High sealing two-component polyurethane sealant, preparation method and application thereof

Abstract

The application provides a high-sealing two-component polyurethane sealant as well as a preparation method and application thereof. The two-component polyurethane sealant comprises component A and component B. The component A comprises the following raw materials in percentage by mass: 10-35% of a first polyol; 35-80% of a filler; and 0.01-32.2% of a first additive. The filler comprises a barrier type filler, and the percentage by mass of the barrier type filler in the raw materials of the component A is 5-20%. The component B comprises the following raw materials in percentage by mass: 68-85% of a curing agent; 1-5% of a thickening agent; and 11-30.5% of a second additive. The mass ratio of the component A to the component B is (13-20):1. The high-sealing two-component polyurethane sealant provided by the application can effectively improve the durability and sealing property of the sealant by using the barrier type filler.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesive materials, in particular to a high-sealing two-component polyurethane sealant as well as a preparation method and application thereof. BACKGROUND

[0002] Sealant is a material used to fill gaps (holes, joints, etc.). Elastic sealant is a product that combines bonding and sealing functions in one. The sealant for double-layer hollow glass is a special product used in the construction field. Double-layer hollow glass is a window glass product sealed around the edges with two pieces of glass and dry air or vacuum in between, which has excellent heat insulation performance and is mainly used for door and window glass. In the production process of hollow glass, which mainly uses double sealing, butyl rubber is used for the first sealing, and polythio (PS), silicone (SR) or polyurethane (PU) elastic sealant is used for the second sealing.

[0003] At present, the main product of elastic sealant used in hollow glass is silicone sealant, which has good weather resistance and is easy to construct, but its long-term air tightness is generally poor, small molecules may seep out, the price fluctuation range is large, and the market is unstable. Polythio sealant has good long-term air tightness and excellent performance, but the odor during construction is serious, which affects the health of construction personnel. Polyurethane sealant is an environmentally friendly material, the price of its raw materials is stable, the water vapor transmission rate and water absorption rate are low, and the air tightness is good. However, most of the polyurethane sealants used on the market need to be primed to ensure good adhesion to glass, and the strength is not high, and there are also problems of poor sealing performance. SUMMARY

[0004] Therefore, it is necessary to provide a high-sealing two-component polyurethane sealant and a preparation method thereof, which have the characteristics of high bonding strength, stable performance and high sealing performance.

[0005] The first aspect of the present application provides a high-sealing two-component polyurethane sealant, which comprises component A and component B, wherein,

[0006] The component A comprises the following raw materials in mass percentage:

[0007] First polyol, 10% to 35%;

[0008] Filler, 35% to 80%;

[0009] First additive, 0.01% to 32.2%;

[0010] The filler comprises a barrier type filler, and the mass percentage of the barrier type filler in the raw materials of the component A is 5% to 20%;

[0011] The component B comprises the following raw materials in mass percentage:

[0012] curing agent, 68%~85%;

[0013] thickening agent, 1%~5%;

[0014] second auxiliary agent, 11%~30.5%;

[0015] the mass ratio of the A component to the B component is (13~20):1.

[0016] In some embodiments of the present application, the barrier type filler includes mica iron oxide and / or glass flake.

[0017] In some embodiments of the present application, the curing agent in the B component includes the following raw materials in percentage by mass:

[0018] isocyanate, 70%~90%;

[0019] second polyol, 8.5%~29%;

[0020] third auxiliary agent, 0~4%;

[0021] wherein the second polyol includes phthalic anhydride polyester polyol, and the phthalic anhydride polyester polyol is in a percentage by mass of 0.5%~4% in the raw materials of the curing agent.

[0022] In some embodiments of the present application, the curing agent in the B component satisfies at least one of the following conditions:

[0023] (1) the third auxiliary agent includes the following raw materials in percentage by mass based on the total mass of the curing agent:

[0024] chain extender, 0~3%; second catalyst, 0~1%;

[0025] Optionally, the chain extender includes one or more of 1,4-butanediol, ethylene glycol, diethylene glycol, and 1,6-hexanediol;

[0026] Optionally, the second catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctoate, zinc bismuth complex catalyst, bismuth isooctoate, and zinc neodecanoate;

[0027] (2) the second polyol further includes polyoxypropylene glycol and / or polycarbonate glycol;

[0028] Optionally, the polyoxypropylene glycol has one or more of a molecular weight of 1000, 2000, 4000, and 8000;

[0029] Optionally, the polycarbonate glycol has one or more of a molecular weight of 1000 and 2000.

[0030] (3) the phthalic anhydride polyester polyol comprises a phthalic anhydride polyester diol;

[0031] Optionally, the phthalic anhydride polyester diol has a molecular weight of one or more of 280, 350, 450, and 560;

[0032] (4) the isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0033] In some embodiments of the present application, the high-sealing two-component polyurethane sealant satisfies at least one of the following conditions:

[0034] (1) the first polyol comprises a polyether polyol and / or a polyester polyol;

[0035] Optionally, the polyether polyol comprises a polypropylene oxide diol and / or a polypropylene oxide triol;

[0036] Optionally, the polyester polyol comprises a polycarbonate diol;

[0037] Further optionally, the polypropylene oxide diol has a molecular weight of one or more of 1000, 2000, 4000, and 8000;

[0038] Further optionally, the polypropylene oxide triol has a molecular weight of one or more of 300, 400, 500, 700, and 1000;

[0039] Further optionally, the polycarbonate diol has a molecular weight of one or more of 1000 and 2000;

[0040] (2) the filler further comprises one or more of nano calcium carbonate, heavy calcium carbonate, active heavy calcium carbonate, talcum powder, and light calcium carbonate;

[0041] (3) the thickening agent comprises fumed silica.

[0042] In some embodiments of the present application, the high-sealing two-component polyurethane sealant satisfies at least one of the following conditions:

[0043] (1) based on the total mass of the A component, the first auxiliary agent comprises the following raw materials in mass percentage:

[0044] a plasticizer, 0-30%; a first catalyst, 0.01%-0.2%; a first coupling agent, 0-2%;

[0045] (2) based on the total mass of the B component, the second auxiliary agent comprises the following raw materials in mass percentage:

[0046] Color paste, 10-20%; second coupling agent, 1-5%; first catalyst, 0-0.5%; plasticizer, 0-5%.

[0047] In some embodiments of the present application, the high-sealing two-component polyurethane sealant satisfies at least one of the following conditions:

[0048] (1) the plasticizer comprises one or more of diisodecyl phthalate, diisononyl phthalate, dibutyl phthalate and dioctyl phthalate;

[0049] (2) the first catalyst comprises one or more of tertiary amine catalysts and organic metal catalysts;

[0050] Optionally, the tertiary amine catalysts comprise one or more of aliphatic amine catalysts, ester ring amine catalysts and aromatic amine catalysts;

[0051] Optionally, the organic metal catalysts comprise one or more of dibutyl tin dilaurate, stannous octoate, lead isooctoate, zinc bismuth complex catalyst, bismuth isooctoate and zinc neodecanoate;

[0052] (3) the first coupling agent comprises one or more of γ-(2,3-epoxypropoxy) propyl trimethoxysilane, γ-aminopropyl triethoxysilane, bis-(γ-trimethoxysilylpropyl) amine and N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane;

[0053] Optionally, the first coupling agent comprises one or more of KH-560, KH-550, Momentive A-1170 and KH-792;

[0054] (4) the color paste comprises one or more of Calor HC460, Calor HC585 and Calor HS461;

[0055] (5) the second coupling agent comprises one or more of γ-(2,3-epoxypropoxy) propyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane;

[0056] Optionally, the second coupling agent comprises one or more of KH-560, A-LINK35 and A-LINK25.

