Polyether-type thiol composition and use thereof

Abstract

The present invention belongs to the field of new materials. Provided are a polyether-type thiol composition and the use thereof. The polyether-type thiol composition comprises a polyether-type thiol compound and a compound as represented by formula (1), wherein the polyether-type thiol compound is mainly obtained by means of a reaction between a polyhydric alcohol, a halogenated hydrocarbon and a sulfhydrylization reagent, with the hydroxyl value of the polyhydric alcohol being 300-600 mgKOH / g; and the compound as represented by formula (1) is 0.01%-8% of the total mass of the polyether-type thiol composition. The polyether-type thiol composition can be used independently or used in a mixture with other thiol compounds; and the polyether-type thiol composition and an epoxy resin are cured under the action of an accelerant and an auxiliary agent so as to prepare an adhesive, and the adhesive can be used as a raw material to prepare a sealant. The polyether-type thiol composition can not only achieve rapid curing of an epoxy resin adhesive at room temperature, but can also improve the flexibility of an adhesive system, thereby improving the long-lasting safety of an application scenario of a sealant product in the building industry, thus maintaining the physical and psychological health of a human body for a long time.

Description

A polyether-type thiol composition and its application CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is based on the Chinese patent application with application number 202410703968.4 and application date May 31, 2024, and claims the priority of the Chinese patent application. The entire content of the Chinese patent application is hereby introduced into this application as a reference. Technical Field

[0002] The present invention belongs to the field of new materials, and in particular relates to epoxy adhesives. It provides a polyether-type thiol composition and application thereof. Background Art

[0003] Decoration grouting is an indispensable process for tile laying in the construction industry. With the continuous improvement of people's quality of life and the development of the construction industry, grouting materials have also undergone updates to cement, grout and epoxy grout.

[0004] Currently, the primary caulking agent on the market is epoxy. Epoxy resin caulking agents are thermosetting polymers with excellent bonding, corrosion resistance, insulation, and high strength properties. They are suitable for bonding a variety of metal and non-metal materials and are widely used in engineering and civil engineering. However, epoxy resin, the mainstream caulking agent, is a thermosetting resin and requires a curing agent. Most curing agents are alicyclic amines and polyetheramines. Their disadvantage is that they cure very slowly at low temperatures, requiring elevated temperatures or the addition of large amounts of accelerators. To address this issue, many manufacturers add large amounts of nonylphenol to their formulations as an accelerator and toughening agent. However, after addition, the nonylphenol does not fully participate in the reaction. As the colloid ages, the nonylphenol is slowly released from the colloid, causing serious health hazards and causing the colloid to yellow and lose toughness. Another drawback of epoxy caulking agents is their poor flexibility and tendency to crack, making them difficult to meet market demand. Some manufacturers use too much polyetheramine to toughen the caulking agent, but this will lead to reduced curing efficiency and construction efficiency. Some manufacturers use diluents for toughening, but the hardness and strength of the cured product will be too low. Some manufacturers use physical methods to toughen, which will affect the density and stability after curing.

[0005] Therefore, there is an urgent need in the art for an epoxy adhesive composition that cures quickly, has good flexibility, and is safe and environmentally friendly. Summary of the Invention

[0006] The present invention addresses the gaps in the prior art and provides a polyether thiol composition and its application, wherein the polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1), wherein the polyether thiol compound is mainly obtained by reacting a polyol, a halogenated hydrocarbon, and a thiol-forming agent, wherein the polyol has a hydroxyl value of 300-600 mgKOH / g; and the compound represented by formula (1) accounts for 0.01%-8% of the total mass of the polyether thiol composition. The polyether thiol composition can be cured alone or with other thiol compounds with an epoxy resin under the action of a promoter and an auxiliary agent to prepare an adhesive, and the adhesive can be used as a raw material to prepare a caulking agent. The polyether thiol composition can not only achieve rapid curing of the epoxy resin adhesive at room temperature, but also improve the flexibility of the adhesive system, enhance the long-term safety of the caulking agent product application scenarios in the construction industry, and maintain the physical and mental health of the human body for a long time.

