A naphthalene-containing polythiol compound, a preparation method and application thereof

Abstract

The application discloses a naphthalene-containing polysulfydryl compound and a preparation method and application thereof. The naphthalene-containing polysulfydryl compound has a general structural formula as shown in the following formula: wherein R 1 , R 2 , R 3 and R 4 are independently selected from one of C1-C5 divalent alkyl groups. The naphthalene-containing polysulfydryl compound is synthesized from 2,7-naphthalenediol which is a low-cost raw material through a multi-step reaction, and the preparation method is simple, low in cost and high in yield, and is suitable for industrial mass production. More importantly, the naphthalene-containing polysulfydryl compound contains a double naphthalene structure and four alkyl mercaptan groups, is a liquid at room temperature and is not easy to hydrolyze, and can be directly used as a curing agent for curing of a resin composition, so that the resin composition can be cured at a low temperature, and the mechanical properties, heat resistance and water resistance of a cured adhesive layer can be effectively improved, and the resin composition composed of the curing agent has a good application prospect in bonding or sealing of electronic components.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis and adhesives, and particularly relates to a naphthalene-containing polysulfide compound and a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the development of electronic devices, electronic circuits need to have better performance to adapt to complex and changeable use environment, which also puts forward higher requirements for adhesive materials. In the assembly and assembly of electronic components, in order to protect the internal integrated circuit chip from the influence of the external environment or to ensure the stability and reliability of the chip operation, regardless of the material of the adherend, a good adhesive strength, heat and humidity resistance and high reliability of the adhesive and sealant are often required.

[0003] The resin composition as an adhesive or sealant usually contains resin and curing agent, because the common resin is generally liquid or semi-solid at room temperature, and needs to be converted to solid state through curing process to realize the adhesion or sealing effect. For example, as one of the common resins, epoxy resin is widely used in the field of electronic packaging due to its various curing modes, high tensile shear strength, high mechanical properties and excellent heat resistance. The epoxy resin can be converted from liquid to solid state under the action of curing agent, but the type of curing agent will directly affect the performance of the cured resin. Among them, the polysulfide compound has multiple mercapto groups, which can react with the epoxy groups or unsaturated groups in the resin at low temperature to form a three-dimensional network structure with high crosslinking density, which is beneficial to realize the low temperature curing of the resin composition, so it has good application prospect in low temperature curing resin system, light curable resin system, light-heat dual curing resin system and other resin systems. However, the polysulfide curing agent used in the above resin systems reported at present generally has the problems of easy crystallization and poor hydrolysis resistance, and the crystallization of the curing agent will reduce the crosslinking density of the cured adhesive, affect the adhesion strength of the adhesive layer, and the easy hydrolysis of the curing agent will lead to poor humidity and heat aging resistance of the adhesive layer prepared by curing, which limits its practical application in the field of electronic assembly.

[0004] Therefore, there is an urgent need for a polysulfide compound with low crystallization temperature, good storage stability and good hydrolysis resistance, which can be used as a curing agent to prepare a resin composition with low temperature curing, high adhesion strength, good humidity and heat resistance and good waterproofness, to meet the application requirements in the field of electronic assembly. SUMMARY

[0005] To solve the above problems, the application provides a naphthalene-containing polysulfydryl compound, a preparation method and application thereof, the naphthalene-containing polysulfydryl compound contains a double naphthalene structure and four alkyl mercaptan groups, is a liquid at room temperature and is not easy to hydrolyze, can be directly used as a curing agent for curing of a resin composition, can realize low-temperature curing of the resin composition, and can effectively improve the mechanical properties, heat resistance and water resistance of a cured adhesive layer, and the resin composition composed of the curing agent has good application prospects in bonding or sealing of electronic components.

[0006] Specifically, the following technical solutions are provided:

[0007] The first aspect of the application provides a naphthalene-containing polysulfydryl compound, which has the general structure as shown below:

[0008]

[0009] wherein R 1 , R 2 , R 3 , R 4 are each independently selected from one of C1-C5 divalent alkyl groups, such as -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, and the like, including but not limited to the above-mentioned divalent alkyl groups.

[0010] The second aspect of the application provides a preparation method of the naphthalene-containing polysulfydryl compound of the first aspect, comprising the following steps:

[0011] S1, reacting 2,7-naphthalenediol with a paraformaldehyde of formula I in the presence of a first base reagent and a first solvent to obtain a first intermediate product of formula II;

[0012] S2, reacting the first intermediate product with a halogenated olefin compound of formula III in the presence of a second base reagent, a phase transfer catalyst and a second solvent to obtain a second intermediate product of formula IV;

[0013] S3, reacting the second intermediate product with thioacetic acid in the presence of a free radical initiator and a third solvent to obtain a third intermediate product of formula V;

[0014] S4, hydrolyzing the third intermediate product in the presence of an acid or a base in a fourth solvent to obtain the naphthalene-containing polysulfydryl compound;

[0015] The structures of the above-mentioned formulas I-V are as follows:

[0016]

[0017] Further, in S1, the first base reagent can be selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, and p-dimethylaminopyridine.