[0057] The second aspect of the present application provides a method for preparing the high-sealing two-component polyurethane sealant of the first aspect of the present application, comprising:

[0058] After mixing the components contained in the A component, heat treatment and dehydration treatment are performed to obtain the A component;

[0059] mixing the components contained in the B component to obtain the B component;

[0060] mixing the A component and the B component in a mass ratio of (13-20):1, and then curing to obtain the high-sealing two-component polyurethane sealant.

[0061] In some embodiments of the present application, the mixing and heat treatment and dehydration treatment of the components contained in the A component comprises:

[0062] mixing the first polyol and the filler containing the barrier type filler, and heating to 80-120°C, and then dehydrating under vacuum for 1-5h until the water content is reduced to below 600ppm to obtain a premix;

[0063] Optionally, the first polyol and the filler containing the barrier type filler are further added with the plasticizer during the mixing process;

[0064] cooling the premix to below 40°C, adding the first catalyst, and then mixing and stirring uniformly under vacuum;

[0065] Optionally, the premix and the first catalyst are further added with the first coupling agent during the mixing process;

[0066] Optionally, the vacuum degree of the vacuum condition is above 0.09MPa.

[0067] In some embodiments of the present application, the mixing of the components contained in the B component comprises:

[0068] mixing the curing agent and the color paste uniformly under vacuum, adding the second coupling agent and mixing uniformly, adding the thickening agent under stirring until the viscosity is (3x10 4 )mPa·s-(12x10 4 )mPa·s;

[0069] Optionally, the first catalyst and / or the plasticizer are further added during the step of adding the second coupling agent;

[0070] Optionally, the stirring rate of the stirring state is 50-500r / min.

[0071] In some embodiments of the present application, the method further comprises the step of preparing the curing agent:

[0072] reacting the isocyanate with the second polyol subjected to dehydration treatment to obtain the curing agent.

[0073] In some embodiments of the present application, the step of preparing the curing agent further comprises:

[0074] pre-reacting the isocyanate with the second polyol subjected to the water removal treatment, wherein the second polyol does not comprise the phthalic anhydride polyester polyol,

[0075] Optionally, the pre-reaction temperature is 70-85℃, the pre-reaction time is 0.5-3h, and the pre-reaction atmosphere is a nitrogen atmosphere.

[0076] Optionally, the second catalyst is also mixed in the second polyol subjected to the water removal treatment.

[0077] Further adding the phthalic anhydride polyester polyol subjected to the water removal treatment for reaction,

[0078] Optionally, the reaction temperature is 70-85℃, the reaction time is 0.5-2h, and the reaction atmosphere is a nitrogen atmosphere.

[0079] Optionally, after the reaction of the phthalic anhydride polyester polyol subjected to the water removal treatment, the chain extender subjected to the water removal treatment is further added for reaction, the reaction temperature is 70-85℃, the reaction time is 0.5-2h, and the reaction atmosphere is a nitrogen atmosphere.

[0080] The third aspect of the present application provides an application of a high-sealing two-component polyurethane sealant in hollow glass, wherein the high-sealing two-component polyurethane sealant comprises the high-sealing two-component polyurethane sealant of the first aspect of the present application or the high-sealing two-component polyurethane sealant prepared by the method of the second aspect of the present application.

[0081] The high-sealing two-component polyurethane sealant provided by the present application can form a coating layer with a parallel overlapping palace structure, i.e., a labyrinthine parallel overlapping winding path, by using a barrier type filler, so that the penetration of moisture and other media in the sealant must pass through countless winding paths, greatly extending the penetration distance, thereby forming a dense anti-permeation layer structure, which can greatly improve the sealing performance of the sealant. DETAILED DESCRIPTION

[0082] In order to facilitate the understanding of the present application, the present application will be described more fully below. However, the present application can be realized in many different forms, and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0083] For simplicity, only some numerical ranges are explicitly recited herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with any other lower limit to form a range not explicitly recited, as can any upper limit with any other upper limit to form a range not explicitly recited. Furthermore, although a range of endpoints is recited, each point or individual number within the range is also included in the range. Thus, each point or individual number can be combined as the lower or upper limit with any other point or individual number or with other lower or upper limits to form a range not explicitly recited.

[0084] 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. It is to be understood that unless otherwise indicated, the terms "and / or," "at least one of," and "one or more" are used in their inclusive sense as the terms are used in the patent law, and are not used in their exclusive sense.

[0085] The foregoing summary of the application does not necessarily describe every disclosed embodiment or implementation of the application. The exemplary embodiments are described more fully below with reference to the accompanying drawings. In several places throughout the application, guidance is provided through a series of examples. The examples can be employed in any number of combinations with one another. In various embodiments, the examples are presented as representative of the possible combinations, but are not to be construed as an exhaustive list of possible combinations.

[0086] The first aspect of the application provides a high-sealing two-component polyurethane sealant, comprising component A and component B, wherein the component A comprises the following raw materials in percentage by mass: first polyol, 10% to 35%; filler, 35% to 80%; first additive, 0.01% to 32.2%; wherein the filler comprises barrier type filler, the percentage by mass of the barrier type filler in the raw materials of the component A is 5% to 20%; the component B comprises the following raw materials in percentage by mass: curing agent, 68% to 85%; thickening agent, 1% to 5%; second additive, 11% to 30.5%; the mass ratio of the component A to the component B is (13 to 20): 1.

[0087] The high sealing double-component polyurethane sealant provided in the application can form a coating layer with a parallel overlapping palace structure, i.e. a labyrinthine parallel overlapping detour channel, by using the barrier type filler, so that the penetration of moisture and other media in the sealant must pass through numerous tortuous paths, greatly extending the penetration distance, thereby forming a dense anti-permeation layer structure, which can greatly improve the sealing performance of the sealant. Meanwhile, the sealant with a cross-linking structure is prepared by adding an appropriate amount of a ternary alcohol, which improves the bonding strength of the sealant, improves the water-ultraviolet treatment performance, and improves the durability and sealing performance of the sealant.

[0088] In some embodiments, the barrier type filler includes one or more of mica iron oxide and glass flake.

[0089] In the application, the use of the above-mentioned barrier type filler enables the sealant coating layer to have a parallel overlapping palace structure, i.e. a labyrinthine parallel overlapping detour channel, so that the penetration of moisture and other media in the sealant must pass through numerous tortuous paths, greatly extending the penetration distance, thereby forming a dense anti-permeation layer structure, which greatly improves the sealing performance of the sealant.

[0090] In some embodiments, in addition to the barrier type filler, the filler can also include other conventional fillers. The type of other conventional fillers is not particularly limited and can be selected according to actual needs. Optionally, the other conventional fillers can include one or more of nano calcium carbonate, heavy calcium carbonate, active heavy calcium carbonate, talc powder and light calcium carbonate.

[0091] In some embodiments, the type of thickening agent is not particularly limited and can be selected according to actual needs. For example, the thickening agent can be fumed silica.

[0092] In some embodiments, the first polyol includes a polyether polyol and / or a polyester polyol.

[0093] In some embodiments, the polyether polyol includes a polypropylene oxide diol and / or a polypropylene oxide triol.

[0094] In some embodiments, the molecular weight of the polypropylene oxide diol is one or more of 1000, 2000, 4000 and 8000.

[0095] In some embodiments, the molecular weight of the polypropylene oxide triol is one or more of 300, 400, 500, 700 and 1000.

[0096] In some embodiments, the polyester polyol includes a polycarbonate diol.

