Two-component silicone sealant and method for producing the same

Abstract

The application discloses a two-component silicone sealant and a preparation method thereof. The two-component silicone sealant is prepared by mixing component A and component B at a mass ratio of 1:1. Raw materials of component A are as follows: base glue A 100 parts; filler 100-200 parts; curing accelerator 5-10 parts; and hydroxyl scavenger 0.8-2 parts. Raw materials of component B are as follows: base glue B 100 parts; active nano calcium carbonate 80-160 parts; hydroxyl scavenger 0.8-2 parts; crosslinking agent 8-20 parts; coupling agent 2-8 parts; and catalyst 0.1-0.5 parts. Base glue A is prepared by compounding alpha, omega-dihydroxy polydimethylsiloxane and alpha, omega-dihydroxy polydimethyl diphenyl siloxane. Base glue B is prepared by compounding alkoxyl-terminated polydimethylsiloxane and methyl phenyl silicone oil. The two-component silicone sealant has the advantages of storage stability, high initial strength and elongation at break, more than 90% retention rate after baking at 300 DEG C for 7 days, good adhesion to a base material and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silicone sealant, in particular to a two-component silicone sealant and a preparation method thereof. BACKGROUND

[0002] The silicone sealant is widely used in the fields of photovoltaic, building, electronic and electrical appliances, rail transit, and automobile industry for bonding and sealing by absorbing moisture in the air, cross-linking and curing into a high polymer with excellent performance, and is an indispensable high polymer material in today's society. According to the packaging form, the silicone sealant can be divided into single-component and two-component. In the two-component, due to the presence of trace amount of moisture in the A component, the A and B components can achieve deep curing effect in a short time after mixing, which greatly improves the transfer efficiency between processes. At present, the mature two-component silicone sealant products on the market are mostly dealcoholized, which have poor storage performance and do not have high temperature resistance, and the adhesion to the substrate is also not as good as that of oxime type glue. Therefore, it is of great significance to develop a two-component product with high temperature resistance and rapid curing in a short time. SUMMARY

[0003] In view of the above-mentioned deficiencies existing at present, the present application provides a two-component silicone sealant and a preparation method thereof, which has the advantages of storage stability, high initial strength and elongation at break, more than 90% retention rate after 300℃ baking for 7 days, good adhesion to the substrate, and low precision requirement for the glue gun.

[0004] In order to achieve the above-mentioned purpose, the present application provides a two-component silicone sealant, which is prepared by mixing A component and B component in a mass ratio of 1:1; according to the mass fraction,

[0005] The raw material composition of the A component is as follows:

[0006]

[0007] The raw material composition of the B component is as follows:

[0008]

[0009]

[0010] The base glue A is compounded by α, ω-dihydroxy polydimethylsiloxane and α, ω-dihydroxy polydimethyl diphenyl siloxane.

[0011] According to one aspect of the present application, the mass ratio of the α, ω-dihydroxy polydimethylsiloxane and the α, ω-dihydroxy polydimethyl diphenyl siloxane is 1:1-5:1.

[0012] According to an aspect of the present application, the base glue B is compounded by alkoxy-terminated polydimethylsiloxane and methyl phenyl silicone oil.

[0013] According to an aspect of the present application, the mass ratio of the alkoxy-terminated polydimethylsiloxane and the methyl phenyl silicone oil is 1:1-5:1.

[0014] According to an aspect of the present application, the viscosity of the α, ω-dihydroxy polydimethylsiloxane at 25℃ is 1000-50000 cp; the mole fraction of phenyl linkage in the α, ω-dihydroxy polydimethylsiloxane is 5%-30%, and the viscosity of the α, ω-dihydroxy polydimethylsiloxane at 25℃ is 5000-80000 cp.

[0015] According to an aspect of the present application, the filler is composed of active nano calcium carbonate and nano iron oxide; the mass ratio of the active nano calcium carbonate and the nano iron oxide is 1:1-5:1.

[0016] According to an aspect of the present application, the particle size of the active nano calcium carbonate is 10-50 nm, and the active nano calcium carbonate is obtained by surface treatment of nano calcium carbonate with a modifier; the modifier is one or more of stearic acid, silazane, silane coupling agent and titanate coupling agent; the particle size of the nano iron oxide is 10-60 nm.

[0017] According to an aspect of the present application, the viscosity of the alkoxy-terminated polydimethylsiloxane at 25℃ is 1000-50000 cp; the mole fraction of phenyl linkage in the methyl phenyl silicone oil is 10%-60%, and the viscosity of the methyl phenyl silicone oil at 25℃ is 1500-20000 cp.

[0018] According to one aspect of the present application, the curing promoter is at least one of sodium aluminum silicate, magnesium aluminum silicate, magnesium sulfate, calcium chloride; the hydroxyl scavenger is hexamethyldisilazane; the crosslinking agent is at least one of phenyltributanoxysilane, methyltributanoxysilane, vinyltributanoxysilane, tetrabutanoxysilane, methylvinyl dibutanoxysilane, methyltripropanoxysilane; the coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-aminoethyl-gamma-aminopropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane, bis(3-trimethoxysilylpropyl) amine, 3-(2,3-epoxypropoxy) propyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane; and the catalyst is at least one of dibutyl tin dilaurate, dioctyl tin dilaurate, hydroxydimethyl tin, dimethyl tin dinipecotate, dibutyl tin diacetate, and dibutyl tin diisooctyl maleate.