[0007] The specific technical solutions of the present invention are as follows:

[0008] The present invention provides a polyether thiol composition, which comprises a polyether thiol compound and a compound represented by formula (1):

[0009] The compound represented by formula (1) accounts for 0.01-8% of the total mass of the polyether thiol composition; the combination of the two can better control the reaction time and improve the flexibility of the reaction system.

[0010] The standard name of the compound of formula (1) is thietan-3-ol, and its CAS number is 10304-16-2. Preferably, its content in the composition is 0.1-5wt%, more preferably 0.5-3wt%. When the ratio is too low, it cannot shorten the curing time and improve the flexibility. When the ratio is too high, the cross-linking degree of the polymer will be affected due to excessive curing, and the heat in the system cannot be removed, resulting in brittleness of the colloid and affecting its bonding strength.

[0011] The above-mentioned polyether thiol compounds are mainly prepared by the reaction of polyols, halogenated hydrocarbons and thiol-forming agents.

[0012] The polyol has a hydroxyl value of 300-600 mgKOH / g, and can be specifically selected from Yantai Wanhua Chemical's R2302 (hydroxyl value of 550), Bluestar Dongda MN-500 (hydroxyl value of 350), Nantong Chenrun GP-303 (hydroxyl value of 510), and Yinuowei New Materials' C303 (hydroxyl value of 490); the molar ratio of the halogenated hydrocarbon to the polyol is (0.5-6):1, and the halogenated hydrocarbon is epichlorohydrin.

[0013] The thiol-forming agent is selected from one of sodium sulfide, sodium hydrosulfide, thiourea and sodium polysulfide, and the molar ratio of the thiol-forming agent to the halogenated hydrocarbon is (1-9):1.

[0014] Preferably, the catalyst that can be added to the preparation method of the above-mentioned polyether-type thiol compound is selected from one of tin tetrachloride, stannous octoate, and tri-n-butyltin chloride; the amount of the catalyst is 0.05-6% of the mass of the polyol, the reaction temperature of the polyol and the halogenated hydrocarbon is 28-65°C; the reaction time is 3-8h; the protective gas that can be used in the preparation method is selected from one of carbon dioxide, nitrogen, hydrogen sulfide and argon; the phase transfer catalyst that can be used in the preparation method is selected from one of tetrabutylammonium chloride, tetrabutylammonium bromide, polyethylene glycol, and glycerol; the amount of the phase transfer catalyst is 0.5-25% of the mass of the polyol.

[0015] Furthermore, in the preparation method of the polyether thiol compound, the amount of the catalyst is 0.3-5% of the mass of the polyol, the thiolating agent is selected from one of sodium hydrosulfide, sodium polysulfide, and thiourea, the molar ratio of the thiolating agent to the halogenated hydrocarbon is (2-6):1, the reaction temperature of the thiolation reaction is 80-120°C, the reaction pressure is 1-6 MPa, the reaction time is 3-7 hours, the protective gas is nitrogen or hydrogen sulfide, and the phase transfer catalyst is selected from tetrabutylammonium bromide or polyethylene glycol, and the amount is 5-10% of the mass of the polyol.

[0016] After obtaining the above-mentioned polyether thiol composition, the present invention further provides an epoxy adhesive composition, which comprises, by weight, 10-90 parts of the polyether thiol composition, 10-90 parts of the epoxy resin, and 0.1-15 parts of the accelerator.

[0017] Preferably, the contents of the components in the composition are as follows, in parts by weight: 30-60 parts of the liquid polythiol compound, 30-60 parts of the epoxy resin, and 2-9 parts of the accelerator.

[0018] The epoxy resin is selected from one or two of glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, alicyclic epoxy resins, epoxidized olefin epoxy resins, hydantoin epoxy resins, imide epoxy resins, silicone epoxy resins, and organic iron epoxy resins; preferably, it is a combination of one or two of glycidyl ether epoxy resins and glycidyl ester epoxy resins.