[0097] In some embodiments, the polycarbonate diol has a molecular weight of one or more of 1000 and 2000.

[0098] In some embodiments, the polycarbonate diol has a molecular weight of one or more of 1000 and 2000.

[0099] In some embodiments, the curing agent in the B component includes, by mass percentage, isocyanate 70-90%, second polyol 8.5-29%, and third additive 0-4%, wherein the second polyol includes phthalic anhydride polyester polyol, and the mass percentage of the phthalic anhydride polyester polyol in the raw materials of the curing agent is 0.5-4%.

[0100] In some embodiments, the curing agent in the B component includes, by mass percentage, isocyanate 70-90%, second polyol 8.5-29%, and third additive 0-4%, wherein the second polyol includes phthalic anhydride polyester polyol, and the mass percentage of the phthalic anhydride polyester polyol in the raw materials of the curing agent is 0.5-4%.

[0101] In some embodiments, the third additive includes, by mass percentage, chain extender 0-3% and second catalyst 0-1%, based on the total mass of the curing agent.

[0102] In some embodiments, the chain extender includes one or more of 1,4-butanediol, ethylene glycol, diethylene glycol, and 1,6-hexanediol.

[0103] In some embodiments, the second catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctoate, zinc bismuth composite catalyst, bismuth isooctoate, and zinc neodecanoate.

[0104] In some embodiments, the second polyol further includes polypropylene oxide diol and / or polycarbonate diol.

[0105] In some embodiments, the polypropylene oxide diol has a molecular weight of one or more of 1000, 2000, 4000, and 8000.

[0106] In some embodiments, the polycarbonate diol has a molecular weight of one or more of 1000 and 2000.

[0107] In some embodiments, the polycarbonate diol has a molecular weight of one or more of 1000 and 2000.

[0108] In some embodiments, the phthalic anhydride polyester polyol includes phthalic anhydride polyester diol.

[0109] In some embodiments, the phthalic anhydride polyester diol has a molecular weight of one or more of 280, 350, 450, and 560.

[0110] The synthesized curing agent of the present application introduces ester bonds into the molecular chain and also plays a certain chain extending role by adding small molecular weight phthalic anhydride polyester diol, thereby increasing the strength and rigidity of the polyurethane sealant.

[0111] In some embodiments, the isocyanate includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0112] In some embodiments, the isocyanate includes one or more of TDI-80, MDI-50, MDI-100, IPDI, and HDI.

[0113] In some embodiments, in the A component, the first auxiliary agent includes, by mass percentage, the following raw materials: plasticizer, 0-30%; first catalyst, 0.01%-0.2%; first coupling agent, 0-2%.

[0114] In some embodiments, in the B component, the second auxiliary agent includes, by mass percentage, the following raw materials: color paste, 10%-20%; second coupling agent, 1%-5%; first catalyst, 0-0.5%; plasticizer, 0-5%.

[0115] In some embodiments, the first coupling agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis-(γ-trimethoxysilylpropyl)amine, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. Optionally, the first coupling agent includes one or more of KH-560, KH-550, Momentive A-1170, and KH-792.

[0116] In some embodiments, the second coupling agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

[0117] Optionally, the second coupling agent includes one or more of KH-560, A-LINK35, and A-LINK25.

[0118] In the present application, after adding a proper coupling agent in the A component and the B component, the coupling agent can interact with the hydroxyl group in the inorganic substance and the long molecular chain in the organic polymer, so that the two materials with different properties are coupled, thereby enhancing the interface interaction between the two-component polyurethane sealant and the glass, further increasing the adhesion of the two-component polyurethane sealant and the glass interface, and then the cohesive failure can be realized.

[0119] In some embodiments, the kind of the plasticizer is not particularly limited and can be selected according to actual needs. The plasticizer in the A component and the B component can be selected from the same material or different materials. Optionally, the plasticizer can include one or more of diisodecyl phthalate, diisononyl phthalate, dibutyl phthalate, and dioctyl phthalate.

[0120] In some embodiments, the first catalyst includes one or more of a tertiary amine catalyst and an organic metal catalyst. It should be noted that the first catalyst selected in the A component and the B component in the present application can be the same or different, and can be selected according to actual needs.

[0121] In some embodiments, the tertiary amine catalyst includes one or more of an aliphatic amine catalyst, an ester ring amine catalyst, and an aromatic amine catalyst. Optionally, it can include one or more of bis(2-dimethylaminoethyl) ether, N-methylmorpholine, and N,N'-dimethylpyridine.

[0122] In some embodiments, the kind of the organic metal catalyst is not particularly limited and can be selected according to actual needs. Optionally, it can include one or more of dibutyl tin dilaurate, stannous octoate, lead isooctoate, zinc bismuth composite catalyst, bismuth isooctoate, and zinc neodecanoate.

[0123] In some embodiments, the kind of the color paste is not particularly limited and can be selected according to actual needs. Optionally, it can include one or more of Koral HC460, Koral HC585, and Koral HS461.

[0124] The second aspect of the present application provides a method for preparing the high-sealing two-component polyurethane sealant of the first aspect of the present application, which can include the following steps:

[0125] S10, mixing the components contained in the A component, and then performing heat treatment and dehydration treatment to obtain the A component;

[0126] S30, mixing the components contained in the B component to obtain the B component;

[0127] S50, curing the A component and the B component mixed in a mass ratio of (13-20):1 to obtain the high-sealing two-component polyurethane sealant.

[0128] In some embodiments, the step S10 can further include the following steps:

[0129] S100, mixing the first polyol and the filler containing the barrier type filler, and heating to 80-120°C, dehydrating under vacuum for 1-5h until the water content is reduced to below 600ppm to obtain a premix; optionally, the first polyol and the filler containing the barrier type filler are mixed with the addition of the plasticizer;

[0130] S110, cooling the premix to below 40°C, adding the first catalyst, and mixing and stirring uniformly under vacuum; optionally, the premix and the first catalyst are mixed with the addition of the first coupling agent.

[0131] As a non-limiting example of preparing the A component, the first polyol, other filler of non-barrier type, and barrier type filler are weighed according to the ratio, optionally with the addition of the plasticizer, and then put into a planetary stirred tank with a rotation speed of 50-500r / min, heated to 80-120°C, vacuum dehydrated for 1-5h until the water content is reduced to below 600ppm; cooled to below 40°C, added with the first catalyst, optionally with the addition of the first coupling agent, with a rotation speed of 50-500r / min, vacuum stirred for 30-120min, and sealed and packaged under nitrogen protection to obtain the A component with uniform appearance and viscous texture.

[0132] In some embodiments, the step S30 can further include the following steps:

[0133] S300, mixing the curing agent and the color paste uniformly under vacuum, adding the second coupling agent and mixing uniformly, adding the thickening agent under stirring until the viscosity is (3x10 4 )mPa·s-(12x10 4 )mPa·s; optionally, the first catalyst and / or the plasticizer are added in the step of adding the second coupling agent.

[0134] As a non-limiting example of preparing the B component, the curing agent and color paste can be weighed and put into a planetary stirring kettle at a speed of 50 r / min to 500 r / min, and stirred under vacuum for 0.5 h to 3 h until uniformly mixed. Then, the second coupling agent can be added, and optionally, the first catalyst and / or plasticizer can be added, and stirred under vacuum for 5 min to 120 min until uniformly mixed. Then, the thickening agent can be added, and stirred under vacuum for 30 min to 180 min until uniformly mixed, and the viscosity reaches (3 x 10 4 )mPa·s to (12 x 10 4 )mPa·s. The mixture is sealed under nitrogen protection to obtain the B component.