[0018] Further, in S1, the first solvent is preferably water.

[0019] Further, in S1, the temperature of the reaction is preferably 40-50°C.

[0020] Further, in S1, a portion of 2,7-naphthalenediol is first mixed with a portion of the first base reagent for 0.5-1.5 h, then the aqueous solution of paraformaldehyde is added for further reaction for 8-24 h, and finally the remaining portion of 2,7-naphthalenediol and the remaining portion of the base reagent are subjected to condensation reflux reaction for 36-48 h to obtain the first intermediate product; preferably, the molar ratio of the portion of 2,7-naphthalenediol to the remaining portion of 2,7-naphthalenediol is 1:(1-2), for example 1:1.5; and the molar ratio of the portion of the first base reagent to the remaining portion of the base reagent is 1:(0.5-1.5), for example 1:1.

[0021] Further, in S2, the second base reagent can be selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, and p-dimethylaminopyridine; in some preferred embodiments, the first base reagent is potassium carbonate, potassium hydroxide, or sodium hydroxide.

[0022] Further, in S2, the phase transfer catalyst can be selected from one or more of crown ether, onium salt, ammonium salt, sulfonium salt, arsenic salt, polyether, acyclic polyether, and tertiary amine catalyst; in some preferred embodiments, the first phase transfer catalyst is 18-crown-6, triethylamine, or tetrabutylammonium bromide.

[0023] Further, in S2, the second solvent is selected from one or more of acetone, ethyl acetate, tetrahydrofuran, N,N’-dimethylformamide, dichloromethane, dioxane, ethanol, and methanol; in some preferred embodiments, the first solvent is acetone.

[0024] Further, in S2, the temperature of the reaction is preferably 60-90°C, and the reaction time is preferably 6-15 h, for example stirring at 70°C for 12 h.

[0025] Further, in S2, the reaction is carried out under a protective atmosphere, which is nitrogen or inert gas.

[0026] Further, in S3, the radical initiator can be selected from one or more of azo, organic peroxide, and oxidation-reduction initiators; in some preferred embodiments, the radical initiator is azobisisobutyronitrile.

[0027] Further, in S3, the third solvent can be selected from one or more of acetone, ethyl acetate, tetrahydrofuran, N,N'-dimethylformamide, dichloromethane, dioxane, ethanol, and methanol; in some preferred embodiments, the third solvent is tetrahydrofuran.

[0028] Further, in S3, the reaction temperature is preferably 60-90°C, and the reaction time is preferably 15-25h, for example, the reaction is stirred at 65°C for 16h.

[0029] Further, in S3, the reaction is carried out under a protective atmosphere, which is nitrogen or an inert gas.

[0030] Further, in S4, the acid is preferably hydrochloric acid and / or sulfuric acid, and the base is preferably caustic soda, or other acids or bases that can be used to hydrolyze the fourth intermediate product can also be used.

[0031] Further, in S4, the fourth solvent can be selected from one or more of acetone, ethyl acetate, tetrahydrofuran, N,N'-dimethylformamide, dichloromethane, dioxane, ethanol, and methanol.

[0032] Further, in S4, the reaction temperature is preferably 55-95°C, and the reaction time is preferably 25-40h.

[0033] Further, in S4, the reaction is carried out under a protective atmosphere, which is nitrogen or an inert gas.

[0034] The third aspect of the present application provides a resin composition comprising a resin, a curing agent, and a curing accelerator; the curing agent is the naphthalene-containing polysulfydryl compound of the first aspect.

[0035] Further, the resin includes one or more of epoxy resin, photosensitive resin, benzaldehyde compound, olefin with carbon-carbon double bond in the molecule, and acrylate compound.

[0036] Further, when the resin is an epoxy resin, the curing accelerator is an amine.

[0037] Preferably, the resin composition comprises 30-55 parts by mass of epoxy resin, 27-50 parts by mass of naphthalene-containing polysulfydryl compound, and 1-5 parts by mass of amine curing accelerator.

[0038] Further, when the resin is an epoxy resin and a photosensitive resin, the curing agent accelerator is an amine and a free radical photoinitiator, and the curing accelerator comprises an amine and a free radical photoinitiator.