[0019] Based on the same inventive concept, the present application also provides a preparation method of the two-component silicone sealant, comprising the following steps:

[0020] S1, adding alpha, omega-dihydroxy polydimethylsiloxane and alpha, omega-dihydroxy polydimethyl diphenyl siloxane into a planetary machine and stirring for 10-20 min to obtain base glue A;

[0021] S2, sequentially adding fillers, a curing promoter and a hydroxyl scavenger into the base glue A, stirring for 20-40 min under a vacuum degree of -0.090 Mpa to remove bubbles, and obtaining component A;

[0022] S3, adding alkoxyl-terminated polydimethylsiloxane and methylphenyl silicone oil into a kneader, stirring for 10-20 min under a vacuum degree of -0.090 Mpa to obtain base glue B;

[0023] S4, adding active nano calcium carbonate into the base glue B, dehydrating and stirring for 90-150 min at a temperature of 100-150 DEG C and a vacuum degree of -0.090 Mpa by using a kneader, and cooling to room temperature; sequentially adding a hydroxyl scavenger, a crosslinking agent, a coupling agent and a catalyst into the cooled base glue B and the active nano calcium carbonate, stirring for 60-150 min under a vacuum degree of -0.090 Mpa by using a planetary machine, discharging and sealing to obtain component B;

[0024] S5, mixing component A and component B according to a mass ratio of 1:1 to obtain the two-component silicone sealant.

[0025] The present application has the following beneficial effects:

[0026] The two-component silicone sealant of the present application uses alpha, omega-dihydroxypolydimethyl diphenyl siloxane with phenyl groups and methyl phenyl silicone oil, and is prepared by certain formula design through matching alpha, omega-dihydroxypolydimethyl siloxane, alkoxyl-terminated polydimethyl siloxane, active nano calcium carbonate, nano iron oxide, and curing accelerators, hydroxyl scavengers, cross-linking agents, coupling agents, and catalysts, and has good temperature resistance, mechanical properties and storage performance. Compared with the common dealcoholized two-component silicone glue on the market, the present application is dealcoholized, has high storage stability, initial strength and elongation at break, more than 90% retention rate after 300 DEG C baking for 7 days, good adhesion to the substrate and other characteristics. The mixing ratio of the present application is 1:1, the precision requirement of the glue machine is low after application to the market, the performance fluctuation of the mixed AB components is small, and the stability of the product is good. DETAILED DESCRIPTION

[0027] In order to make the present application easier to understand, the present application is further described below in combination with specific examples. It should be understood that these examples are only used to illustrate the present application and are not used to limit the scope of the present application. Obviously, the described examples are only a part of the examples of the present application, but not all the examples. Based on the examples in the present application, all other examples obtained by those skilled in the art without creative labor are within the scope of protection of the present application. Unless otherwise defined, the professional terms used below are consistent with the meanings understood by those skilled in the art; unless otherwise specified, the raw materials and reagents involved in the present application can be purchased from the market or prepared by known methods.

[0028] Example 1

[0029] A two-component silicone sealant is prepared by mixing A component and B component in a mass ratio of 1:1; according to weight fraction,

[0030] A component:

[0031] Base glue A:

[0032] Alpha, omega-dihydroxypolydimethyl siloxane, 20000 cp, 50 parts;

[0033] Alpha, omega-dihydroxypolydimethyl diphenyl siloxane, 20000 cp, 50 parts;

[0034] Filler:

[0035] Active nano calcium carbonate, 20 nm, 70 parts;

[0036] Nano iron oxide, 15 nm, 70 parts;

[0037] Curing accelerator: sodium aluminum silicate, 6 parts;

[0038] Hydroxyl scavenger: hexamethyldisilazane, 1 part.

[0039] B component:

[0040] Base glue B:

[0041] Alkoxyl terminated polydimethylsiloxane, 20000 cp, 80 parts;

[0042] Methyl phenyl silicone oil, 5000 cp, 20 parts;

[0043] Active nano calcium carbonate: 20 nm, 140 parts;

[0044] Hydroxyl scavenger: hexamethyldisilazane, 1 part;

[0045] Crosslinking agent:

[0046] Vinyl tributanone oxime silane, 4 parts;

[0047] Methyl tributanone oxime silane, 13 parts;

[0048] Coupling agent:

[0049] N-aminoethyl-gamma-aminopropyl trimethoxysilane, 3.5 parts;

[0050] 3-(2,3-epoxypropoxy) propyl trimethoxysilane, 1.5 parts;

[0051] Catalyst: di-n-butyl tin diacetate, 0.2 parts.

[0052] A preparation method of a two-component silicone sealant, comprising the following steps:

[0053] 50 parts of α, ω-dihydroxy polydimethylsiloxane with a viscosity of 20000 cp and 50 parts of α, ω-dihydroxy polydimethylphenylsiloxane with a viscosity of 20000 cp and a phenyl chain molar fraction of 5% are added to a planetary machine and stirred for 10 min to obtain base glue A; 70 parts of active nano calcium carbonate with a particle size of 20 nm and treated with stearic acid and titanate coupling agent and 70 parts of nano iron oxide with a particle size of 15 nm, 6 parts of sodium aluminum silicate and 1 part of hexamethyldisilazane are added to base glue A, stirred for 30 min under a vacuum degree of -0.090 Mpa and the bubbles are removed to obtain component A.