[0135] In some embodiments, the vacuum degree of the vacuum condition is 0.09 MPa or more.

[0136] In some embodiments, the stirring speed of the stirring state is 50 r / min to 500 r / min.

[0137] In some embodiments, the method can further comprise the following step S20 of preparing the curing agent:

[0138] S20, reacting the isocyanate with the second polyol treated by water removal to obtain the curing agent.

[0139] In some embodiments, the above step S20 can further comprise the following steps:

[0140] S200, reacting the second polyol treated by water removal with isocyanate, wherein the second polyol used in this step does not contain phthalic anhydride polyester polyol; the reaction temperature is 70°C to 85°C, the reaction time is 0.5 h to 3 h, and the reaction atmosphere is a nitrogen protective atmosphere; optionally, the second polyol treated by water removal is further mixed with the second catalyst;

[0141] S210, further adding the phthalic anhydride polyester polyol treated by water removal to react, the reaction temperature is 70°C to 85°C, the reaction time is 0.5 h to 2 h, and the reaction atmosphere is a nitrogen protective atmosphere;

[0142] S220, optionally, after adding the phthalic anhydride polyester polyol treated by water removal to react, further adding the chain extender treated by water removal to continue to react, the reaction temperature is 70°C to 85°C, the reaction time is 0.5 h to 2 h, and the reaction atmosphere is a nitrogen protective atmosphere.

[0143] As a non-limiting example of preparing the curing agent of the B component, the second polyol not containing phthalic anhydride polyester polyol is put into a reaction kettle according to the ratio, heated to 90-110°C, and water is removed under vacuum for 1-2h. The temperature is lowered to 70-85°C, the isocyanate component is put in, and optionally, a second catalyst is also added into the reaction kettle, and the reaction is carried out under nitrogen protection for 0.5-3h; then the phthalic anhydride polyester polyol after water removal is put in, and the reaction is carried out under nitrogen protection for 0.5-2h; optionally, the chain extender after water removal is added again, and the reaction is carried out under nitrogen protection for 0.5-2h, to obtain the curing agent, which is sealed and stored for use.

[0144] The third aspect of the present application provides an application of the high-sealing two-component polyurethane sealant in hollow glass, wherein the high-sealing two-component polyurethane sealant comprises the high-sealing two-component polyurethane sealant of the first aspect of the present application or the high-sealing two-component polyurethane sealant prepared according to the method of the second aspect of the present application.

[0145] Embodiment

[0146] The following are specific examples, which more specifically describe the content disclosed in the present application, and these examples are only used for illustrative description, because various modifications and changes within the scope of the content disclosed in the present application are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods, and can be directly used without further treatment, and the instruments used in the examples are commercially available.

[0147] The raw materials used in the following examples are as follows:

[0148] The polyoxypropylene diol is from Shandong Lansheng Dongda, with a molecular weight of 1000, a model number of DL-1000D; a molecular weight of 2000, a model number of DL-2000D; a molecular weight of 4000, a model number of DL-4000D; and a molecular weight of 8000, a model number of DL-8000D.

[0149] The polyoxypropylene triol is from Shandong Lansheng Dongda, with a molecular weight of 300, a model number of MN-300; a molecular weight of 400, a model number of MN-400; a molecular weight of 500, a model number of MN-500; a molecular weight of 700, a model number of MN-700; and a molecular weight of 1000, a model number of MN-1000.

[0150] The polycarbonate diol is from Asahi Kasei Chemicals Corporation, Japan, with a molecular weight of 1000, a model number of T5651; and a molecular weight of 2000, a model number of T5652.

[0151] The filler nano calcium carbonate was purchased from Guangxi Huana New Material Technology Co., Ltd., and the brand was CCS-23; the heavy calcium carbonate was purchased from Lingyuan City Xinli Calcium Industry, and the specification was 800 mesh; the active heavy calcium carbonate was purchased from Jiangxi Guangyuan Chemical Industry Co., Ltd., and the brand was HX-1250; the talc powder was purchased from Haiyan Talc Powder Factory, and the brand was HY-9246; and the light calcium carbonate was purchased from Shandong Zhongtian Mining, and the brand was ZT501.

[0152] The barrier type filler mica iron oxide was purchased from Shanghai Yipin Pigment Co., Ltd.; and the glass flake was purchased from Hebei Kangding Anticorrosion Material Co., Ltd.

[0153] The thickening agent fumed silica was purchased from Wacker, and the brand was R974.

[0154] The phthalic anhydride polyester diol was purchased from Nanjing Jinling Stepan Chemical Co., Ltd., and the molecular weight was 280, 350, 450 and 560.

[0155] The isocyanate included toluene diisocyanate, diphenyl methane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, which were all purchased from Wanhua Chemical Group Co., Ltd.

[0156] The plasticizer diisodecyl phthalate, diisononyl phthalate, dibutyl phthalate and dioctyl phthalate were all purchased from Shandong Qilu Plasticizer Co., Ltd.

[0157] The first coupling agent KH-560, KH-550 and KH-792 were all purchased from Jiangxi Chen Guang New Material Co., Ltd.; and A-1170 was purchased from Mitui High-Tech Materials (China) Co., Ltd.

[0158] The tertiary amine catalyst included bis(2-dimethylaminoethyl) ether, N-methyl morpholine and N,N'-dimethyl pyridine, which were all purchased from Mitui High-Tech Materials (China) Co., Ltd.; and the organic metal catalyst included dibutyl tin dilaurate, stannous octoate, lead isooctoate, zinc bismuth composite catalyst, bismuth isooctoate and zinc neodecanoate, which were all purchased from Xindian Chemical.

[0159] The color paste HC460, HC585 and HS461 were all purchased from Kolor New Material Co., Ltd.

[0160] The second coupling agent KH-560 was purchased from Jiangxi Chen Guang New Material Co., Ltd.; and A-LINK35 and A-LINK25 were both purchased from Mitui High-Tech Materials (China) Co., Ltd.

[0161] The chain extender 1,4-butanediol, ethylene glycol, diethylene glycol and 1,6-hexanediol were all purchased from Arald.

[0162] Other raw materials not specifically mentioned were all ordinary commercially available products.

[0163] Example 1

[0164] Take polyoxypropylene triol with a molecular weight of 400 4g, polyoxypropylene triol with a molecular weight of 1000 4g, polycarbonate diol with a molecular weight of 1000 70g, polycarbonate diol with a molecular weight of 2000 22g, diisodecyl phthalate 300g, nano calcium carbonate 150g, active heavy calcium 229.9g, mica iron oxide 200g, into a planetary stirred tank, the speed is 300r / min, the temperature is raised to 100℃, the vacuum degree is above 0.09MPa, and the water is removed for 2h, the water content is reduced to below 600ppm; cool down to below 40℃, add KH-560 20g, bis(2-dimethylaminoethyl) ether 0.1g, stir at a speed of 300r / min under the condition of a vacuum degree of above 0.09MPa for 40min, seal and package under nitrogen protection, and the A component with uniform appearance and viscous texture is obtained.

[0165] Take polycarbonate diol with a molecular weight of 1000 250g into a reaction kettle, raise the temperature to 110℃, remove water under the condition of a vacuum degree of above 0.09MPa for 2h; cool down to 85℃, add dibutyltin dilaurate 10g, mix uniformly, then add HDI 700g, and react under nitrogen protection for 3h; then add phthalic anhydride polyester diol with a molecular weight of 280 after water removal 10g, and react under nitrogen protection for 1h; then add diethylene glycol after water removal 30g, and react under nitrogen protection for 2h to obtain a curing agent, which is sealed and stored for standby use.