[0019] The accelerator is selected from ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,5-diaminopentane, hexamethylenediamine, tetramethylenediamine, trimethylhexamethylenediamine, 2-methyl-1,5-diaminopentane, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylenepropylamine, polyamide, isophoronediamine, N-aminoethylpiperazine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, dicyandiamide, adipic acid dihydrazide, dipropylenetriamine, bis(hexamethylene)triamine, 2,4,6-tris(di methylaminomethylphenol), 2,4,6-tris(dimethylaminomethylphenol) tris(2-ethylhexanoate), 2,4,6-tris(dimethylaminomethylphenol) trioleate, benzyldimethylamine, ethylenediamine, triethanolamine, o-hydroxybenzyldimethylamine, acetylacetonate metal salts, triphenylphosphine and its phosphine salts, active tris(2-ethylhexanoate)chromium, organic acid salt amine complex, 1,8-diaza-bicyclo(5,4,0)-7-undecene, 2-thiolbenzothiazole, thiourea and its derivatives, cycloalkylimidazoline, 2-imidazoline, aromatic tertiary amines containing epoxy groups, phthalate ester accelerators, etc.

[0020] It is preferably selected from 2,4,6-tris(dimethylaminomethylphenol), benzyldimethylamine, ethylenediamine, triethanolamine, o-hydroxybenzyldimethylamine, triphenylphosphine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0021] Compared with the prior art, the epoxy adhesive composition can regulate the reaction time and improve the flexibility of the reaction system due to the addition of the polyether thiol composition; furthermore, the epoxy adhesive composition can be used as the main raw material of a caulking agent.

[0022] In summary, the present invention provides a polyether thiol composition, and further provides an epoxy adhesive composition, which can not only achieve rapid curing of epoxy resin adhesives at room temperature, but also shorten the gel time to 2-4 minutes, which is significantly reduced compared to the curing time of 5-6 minutes of existing thiol compounds at room temperature; at the same time, it can also improve the flexibility of the adhesive system, enhance the long-term safety of the application scenarios of caulking agent products in the construction industry, and maintain the physical and mental health of the human body for a long time. When the content of compound (2) is within the specified range of the present invention, the synthesized adhesive material can be rapidly cured at room temperature, has good flexibility, and has no cracks or creases on the bent surface; the obtained epoxy resin adhesive has a tensile strength of ≥50MPa and a shear strength of ≥6MPa.

[0023] When the content of compound (1) is below the specified range of the present invention, the adhesive material will cure slowly and have poor flexibility. When the content of compound (1) exceeds the specified range of the present invention, the adhesive material will cure too quickly, affecting the cross-linking degree of the polymer, thereby causing the colloid to become brittle and affecting its bonding strength. DETAILED DESCRIPTION

[0024] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0025] The detection methods in the following embodiments are exemplified as follows:

[0026] 1. Determination of gel time

[0027] Weigh all ingredients, put them into a plastic cup, mix and stir with a glass rod for 30 seconds, and then cure them in a laboratory controlled at 25% and 50% RH. Observe the reaction process visually and touch the outside of the plastic cup with your finger during the process to record the time it takes for the liquid to gel.

[0028] 2. Flexibility of the rubber strip

[0029] The adhesive sample was prepared into an adhesive strip with a diameter of 6 mm ± 0.2 mm, and after curing at room temperature for 72 hours, the adhesive strip was bent 30 times at 150 degrees, and the surface of the adhesive strip was observed.

[0030] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0031] 150 g of polyol (R2302 from Yantai Wanhua Chemical) and 0.74 g of SnCl4·5H2O catalyst were added to a reaction vessel. 177 g of epichlorohydrin (99.5%) was slowly added dropwise at 60°C for 5 h. Then, 292 g of NaHS solution (44 wt%) and 14 g of tetrabutylammonium chloride were added in sequence. Protective H2S gas (pressure 0.5 MPa) was introduced, and the reaction was maintained at 100°C for 5 h.

[0032] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5, stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 275.00 g of polyether thiol compound was obtained by rotary evaporation.

[0033] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 0.01% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained. Example 2

[0034] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0035] To a reaction vessel, 150g of polyol (Bluestar Dongda MN-500) and 1.15g of stannous octoate catalyst were added. 114g of epichlorohydrin (99.5%) was slowly added dropwise at 50°C for approximately 6 hours. 256g of NaHS solution (32wt%) and 16g of glycerol were then added sequentially. N2 protective gas (0.6 MPa) was introduced, and the reaction was maintained at 90°C for 7 hours.

