispersant;
The component B comprises 60-115 parts of polythiol curing agent, 1-5 parts of mercapto coupling agent, 1-20 parts of diluent, 40-100 parts of pigment and filler, 0.1-1 part of second defoamer and 0.1-1 part of second wetting dispersant;
the polythiol curing agent comprises the following components in percentage by weight: 1 and a second polythiol; the first polythiol is linear polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups.
The rock plate adhesive adopts a curing system of epoxy resin-polythiol, in order to be suitable for the specificity of rock plate stones and the splicing process in the processing flow, the polythiol curing agent is compounded by adopting two polythiols, wherein the first polythiol is synthesized by adopting trimethylolpropane and 2-mercaptopropionic acid, the synthesized first polythiol has more mercapto groups, higher activity, smaller molecular weight and lower viscosity, is easy to use, has smaller odor, has lower hardness in a short time after the first polythiol is in a linear structure for curing, and can be quickly cured by adding a tertiary amine accelerator; therefore, the second polythiol containing the bodily form structure and the tertiary amine structure is introduced, the bodily form structure can well play a role in increasing the surface hardness of a cured product, and the tertiary amine structure can promote curing, but the epoxy rock plate adhesive for splicing the rock plates has the advantages of high curing speed, high bonding strength, strong initial adhesion positioning capability, good construction experience, good weather resistance, better water resistance, balanced comprehensive performance and the like by adjusting the dosage of the first polythiol and the second polythiol.
The invention also provides a preparation method of the epoxy rock plate adhesive for splicing the rock plates, which comprises the following steps:
preparation of component A: uniformly mixing liquid epoxy resin, a reactive diluent and a first defoamer under a negative pressure condition to obtain a first component premix; uniformly mixing the component A premix, the epoxy silane coupling agent and the pigment and filler under the negative pressure condition to obtain a component A;
Preparation of component B: uniformly mixing a polythiol curing agent, a diluent and a second defoamer under a negative pressure condition to obtain a component B premix; uniformly mixing the component B premix, the mercapto-terminated coupling agent, the pigment and filler and the wetting dispersant under the negative pressure condition to obtain the component B;
And packaging the component A and the component B respectively.
The invention also provides a use method of the epoxy rock plate adhesive for splicing the rock plates, which comprises the following steps:
the weight ratio is 0.8-1.2: and 1, uniformly mixing the component A and the component B at room temperature, rapidly coating the mixture on a spliced seam of a rock plate, and pressing and curing for 2-5min.
The following describes the technical scheme of the present invention in detail through specific embodiments:
the raw materials selected in the invention can be commercially available raw materials unless otherwise specified, and the sources of the raw materials used in the examples are shown in Table 1:
Table 1: raw material name (model) and manufacturer
Examples
Synthesis of the first polythiol: dissolving trimethylolpropane and p-toluenesulfonic acid serving as a catalyst in 2-mercaptopropionic acid, heating in an oil bath at about 80 ℃ until the trimethylolpropane, the p-toluenesulfonic acid and the catalyst are uniformly mixed, and then reducing the pressure to-0.1 MPa for reaction for 3-4 hours. After the reaction is finished, removing excessive 2-mercaptopropionic acid and catalyst p-toluenesulfonic acid in a reaction system by a water washing method to obtain first polythiol; wherein: the molar ratio of the trimethylolpropane to the 2-mercaptopropionic acid is 1:3; the mass of the p-toluenesulfonic acid is 2% of the total mass of the trimethylolpropane and the 2-mercaptopropionic acid.
Synthesis of the second polythiol: adding 3-mercaptopropyl triethoxysilane and (N, N-dimethyl-3-aminopropyl) trimethoxysilane into a flask equipped with a magnetic stirring and condenser, simultaneously adding concentrated hydrochloric acid and methanol, reacting the mixture at 75-95 ℃ for 24-72 h under stirring, cooling, removing methanol solvent, and vacuum drying to obtain viscous liquid, thus obtaining second polythiol; wherein: 3-mercaptopropyl triethoxysilane, (N, N-dimethyl-3-aminopropyl) trimethoxysilane in a molar ratio of 1:1; the volume of the concentrated hydrochloric acid is 1.5 times of the total volume of the 3-mercaptopropyl triethoxysilane and the (N, N-dimethyl-3-aminopropyl) trimethoxysilane; the volume of methanol was 10 times the total volume of 3-mercaptopropyl triethoxysilane and (N, N-dimethyl-3-aminopropyl) trimethoxysilane.