[0166] Take the prepared curing agent 680g and Calorel HS461 200g into a planetary stirred tank, stir at a speed of 300r / min under the condition of a vacuum degree of above 0.09MPa for 3h until mixed uniformly, then add KH-560 40g, stannous octoate 5g, dioctyl phthalate 30g, and stir at a speed of 300r / min under the condition of a vacuum degree of above 0.09MPa for 20min until mixed uniformly, then add fumed silica 45g, and stir at a speed of 300r / min under the condition of a vacuum degree of above 0.09MPa for 180min until mixed uniformly, the viscosity reaches 11.5×10 4 mPa·s, seal and package under nitrogen protection, and the B component is obtained.

[0167] Mix the prepared A component and B component uniformly according to a mass ratio of 15:1, and after curing at room temperature, a high-sealing two-component polyurethane sealant is obtained.

[0168] Example 2

[0169] Take polyoxypropylene diol with molecular weight of 4000 109g, polyoxypropylene triol with molecular weight of 300 11g, polycarbonate diol with molecular weight of 1000 30g, dioctyl phthalate 270g, talc 190g, heavy calcium 338g, glass flake 50g, put into a planetary stirred tank, rotate at 400r / min, heat to 110℃, dehydrate under the condition of vacuum degree above 0.09MPa for 5h, the water content is reduced to below 600ppm; cool to below 40℃, add N,N'-dimethylpyridine 2g, rotate at 400r / min, stir under the condition of vacuum degree above 0.09MPa for 60min, seal and package under nitrogen protection, thus the A component with uniform appearance and viscous texture is obtained.

[0170] Take polycarbonate diol with molecular weight of 2000 135g, put into a reaction kettle, heat to 100℃, remove water under the condition of vacuum degree above 0.09MPa for 1.5h; cool to 72℃, add zinc neodecanoate 5g, mix uniformly, then put IPDI 800g, react under nitrogen protection for 1h; then put anhydride polyester diol with molecular weight of 350 after dehydration 40g, react under nitrogen protection for 2h; then add ethylene glycol 20g after dehydration, react under nitrogen protection for 1.5h, thus the curing agent is obtained, which is sealed and stored for standby use.

[0171] Take the prepared curing agent 720g, calore HC585 220g, put into a planetary stirred tank, rotate at 400r / min, stir under the condition of vacuum degree above 0.09MPa for 2h, until mixed uniformly, then add A-LINK352 20g, diisodecyl phthalate 5g, rotate at 400r / min, stir under the condition of vacuum degree above 0.09MPa for 40min, until mixed uniformly, then add fumed silica 35g, rotate at 400r / min, stir under the condition of vacuum degree above 0.09MPa for 150min, mix uniformly, the viscosity reaches 10.5×10 4 mPa·s, seal and package under nitrogen protection, thus the B component is obtained.

[0172] Mix the prepared A component and B component uniformly according to the mass ratio of 13:1, after curing at room temperature, thus a high sealing two-component polyurethane sealant is obtained.

[0173] Example 3

[0174] Take polyoxypropylene glycol with molecular weight of 2000 70g, polyoxypropylene glycol with molecular weight of 8000 207.5g, polyoxypropylene triol with molecular weight of 500 22.5g, diisononyl phthalate 209.2g, light calcium carbonate 100g, heavy calcium 200g, mica iron oxide 90g, glass flake 90g, into the planetary stirred tank, the speed is 200r / min, the temperature is raised to 90℃, the vacuum degree is above 0.09MPa, dehydration for 3h, the water content is reduced to below 600ppm; the temperature is reduced to below 40℃, KH-550 10g, N-methylmorpholine 0.8g are added, stirring for 50min under the condition of the speed of 200r / min and the vacuum degree of above 0.09MPa, it is sealed and packaged under the protection of nitrogen, the appearance of the obtained A component is viscous and the texture is uniform.

[0175] Take polyoxypropylene glycol with molecular weight of 1000 150g, polyoxypropylene glycol with molecular weight of 8000 57g, into the reaction kettle, the temperature is raised to 105℃, dehydration for 2h under the condition of the vacuum degree of above 0.09MPa; the temperature is reduced to 83℃, bismuth isooctoate 3g is added, after mixing uniformly, TDI-80 750g is added, reaction for 2.5h under the protection of nitrogen; then polyesterglycol with molecular weight of 450 after dehydration 30g is added, reaction for 1.5h under the protection of nitrogen; then 1,4-butanediol after dehydration 10g is added, reaction for 1.5h under the protection of nitrogen, a curing agent is obtained, which is sealed and stored for standby use.

[0176] Take the prepared curing agent 770g, calore HC460 140g, into the planetary stirred tank, stirring for 1h under the condition of the speed of 500r / min and the vacuum degree of above 0.09MPa, until mixing uniformly, KH-560 25g, A-LINK 25 25g, dibutyl phthalate 12g, lead isooctoate 1g are added, stirring for 5min under the condition of the speed of 500r / min and the vacuum degree of above 0.09MPa, until mixing uniformly, fumed silica 27g is added, stirring for 30min under the condition of the speed of 500r / min and the vacuum degree of above 0.09MPa, mixing uniformly, the viscosity reaches 8.5×10 4 mPa·s, it is sealed and packaged under the protection of nitrogen, the B component is obtained.

[0177] Mix the prepared A component and B component uniformly according to the mass ratio of 16:1, after curing at room temperature, a high sealing two-component polyurethane sealant is obtained.

[0178] Example 4

[0179] Take the molecular weight of 2000 polyoxypropylene diol 40g, molecular weight of 4000 polyoxypropylene diol 100g, molecular weight of 700 polyoxypropylene triol 16g, molecular weight of 2000 polycarbonate diol 44g, dibutyl phthalate 123.8g, nano calcium carbonate 240g, talc 360g, iron oxide 60g, into the planetary stirred tank, the speed of 100r / min, the temperature is raised to 80℃, the vacuum degree is above 0.09MPa, the water is removed for 4h, the water content is reduced to below 600ppm; the temperature is reduced to below 40℃, the Miti A-1170 15g, dibutyl tin dilaurate 1.2g is added, the speed of 100r / min, the vacuum degree is above 0.09MPa, the stirring is carried out for 70min, it is sealed under the protection of nitrogen, the appearance of the said A component is obtained.

[0180] Take the molecular weight of 4000 polyoxypropylene diol 80g, put it into the reaction kettle, the temperature is raised to 90℃, the water is removed above 0.09MPa, the vacuum degree is 1h; the temperature is reduced to 70℃, MDI-50 900g is put in, the reaction is carried out under the protection of nitrogen for 1h; the molecular weight of 560 phthalic anhydride polyester diol 5g is put in after water removal, the reaction is carried out under the protection of nitrogen for 0.5h; 1,6-hexanediol 15g is added after water removal, the reaction is carried out under the protection of nitrogen for 1h, the curing agent is obtained, and it is sealed and stored for standby use.

[0181] Take the prepared curing agent 830g, calor HS461 130g, put it into the planetary stirred tank, the speed of 200r / min, the vacuum degree is above 0.09MPa, the stirring is carried out for 1.5h, until the mixture is uniform, then KH-560 13g, diisononyl phthalate 15g, zinc bismuth composite catalyst 2g are added, the speed of 200r / min, the vacuum degree is above 0.09MPa, the stirring is carried out for 60min, until the mixture is uniform, then fumed silica 10g is added, the speed of 200r / min, the vacuum degree is above 0.09MPa, the stirring is carried out for 50min, the mixture is uniform, the viscosity reaches 3×10 4 mPa·s, it is sealed and packaged under the protection of nitrogen, the said B component is obtained.

