Silane modified polyurethane resin, low-temperature-resistant polyurethane toughened modified epoxy daub as well as preparation method and application of low-temperature-resistant polyurethane toughened modified epoxy daub

Abstract

The invention discloses silane modified polyurethane resin, low-temperature-resistant polyurethane toughened and modified epoxy daub as well as a preparation method and application of the low-temperature-resistant polyurethane toughened and modified epoxy daub. The silane modified polyurethane resin disclosed by the invention is prepared from raw materials including a hydroxyl component, a monofunctional NCO-based silane substance and a polyfunctional NCO component. The prepared silane modified polyurethane resin is added into the low-temperature-resistant polyurethane toughening modified epoxy plaster disclosed by the invention. According to the invention, new silane modified polyurethane resin is prepared, and the silane modified polyurethane resin is adopted to carry out toughening modification on epoxy resin according to the structure-function relationship between the structure and the performance of a high polymer material, so that the material has a lower glass transition temperature and a suitable rigid-flexible chain segment ratio, and the purpose of toughening modification is achieved; and the adhesive property and the mechanical property are better at low temperature.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial adhesives for energy transportation and storage, and more particularly to a silane-modified polyurethane resin, a low-temperature-resistant polyurethane toughened modified epoxy mortar, and a preparation method and application thereof. Background Art

[0002] Liquefied oil and gas transportation and storage facilities primarily include liquefied oil and gas vessels, shore tanks, and pipelines. Their construction involves bonding the outer layers of insulation panels, such as polyurethane foam, to the steel plates of the vessel's tank and pipe walls. Epoxy mortar is widely used in this area due to its excellent properties, including load-bearing capacity, excellent compression creep resistance, and good bonding properties.

[0003] However, epoxy putty is hard and brittle after curing, which is more pronounced when used under low temperature conditions. The main reason is that in low temperature environments, the thermal motion of the molecular chain slows down, the flexibility of the molecular chain decreases, the distance between molecules decreases, and the stress between molecules and within molecules increases, which will change the performance of epoxy putty.

[0004] Therefore, how to effectively carry out toughening modification of epoxy putty is a technical problem that needs to be solved at present. Summary of the Invention

[0005] To address the problems encountered in the prior art, the present invention proposes a silane-modified polyurethane resin, a low-temperature-resistant polyurethane toughened modified epoxy mortar, and their preparation methods and applications. The present invention prepares a new silane-modified polyurethane resin and, based on the structure-activity relationship between polymer structure and performance, uses the silane-modified polyurethane resin to toughen and modify the epoxy resin. This results in a material with a lower glass transition temperature and an appropriate ratio of rigid to flexible segments, achieving the desired toughening and modification, and exhibiting superior low-temperature adhesive and mechanical properties.

[0006] One of the purposes of the present invention is to provide a silane-modified polyurethane resin, wherein the silane-modified polyurethane resin is prepared from raw materials including a hydroxyl component, a monofunctional NCO-based silane substance, and a multifunctional NCO component.

[0007] In the silane-modified polyurethane resin of the present invention, preferably,

[0008] The hydroxyl component is selected from at least one of polyether, polybutylene adipate, castor oil or soybean oil; preferably, the polyether is selected from at least one of polypropylene glycol, polyethylene glycol or polybutylene glycol; further preferably, the hydroxyl component is selected from at least one of polyether or a combination of polyether and castor oil; further preferably, when the hydroxyl component is selected from the combination of polyether and castor oil, the mass ratio of polyether to castor oil is 50-100:30-35; and / or,

[0009] The monofunctional NCO-based silane substance is selected from NCO-terminated silanes; preferably, the monofunctional NCO-based silane substance is selected from at least one of 3-isocyanate propyl trimethoxysilane (A-Link35) or 3-isocyanate propyl triethoxysilane (A-Link25), and the above 3-isocyanate propyl trimethoxysilane (A-Link35) or 3-isocyanate propyl triethoxysilane (A-Link25) can be purchased from Momentive; and / or,

[0010] The polyfunctional NCO component is selected from at least one of diisocyanates and polymers formed with diisocyanates as raw materials; preferably, the diisocyanate is selected from at least one of TDI (toluene-2,4-diisocyanate), MDI-50 (a mixture of 2,4-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate), MDI (diphenylmethane diisocyanate), IPDI (isophorone diisocyanate), and HDI (hexamethylene diisocyanate).