[0039] Preferably, the resin composition comprises 15-30 parts by mass of the epoxy resin, 15-30 parts by mass of the photosensitive resin, 10-25 parts by mass of the naphthalene-containing polythiol compound, 1-5 parts by mass of the free radical photoinitiator, and 1-5 parts by mass of the amine curing accelerator.

[0040] Further, when the resin is a benzaldehyde compound, the curing accelerator is trifluoroacetic acid.

[0041] Preferably, the resin composition comprises 30-55 parts by mass of the benzaldehyde compound, 60-115 parts by mass of the naphthalene-containing polythiol compound, and 1-5 parts by mass of the trifluoroacetic acid.

[0042] Further, when the resin is an olefin compound and / or an acrylate compound having a carbon-carbon double bond in the molecule, the curing accelerator is a free radical photoinitiator.

[0043] Preferably, the resin composition comprises 30-55 parts by mass of the resin, 50-100 parts by mass of the naphthalene-containing polythiol compound, and 1-5 parts by mass of the free radical photoinitiator.

[0044] Further, the amine curing accelerator includes, but is not limited to, PN23, and the free radical photoinitiator includes, but is not limited to, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, 2,2-dimethoxy-2-phenylacetophenone

[0045] The fourth aspect of the present application provides a use of the resin composition of the third aspect in preparing an adhesive or a sealant.

[0046] Compared with the prior art, the present application has the following beneficial effects:

[0047] 1. The present application provides a naphthalene-containing polythiol compound, which has a double naphthalene structure in the molecule, can effectively improve the adhesion between the resin composition containing the naphthalene-containing polythiol compound and the object to be adhered, and is beneficial to improving the flexibility, hydrolysis resistance and aging resistance of the cured adhesive layer; meanwhile, the naphthalene-containing polythiol compound also contains four alkyl mercaptan groups in the molecule, and the cured resin composition has high crosslinking density, which can effectively improve the mechanical properties and heat resistance of the adhesive layer. In addition, when the naphthalene-containing polythiol compound is used as a curing agent of the resin composition, the resin composition can be rapidly cured under low temperature conditions, and the internal stress and shrinkage degree generated during curing are small, water vapor is effectively isolated, and the performance and service life of the electronic product bonded or sealed by the resin composition are improved.

[0048] 2、The naphthalene-containing polysulfydryl compound provided by the application is liquid at normal temperature, has little odor and low viscosity, can be directly used as a curing agent for curing of a resin composition, and does not need to be used in combination with other polysulfydryl compounds; and the compound is not easy to hydrolyze, so that the resin composition cured by the compound has good moisture and heat resistance.

[0049] 3、The naphthalene-containing polysulfydryl compound is prepared by using low-cost 2,7-naphthalenediol as a raw material through a multi-step reaction, the method is simple to operate, controllable and high in yield, can realize low-cost preparation of the polysulfydryl compound, and is suitable for batch production. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 A real object diagram of the naphthalene-containing polysulfydryl compound prepared in Example 1;

[0051] Figure 2 An infrared diagram of the naphthalene-containing polysulfydryl compound prepared in Example 1. DETAILED DESCRIPTION

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0053] The application will be further described below in conjunction with the drawings and specific embodiments, so that those skilled in the art can better understand the application and implement it, but the embodiments are not intended to limit the application.

[0054] Some raw materials used in the following examples and comparative examples are as follows:

[0055]

[0056]

[0057] Example 1

[0058] This embodiment provides preparation of a naphthalene-containing polysulfydryl compound 3,3',3",3"'-((methylenebis(1,2,7-naphthalenetriyl))tetraoxy)tetra(1-propanethiol), and the specific preparation method is as follows:

[0059] (1) 16.02 g of 2,7-naphthalenediol (M = 160.17, 0.1 mol) was placed in a single-necked flask, a solution of 100 mL of water and 4 g of NaOH (0.1 mol) was added, and the reaction was carried out at 45°C for 30 min in an air atmosphere, then 10 mL of a 40% aqueous solution of paraformaldehyde (1.22 mol / 100 mL, 0.12 mol) was added dropwise, and the reaction was continued under the same conditions for 12 h. In addition, 24.03 g (0.15 mol) of 2,7-naphthalenediol and 4 g of NaOH (0.1 mol) were further added to the system, and the reaction was continued under reflux condensation for 72 h to obtain a crude product. Hydrochloric acid was added dropwise to the crude product to adjust the pH to less than 7. The liquid was spin-dried, and then post-treated to obtain the first intermediate product with a yield of 90%.