[0182] The prepared A component and B component are mixed uniformly according to the mass ratio of 17:1, and a high sealing two-component polyurethane sealant is obtained after curing at room temperature.

[0183] Example 5

[0184] Take polyoxypropylene diol with molecular weight of 1000 70 g, polyoxypropylene diol with molecular weight of 4000 190 g, polyoxypropylene triol with molecular weight of 500 20 g, diisodecyl phthalate 60 g, dibutyl phthalate 100 g, nano calcium carbonate 180 g, heavy calcium 273.3 g, glass flake 100 g, put into a planetary stirred tank, rotate at 500 r / min, heat to 120℃, dehydrate under the condition of vacuum degree above 0.09 MPa for 1 h, the water content is reduced to below 600 ppm; cool to below 40℃, add KH-792 5 g, zinc neodecanoate 1.7 g, rotate at 500 r / min, stir under the condition of vacuum degree above 0.09 MPa for 30 min, seal and package under nitrogen protection, thus the A component with uniform appearance and viscous texture is obtained.

[0185] Take polyoxypropylene diol with molecular weight of 2000 50 g, polyoxypropylene diol with molecular weight of 8000 57 g, put into a reaction kettle, heat to 102℃, remove water under the condition of vacuum degree above 0.09 MPa for 1.5 h; cool to 85℃, add zinc bismuth composite catalyst 6 g, mix uniformly, then put in TDI-80 844 g, react under nitrogen protection for 0.5 h; then put in water-removed phthalic anhydride polyester diol with molecular weight of 450 20 g, react under nitrogen protection for 1.5 h; then add water-removed 1,6-hexanediol 23 g, react under nitrogen protection for 1.5 h, thus the curing agent is obtained, which is sealed and stored for standby use.

[0186] Take the prepared curing agent 800 g, Kaylor HC585 100 g, put into a planetary stirred tank, rotate at 50 r / min, stir under the condition of vacuum degree above 0.09 MPa for 2.5 h, until mixed uniformly, then add KH-560 20 g, A-LINK35 20 g, diisodecyl phthalate 37 g, bismuth isooctoate 3 g, rotate at 50 r / min, stir under the condition of vacuum degree above 0.09 MPa for 120 min, until mixed uniformly, then add fumed silica 20 g, rotate at 50 r / min, stir under the condition of vacuum degree above 0.09 MPa for 100 min, mix uniformly, the viscosity reaches 7×10 4 mPa·s, seal and package under nitrogen protection, thus the B component is obtained.

[0187] Mix the prepared A component and B component uniformly according to the mass ratio of 14:1, after curing at room temperature, thus a high-sealing two-component polyurethane sealant is obtained.

[0188] Example 6

[0189] Take polyoxypropylene diol with molecular weight of 4000 104g, polyoxypropylene diol with molecular weight of 8000 187g, polyoxypropylene triol with molecular weight of 700 24g, polycarbonate diol with molecular weight of 2000 35g, light calcium carbonate 200g, active heavy calcium 300g, mica iron oxide 140g, put into the planetary stirred tank, the speed is 300r / min, the temperature is raised to 100℃, the vacuum degree is above 0.09MPa, and the water is removed for 3h, and the water content is reduced to below 600ppm; cool down to below 40℃, add KH-560 8.5g, bismuth isooctanoate 1.5g, stir at a speed of 300r / min under the condition of vacuum degree above 0.09MPa for 80min, seal and package under nitrogen protection, and the appearance of the obtained A component is viscous and uniform in texture.

[0190] Take polycarbonate diol with molecular weight of 2000 25g and polyoxypropylene diol with molecular weight of 4000 160g, put into the reaction kettle, heat to 110℃, remove water under the condition of vacuum degree above 0.09MPa for 2h; cool down to 80℃, put in MDI-10078 80g, react under nitrogen protection for 2h; then put in water-removed phthalic anhydride polyester diol with molecular weight of 560 35g, react under nitrogen protection for 2h, get the curing agent, seal and save for later use.

[0191] Take the prepared curing agent 808g and kaylor HC460 100g, put into the planetary stirred tank, stir at a speed of 150r / min under the condition of vacuum degree above 0.09MPa for 2h, until mixed evenly, add A-LINK25 10g, A-LINK35 10g, diisononyl phthalate 28g, zinc neodecanoate 4g, stir at a speed of 150r / min under the condition of vacuum degree above 0.09MPa for 100min, until mixed evenly, add fumed silica 40g, stir at a speed of 150r / min under the condition of vacuum degree above 0.09MPa for 80min, mix evenly, the viscosity reaches 11×10 4 mPa·s, seal and package under nitrogen protection, and the B component is obtained.

[0192] Mix the prepared A component and B component according to the mass ratio of 13.5:1 evenly, and after curing at room temperature, a high sealing two-component polyurethane sealant is obtained.

[0193] Example 7

[0194] Take polyoxypropylene diol with molecular weight of 4000 150 g, polyoxypropylene triol with molecular weight of 400 20 g, polycarbonate diol with molecular weight of 2000 80 g, diisononyl phthalate 51 g, nano calcium carbonate 220 g, heavy calcium 340 g, glass flake 120 g, put into a planetary stirred tank, rotate at 50 r / min, raise the temperature to 90℃, dehydrate under the condition of vacuum degree above 0.09 MPa for 5 h, the water content is reduced to below 600 ppm; cool down to below 40℃, add KH-560 9 g, KH-550 9 g, zinc bismuth composite catalyst 1 g, rotate at 50 r / min, stir under the condition of vacuum degree above 0.09 MPa for 110 min, seal and package under nitrogen protection, thus the A component with uniform appearance and viscous texture is obtained.

[0195] Take polycarbonate diol with molecular weight of 1000 100 g, polyoxypropylene diol with molecular weight of 4000 58 g, put into a reaction kettle, raise the temperature to 93℃, remove water under the condition of vacuum degree above 0.09 MPa for 1.5 h; cool down to 76℃, add lead isooctoate 2 g, mix uniformly, then put in HDI 820 g, react under nitrogen protection for 1.5 h; then put in phthalic anhydride polyester diol with molecular weight of 350 after water removal 15 g, react under nitrogen protection for 1 h; then add 1,4-butanediol after water removal 5 g, react under nitrogen protection for 0.5 h, thus the curing agent is obtained, which is sealed and stored for standby use.

[0196] Take the prepared curing agent 850 g, Kaylor HS461 124.5 g, put into a planetary stirred tank, rotate at 450 r / min, stir under the condition of vacuum degree above 0.09 MPa for 0.5 h, until mixed uniformly, then add KH-560 11 g, dibutyltin dilaurate 1.5 g, rotate at 450 r / min, stir under the condition of vacuum degree above 0.09 MPa for 80 min, until mixed uniformly, then add fumed silica 13 g, rotate at 450 r / min, stir under the condition of vacuum degree above 0.09 MPa for 120 min, mix uniformly, the viscosity reaches 5×10 4 mPa·s, seal and package under nitrogen protection, thus the B component is obtained.

[0197] Mix the prepared A component and B component uniformly according to the mass ratio of 18:1, after room temperature curing, thus a high sealing two-component polyurethane sealant is obtained.