[0011] In the silane-modified polyurethane resin of the present invention, preferably,

[0012] In parts by weight,

[0013] The hydroxyl component is 30-150 parts; preferably 30-135 parts; for example: 30, 60, 90, 120, 150 parts;

[0014] The monofunctional NCO-based silane substance is 6-12 parts; preferably 6-10 parts; for example: 6, 7, 8, 9, 10, 11, 12 parts;

[0015] The polyfunctional NCO component is 9-15 parts, preferably 11-13 parts, such as 9, 10, 11, 12, 13, 14, 15 parts.

[0016] A second object of the present invention is to provide a method for preparing the silane-modified polyurethane resin as described in one of the objects of the present invention, comprising the following steps:

[0017] The hydroxyl component first reacts with a monofunctional NCO-based silane substance and then a multifunctional NCO component is added to react to obtain a silane-modified polyurethane resin;

[0018] Preferably,

[0019] (1) After heating the hydroxyl component with stirring, add a monofunctional NCO-based silane substance and continue to heat the reaction until the NCO value is less than 0.02%;

[0020] (2) Cooling, adding multifunctional NCO components, raising the temperature to react until the NCO value is less than 0.02%, measuring the hydroxyl value of the resin, and discharging the material after the hydroxyl value is qualified.

[0021] The silane-modified polyurethane resin of the present invention is a hydroxyl-terminated polyurethane resin with a hydroxyl value of 50-180 mgKOH / g, for example, 50, 80, 110, 140, 170, 180 mgKOH / g.

[0022] The silane-modified polyurethane resin prepared by the present invention through reasonable proportion of hydroxyl components, monofunctional NCO-based silane substances and multifunctional NCO components and designed reaction conditions can perform toughening modification on epoxy resin.

[0023] In the preparation method of the silane-modified polyurethane resin of the present invention, preferably,

[0024] In step (1), the heating temperature is 50-60°C; for example, 50°C, 52°C, 54°C, 56°C, 58°C, 60°C;

[0025] Continue to heat the reaction to a temperature of 80-90°C; for example: 80°C, 82°C, 84°C, 86°C, 88°C, 90°C;

[0026] Continue heating the reaction for ≥ 2 hours. Preferably, after 2 hours of reaction, measure the NCO value every 0.5 hours until the NCO value is less than 0.02%;

[0027] In step (2), the cooling temperature is below 50°C;

[0028] The temperature of the temperature-raising reaction is 80-90°C; for example: 80°C, 82°C, 84°C, 86°C, 88°C, 90°C;

[0029] The temperature-raising reaction time is ≥ 2 hours. Preferably, after 2 hours of reaction, the NCO value is measured every 0.5 hours until the NCO value is less than 0.02%.

[0030] The third object of the present invention is to provide a low-temperature resistant polyurethane toughened modified epoxy mortar, wherein the mortar is prepared from raw materials including component A and component B;

[0031] Wherein, component A includes, by weight: 15-50 parts of epoxy resin, such as 15, 20, 25, 30, 35, 40, 45, 50 parts; 5-30 parts of silane-modified polyurethane resin, such as 5, 10, 15, 20, 25, 30 parts; 1-10 parts of diluent, such as 1, 3, 5, 7, 10 parts; 40-75 parts of filler, such as 40, 45, 50, 55, 60, 65, 70, 75 parts; 0.5-5 parts of thixotropic agent, such as 0.5, 1, 2, 3, 4, 5 parts; 0.1-1 part of pigment, such as 0.1, 0.3, 0.5, 0.7, 1 part;

[0032] The silane-modified polyurethane resin is selected from the silane-modified polyurethane resin described in one of the objectives of the present invention or the silane-modified polyurethane resin prepared by the method described in the second objective of the present invention;

[0033] In parts by weight, component B includes: 30-50 parts of amine curing agent, such as: 30, 35, 40, 45, 50 parts, 0.5-5 parts of curing accelerator, such as: 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 parts, 40-65 parts of filler, such as: 40, 45, 50, 55, 60, 65 parts, 0.5-5 parts of diluent, such as: 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 parts;

[0034] The mass ratio of component A to component B is 1:(0.5-1.5), for example: 1:0.5, 1:0.75, 1:1, 1:1.25, 1:1.5.