[0060] (2) 33.24 g of the first intermediate product and 72.6 g of allyl bromide were dissolved in 250 mL of acetone, then 110.6 g of anhydrous potassium carbonate and 5.2 g of 18-crown-6 ether were added, and the reaction was carried out at 70°C for 12 h under stirring in an N2 atmosphere. After filtration, the solvent and excess raw materials in the filtrate were removed by distillation under reduced pressure, and then washed with water and dried to obtain the second intermediate product with a yield of 94%.

[0061] (3) 49.3 g of the second intermediate product and 45.7 g of thioacetic acid were dissolved in 300 mL of tetrahydrofuran, then 3.3 g of azobisisobutyronitrile was added, and the reaction was carried out at 65°C for 16 h under stirring in an N2 atmosphere. After filtration, the solvent and excess raw materials in the filtrate were removed by distillation under reduced pressure, and then washed with water and dried to obtain the third intermediate product with a yield of 80%.

[0062] (4) 79.7 g of the fourth intermediate product and 10 g of concentrated hydrochloric acid were dissolved in 150 mL of tetrahydrofuran and 150 mL of methanol, and the reaction was carried out at 65°C for 33 h under stirring in an N2 atmosphere. After filtration, the solvent and excess raw materials in the filtrate were removed by distillation under reduced pressure, and then washed with water and dried to obtain the naphthalene-containing polysulfide compound with a yield of 88%. The naphthalene-containing polysulfide compound is a liquid at room temperature, is light yellow, has a viscosity of 3.1 Pa·s, and has an infrared spectrum as shown in Figure 1 . Figure 2 .

[0063] Example 2

[0064] The present example provides a heat-curable resin composition comprising the following components by mass fraction: 42 parts of a bisphenol A type epoxy resin jER828, 38 parts of the naphthalene-containing polysulfide compound prepared in Example 1, 3 parts of a latent curing accelerator PN23, 1 part of fumed silica QS-10, 1 part of a stabilizer triisopropyl borate, and 1 part of a silane coupling agent KBM403.

[0065] The above raw materials are mixed uniformly at room temperature, then vacuum defoaming treatment is carried out, and the product is packed into airtight rubber tube to obtain the resin composition.

[0066] Example 3

[0067] The present example provides a thermosetting resin composition, which is different from Example 2 only in that the mass fraction of bisphenol A type epoxy resin jER828 is 30 parts, the mass fraction of naphthalene type polysulfane compound is 27 parts, and the rest is consistent, and the corresponding resin composition is prepared.

[0068] Example 4

[0069] The present example provides a thermosetting resin composition, which is different from Example 2 only in that the mass fraction of bisphenol A type epoxy resin jER828 is 55 parts, the mass fraction of naphthalene type polysulfane compound is 50 parts, and the rest is consistent, and the corresponding resin composition is prepared.

[0070] Example 5

[0071] The present example provides a thermosetting resin composition, which is different from Example 2 only in that the mass fraction of bisphenol A type epoxy resin jER828 is 35 parts, the mass fraction of naphthalene type polysulfane compound is 31 parts, and the rest is consistent, and the corresponding resin composition is prepared.

[0072] Example 6

[0073] The present example provides a thermosetting resin composition, which is different from Example 2 only in that the mass fraction of bisphenol A type epoxy resin jER828 is 50 parts, the mass fraction of naphthalene type polysulfane compound is 45 parts, and the rest is consistent, and the corresponding resin composition is prepared.

[0074] Example 7

[0075] The present example provides a thermosetting resin composition, which is different from Example 2 only in that the mass fraction of bisphenol A type epoxy resin jER828 is 60 parts, the mass fraction of naphthalene type polysulfane compound is 54 parts, and the rest is consistent, and the corresponding resin composition is prepared.

[0076] Example 8

[0077] The present example provides a thermosetting resin composition, which is different from Example 2 only in that the mass fraction of bisphenol A type epoxy resin jER828 is 25 parts, the mass fraction of naphthalene type polysulfane compound is 23 parts, and the rest is consistent, and the corresponding resin composition is prepared.

[0078] Example 9

[0079] The present example provides a photocurable resin composition, which comprises the following components by mass fraction: 42 parts of triallyl isocyanurate, 74 parts of the naphthalene-containing polysulfydryl compound prepared in Example 1, 2 parts of a photoinitiator 2,2-dimethoxy-2-phenylacetophenone, 1 part of fumed silica QS-10, 0.3 parts of a polymerization inhibitor p-hydroxyanisole, and 1 part of a silane coupling agent KBM503.

[0080] The above raw materials are mixed uniformly at room temperature and in the dark, and then subjected to vacuum defoaming treatment. The product is discharged and packaged in black or brown airtight rubber tubes to obtain the resin composition.