[0054] 80 parts of alkoxyl terminated polydimethylsiloxane with viscosity of 20000 cp and 20 parts of methyl phenyl silicone oil with viscosity of 5000 cp and phenyl linkage mole fraction of 30% were added into a kneader, stirred for 15 min under vacuum degree of -0.090 Mpa, to obtain base glue B; 140 parts of active nano calcium carbonate with particle size of 20 nm and treated by stearic acid and titanate coupling agent were added into base glue B, dehydrated and stirred for 130 min at temperature of 130 °C and vacuum degree of -0.090 Mpa by a kneader, and cooled to room temperature. 1 part of hexamethyldisilazane, 4 parts of vinyl tributanone oxime silane, 13 parts of methyl tributanone oxime silane, 3.5 parts of N-aminoethyl-γ-aminopropyl trimethoxysilane, 1.5 parts of 3-(2,3-epoxypropoxy) propyl trimethoxysilane and 0.2 parts of di-n-butyl tin diacetate were added into the above cooled base glue B and active nano calcium carbonate step by step in sequence, stirred for 130 min under vacuum degree of -0.090 Mpa by using a planetary machine, discharged and sealed to store, to obtain component B.

[0055] During construction, the component A and the component B can be mixed uniformly by a glue injection equipment according to mass ratio of 1:1.

[0056] Example 2

[0057] A two-component silicone sealant was prepared by mixing component A and component B according to mass ratio of 1:1; according to weight fraction,

[0058] Component A:

[0059] Base glue A:

[0060] α, ω-dihydroxyl polydimethylsiloxane, 15000 cp, 60 parts;

[0061] α, ω-dihydroxyl polydimethyl diphenyl siloxane, 30000 cp, 40 parts;

[0062] Filler:

[0063] Active nano calcium carbonate, 25 nm, 90 parts;

[0064] Nano iron oxide, 20 nm, 50 parts;

[0065] Curing accelerator: magnesium aluminum silicate, 5 parts;

[0066] Hydroxyl scavenger: hexamethyldisilazane, 1 part.

[0067] Component B:

[0068] Base glue B:

[0069] Alkoxyl terminated polydimethylsiloxane, 15000 cp, 75 parts;

[0070] Methylphenyl silicone oil, 3000 cp, 25 parts;

[0071] Active nano calcium carbonate: 25 nm, 140 parts;

[0072] Hydroxyl scavenger: hexamethyldisilazane, 1.5 parts;

[0073] Crosslinking agent:

[0074] Methyltributanoxysilane, 5 parts;

[0075] Tetrabutanoxysilane, 13 parts;

[0076] Coupling agent:

[0077] Bis(3-trimethoxysilylpropyl)amine, 3.5 parts;

[0078] 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 1.5 parts;

[0079] Catalyst: dibutyl tin dilaurate, 0.25 parts.

[0080] A preparation method of a two-component silicone sealant, comprising the following steps:

[0081] 60 parts of α, ω-dihydroxypolydimethylsiloxane with a viscosity of 15000 cp and 40 parts of α, ω-dihydroxypolydimethylphenylsiloxane with a viscosity of 30000 cp and a phenyl chain linkage mole fraction of 10% are added to a planetary machine and stirred for 15 min to obtain base glue A; 90 parts of active nano calcium carbonate with a particle size of 25 nm and treated with stearic acid and titanate coupling agent and 50 parts of nano iron oxide with a particle size of 20 nm, 5 parts of magnesium aluminum silicate and 1 part of hexamethyldisilazane are added to the base glue A, stirred for 30 min under a vacuum degree of -0.090 Mpa and the bubbles are removed to obtain component A.

[0082] Put 75 parts of alkoxy-terminated polydimethylsiloxane with viscosity of 15000 cp and 25 parts of methylphenyl silicone oil with viscosity of 3000 cp and phenyl chain linkage mole fraction of 35% into a kneader, stir for 10 min under vacuum degree of -0.090 Mpa, to obtain base glue B; put 140 parts of active nano calcium carbonate with particle size of 25 nm and treated by stearic acid and titanate coupling agent into base glue B, dehydrate and stir for 120 min at temperature of 120°C and vacuum degree of -0.090 Mpa by a kneader, and cool to room temperature. Step by step, add 1.5 parts of hexamethyldisilazane, 5 parts of methyltributylketoximosilane, 13 parts of tetrabutylketoximosilane, 3.5 parts of bis(3-trimethoxysilylpropyl)amine, 1.5 parts of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 0.25 parts of dibutyltin dilaurate into the above cooled base glue B and active nano calcium carbonate, stir for 120 min under vacuum degree of -0.090 Mpa by using a planetary machine, discharge and seal to preserve, to obtain component B.

[0083] During construction, mix component A and component B uniformly by a glue injection equipment according to mass ratio of 1:1.

[0084] Example 3

[0085] A two-component silicone sealant is prepared by mixing component A and component B according to mass ratio of 1:1; according to weight fraction,

[0086] Component A:

[0087] Base glue A:

[0088] α, ω-dihydroxypolydimethylsiloxane, 12000 cp, 70 parts;

[0089] α, ω-dihydroxypolydimethylphenylsiloxane, 25000 cp, 30 parts;

[0090] Filler:

[0091] Active nano calcium carbonate, 15 nm, 70 parts;

[0092] Nano iron oxide, 25 nm, 60 parts;

[0093] Curing accelerator: magnesium silicate, 5.5 parts;

[0094] Hydroxyl scavenger: hexamethyldisilazane, 1.5 parts.

[0095] Component B:

[0096] Base glue B:

[0097] Alkoxy-terminated polydimethylsiloxane, 12000 cp, 77 parts;

[0098] Methylphenyl silicone oil, 2500 cp, 23 parts;

[0099] Active nano calcium carbonate: 15 nm, 130 parts;

[0100] Hydroxyl scavenger: hexamethyldisilazane, 1.6 parts;

[0101] Crosslinking agent:

[0102] Vinyl tributanone oxime silane, 4 parts;

[0103] Phenyl tributanone oxime silane, 13 parts;

[0104] Coupling agent:

[0105] Gamma-aminopropyl trimethoxysilane, 4 parts;

[0106] 2-(3,4-epoxy cyclohexane) ethyl triethoxysilane, 2 parts;

[0107] Catalyst: dioctyl tin dilaurate, 0.22 parts.