Experimental discussion of the reaction ratio of epoxy resin and polythiol:
Table 2: reaction ratio of epoxy resin and polythiol
-Represents no addition.
Comparative example 1a polythiol Capcure-CB from new materials science, inc. Of jiadeda was used instead of the first polythiol and the second polythiol of example 15, and a tertiary amine accelerator was added at 2wt% of the polythiol.
The materials were mixed uniformly according to the proportions of the examples in Table 2, and after curing for 30 minutes, the mechanical properties were tested, and the specific results are shown in the following Table:
Table 3: performance testing
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The data in Table 3 shows that the preferred examples are 8, 9, 10, 14, 15, 16, with example 15 performing optimally. The comparison of the initial set times of examples 1, 2,3, 5 shows that the first polythiol achieves rapid cure only in the presence of tertiary amine accelerators in the system, while the second polythiol achieves rapid cure due to the tertiary amine structure present in the structure, and the comparison of the hardness data shows that the second polythiol in the bulk structure has a higher hardness than the first polythiol in the linear structure after cure. Comparison of examples 2-5 shows that the hardness of cure is lower when the first polythiol is used alone because the first polythiol is linear and the cured product has less rigid structure after curing with a smaller molecular weight in the system, and that the bond strength is slightly lower when the second polythiol is used alone because the second polythiol is of bulk structure and has a larger molecular weight, and the bulk hardness is higher after mixing with epoxy resin for curing, but the initial setting time is too short and the permeability to the rock is poor due to the higher viscosity of the second polythiol, and the performance differences are not so pronounced when E51, E44 are used alone. Examples 6-13 show that the test performance is improved significantly as the second polythiol content increases in the system, and that the test performance is reduced significantly after 30 parts when the second polythiol content exceeds 20 parts, which shows that the press shear data changes significantly as the second polythiol content increases, and that the highest point is the optimum compounding ratio when the second polythiol content in the system is 20 parts, indicating the ratio of the first polythiol to the second polythiol in example 9. Examples 14-16 demonstrate that the compounding of E51, E44 can have the effect of increasing test performance, but is less pronounced, with the preferred example being example 15.
Compared with comparative example 1, the 30min compression shear strength is improved by 269%, the 30min Shore hardness is improved by 232%, the initial setting time is improved by 31%, and the data comparison shows that under the condition that the initial setting time of the compound of the first polythiol and the second polythiol is not greatly different from that of the commercially available polythiol, the 30min compression shear strength and the 30min Shore hardness are improved obviously, so that the compound of the first polythiol and the second polythiol has obvious advantages compared with the commercially available polythiol.
Compared with the embodiment 3 and the embodiment 4, the embodiment 9 has the advantages that the pressing shearing strength of 30min is improved by 124 percent, 62 percent, the Shore hardness of 30min is improved by 102 percent, the initial setting time is improved by 26.8 percent, and the initial setting time is improved by-329 percent, and the pressing shearing strength of 30min after the first polythiol and the second polythiol are compounded is obviously better than that of the first polythiol and the second polythiol which are independently used; the hardness of the first polythiol is obviously improved compared with that of the second polythiol alone, but the hardness is basically the same as that of the second polythiol alone, because the hardness is improved by the body type molecular structure of the second polythiol, but the improvement effect is not obvious after a certain proportion is reached, the curing time is obviously reduced compared with that of the second polythiol alone, but the compression shearing strength is obviously improved, because the tertiary amine structure which plays a role in promoting the curing is derived from the second polythiol, but when the content of the second polythiol is too high, the curing is too fast, the system viscosity is too high, the permeability of a curing system to a rock plate is influenced, the compression shearing is reduced, and the hardness of the body curing is basically unchanged. The initial setting time is not as fast as it is, and a suitable pot life is required. The complex of the first polythiol and the second polythiol not only has more proper pot life, ensures that the system has enough permeation time, can achieve higher pressing strength in 30 minutes, but also can achieve higher Shore hardness of the body after the system is cured in 30 minutes, thereby fully embodying the superiority of the complex of the first polythiol and the second polythiol.
The epoxy rock plate adhesive for splicing the rock plates can be obtained by bringing the compounding proportion of the optimal embodiment 15 into a preparation method of the component A and the component B.