[0081] Example 10

[0082] The present example provides a photocurable resin composition, which is different from Example 9 only in that the mass fraction of triallyl isocyanurate is 30 parts, the mass fraction of the naphthalene-containing polysulfydryl compound is 53 parts, and the rest are consistent. The corresponding resin composition is prepared.

[0083] Example 11

[0084] The present example provides a photocurable resin composition, which is different from Example 9 only in that the mass fraction of triallyl isocyanurate is 55 parts, the mass fraction of the naphthalene-containing polysulfydryl compound is 97 parts, and the rest are consistent. The corresponding resin composition is prepared.

[0085] Example 12

[0086] The present example provides a photocurable resin composition, which is different from Example 9 only in that the mass fraction of triallyl isocyanurate is 34 parts, the mass fraction of the naphthalene-containing polysulfydryl compound is 60 parts, and the rest are consistent. The corresponding resin composition is prepared.

[0087] Example 13

[0088] The present example provides a photocurable resin composition, which is different from Example 9 only in that the mass fraction of triallyl isocyanurate is 51 parts, the mass fraction of the naphthalene-containing polysulfydryl compound is 90 parts, and the rest are consistent. The corresponding resin composition is prepared.

[0089] Example 14

[0090] The present example provides a photocurable resin composition, which is different from Example 9 only in that the mass fraction of triallyl isocyanurate is 57 parts, the mass fraction of the naphthalene-containing polysulfydryl compound is 102 parts, and the rest are consistent. The corresponding resin composition is prepared.

[0091] Example 15

[0092] The embodiment provides a photocuring resin composition, which is only different from the embodiment 9 in that the mass fraction of triallyl isocyanurate is 28 parts, the mass fraction of the naphthalene type polysulfydryl compound is 49 parts, and the rest is consistent.

[0093] Embodiment 16

[0094] The embodiment provides a photo-thermal dual-curing resin composition, which comprises the following components in mass fractions: 21 parts of bisphenol A type epoxy resin jER828, 21 parts of photosensitive resin tricyclodecane dimethylol diacrylate, 17 parts of the naphthalene type polysulfydryl compound prepared in the embodiment 1, 1.5 parts of latent curing accelerator PN23, 1 part of free radical photoinitiator (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide, 1 part of fumed silica QS-10, 0.2 parts of stabilizer triisopropyl borate, 0.3 parts of polymerization inhibitor p-hydroxyanisole, and 1 part of silane coupling agent Z-6062.

[0095] The raw materials are uniformly mixed in the dark and at room temperature, and then subjected to defoaming treatment, and the obtained resin composition is discharged and packaged into black or brown airtight rubber tubes.

[0096] Embodiment 17

[0097] The embodiment provides a photo-thermal dual-curing resin composition, which is only different from the embodiment 16 in that the mass fraction of bisphenol A type epoxy resin jER828 is 15 parts, the mass fraction of tricyclodecane dimethylol diacrylate is 15 parts, and the mass fraction of the naphthalene type polysulfydryl compound is 12 parts, and the rest is consistent.

[0098] Embodiment 18

[0099] The embodiment provides a photo-thermal dual-curing resin composition, which is only different from the embodiment 16 in that the mass fraction of bisphenol A type epoxy resin jER828 is 28 parts, the mass fraction of tricyclodecane dimethylol diacrylate is 28 parts, and the mass fraction of the naphthalene type polysulfydryl compound is 23 parts, and the rest is consistent.

[0100] Embodiment 19

[0101] The embodiment provides a photo-thermal dual-curing resin composition, which is only different from the embodiment 16 in that the mass fraction of bisphenol A type epoxy resin jER828 is 17 parts, the mass fraction of tricyclodecane dimethylol diacrylate is 17 parts, and the mass fraction of the naphthalene type polysulfydryl compound is 14 parts, and the rest is consistent.

[0102] Embodiment 20

[0103] The embodiment provides a photo-thermal dual-curing resin composition, which is different from the embodiment 16 only in that the mass fraction of the bisphenol A type epoxy resin jER828 is 26 parts, the mass fraction of the tricyclodecane dimethylol diacrylate is 26 parts, the mass fraction of the naphthalene type polysulfydryl compound is 21 parts, and the rest are consistent, and the corresponding resin composition is prepared.

[0104] Embodiment 21

[0105] The embodiment provides a photo-thermal dual-curing resin composition, which is different from the embodiment 16 only in that the mass fraction of the bisphenol A type epoxy resin jER828 is 11 parts, the mass fraction of the tricyclodecane dimethylol diacrylate is 11 parts, the mass fraction of the naphthalene type polysulfydryl compound is 10 parts, and the rest are consistent, and the corresponding resin composition is prepared.