[0035] In the low-temperature resistant polyurethane toughened modified epoxy putty described in the present invention, preferably,

[0036] Component A comprises 30-45 parts of epoxy resin, 5-20 parts of silane-modified polyurethane resin, 3-8 parts of diluent, 50-65 parts of filler, 1-3 parts of thixotropic agent, and 0.1-1 part of pigment; and / or

[0037] In component A,

[0038] The epoxy resin is a bisphenol A epoxy resin; preferably, the epoxy equivalent of the epoxy resin is 0.13-0.56 eq / 100 g and the viscosity is 8000-20000 mPa·s; more preferably, the bisphenol A epoxy resin has an epoxy equivalent of 0.40-0.56 eq / 100 g and a viscosity of 12000-18000 mPa·s;

[0039] and / or,

[0040] The diluent is selected from at least one of C2-C16 glycidyl ethers; preferably, the diluent is selected from at least one of dodecyl glycidyl ether, ethylene glycol glycidyl ether, and 1,4-butanediol diglycidyl ether; and / or,

[0041] The filler is selected from at least one of inorganic fillers; preferably, the filler is selected from at least one of fumed silica, wollastonite, heavy calcium carbonate, light calcium carbonate or quartz powder; and / or,

[0042] The thixotropic agent is selected from at least one of hydrogenated castor oil, polyamide wax, fumed silica or light calcium carbonate; and / or,

[0043] The pigment is selected from at least one of azo pigments, preferably, the pigment is selected from dioxazine pigments, and further preferably, the pigment is selected from CI pigment series.

[0044] In the low-temperature resistant polyurethane toughened modified epoxy putty described in the present invention, preferably,

[0045] In component B, 35-45 parts of amine curing agent, 1-4 parts of curing accelerator, 45-60 parts of filler, and 1-4 parts of diluent; and / or,

[0046] In component B,

[0047] The amine curing agent is selected from at least one of polyamide curing agents; preferably, the active hydrogen equivalent of the amine curing agent is 90-250 g / eq and the viscosity is 100-4000 mPa·s; and / or,

[0048] The curing accelerator is selected from at least one of small molecule amines or piperazine accelerators; preferably, the curing accelerator is selected from at least one of triethanolamine, N-aminoethylpiperazine, 2-ethyl-4-methylimidazole, benzoyl peroxide, and nonylphenol; and / or,

[0049] The filler is selected from at least one of inorganic fillers; preferably, the filler is selected from at least one of fumed silica, wollastonite, heavy calcium carbonate, light calcium carbonate or quartz powder; and / or,

[0050] The diluent is selected from at least one low-volatile organic solvent; preferably, the diluent is selected from at least one alcohol solvent; further preferably, the diluent is selected from at least one of benzyl alcohol, n-butanol or methanol.

[0051] A fourth object of the present invention is to provide a method for preparing the low-temperature resistant polyurethane toughened modified epoxy mortar as described in any one of the third objects of the present invention, comprising the following steps:

[0052] The raw materials in component A are heated and mixed; the raw materials in component B are heated and mixed, and then components A and B are mixed evenly to obtain the low-temperature resistant polyurethane toughened modified epoxy putty;

[0053] Preferably,

[0054] When the raw materials in component A and component B are heated and mixed, the heating and mixing temperature is independently selected from 30-80° C.; the mixing and stirring time is independently selected from 1-2 hours, and the materials are independently dispersed 2-4 times by a three-roll mill before being discharged.

[0055] The fifth object of the present invention is to provide an application of a low-temperature resistant polyurethane toughened modified epoxy putty as described in any one of the third objects of the present invention as an adhesive; preferably, it is used as an adhesive for transportation and storage devices of clean energy; further preferably, it is used as an adhesive for bonding metal and wood materials in liquefied oil and gas ships, shore tanks, and shore station liquid cargo containment systems.

[0056] The endpoints and any values of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and a separate point value, and the separate point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in this article.

[0057] Compared with the prior art, the present invention has at least the following advantages:

[0058] The present invention prepares a new silane-modified polyurethane resin, and based on the structure-activity relationship between the structure and performance of polymer materials, uses the silane-modified polyurethane resin to toughen and modify the epoxy resin, so that the material itself has a lower glass transition temperature and a suitable ratio of rigid and flexible segments, achieving the purpose of toughening and modification, and having better bonding and mechanical properties at low temperatures. DETAILED DESCRIPTION

[0059] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0060] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0061] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the scope of protection of the present invention.

[0062] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0063] Performance testing method:

[0064] 1: Low-temperature mechanical properties: dumbbell-shaped specimens were made according to ISO 604 standard. After curing at 100°C for 3 hours, mechanical properties tests were performed at -40°C and 23°C, and data such as tensile strength and elongation at break were collected.

[0065] 2. Low-temperature bonding performance: According to ISO 4587, epoxy putty was bonded to stainless steel plates. After curing at 100°C for 3 hours, the bonded specimens were subjected to shear performance tests at -40°C and 23°C, and shear performance data was collected.