[0108] A preparation method of a two-component silicone sealant, comprising the following steps:

[0109] 70 parts of α, ω-dihydroxy polydimethyl siloxane with a viscosity of 12000 cp and 30 parts of α, ω-dihydroxy polydimethyl diphenyl siloxane with a viscosity of 25000 and a phenyl chain junction mole fraction of 15% are added to a planetary machine and stirred for 10 min to obtain base glue A; 70 parts of active nano calcium carbonate with a particle size of 15 nm and treated with stearic acid and titanate coupling agent and 60 parts of nano iron oxide with a particle size of 25 nm, 5.5 parts of magnesium silicate and 1.5 parts of hexamethyldisilazane are added to the base glue A, stirred for 35 min under a vacuum degree of -0.090 Mpa and the air bubbles are removed to obtain component A.

[0110] Put 77 parts of alkoxyl terminated polydimethylsiloxane with viscosity of 12000 cp and 23 parts of methyl phenyl silicone oil with viscosity of 2500 cp and phenyl linkage mole fraction of 40% into a kneader, stir for 12 min under vacuum of -0.090 Mpa, to obtain base glue B. Put 130 parts of active nano calcium carbonate with particle size of 15 nm and treated with stearic acid and titanate coupling agent into base glue B, dehydrate and stir for 125 min at temperature of 130 °C and vacuum of -0.090 Mpa by kneader, and cool to room temperature. Add 1.6 parts of hexamethyldisilazane, 4 parts of vinyl tributanone oxime silane, 13 parts of phenyl tributanone oxime silane, 4 parts of γ-aminopropyl trimethoxysilane, 2 parts of 2-(3,4-epoxy cyclohexane) ethyl triethoxysilane and 0.22 parts of dioctyl tin dilaurate into the above cooled base glue B and active nano calcium carbonate step by step, stir for 125 min under vacuum of -0.090 Mpa by using a planetary machine, discharge and seal to preserve, to obtain component B.

[0111] During construction, mix component A and component B uniformly by 1:1 in mass ratio through glue injection equipment.

[0112] Example 4

[0113] A two-component silicone sealant is prepared by mixing component A and component B in mass ratio of 1:1; according to weight fraction,

[0114] Component A:

[0115] Base glue A:

[0116] α, ω-dihydroxy polydimethylsiloxane, 20000 cp, 50 parts;

[0117] α, ω-dihydroxy polydimethyl diphenyl siloxane, 20000 cp, 50 parts;

[0118] Filler:

[0119] Active nano calcium carbonate, 20 nm, 70 parts;

[0120] Nano iron oxide, 15 nm, 70 parts;

[0121] Curing accelerator: sodium aluminum silicate, 6 parts;

[0122] Hydroxyl scavenger: hexamethyldisilazane, 1 part;

[0123] Component B:

[0124] Base glue B:

[0125] Alkoxyl terminated polydimethylsiloxane, 20000 cp, 80 parts;

[0126] Methyl phenyl silicone oil, 5000 cp, 20 parts;

[0127] Active nano calcium carbonate: 20 nm, 140 parts;

[0128] Hydroxyl scavenger: hexamethyl disilazane, 1 part;

[0129] Crosslinking agent:

[0130] Vinyl tributanone oxime silane, 4 parts;

[0131] Methyl tributanone oxime silane, 13 parts;

[0132] Coupling agent:

[0133] N-aminoethyl-gamma-aminopropyl trimethoxysilane, 3.5 parts;

[0134] 3-(2,3-epoxypropoxy) propyl trimethoxysilane, 1.5 parts;

[0135] Catalyst: di-n-butyl tin diacetate, 0.2 parts.

[0136] A preparation method of a two-component silicone sealant, comprising the following steps:

[0137] 50 parts of α, ω-dihydroxy polydimethyl siloxane with a viscosity of 20000 cp and 50 parts of α, ω-dihydroxy polydimethyl diphenyl siloxane with a viscosity of 20000 and a phenyl chain connection mole fraction of 15% are added to a planetary machine and stirred for 10 min to obtain base glue A; 70 parts of active nano calcium carbonate with a particle size of 20 nm and treated with stearic acid and titanate coupling agent and 70 parts of nano iron oxide with a particle size of 15 nm, 6 parts of sodium aluminum silicate and 1 part of hexamethyl disilazane are added to the base glue A, stirred for 30 min under a vacuum degree of -0.090 Mpa and the bubbles are removed to obtain component A.

[0138] 80 parts of alkoxyl terminated polydimethylsiloxane with viscosity of 20000 cp and 20 parts of methyl phenyl silicone oil with viscosity of 5000 cp and phenyl linkage mole fraction of 30% were added into a kneader, stirred for 15 min under vacuum degree of -0.090 Mpa, to obtain base glue B; 140 parts of active nano calcium carbonate with particle size of 20 nm and treated by stearic acid and titanate coupling agent were added into base glue B, dehydrated and stirred for 130 min at temperature of 130 °C and vacuum degree of -0.090 Mpa by a kneader, and cooled to room temperature. 1 part of hexamethyldisilazane, 4 parts of vinyl tributanone oxime silane, 13 parts of methyl tributanone oxime silane, 3.5 parts of N-aminoethyl-γ-aminopropyl trimethoxysilane, 1.5 parts of 3-(2,3-epoxypropoxy) propyl trimethoxysilane and 0.2 parts of di-n-butyl tin diacetate were added into the above cooled base glue B and active nano calcium carbonate step by step in sequence, stirred for 130 min under vacuum degree of -0.090 Mpa by using a planetary machine, discharged and sealed to store, to obtain component B.