[0106] Embodiment 22

[0107] The embodiment provides a photo-thermal dual-curing resin composition, which is different from the embodiment 16 only in that the mass fraction of the bisphenol A type epoxy resin jER828 is 31 parts, the mass fraction of the tricyclodecane dimethylol diacrylate is 31 parts, the mass fraction of the naphthalene type polysulfydryl compound is 25 parts, and the rest are consistent, and the corresponding resin composition is prepared.

[0108] Embodiment 23

[0109] The embodiment provides a room-temperature curing resin composition, which comprises the following components in parts by mass: the A component comprises 42 parts of 4-hydroxy-3-methoxybenzaldehyde and 3 parts of trifluoroacetic acid, the B component comprises 87 parts of the naphthalene type polysulfydryl compound prepared in the embodiment 1, 1 part of fumed silica QS-10 and 1 part of silane coupling agent KBM403.

[0110] The raw materials of the A component and the B component are mixed uniformly at normal temperature, and then vacuum degassing treatment is carried out, and the material is discharged and packaged into airtight A and B double tubes, so that the resin composition is obtained.

[0111] Embodiment 24

[0112] The embodiment provides a room-temperature curing resin composition, which is different from the embodiment 23 only in that the mass fraction of the 4-hydroxy-3-methoxybenzaldehyde is 30 parts, the mass fraction of the naphthalene type polysulfydryl compound is 62 parts, and the rest are consistent, and the corresponding resin composition is prepared.

[0113] Embodiment 25

[0114] The present example provides a room temperature curing resin composition, which is identical to that of Example 23 except that the mass fraction of 4-hydroxy-3-methoxybenzaldehyde is 55 parts, the mass fraction of the naphthalene type polysulfϊd compound is 114 parts, and the rest is identical.

[0115] Example 26

[0116] The present example provides a room temperature curing resin composition, which is identical to that of Example 23 except that the mass fraction of 4-hydroxy-3-methoxybenzaldehyde is 35 parts, the mass fraction of the naphthalene type polysulfϊd compound is 73 parts, and the rest is identical.

[0117] Example 27

[0118] The present example provides a room temperature curing resin composition, which is identical to that of Example 23 except that the mass fraction of 4-hydroxy-3-methoxybenzaldehyde is 50 parts, the mass fraction of the naphthalene type polysulfϊd compound is 104 parts, and the rest is identical.

[0119] Example 28

[0120] The present example provides a room temperature curing resin composition, which is identical to that of Example 23 except that the mass fraction of 4-hydroxy-3-methoxybenzaldehyde is 60 parts, the mass fraction of the naphthalene type polysulfϊd compound is 124 parts, and the rest is identical.

[0121] Example 29

[0122] The present example provides a room temperature curing resin composition, which is identical to that of Example 23 except that the mass fraction of 4-hydroxy-3-methoxybenzaldehyde is 25 parts, the mass fraction of the naphthalene type polysulfϊd compound is 52 parts, and the rest is identical.

[0123] Comparative Example 1

[0124] The present comparative example provides a heat curing resin composition, which is identical to that of Example 2 except that an equal amount of a commercial polysulfϊd curing agent, pentaerythritol tetra(3-mercaptopropionate), is used instead of the naphthalene type polysulfϊd compound, and the rest is identical.

[0125] Comparative Example 2

[0126] The present comparative example provides a light curing resin composition, which is identical to that of Example 9 except that an equal amount of a commercial polysulfϊd curing agent, pentaerythritol tetra(3-mercaptopropionate), is used instead of the naphthalene type polysulfϊd compound, and the rest is identical.

[0127] Comparative Example 3

[0128] This comparative example provides a photothermal dual-curing resin composition, which is identical to Example 16 except that an equal amount of a commercial multi-thiol curing agent pentaerythritol tetra(3-mercaptopropionate) is used instead of the naphthalene-containing multi-thiol compound, and the rest is consistent.

[0129] Comparative Example 4

[0130] This comparative example provides a room temperature curing resin composition, which is identical to Example 23 except that a commercial multi-thiol curing agent pentaerythritol tetra(3-mercaptopropionate) is used instead of the naphthalene-containing multi-thiol compound, and the rest is consistent.

[0131] Performance test

[0132] The resin compositions prepared in Examples 2-29 and Comparative Examples 1-4 above were tested for performance, as follows:

[0133] Curing conditions:

[0134] The resin compositions prepared in Examples 2-8 and Comparative Example 1 were extruded from a glue pipe using a dispensing machine, and then cured at 80°C for 60 minutes to obtain the cured samples.