[0036] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 273.00 g of a polyether thiol compound was obtained by rotary evaporation.

[0037] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 8% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained.

[0038] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0039] To a reaction vessel, add 150g of polyol (Nantong Chenrun GP-303) and 1.48g of tributyltin chloride catalyst. Slowly add 165g of epichlorohydrin (99.5%) dropwise at 50°C for 7 hours. Then, add 361g of NaHS solution (33wt%) and 25g of tetrabutylammonium bromide, followed by H2S protective gas (0.3 MPa). The reaction is maintained at 110°C for 3 hours.

[0040] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 278.00 g of a polyether thiol compound was obtained by rotary evaporation.

[0041] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 0.1% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained.

[0042] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0043] 150g of polyol (Yinowei New Material C303) and 0.58g of catalyst SnCl4·5H2O were added to the reaction vessel. 159g of epichlorohydrin (99.5%) was slowly added dropwise to the bottle at 55°C for about 5 hours. After the addition was complete, the temperature was raised to 60°C and kept warm for 2 hours. 358.27g of NaHS solution (32wt%) and 13.7g of tetrabutylammonium chloride were added in sequence. Protective CO2 gas (pressure 0.6MPa) was introduced and the reaction was kept warm at 120°C for 3 hours.

[0044] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 268.00 g of a polyether thiol compound was obtained by rotary evaporation.

[0045] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 5% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained. Example 5

[0046] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0047] A reaction vessel was charged with 150g of polyol (R2302 from Yantai Wanhua Chemical) and 0.74g of SnCl4·5H2O catalyst. 177.72g of epichlorohydrin (99.5%) was slowly added dropwise at 60°C for approximately 3.5 hours. 292g of NaHS solution (44wt%) and 15g of tetrabutylammonium chloride were then added sequentially. H2S protective gas (pressure 0.5 MPa) was introduced, and the reaction was maintained at 100°C for 5 hours.

[0048] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 277.1 g of a polyether thiol compound was obtained by rotary evaporation.

[0049] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 0.5% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained. Example 6

[0050] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0051] A reaction vessel was charged with 150g of polyol (R2302 from Yantai Wanhua Chemical) and 0.74g of SnCl4·5H2O catalyst. 177.73g of epichlorohydrin (99.5%) was slowly added dropwise at 65°C for approximately 4 hours. 291.97g of NaHS solution (44wt%) and 15g of tetrabutylammonium chloride were then added. H2S protective gas (pressure 0.5 MPa) was introduced, and the reaction was maintained at 100°C for 5 hours.

[0052] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 277.08 g of a polyether thiol compound was obtained by rotary evaporation.

[0053] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 3% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained.

[0054] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0055] To a reaction vessel, 150g of polyol (Bluestar Dongda MN-500) and 1.15g of stannous octoate catalyst were added. 114g of epichlorohydrin (99.5%) was slowly added dropwise at 50°C for approximately 6 hours. 256g of NaHS solution (32wt%) and 16g of glycerol were then added sequentially. N2 protective gas (0.6 MPa) was introduced, and the reaction was maintained at 90°C for 7 hours.

[0056] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 277.34 g of a polyether thiol compound was obtained by rotary evaporation.

[0057] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 0.005% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained.

[0058] A polyether thiol composition comprises a polyether thiol compound and a compound represented by formula (1); the preparation method of the polyether thiol compound is as follows:

[0059] 150g of polyol (Yinowei New Material C303) and 0.58g of catalyst SnCl4·5H2O were added to the reaction vessel. 159g of epichlorohydrin (99.5%) was slowly added dropwise to the bottle at 55°C for about 5 hours. After the addition was complete, the temperature was raised to 60°C and kept warm for 2 hours. 358.27g of NaHS solution (32wt%) and 13.7g of tetrabutylammonium chloride were added in sequence. Protective CO2 gas (pressure 0.6MPa) was introduced and the reaction was kept warm at 120°C for 3 hours.