[0139] During construction, the component A and the component B can be mixed uniformly by a glue injection equipment according to mass ratio of 1:1.

[0140] Example 5

[0141] A two-component silicone sealant is prepared by mixing component A and component B according to mass ratio of 1:1; according to weight fraction,

[0142] Component A:

[0143] Base glue A:

[0144] α, ω-dihydroxyl polydimethylsiloxane, 15000 cp, 60 parts;

[0145] α, ω-dihydroxyl polydimethyl diphenyl siloxane, 30000 cp, 40 parts;

[0146] Filler:

[0147] Active nano calcium carbonate, 25 nm, 70 parts;

[0148] Nano iron oxide, 20 nm, 70 parts;

[0149] Curing accelerator: magnesium aluminum silicate, 5 parts;

[0150] Hydroxyl scavenger: hexamethyldisilazane, 2 parts.

[0151] Component B:

[0152] Base glue B:

[0153] Alkoxyl terminated polydimethylsiloxane, 15000 cp, 75 parts;

[0154] Methyl phenyl silicone oil, 3000 cp, 25 parts;

[0155] Active nano calcium carbonate: 25 nm, 140 parts;

[0156] Hydroxyl scavenger: hexamethyldisilazane, 3 parts;

[0157] Crosslinking agent:

[0158] Methyl tributyl ketoxime silane, 5 parts;

[0159] Tetrabutyl ketoxime silane, 13 parts;

[0160] Coupling agent:

[0161] Bis (3-trimethoxysilylpropyl) amine, 3.5 parts;

[0162] 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxysilane, 1.5 parts;

[0163] Catalyst: dibutyl tin dilaurate, 0.25 parts.

[0164] A preparation method of a two-component silicone sealant, comprising the following steps:

[0165] 60 parts of α, ω-dihydroxy polydimethyl siloxane with a viscosity of 15000 cp and 40 parts of α, ω-dihydroxy polydimethyl diphenyl siloxane with a viscosity of 30000 and a phenyl chain junction mole fraction of 10% are added to a planetary machine and stirred for 15 min to obtain base glue A; 90 parts of active nano calcium carbonate with a particle size of 25 nm and treated with stearic acid and titanate coupling agent and 50 parts of nano iron oxide with a particle size of 20 nm, 5 parts of magnesium aluminum silicate and 2 parts of hexamethyldisilazane are added to the base glue A, stirred for 30 min under a vacuum degree of -0.090 Mpa and the air bubbles are removed to obtain component A.

[0166] Put 75 parts of alkoxy-terminated polydimethylsiloxane with viscosity of 15000 cp and 25 parts of methylphenyl silicone oil with viscosity of 3000 cp and phenyl chain linkage mole fraction of 35% into a kneader, stir for 10 min under vacuum degree of -0.090 Mpa, to obtain base glue B; put 140 parts of active nano calcium carbonate with particle size of 25 nm and treated with stearic acid and titanate coupling agent into base glue B, dehydrate and stir for 120 min at temperature of 120℃ and vacuum degree of -0.090 Mpa by means of a kneader, and cool to room temperature. Add 3 parts of hexamethyldisilazane, 5 parts of methyltributylketoximosilane, 13 parts of tetrabutylketoximosilane, 3.5 parts of bis(3-trimethoxysilylpropyl)amine, 1.5 parts of 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and 0.25 parts of dibutyltin dilaurate into the above cooled base glue B and active nano calcium carbonate step by step in sequence, stir for 120 min under vacuum degree of -0.090 Mpa by using a planetary machine, discharge and seal to preserve, to obtain component B.

[0167] During construction, component A and component B can be mixed uniformly by means of a glue dispensing equipment at mass ratio of 1:1.

[0168] Comparative Example 1

[0169] This comparative example is a commercially available brand of 1:1 two-component alcohol-removed silicone sealant.

[0170] Comparative Example 2

[0171] This comparative example is also a 1:1 alcohol-removed two-component silicone sealant, and the difference lies in that the raw materials used are traditional 107 glue (α, ω-dihydroxy polydimethylsiloxane), dimethyl silicone oil and active nano calcium carbonate. Specifically:

[0172] Component A:

[0173] α, ω-dihydroxy polydimethylsiloxane, 20000 cp, 100 parts;

[0174] Active nano calcium carbonate, 35 nm, 140 parts;

[0175] Curing accelerator: sodium aluminum silicate, 6 parts;

[0176] Component B:

[0177] Base glue:

[0178] α, ω-dihydroxy polydimethylsiloxane, 20000 cp, 80 parts;

[0179] Dimethyl silicone oil, 5000 cp, 20 parts;

[0180] Active nano calcium carbonate: 35 nm, 140 parts;

[0181] Crosslinker:

[0182] Vinyl tributanone oxime silane, 4 parts;

[0183] Methyl tributanone oxime silane, 13 parts;

[0184] Coupling agent:

[0185] Gamma-aminopropyl triethoxysilane, 3.5 parts;

[0186] 3-(2,3-epoxypropoxy) propyl trimethoxysilane, 1.5 parts;

[0187] Catalyst: di-n-butyl tin diacetate, 0.2 parts;

[0188] A preparation method of a deoxime type two-component silicone sealant, comprising the following steps:

[0189] 100 parts of α, ω-dihydroxyl polydimethyl siloxane with a viscosity of 20000 cp, 140 parts of active nano calcium carbonate with a particle size of 35 nm, and 6 parts of sodium aluminum silicate are added into a planetary machine, stirred for 30 min under a vacuum degree of -0.090 Mpa to remove bubbles, and a component A is obtained.