[0135] The resin compositions prepared in Examples 9-15 and Comparative Example 2 were extruded from a glue pipe using a dispensing machine, and then cured by irradiation with a UV light source (wavelength 365 nm, light intensity 1000 mW / cm 2 ) for 15 seconds to obtain the cured samples.

[0136] The resin compositions prepared in Examples 16-22 and Comparative Example 3 were extruded from a glue pipe using a dispensing machine, and then cured by irradiation with a UV light source (wavelength 365 nm, light intensity 1000 mW / cm 2 ) for 5 seconds, followed by curing at 80°C for 60 minutes to obtain the cured samples.

[0137] The resin compositions prepared in Examples 23-29 and Comparative Example 4 were extruded from a double-tube package using a dispensing machine, mixed through a static mixer, and then cured at room temperature for 24 hours to obtain the cured samples.

[0138] (1) Glass transition temperature (°C): The resin composition prepared in the above examples and comparative examples was cured completely, and a sample bar of 50 mm x 10 mm x 1 mm was prepared. The glass transition temperature Tg (°C) of the cured resin composition was determined using a dynamic mechanical analysis tester (DMA) of Q-800 type of TA Instruments, USA, in a temperature range of 30 to 150 °C at a heating rate of 3 °C / min, using nitrogen protection during the test, and at a test frequency of 1 Hz. g

[0139] (2) Adhesion strength (MPa): The resin composition prepared in the above examples and comparative examples was coated on a stainless steel sheet to prepare a test sample, with an adhesive area of 12.5 mm x 25 mm and a thickness of the adhesive layer of 0.1 mm. The test sample was cured, and then the cured sample was pulled apart in opposite directions using a universal testing machine at an ambient temperature of 25 °C. The force value was recorded as the strength (MPa). The cured sample was treated under the conditions of 85 °C / 85% RH / 1000 h, and then the shear adhesion strength (MPa) of the sample at an ambient temperature of 25 °C was tested using a universal testing machine and recorded.

[0140] (3) Tensile strength (MPa): The resin composition prepared in the above examples and comparative examples was prepared into dumbbell-shaped samples, and a sample bar was prepared according to GB / T 1040.2-2006, which was a standard dumbbell-shaped sample bar of type 5B. The test sample was cured, and then the cured sample was subjected to an external force in opposite directions using a universal testing machine. Five sample bars were tested as a group at a tensile speed of 5 mm / min. The breaking force value of the sample was recorded as the strength (MPa).

[0141] (4) Chemical resistance: The resin composition prepared in the above examples and comparative examples was prepared into a block-shaped sample to prepare a test sample. The test sample was cured, and then 40 mg of the cured sample was immersed in a 10 wt% aqueous sodium hydroxide solution at 80 °C for 48 h. The sample was taken out and dried to weigh, and the mass loss rate (%) was calculated.

[0142] The above test results are shown in Table 1 below:

[0143] Table 1

[0144]

[0145]

[0146] ​As shown in Table 1, compared with the different resin composition systems prepared by using commercially available pentaerythritol tetra(3-mercaptopropionate) as the curing agent in Comparative Examples 1-4, the resin compositions prepared by using the naphthalene type polythiol compound as the curing agent in Example 1 (Examples 2, 9, 16, and 24) have obviously better bonding strength, tensile strength, and chemical resistance, and exhibit better wet heat resistance, and can be applied to the bonding or sealing of electronic components as adhesives or sealants, which is beneficial to improving the performance and reliability of electronic products.

[0147] The above examples are only preferred examples for fully illustrating the present application, and the protection scope of the present application is not limited thereto. Any equivalent replacement or transformation made by those skilled in the art based on the present application is within the protection scope of the present application. The protection scope of the present application is subject to the claims.

Claims

1. A naphthalene-containing polythiol compound characterized in that, The naphthalene-containing polysulfide compound has a general structural formula as shown below: ， wherein R 1 , R 2 , R 3 , R 4 are each independently selected from one of C1-C5 divalent alkyl groups.