[0060] After the reaction, the aqueous phase was removed, 600 g of water was added to the organic phase, and then dilute sulfuric acid was added to adjust the pH to 3-5. The mixture was stirred for 5 hours, allowed to stand for separation, and then 600 g of water was added to the organic phase, washed with water for 5 hours, separated, and 277.31 g of a polyether thiol compound was obtained by rotary evaporation.

[0061] The compound represented by formula (1) is added to the above polyether thiol compound so that it accounts for 10% of the total mass of the polyether thiol composition; the target polyether thiol composition is obtained.

[0062] A polyether thiol composition comprising only a polyether thiol compound, wherein the preparation method of the polyether thiol compound is as follows:

[0063] Add 150g of polyol (Yinowei New Material C303) 343 and 0.58g of catalyst SnCl4·5H2O to the reaction vessel, and slowly add 159g of epichlorohydrin (99.5%) dropwise to the bottle at 55°C for about 5 hours. After the addition is complete, raise the temperature to 60°C and keep it for 2 hours. Then, add 358.27g of NaHS solution (32wt%) and 13.7g of tetrabutylammonium chloride in sequence. Fill with protective gas CO2 (pressure 0.6MPa) and keep the reaction at 120°C for 3 hours.

[0064] After the reaction is completed, the aqueous phase is removed, 600 g of water is added to the organic phase, and then dilute sulfuric acid is added to adjust the pH to 3-5, stirred for 5 hours, allowed to stand for separation, and then 600 g of water is added to the organic phase, washed with water for 5 hours, separated, and 277.39 g of a polyether thiol compound is obtained by rotary evaporation. Application Example 1

[0065] At 25°C and 50% RH, 50 g of the polyether thiol composition obtained in Example 1 and 2.5 g of 2,4,6-tris(dimethylaminomethylphenol) were mixed, and 50 g of epoxy resin E51 was added. The mixture was premixed with a spatula for 30 seconds, and the reaction process was visually observed. During this process, the plastic cup was touched with a finger from the outside to record the time it took for the liquid to turn into a gel.

[0066] At 25°C and 50% RH, 50g of the polyether thiol composition obtained in Example 1 was mixed with 2.5g of 2,4,6-tris(dimethylaminomethylphenol), and 50g of epoxy resin E51 was added. The mixture was pre-mixed with a spatula for 30 seconds, and then degassed and poured into a mold to prepare a rubber strip with a diameter of 6mm±0.2mm. The strip was cured at room temperature for 72 hours and then demolded. The strip was then bent 150° 30 times and the surface of the strip was observed. Application Examples 2-6

[0067] Other conditions remained unchanged, the polyether thiol composition in Application Example 1 was replaced with the polyether thiol composition obtained in Examples 2-6, and the types and amounts of epoxy resin and accelerator remained unchanged, and gelation time and flexibility tests were performed respectively. Application Examples 7-10

[0068] According to the operating scheme of Application Example 5, the epoxy resins were replaced in the order of the examples: E51, E44, E51, E44; the accelerators were replaced in the order of the examples: benzyldimethylamine, benzyldimethylamine, diethylenetriamine, triethylenetetramine, and the gelation time and flexibility tests were carried out respectively. Application Comparative Examples 1-3

[0069] Other conditions remain unchanged, the polyether thiol composition in Application Example 1 is replaced by the polyether thiol composition obtained in Comparative Examples 1-3, and the types and amounts of epoxy resin and accelerator remain unchanged, and gelation time and flexibility tests are performed respectively.

[0070] Other conditions remained unchanged, the polyether thiol composition in Application Example 1 was replaced by a polyether thiol compound + 0.01 wt % dibutyl phthalate, and the types and amounts of the epoxy resin and accelerator remained unchanged, and gel time and flexibility tests were performed respectively.

[0071] The final product performance of each embodiment and comparative example is shown in the table below:

[0072] As can be seen from the table above, different contents of Formula 1 in Application Examples 1-6 result in different curing times. However, regardless of the combination, as long as the content of Formula 1 is controlled within the range specified in the specification, the curing time can be controlled within 2-4 minutes, which is significantly reduced compared to the curing time of 5-6 minutes of existing thiol compounds at room temperature.