[0190] 80 parts of α, ω-dihydroxyl polydimethyl siloxane with a viscosity of 20000 cp and 20 parts of dimethyl silicone oil with a viscosity of 5000 cp are added into a kneader, stirred for 15 min under a vacuum degree of -0.090 Mpa, a base glue is obtained; 140 parts of active nano calcium carbonate with a particle size of 35 nm is added into the base glue, dehydrated and stirred for 130 min under a temperature of 130 DEG C and a vacuum degree of -0.090 Mpa through a kneader, and cooled to room temperature. 4 parts of vinyl tributanone oxime silane, 13 parts of methyl tributanone oxime silane, 3.5 parts of gamma-aminopropyl triethoxysilane, 1.5 parts of 3-(2, 3-epoxypropoxy) propyl trimethoxysilane, and 0.2 parts of di-n-butyl tin diacetate are added into the cooled base glue and active nano calcium carbonate in steps, stirred for 130 min under a vacuum degree of -0.090 Mpa through a planetary machine, discharged and sealed for storage, and a component B is obtained.

[0191] During construction, the component A and the component B are mixed uniformly through a glue injection equipment according to a mass ratio of 1:1.

[0192] Comparative Example 3

[0193] The preparation method of the present comparative example is basically the same as that of Example 1, and the only difference is that the base glue B in the component B is combined by α, ω-dihydroxyl polydimethyl siloxane and methyl phenyl silicone oil. Specifically:

[0194] Component A:

[0195] Base A:

[0196] Alpha, omega-dihydroxypolydimethylsiloxane, 20000 cp, 50 parts;

[0197] Alpha, omega-dihydroxypolydimethylphenylsiloxane, 20000 cp, 50 parts;

[0198] Filler:

[0199] Active nano calcium carbonate, 20 nm, 70 parts;

[0200] Nano iron oxide, 15 nm, 70 parts;

[0201] Curing accelerator: sodium aluminum silicate, 6 parts;

[0202] Hydroxyl scavenger: hexamethyldisilazane, 1 part.

[0203] B component:

[0204] Base B:

[0205] Alpha, omega-dihydroxypolydimethylsiloxane, 20000 cp, 80 parts;

[0206] Methyl phenyl silicone oil, 5000 cp, 20 parts;

[0207] Active nano calcium carbonate: 20 nm, 140 parts;

[0208] Hydroxyl scavenger: hexamethyldisilazane, 1 part;

[0209] Crosslinking agent:

[0210] Vinyl tributanone oxime silane, 4 parts;

[0211] Methyl tributanone oxime silane, 13 parts;

[0212] Coupling agent:

[0213] N-aminoethyl-gamma-aminopropyltrimethoxysilane, 3.5 parts;

[0214] 3-(2,3-epoxypropoxy) propyltrimethoxysilane, 1.5 parts;

[0215] Catalyst: di-n-butyl tin diacetate, 0.2 parts.

[0216] A preparation method of a deoxime type two-component silicone sealant, comprising the following steps:

[0217] A. 50 parts of α, ω-dihydroxypolydimethylsiloxane with viscosity of 20000 cp and 50 parts of α, ω-dihydroxypolydimethylphenylsiloxane with viscosity of 20000 cp and phenyl chain linkage mole fraction of 5% were added into a planetary mixer and stirred for 10 minutes to obtain base gum A. 70 parts of active nano calcium carbonate with particle size of 20 nm and treated with stearic acid and titanate coupling agent and 70 parts of nano iron oxide with particle size of 15 nm, 6 parts of sodium aluminum silicate and 1 part of hexamethyldisilazane were added into base gum A, stirred for 30 minutes under vacuum degree of -0.090 Mpa and removed bubbles to obtain component A.

[0218] B. 80 parts of α, ω-dihydroxypolydimethylsiloxane with viscosity of 20000 cp and 20 parts of methyl phenyl silicone oil with viscosity of 5000 cp and phenyl chain linkage mole fraction of 30% were added into a kneader, stirred for 15 minutes under vacuum degree of -0.090 Mpa to obtain base gum B. 140 parts of active nano calcium carbonate with particle size of 20 nm and treated with stearic acid and titanate coupling agent were added into base gum B, dehydrated and stirred for 130 minutes at temperature of 130 °C and vacuum degree of -0.090 Mpa by means of a kneader and cooled to room temperature. 1 part of hexamethyldisilazane, 4 parts of vinyl tributanone oxime silane, 13 parts of methyl tributanone oxime silane, 3.5 parts of N-aminoethyl-γ-aminopropyl trimethoxysilane, 1.5 parts of 3-(2,3-epoxypropoxy) propyl trimethoxysilane and 0.2 parts of di-n-butyl tin diacetate were added into the above cooled base gum B and active nano calcium carbonate in steps and in sequence, stirred for 130 minutes under vacuum degree of -0.090 Mpa by means of a planetary mixer, discharged and sealed for storage to obtain component B.

[0219] During construction, components A and B were mixed uniformly by a glue injection equipment at mass ratio of 1:1.