2. A method for producing the naphthalene-containing polythiol compound according to claim 1, characterized by, The method comprises the following steps: S1, reacting 2,7-naphthalenediol with paraformaldehyde shown in formula I in the presence of a first base reagent and a first solvent to obtain a first intermediate product shown in formula II; S2, reacting the first intermediate product with a halogenated olefin compound shown in formula III in the presence of a second base reagent, a phase transfer catalyst and a second solvent to obtain a second intermediate product shown in formula IV; S3, reacting the second intermediate product with thioacetic acid in the presence of a free radical initiator and a third solvent to obtain a third intermediate product shown in formula V; S4, hydrolyzing the third intermediate product in the presence of an acid or a base in a fourth solvent to obtain the naphthalene-containing polysulfide compound; The structures of the above formulas I-V are as follows: ， 。 3. The preparation method according to claim 2, characterized in that, In S1, at least one of the following characteristics is included: (1) the first base reagent is selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine and p-dimethylaminopyridine; (2) the first solvent is water; (3) the reaction temperature is 40-50 ℃; (4) part of the 2,7-naphthalenediol is mixed with part of the first base reagent for reaction for 0.5-1.5 h, then an aqueous solution of the paraformaldehyde is added for continuous reaction for 8-24 h, finally the remaining part of the 2,7-naphthalenediol and the remaining part of the base reagent are added for condensation reflux reaction for 36-84 h to obtain the first intermediate product.

4. The preparation method according to claim 2, characterized in that, In S2, at least one of the following characteristics is included: (1) the second base reagent is selected from one or more of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine and p-dimethylaminopyridine; (2) the phase transfer catalyst is selected from one or more of crown ether, onium salt, ammonium salt, sulfonium salt, arsenic salt, polyether, acyclic polyether and tertiary amine catalyst; (3) the second solvent is selected from one or more of acetone, ethyl acetate, tetrahydrofuran, N,N'-dimethylformamide, dichloromethane, dioxane, ethanol and methanol; (4) the reaction temperature is 60-90 ℃, and the reaction time is 6-15 h; (5) the reaction is carried out in a protective atmosphere, and the protective atmosphere is nitrogen or inert gas.

5. The preparation method according to claim 2, characterized in that, In S3, at least one of the following characteristics is included: (1) the free radical initiator is selected from one or more of azo, organic peroxide and oxidation-reduction initiators; (2) the third solvent is selected from one or more of acetone, ethyl acetate, tetrahydrofuran, N,N'-dimethylformamide, dichloromethane, dioxane, ethanol and methanol; (3) the reaction temperature is 60-90 ℃, and the reaction time is 15-25 h; (4) the reaction is carried out in a protective atmosphere, and the protective atmosphere is nitrogen or inert gas.

6. The preparation method according to claim 2, characterized in that, In S4, at least one of the following characteristics is included: (1) the acid is hydrochloric acid and / or sulfuric acid, and the base is caustic alkali; (2) the fourth solvent is selected from one or more of acetone, ethyl acetate, tetrahydrofuran, N,N'-dimethylformamide, dichloromethane, dioxane, ethanol and methanol; (3) the reaction temperature is 55-95 ℃, and the reaction time is 25-40 h; (4) the reaction is carried out under a protective atmosphere, and the protective atmosphere is nitrogen or inert gas.

7. A resin composition characterized by comprising: The resin composition comprises a resin, a curing agent and a curing accelerator; the curing agent is the naphthalene-containing polysulfydryl compound according to claim 1.

8. The resin composition according to claim 7, characterized by The resin comprises one or more of an epoxy resin, a photosensitive resin, a benzaldehyde compound, an olefin having a carbon-carbon double bond in the molecule, and an acrylate compound.

9. The resin composition according to claim 8, characterized by When the resin is an epoxy resin, the curing accelerator is an amine, and the resin composition comprises 30-55 parts by mass of the epoxy resin, 27-50 parts by mass of the naphthalene-containing polysulfydryl compound, and 1-5 parts by mass of the amine curing accelerator; When the resin is an epoxy resin and a photosensitive resin, the curing accelerator is an amine and a free radical photoinitiator, and the resin composition comprises 15-30 parts by mass of the epoxy resin, 15-30 parts by mass of the photosensitive resin, 10-25 parts by mass of the naphthalene-containing polysulfydryl compound, 1-5 parts by mass of the free radical photoinitiator, and 1-5 parts by mass of the amine curing accelerator; When the resin is a benzaldehyde compound, the curing accelerator is trifluoroacetic acid, and the resin composition comprises 30-55 parts by mass of the benzaldehyde compound, 60-115 parts by mass of the naphthalene-containing polysulfydryl compound, and 1-5 parts by mass of the trifluoroacetic acid; When the resin is an olefin having a carbon-carbon double bond in the molecule and / or an acrylate compound, the curing accelerator is a free radical photoinitiator, and the resin composition comprises 30-55 parts by mass of the resin, 50-100 parts by mass of the naphthalene-containing polysulfydryl compound, and 1-5 parts by mass of the free radical photoinitiator.

10. Use of the resin composition according to any one of claims 7-9 in the preparation of an adhesive or a sealant.

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