[0198] Example 8

[0199] Take polyoxypropylene glycol with molecular weight of 4000 157 g, polyoxypropylene triol with molecular weight of 400 8 g, polyoxypropylene triol with molecular weight of 500 5 g, diisodecyl phthalate 100 g, diisononyl phthalate 70 g, light calcium carbonate 187.5 g, talc 300 g, mica iron oxide 160 g, put into a planetary stirred tank, rotate at 250 r / min, heat to 105℃, dehydrate under the condition of vacuum degree above 0.09 MPa for 2.5 h, the water content is reduced to below 600 ppm; cool to below 40℃, add Mito A-1170 12 g, lead isooctoate 0.5 g, stir under the condition of rotate at 250 r / min and vacuum degree above 0.09 MPa for 90 min, seal and package under nitrogen protection, thus the A component with uniform appearance and viscous texture is obtained.

[0200] Take polyoxypropylene glycol with molecular weight of 1000 200 g, polyoxypropylene glycol with molecular weight of 8000 28 g, put into a reaction kettle, heat to 98℃, remove water under the condition of vacuum degree above 0.09 MPa for 2 h; cool to 83℃, add stannous octoate 8 g, mix uniformly, then put in TDI-80 730 g, react under nitrogen protection for 2 h; then put in phthalic anhydride polyester diol with molecular weight of 280 after water removal 8 g, react under nitrogen protection for 0.5 h; then add diethylene glycol after water removal 26 g, react under nitrogen protection for 2 h, thus the curing agent is obtained, which is sealed and stored for standby use.

[0201] Take the prepared curing agent 762 g, Kaylor HC585 154 g, put into a planetary stirred tank, stir under the condition of rotate at 250 r / min and vacuum degree above 0.09 MPa for 1 h until mixed uniformly, then add A-LINK 3510 g, dibutyl phthalate 50 g, N-methyl morpholine 2 g, stir under the condition of rotate at 250 r / min and vacuum degree above 0.09 MPa for 15 min until mixed uniformly, then add fumed silica 22 g, stir under the condition of rotate at 250 r / min and vacuum degree above 0.09 MPa for 60 min until mixed uniformly, the viscosity reaches 7.5×10 4 mPa·s, seal and package under nitrogen protection, thus the B component is obtained.

[0202] Mix the prepared A component and B component uniformly according to the mass ratio of 20:1, after curing at room temperature, thus a high sealing two-component polyurethane sealant is obtained.

[0203] Example 9

[0204] Take polyoxypropylene diol with molecular weight of 1000 18 g, polyoxypropylene diol with molecular weight of 8000 279 g, polyoxypropylene triol with molecular weight of 300 3 g, polyoxypropylene triol with molecular weight of 1000 20 g, dioctyl phthalate 100 g, dibutyl phthalate 130 g, light calcium carbonate 150 g, active heavy calcium 205 g, glass flake 80 g, put into a planetary stirred tank, rotate at 320 r / min, heat to 115℃, dehydrate under the condition of vacuum degree above 0.09 MPa for 3.5 h, the water content is reduced to below 600 ppm; cool to below 40℃, add KH-792 14 g, stannous octoate 1 g, stir under the condition of rotate at 320 r / min and vacuum degree above 0.09 MPa for 120 min, seal and package under nitrogen protection, thus the A component with uniform appearance and viscous texture is obtained.

[0205] Take polyoxypropylene diol with molecular weight of 2000 50 g, polyoxypropylene diol with molecular weight of 4000 50 g, put into a reaction kettle, heat to 95℃, remove water under the condition of vacuum degree above 0.09 MPa for 1.5 h; cool to 73℃, add dibutyltin dilaurate 1 g, mix uniformly, then put MDI-50 870 g, react under nitrogen protection for 2.5 h; then put the water-removed benzoic anhydride polyester diol with molecular weight of 560 25 g, react under nitrogen protection for 1.5 h; then add water-removed 1,6-hexanediol 4 g, react under nitrogen protection for 0.5 h, thus the curing agent is obtained, which is sealed and stored for standby use.

[0206] Take the prepared curing agent 750 g, Kaylor HC460 180 g, put into a planetary stirred tank, stir under the condition of rotate at 150 r / min and vacuum degree above 0.09 MPa for 2.5 h, until mixed uniformly, then add A-LINK25 18 g, N,N'-dimethylpyridine 1 g, bis(2-dimethylaminoethyl) ether 1 g, stir under the condition of rotate at 150 r / min and vacuum degree above 0.09 MPa for 50 min, until mixed uniformly, then add fumed silica 50 g, stir under the condition of rotate at 150 r / min and vacuum degree above 0.09 MPa for 90 min, mix uniformly, the viscosity reaches 12×10 4 mPa·s, seal and package under nitrogen protection, thus the B component is obtained.

[0207] Mix the prepared A component and B component uniformly according to the mass ratio of 15.5:1, after room temperature curing, thus a high sealing two-component polyurethane sealant is obtained.

[0208] Example 10

[0209] The preparation method of Example 10 is similar to that of Example 1, except that polyoxypropylene glycol with molecular weight of 1000 and 2000 is used to replace polycarbonate glycol with molecular weight of 1000 and 2000 in the A component; polyoxypropylene glycol with molecular weight of 1000 is used to replace polycarbonate glycol with molecular weight of 1000 in the B component curing agent.

[0210] Example 11

[0211] The preparation method of Example 11 is similar to that of Example 1, except that the common curing agent MDI prepolymer (Kaneka E22) is used to replace the curing agent prepared in Example 1 in the B component.

[0212] Comparative Example 1

[0213] The preparation method of Comparative Example 1 is similar to that of Example 2, except that the barrier type filler is not contained in the A component.

[0214] Table 1

[0215]

[0216] As can be seen from the above Table 1, the performance of the high-sealing two-component polyurethane sealant prepared in the application meets and exceeds the various requirements in the GB / T 29755-2013 standard, and the sealant has high tensile bonding strength, good elasticity, and no bonding damage under standard experimental conditions; the tensile bonding strength of the examples using polycarbonate glycol is higher, the elasticity is better, the tensile bonding strength decreases by 20%-25% after water and ultraviolet treatment, the elongation at maximum tensile bonding strength increases by 100%-105%; after hot air aging, the tensile bonding strength slightly increases, and the elongation at maximum tensile bonding strength does not change; the tensile bonding strength of the examples not using polycarbonate glycol decreases by 25%-30% after water and ultraviolet treatment, the elongation at maximum tensile bonding strength increases by 90%-100%; after hot air aging, the tensile bonding strength slightly increases, and the elongation at maximum tensile bonding strength does not change.

[0217] Comparing Example 1 using polycarbonate glycol with Example 10 using polyoxypropylene glycol, the tensile bonding strength under standard experimental conditions increases by 19.8%, the elongation at maximum tensile bonding strength increases by 16.7%; the tensile bonding strength after water and ultraviolet treatment increases by 22.5%, the elongation at maximum tensile bonding strength increases by 20.3%; after hot air aging, the tensile bonding strength increases by 19.4%, the elongation at maximum tensile bonding strength increases by 16.7%.

[0218] Comparative Example 1, the tensile bonding strength decreased by 49%, the water vapor transmission rate index increased by 2400%, and the performance of the sealant decreased.

[0219] The water vapor transmission rate index of the comparative example without adding a barrier filler was 4 g / (m 2 ·d, while the water vapor transmission rate index of the high-sealing two-component polyurethane sealant of the present application was (0-1) g / (m 2 ·d, and the sealing performance was greatly improved.

Claims

1. A high sealing two-component polyurethane sealant, characterized by, Comprise a group A and a group B, wherein, The A group comprises the following raw materials by mass percentage: A first polyol, 10%~35%; A filler, 35%~80%; A first auxiliary agent, 0.01%~32.2%; Wherein, the filler comprises a barrier type filler, the mass percentage of the barrier type filler in the raw materials of the A group is 5%~20%; The B group comprises the following raw materials by mass percentage: A curing agent, 68%~85%; A thickening agent, 1%~5%; A second auxiliary agent, 11%~30.5%; The mass ratio of the A group to the B group is (13~20):1; The curing agent in the B group comprises the following raw materials by mass percentage: Isocyanate, 70%~90%; A second polyol, 8.5%~29%; A third auxiliary agent, 0~4%; Wherein, the second polyol comprises phthalic anhydride polyester polyol, and polyoxypropylene glycol and / or polycarbonate glycol.