[0220] Comparative Example 4

[0221] The preparation method of this comparative example was basically the same as that of Example 3, the only difference being that the base gum A in component A was all α, ω-dihydroxypolydimethylphenylsiloxane. Specifically:

[0222] Component A:

[0223] Base gum A:

[0224] α, ω-dihydroxypolydimethylphenylsiloxane, 25000 cp, 100 parts;

[0225] Filler:

[0226] Active nano calcium carbonate, 15 nm, 70 parts;

[0227] Nano iron oxide, 25 nm, 60 parts;

[0228] Curing accelerator: magnesium silicate, 5.5 parts;

[0229] Hydroxyl scavenger: hexamethyldisilazane, 1.5 parts.

[0230] B component:

[0231] Base glue B:

[0232] Alkoxy-terminated polydimethylsiloxane, 12000 cp, 77 parts;

[0233] Methylphenyl silicone oil, 2500 cp, 23 parts;

[0234] Active nano calcium carbonate: 15 nm, 130 parts;

[0235] Hydroxyl scavenger: hexamethyldisilazane, 1.6 parts;

[0236] Crosslinking agent:

[0237] Vinyl tributanone oxime silane, 4 parts;

[0238] Phenyl tributanone oxime silane, 13 parts;

[0239] Coupling agent:

[0240] Gamma-aminopropyl trimethoxysilane, 4 parts;

[0241] 2-(3,4-epoxy cyclohexane) ethyl triethoxysilane, 2 parts;

[0242] Catalyst: dioctyltin dilaurate, 0.22 parts.

[0243] A preparation method of a deoxime type two-component silicone sealant, comprising the following steps:

[0244] 100 parts of α, ω-dihydroxy polydimethyl diphenyl siloxane with a viscosity of 25000 and a phenyl chain molar fraction of 15%, 70 parts of active nano calcium carbonate with a particle size of 15 nm and treated with stearic acid and titanate coupling agent, and 60 parts of nano iron oxide with a particle size of 25 nm, 5.5 parts of magnesium silicate and 1.5 parts of hexamethyldisilazane are sequentially added to a planetary machine, stirred for 35 min under a vacuum degree of -0.090 Mpa and the bubbles are removed, to obtain the A component.

[0245] Put 77 parts of alkoxy-terminated polydimethylsiloxane with viscosity of 12000 cp and 23 parts of methylphenyl silicone oil with viscosity of 2500 cp and phenyl chain linkage mole fraction of 40% into a kneader, stir for 12 min under vacuum degree of -0.090 Mpa, to obtain base glue B. Put 130 parts of active nano calcium carbonate with particle size of 15 nm and treated with stearic acid and titanate coupling agent into base glue B, dehydrate and stir for 125 min at temperature of 130℃ and vacuum degree of -0.090 Mpa by kneader, and cool to room temperature. Stepwise add 1.6 parts of hexamethyldisilazane, 4 parts of vinyl tributanone oxime silane, 13 parts of phenyl tributanone oxime silane, 4 parts of γ-aminopropyl trimethoxysilane, 2 parts of 2-(3,4-epoxy cyclohexane) ethyl triethoxysilane and 0.22 parts of dioctyltin dilaurate into the above cooled base glue B and active nano calcium carbonate, stir for 125 min under vacuum degree of -0.090 Mpa by using a planetary machine, discharge and seal to obtain component B.

[0246] During construction, mix component A and component B uniformly in mass ratio of 1:1 by gluing equipment.

[0247] Performance detection and result analysis:

[0248] Test the two-component silicone sealant obtained in each of the above examples and the comparative example by using the following standards and methods, wherein the tensile strength and elongation at break are tested according to the requirements of type 1 sample (non-standard thickness) in GB / T 528-2009, the Shore A hardness is tested according to GB / T 531-2008, the adhesion is tested according to method two in Appendix D1.2 of GB 16776-2005, and the pull-off time is tested according to Appendix D.5 of GB 16776-2005, and the test results are shown in Table 1 and Table 2.

[0249] Table 1: Test results of comprehensive performance of each example and comparative example at room temperature

[0250]

[0251] Note: The bonding substrates are float glass, anodized aluminum and 304 stainless steel, √ represents 100% cohesive failure, and × represents 100% interfacial failure.

[0252] Table 2: Test results of comprehensive performance of each example and comparative example after baking at 300℃ for 7 days

[0253]

[0254] Note: The bonding substrates are float glass, anodized aluminum and 304 stainless steel, √ represents 100% cohesive failure, and × represents 100% interfacial failure.

[0255] From the data in Table 1-2, it can be seen that the tensile strength and elongation at break of the two-component silicone sealant prepared in Examples 1-5, as well as the retention rate after baking at 300℃ for 7 days and the storage performance, are all better than those of Comparative Example 1 and Comparative Example 2. Comparative Example 1 is a dealcoholized two-component sealant, and after baking at 300℃ for 7 days, the sealant powderizes, and after 5 days of accelerated aging at 90℃, the mixed sealant has a tensile breaking time that is 4.3 times that before aging, and the storage performance is far worse than that of the examples. Although Comparative Example 2 is also a dealcoholized two-component sealant, the raw materials are single, and the temperature resistance and storage performance are also not as good as those of the examples. As can be seen from Comparative Example 3 and Example 1, the use of alkoxyl-terminated polydimethylsiloxane in the base gum of the B component can greatly improve the storage performance of the two-component sealant. As can be seen from Comparative Example 4 and Example 3, the use of α,ω-dihydroxypolydimethylsiloxane and α,ω-dihydroxypolydimethylphenylsiloxane in the base gum of the A component can maintain a high tensile strength and elongation at break at room temperature, while also taking into account the temperature resistance. In addition, as can be seen from Example 1 and Example 4, increasing the molar fraction of phenyl linkages in α,ω-dihydroxypolydimethylphenylsiloxane and methylphenylsilicone can improve the retention rate of mechanical properties after high-temperature baking, but the initial tensile strength decreases and the elongation at break increases. As can be seen from Example 2 and Example 5, increasing the amount of nano iron oxide and hexamethyldisilazane can also improve the retention rate of mechanical properties after high-temperature baking.