[0073] The optimal content of Formula 1 was selected by using Examples 7-10, and then the component types in the formula were adjusted. The results showed that for different epoxy resins and accelerators, the corresponding polyether thiol compositions could achieve the expected effects.

[0074] From Comparative Examples 1-3, it can be seen that when the content of Formula 1 is lower than the lower limit in the specification, the curing time is prolonged and the flexibility of the product is affected. When its content is higher than the upper limit, although the curing time is further shortened, its flexibility is also affected. When it is not added directly, the curing time is further prolonged and its flexibility is poor. Therefore, the best choice is that the compound represented by Formula (1) accounts for 0.01-8% of the total mass of the polyether thiol composition.

[0075] It can be seen from Comparative Example 4 that, when a toughening agent commonly used in the epoxy field is used, although the toughness of the system can be improved, segregation will occur over time, affecting the use effect.

[0076] The above embodiments enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest possible manner consistent with the principles and novel features disclosed herein.

Claims

1. A polyether thiol composition, characterized in that It includes a polyether type thiol compound and a compound represented by formula (1): The polyether thiol compound is obtained by reacting a polyol, a halogenated hydrocarbon and a thiol-forming agent, wherein the hydroxyl value of the polyol is 300-600 mgKOH / g; The compound represented by formula (1) accounts for 0.01-8% of the total mass of the polyether thiol composition.

2. The polyether thiol composition according to claim 1, characterized in that: The content of the compound of formula (1) in the composition is 0.1-5 wt%.

3. The polyether thiol composition according to claim 1 or 2, characterized in that: The content of the compound of formula (1) in the composition is 0.5-3 wt%.

4. An epoxy adhesive composition comprising the polyether thiol composition according to any one of claims 1 to 3, characterized in that: The composition of the invention is as follows in parts by weight: 10-90 parts of a polyether type thiol composition, 10-90 parts of an epoxy resin and 0.1-15 parts of an accelerator.

5. The epoxy adhesive composition according to claim 4, characterized in that: The composition is calculated by weight as follows: 30-60 parts of polyether thiol composition, 30-60 parts of epoxy resin, and 2-9 parts of accelerator.

6. The epoxy adhesive composition according to claim 4 or 5, characterized in that: The epoxy resin is selected from one or two of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxidized olefin epoxy resin, hydantoin epoxy resin, imide epoxy resin, silicone epoxy resin and organoferric epoxy resin.

7. The epoxy adhesive composition according to claim 4 or 5, characterized in that: The accelerator is selected from ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,5-diaminopentane, hexamethylenediamine, tetramethylenediamine, trimethylhexamethylenediamine, 2-methyl-1,5-diaminopentane, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylenepropylamine, polyamide, isophoronediamine, N-aminoethylpiperazine, meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, meta-phenylenediamine, dicyandiamide, adipic acid dihydrazide, dipropylenetriamine, bis(hexamethylene)triamine, 2,4,6-tri(dimethylamino) The invention relates to one of the following agents: 1,2-dimethyl-2-nitro-1-nitro-2-nitro-2-nitro-3-ol; 2,4,6-tris(dimethylaminomethylphenol) tris(2-ethylhexanoate) salt; 2,4,6-tris(dimethylaminomethylphenol) trioleate; benzyldimethylamine; ethylenediamine; triethanolamine; o-hydroxybenzyldimethylamine; acetylacetone metal salt; triphenylphosphine and its phosphonate; active tris(2-ethylhexanoate) chromium; organic acid salt amine complex; 1,8-diaza-bicyclo(5,4,0)-7-undecene; 2-thiolbenzothiazole; thiourea and its derivatives; cycloalkylimidazoline; 2-imidazoline; aromatic tertiary amine containing epoxy group; and phthalate accelerator.

8. The epoxy adhesive composition according to claim 4 or 5, characterized in that: The epoxy resin is selected from one or a combination of glycidyl ether epoxy resin and glycidyl ester epoxy resin; the accelerator is selected from one of 2,4,6-tris(dimethylaminomethylphenol), benzyldimethylamine, ethylenediamine, triethanolamine, o-hydroxybenzyldimethylamine, triphenylphosphine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

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