2. The high sealing two-component polyurethane sealant according to claim 1, characterized in that, The barrier type filler comprises mica iron oxide and / or glass flake.

3. The high-sealing two-component polyurethane sealant according to claim 1 or 2, characterized in that, The mass percentage of the phthalic anhydride polyester polyol in the raw materials of the curing agent is 0.5%~4%.

4. The high sealing two-component polyurethane sealant according to claim 3, characterized in that, The curing agent in the B group satisfies at least one of the following conditions: (1) Based on the total mass of the curing agent, the third auxiliary agent comprises the following raw materials by mass percentage: Chain extender, 0~3%; Second catalyst, 0~1%; Optionally, the chain extender comprises one or more of 1,4-butanediol, ethylene glycol, diethylene glycol and 1,6-hexanediol; Optionally, the second catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, lead isooctoate, zinc bismuth composite catalyst, bismuth isooctoate and zinc neodecanoate; (2) The molecular weight of the polyoxypropylene glycol is one or more of 1000, 2000, 4000 and 8000; The molecular weight of the polycarbonate glycol is one or more of 1000 and 2000; (3) The phthalic anhydride polyester polyol comprises phthalic anhydride polyester glycol; Optionally, the molecular weight of the phthalic anhydride polyester glycol is one or more of 280, 350, 450 and 560; (4) The isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.

5. The high-sealing two-component polyurethane sealant according to claim 1 or 2, characterized in that, The high-sealing two-component polyurethane sealant satisfies at least one of the following conditions: (1) The first polyol comprises polyether polyol and / or polyester polyol; Optionally, the polyether polyol comprises polyoxypropylene glycol and / or polyoxypropylene triol; Optionally, the polyester polyol comprises polycarbonate glycol; Further optionally, the molecular weight of the polyoxypropylene glycol is one or more of 1000, 2000, 4000 and 8000; Further optionally, the molecular weight of the polyoxypropylene triol is one or more of 300, 400, 500, 700 and 1000; Further optionally, the molecular weight of the polycarbonate glycol is one or more of 1000 and 2000; (2) the filler further comprises one or more of nano calcium carbonate, heavy calcium carbonate, active heavy calcium carbonate, talcum powder, and light calcium carbonate; (3) the thickening agent comprises fumed silica.

6. The high-sealing two-component polyurethane sealant according to claim 1 or 2, characterized in that, The high-sealing two-component polyurethane sealant satisfies at least one of the following conditions: (1) based on the total mass of the A component, the first additive comprises the following raw materials in mass percentage: a plasticizer, 0-30%; a first catalyst, 0.01%-0.2%; a first coupling agent, 0-2%; (2) based on the total mass of the B component, the second additive comprises the following raw materials in mass percentage: a color paste, 10%-20%; a second coupling agent, 1%-5%; a first catalyst, 0-0.5%; a plasticizer, 0-5%.

7. The high-sealing two-component polyurethane sealant according to claim 6, characterized in that, The high-sealing two-component polyurethane sealant satisfies at least one of the following conditions: (1) the plasticizer comprises one or more of diisodecyl phthalate, diisononyl phthalate, dibutyl phthalate, and dioctyl phthalate; (2) the first catalyst comprises one or more of a tertiary amine catalyst and an organic metal catalyst; Optionally, the tertiary amine catalyst comprises one or more of an aliphatic amine catalyst, an ester ring amine catalyst, and an aromatic amine catalyst; Optionally, the organic metal catalyst comprises one or more of dibutyl tin dilaurate, stannous octoate, lead isooctoate, zinc bismuth composite catalyst, bismuth isooctoate, and zinc neodecanoate; (3) the first coupling agent comprises one or more of γ-(2,3-epoxypropoxy)propyl trimethoxysilane, γ-aminopropyl triethoxysilane, bis-(γ-trimethoxysilylpropyl) amine, and N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane; Optionally, the first coupling agent comprises one or more of KH-560, KH-550, Momentive A-1170, and KH-792; (4) the color paste comprises one or more of Kahl HC460, Kahl HC585, and Kahl HS461; (5) the second coupling agent comprises one or more of γ-(2,3-epoxypropoxy)propyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane; Optionally, the second coupling agent comprises one or more of KH-560, A-LINK35, and A-LINK25.

8. A process for the preparation of the high sealing two-component polyurethane sealant according to any one of claims 1 to 7, characterized in that, Comprise: mixing the components contained in the A component, and then performing heat treatment and dehydration treatment to obtain the A component; mixing the components contained in the B component to obtain the B component; mixing the A component and the B component in a mass ratio of (13-20):1, and then performing solidification to obtain the high-sealing two-component polyurethane sealant.

9. The method of claim 8, wherein, The mixing of the components contained in the A component, and then performing heat treatment and dehydration treatment, comprises: mixing the first polyol and the filler containing the barrier type filler, and then heating to 80-120°C, and dehydrating under vacuum for 1-5h until the water content is reduced to below 600ppm to obtain a premix; Optionally, a plasticizer is added during the mixing of the first polyol and the filler containing the barrier type filler; The premix is cooled to below 40℃, a first catalyst is added, and the mixture is mixed and stirred under vacuum until uniform; Optionally, a first coupling agent is added during the mixing of the premix and the first catalyst; Optionally, the vacuum degree of the vacuum condition is above 0.09 MPa.

10. The method of claim 8, wherein, The mixing of the components contained in the B component includes: After the curing agent and the color paste are mixed evenly under vacuum, the second coupling agent is added and mixed evenly, and the thickening agent is added under stirring until the viscosity is (3 x 10 4 )mPa.s~(12 x 10 4 )mPa.s; Optionally, a first catalyst and / or a plasticizer are added during the step of adding the second coupling agent; Optionally, the stirring rate of the stirring state is 50 r / min to 500 r / min.

11. The method according to any one of claims 8-10, characterized in that, The step of preparing the curing agent further includes: reacting the isocyanate with the second polyol treated by water removal to obtain the curing agent.

12. The method of claim 11, wherein, The step of preparing the curing agent further includes: pre-reacting the isocyanate with the second polyol treated by water removal, wherein the second polyol does not contain phthalic anhydride polyester polyol, Optionally, the pre-reaction temperature is 70℃ to 85℃, the pre-reaction time is 0.5h to 3h, and the pre-reaction atmosphere is a nitrogen atmosphere, Optionally, a second catalyst is mixed in the second polyol treated by water removal; reacting with the phthalic anhydride polyester polyol treated by water removal, Optionally, the reaction temperature is 70℃ to 85℃, the reaction time is 0.5h to 2h, and the reaction atmosphere is a nitrogen atmosphere; Optionally, after the reaction of the phthalic anhydride polyester polyol treated by water removal, a chain extender treated by water removal is added for further reaction, the reaction temperature is 70℃ to 85℃, the reaction time is 0.5h to 2h, and the reaction atmosphere is a nitrogen atmosphere.

13. Use of a high sealing two-component polyurethane sealant in insulating glass, characterized in that The high-sealing two-component polyurethane sealant includes the high-sealing two-component polyurethane sealant of any one of claims 1-7 or the high-sealing two-component polyurethane sealant prepared according to the method of any one of claims 8-12.

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