The preparation method of the component A comprises the following steps:
Step one: preparing premix, namely stirring and dispersing two epoxy resins, a reactive diluent and a first defoamer for 30-60 min by a planetary stirrer under the condition of negative pressure of 0.05-0.1 MPa according to the formula in the table 4 until the two epoxy resins, the reactive diluent and the first defoamer are uniformly mixed to obtain a component A premix;
Step two: and (3) preparing the component A, namely stirring and dispersing the component A premix, the epoxy coupling agent and the pigment and filler for 50-70 min by using a planetary stirrer under the condition of negative pressure of 0.05-0.1 MPa according to the formula in the table 4 until the components are fully stirred and uniformly mixed, so as to obtain the epoxy rock plate adhesive component A.
The preparation method of the component B comprises the following steps:
Step one: preparing premix, namely stirring and dispersing two polythiols, a diluent and a second defoamer for 30-60 min by a planetary stirrer under the condition of negative pressure of 0.05-0.1 MPa according to the formula 4 until the polythiols, the diluent and the second defoamer are uniformly mixed to obtain a component B premix;
Step two: and (3) preparing the component B, namely stirring and dispersing the component B premix, the mercapto coupling agent, the pigment and filler and the wetting and dispersing agent for 50-70 min by using a planetary stirrer under the condition of negative pressure of 0.05-0.1 MPa according to the formula in the table 4 until the components are fully stirred and uniformly mixed, so as to obtain the epoxy rock plate adhesive component B.
The components of the epoxy rock plate adhesive for splicing the rock plates provided by the invention are shown in the following table:
Table 4 epoxy rock laminate adhesive composition formulation
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-Indicating no addition.
Comparative example 2a rock laminate was prepared using polythiol Capcure-CB from new material science and technology co-ltd, in place of the first polythiol and the second polythiol, and adding a tertiary amine accelerator in an amount of 2% of the amount of polythiol and proportioning according to example 7.
Comparative example 3 is a commercially available epoxy-amine-based rock-board glue.
Comparative example 4 commercially available acrylic acid ester rock laminate.
Comparative example 5 commercially available unsaturated resin rock laminate glue.
Comparative example 6 is a commercially available epoxy-polythiol-based rock-board glue.
Examples 17 to 25 and comparative example 2 were prepared in a weight ratio of component A to component B of 1:1, mixing uniformly for performance test, and mixing uniformly according to the recommended proportion of the product in comparative examples 2-6, wherein the test standard is as follows:
Adhesive force test under different conditions, tensile shear strength, flexural modulus of elasticity, impact strength test reference: JC 887-2001. The test stone material selects a rock plate, and the curing time is 30min.
Destructive testing (45 ° corner panel splice): the testing method comprises the following steps: selecting two rock plates with the angle of 45 degrees and the splicing surface size of 10cm x 1cm, cleaning, drying for standby, uniformly coating the mixed rock plate adhesive on the splicing surface for bonding, knocking by a hammer after 30min, and grading according to the damage condition. The failure level is shown in the following table:
Table 5: failure grade
| Grade level | State description |
| Level 1 | The adhesive layer is damaged, and the rock plate is intact |
| Level 2 | Most of the adhesive layers are destroyed, and a small part of the rock plates are destroyed |
| 3 Grade | Half of the glue layer is destroyed and half of the rock plate is destroyed |
| Grade 4 | A small part of the adhesive layer is damaged, and a large part of the rock plate is damaged |
| Grade 5 | The adhesive layer is intact, and the rock plate is damaged |
Odor grade test reference: HGT 4065-2008/adhesive odor evaluation method.
Yellowing resistance, 25 ℃ pot life, curing time, 0 ℃ pot life: refer to GB/T23997-2009 test standard.
Hardness: reference is made to GB 2411-1980 test standard. The test time was 30min after mixing.
Table 6: examples and comparative examples Performance test
Table 7: examples and comparative examples Performance test
Since the epoxy rock-board glue curing speed is too slow, the tensile shear strength, the flexural modulus of elasticity, the impact strength and the Shore hardness data in the table are test data after 7 days.
The data in tables 6 and 7 show that the performance of example 19, example 20 and example 23 are all superior to the commercial products (comparative examples 2-6), the most preferred example being example 23. The epoxy rock plate adhesive for rock plate splicing has obvious advantages in performance indexes such as adhesive force test under different conditions, tensile shear strength, flexural modulus, impact strength (toughness), destructive test (45 DEG angle rock plate splicing) (bonding effect), odor grade (environmental protection), yellowing resistance, 25 ℃ pot life (initial setting time), 0 ℃ pot life (initial setting time), curing time (complete curing time of an adhesive layer), 30min adhesive layer hardness, and the like, and has excellent comprehensive performance and obvious bonding effect.
In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "a particular example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.