[0256] In summary, the use of α,ω-dihydroxypolydimethylphenylsiloxane with a phenyl group and methylphenylsilicone, in combination with α,ω-dihydroxypolydimethylsiloxane, alkoxyl-terminated polydimethylsiloxane, active nano calcium carbonate and nano iron oxide, and curing accelerators, hydroxyl scavengers, crosslinking agents, coupling agents, and catalysts, as raw materials, through formula design for a dealcoholized two-component system, can significantly improve the retention rate of mechanical properties of the sealant after high-temperature baking, while also taking into account the excellent storage performance and mechanical properties at room temperature of the sealant.

[0257] The above description is merely a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or replacements within the scope of the disclosed technology can be easily thought of by those skilled in the art, and should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A two-component silicone sealant, characterized by, The two-component silicone sealant is prepared by mixing the A component and the B component in a mass ratio of 1:1; according to the mass fraction, The raw material composition of the A component is: Base glue A 100 parts; Filler 100-200 parts; Curing accelerator 5-10 parts; Hydroxyl scavenger 0.8-2 parts; The raw material composition of the B component is: Base glue B 100 parts; Active nano calcium carbonate 80-160 parts; Hydroxyl scavenger 0.8-2 parts; Crosslinking agent 8-20 parts; Coupling agent 2-8 parts; Catalyst 0.1-0.5 parts; The base glue A is compounded by α, ω-dihydroxy polydimethylsiloxane and α, ω-dihydroxy polydimethyl diphenyl siloxane; the mass ratio of the α, ω-dihydroxy polydimethylsiloxane and the α, ω-dihydroxy polydimethyl diphenyl siloxane is 1:1-5:1; The base glue B is compounded by alkoxyl-terminated polydimethylsiloxane and methyl phenyl silicone oil; the mass ratio of the alkoxyl-terminated polydimethylsiloxane and the methyl phenyl silicone oil is 1:1-5:1; The filler is composed of active nano calcium carbonate and nano iron oxide; the mass ratio of the active nano calcium carbonate and the nano iron oxide is 1:1-5:

1.

2. The two-component silicone sealant according to claim 1, characterized in that, The viscosity of the α, ω-dihydroxy polydimethylsiloxane at 25°C is 1000-50000 cp; the mole fraction of phenyl linkers in the α, ω-dihydroxy polydimethyl diphenyl siloxane is 5%-30%, and the viscosity of the α, ω-dihydroxy polydimethyl diphenyl siloxane at 25°C is 5000-80000 cp.

3. The two-component silicone sealant according to claim 1, characterized in that, The particle size of the active nano calcium carbonate is 10-50 nm, and the active nano calcium carbonate is obtained by surface treatment of nano calcium carbonate with a modifier; the modifier is one or more of stearic acid, silazane, silane coupling agent and titanate coupling agent; the particle size of the nano iron oxide is 10-60 nm.

4. The two-component silicone sealant according to claim 1, characterized in that, The viscosity of the alkoxyl-terminated polydimethylsiloxane at 25°C is 1000-50000 cp; the mole fraction of phenyl linkers in the methyl phenyl silicone oil is 10%-60%, and the viscosity of the methyl phenyl silicone oil at 25°C is 1500-20000 cp.

5. The two-component silicone sealant according to claim 1, characterized in that, The curing accelerator is at least one of sodium aluminum silicate, magnesium aluminum silicate, magnesium sulfate, calcium chloride; the hydroxyl scavenger is hexamethyldisilazane; the crosslinking agent is at least one of phenyltributanoxysilane, methyltributanoxysilane, vinyltributanoxysilane, tetrabutanoxysilane, methylvinyl-dibutanoxysilane, methyltripropanoxysilane; the coupling agent is at least one of gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; the catalyst is at least one of dibutyltin dilaurate, dioctyltin dilaurate, hydroxydimethyltin, dimethyltin dilinoleate, dibutyltin diacetate, dibutyltin diisooctylmaleate.

6. The method of making a two-component silicone sealant according to any one of claims 1 to 5, characterized in that, The preparation method comprises the following steps: S1, adding α, ω-dihydroxypolydimethylsiloxane and α, ω-dihydroxypolydimethylphenylsiloxane into a planetary machine and stirring for 10-20 min to obtain base glue A; S2, sequentially adding fillers, a curing accelerator and a hydroxyl scavenger into the base glue A, stirring for 20-40 min under a vacuum degree of-0.090 Mpa and removing air bubbles to obtain component A; S3, adding alkoxyl-terminated polydimethylsiloxane and methylphenylsilicone oil into a kneader, stirring for 10-20 min under a vacuum degree of-0.090 Mpa to obtain base glue B; S4, adding active nano calcium carbonate into the base glue B, dehydrating and stirring for 90-150 min at a temperature of 100-150 DEG C and a vacuum degree of-0.090 Mpa through a kneader and cooling to room temperature; sequentially adding a hydroxyl scavenger, a crosslinking agent, a coupling agent and a catalyst into the cooled base glue B and active nano calcium carbonate in steps, stirring for 60-150 min under a vacuum degree of-0.090 Mpa using a planetary machine, discharging and sealing to preserve to obtain component B; S5, uniformly mixing component A and component B according to a mass ratio of 1:1 to obtain a two-component silicone sealant.

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