It should be noted that in the present application, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. In the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically specified otherwise.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A polythiol having the formula:
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
R2 represents- (CH 2)mN(CH3)2) and m is 1-10.
2. The polythiol of claim 1 wherein:
R1 represents: -CH 2-CH2-CH2 -SH;
R2 represents:
3. A process for preparing the polythiol of claim 1 comprising: reacting (R3O) 3Si(CH2)n SH and (R3O) 3Si(CH2)mN(CH3)2 with a molar ratio of 1:0.8-1.2 in an alcohol solvent at 75-95 ℃ under the catalysis of concentrated hydrochloric acid, and purifying the product to obtain the polythiol of claim 1;
Wherein:
R1 represents- (CH 2)n SH, n is 1-10);
r2 represents- (CH 2)mN(CH3)2, m is 1-10);
R3 represents methyl or ethyl.
4. A polythiol curing agent characterized in that: comprises the following components in percentage by weight of 1-5:1 and a second polythiol; the first polythiol is linear polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups.
5. The polythiol curing agent of claim 4, wherein: the structural formula of the first polythiol is as follows:
The second polythiol is the polythiol of claim 1.
6. The epoxy rock plate adhesive for splicing the rock plates is characterized by comprising a component A and a component B, wherein the epoxy rock plate adhesive comprises the following components in parts by weight:
The component A comprises 100 parts of liquid epoxy resin, 1-5 parts of epoxy silane coupling agent, 1-20 parts of reactive diluent, 10-70 parts of pigment and filler, 0.1-1 part of first defoamer and 0.1-1 part of first wetting dispersant;
The component B comprises 60-115 parts of polythiol curing agent, 1-5 parts of mercapto coupling agent, 1-20 parts of diluent, 40-100 parts of pigment and filler, 0.1-1 part of second defoamer and 0.1-1 part of second wetting dispersant;
the polythiol curing agent comprises the following components in percentage by weight: 1 and a second polythiol; the first polythiol is linear polythiol; the second polythiol is a bulk structure polythiol containing a plurality of tertiary amine groups.
7. The epoxy panel glue for panel splicing according to claim 6, wherein:
the structural formula of the first polythiol is as follows:
The second polythiol is the polythiol of claim 1.
8. The epoxy panel glue for panel splicing according to claim 6, wherein:
the liquid epoxy resin is one or more of E44 and E51;
The epoxy silane coupling agent is one or more of 3- (2, 3-glycidoxy) propyl trimethoxy silane and 3- (2, 3-glycidoxy) propyl methyl diethoxy silane;
The sulfhydryl coupling agent is one or more of 3-mercaptopropyl triethoxysilane and 3-mercaptopropyl trimethoxysilane;
the reactive diluent is one or more of 1,4 butanediol diglycidyl ether and trimethylolpropane triglycidyl ether;
the diluent is one or more of benzyl alcohol and diethylene glycol;
The pigment filler is one or more of whisker silicon, titanium dioxide and hydrophobic fumed silica;
The first defoamer is one or more of a foam breaking polymer solution and a polyether modified methane-based siloxane copolymer solution which do not contain organic silicon;
The second defoaming agent is one or more of solution of foam breaking polymer and polysiloxane and polymethyl alkyl siloxane;
The first wetting dispersant is an alkyl ammonium salt of a high molecular weight copolymer;
The second wetting dispersant is a polyglycol-polyester modified polyolefin imine.
9. The preparation method of the epoxy rock plate adhesive for splicing the rock plates is characterized by comprising the following steps of:
Preparation of component A: uniformly mixing liquid epoxy resin, reactive diluent and first defoamer according to the proportion shown in claim 4 under the negative pressure condition to obtain a first component premix; uniformly mixing the component A premix, the epoxy silane coupling agent and the pigment and filler under the negative pressure condition to obtain a component A;
Preparation of component B: uniformly mixing a polythiol curing agent, a diluent and a second defoamer according to the proportion shown in claim 4 under the negative pressure condition to obtain a component B premix; uniformly mixing the component B premix, the mercapto-terminated coupling agent, the pigment and filler and the wetting dispersant under the negative pressure condition to obtain the component B;
And packaging the component A and the component B respectively.
10. The application method of the epoxy rock plate adhesive for splicing the rock plates is characterized by comprising the following steps of:
the weight ratio is 0.8-1.2: and 1, uniformly mixing the component A and the component B at room temperature, rapidly coating the mixture on a spliced seam of a rock plate, and pressing and curing for 2-5min.
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