[0066] Example 1

[0067] The preparation method of the silane-modified polyurethane resin comprises the following steps, and the amounts of the raw materials used are shown in Table 1:

[0068] (1) Add PPG1000 and PPG400 into the reactor, mix and stir, and heat to 50°C;

[0069] (2) Add A-link35 according to the recipe and slowly raise the temperature to 85°C;

[0070] (3) After reacting for 2 h at 85°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0071] (4) Cool down to below 50°C, add MDI according to the formula, and slowly raise the temperature to 85°C;

[0072] (5) After reacting for 2 h at 85°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0073] (6) Discharge the material after the hydroxyl value is qualified.

[0074] Table 1 Silane modified polyurethane resin 1# composition and weight parts are as follows:

[0075]

[0076] The preparation method of low-temperature resistant polyurethane toughened modified epoxy mortar has the following steps, and the amounts of the raw materials used are shown in Table 2 and Table 3:

[0077] (1) Bisphenol A epoxy resin, silane-modified polyurethane resin 1#, heavy calcium carbonate, 1,4-butanediol diglycidyl ether, fumed silica, and C.I Pigment Red were added to a reaction kettle in sequence, heated to 55°C, mixed and stirred for 1 hour, and dispersed four times on a three-roll mill before discharging to obtain component A;

[0078] (2) polyamide resin, N-aminoethylpiperazine, heavy calcium carbonate and benzyl alcohol were added to a reaction kettle in sequence, heated to 55°C, mixed and stirred for 1 hour, dispersed four times on a three-roll mill, and then discharged to obtain component B;

[0079] (3) Component A of step (1) and component B of step (2) are mixed uniformly in a weight ratio of 1:0.9 to obtain a low-temperature resistant polyurethane toughened modified epoxy putty.

[0080] The composition and weight parts of the components in Table 2A are as follows:

[0081] raw material Epoxy equivalent eq / 100g Hydroxyl value mgKOH / g Number of copies Bisphenol A epoxy resin 0.51 37 Heavy calcium carbonate 58 Silane modified polyurethane resin 1# 140 15 1,4-Butanediol diglycidyl ether 6 Fumed silica 2.5 C.IPigment Red 0.5

[0082] Table 3B components and weight parts are as follows:

[0083] raw material Active hydrogen equivalent g / eq Number of copies polyamide resin 230 46 Heavy calcium carbonate 56 N-Aminoethylpiperazine 3 Benzyl alcohol 2

[0084] Example 2

[0085] The preparation method of the silane-modified polyurethane resin 2# comprises the following steps, and the amounts of the raw materials used are shown in Table 4:

[0086] (1) Add PPG1000 to the reactor, stir and heat to 60°C;

[0087] (2) Add A-link25 according to the recipe and slowly raise the temperature to 80°C;

[0088] (3) After reacting for 2 h at 80°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0089] (4) Cool down to below 50°C, add MDI according to the formula, and slowly raise the temperature to 80°C;

[0090] (5) After reacting for 2 h at 80°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0091] (6) Discharge the material after the hydroxyl value is qualified.

[0092] Table 4 Silane modified polyurethane resin 2# composition and weight parts are as follows:

[0093]

[0094] The preparation method of the above-mentioned low-temperature resistant polyurethane toughened modified epoxy mortar has the following steps, and the amounts of the raw materials used are shown in Table 5 and Table 6:

[0095] (1) Bisphenol A epoxy resin, silane-modified polyurethane resin 2#, heavy calcium carbonate, lauryl glycidyl ether, fumed silica, and C.I Pigment Green were added to a reactor in sequence, heated to 45°C, mixed and stirred for 1 hour, and dispersed four times on a three-roll mill before discharging to obtain component A;

[0096] (2) polyamide resin, N-aminoethylpiperazine, heavy calcium carbonate and methanol were added to a reaction kettle in sequence, heated to 45°C, mixed and stirred for 1 hour, dispersed four times on a three-roll mill and then discharged to obtain component B;

[0097] (3) Component A of step (1) and component B of step (2) are mixed uniformly in a weight ratio of 1:1.1 to obtain a low-temperature resistant polyurethane toughened modified epoxy putty.

[0098] The composition and weight parts of the components in Table 5A are as follows:

[0099] raw material Epoxy equivalent eq / 100g Hydroxyl value mgKOH / g Parts by weight Bisphenol A epoxy resin 0.55 35 Heavy calcium carbonate 65 Silane modified polyurethane resin 2# 60 5 Dodecyl glycidyl ether 5 Fumed silica 3 C.IPigment Green 0.5

[0100] Table 6B components and weight parts are as follows:

[0101] raw material Active hydrogen equivalent g / eq Number of copies polyamide resin 240 40 Heavy calcium carbonate 55 N-Aminoethylpiperazine 3 Methanol 2

[0102] Example 3

[0103] The preparation method of silane-modified polyurethane resin 3# is as follows. The amounts of the raw materials used are shown in Table 7:

[0104] (1) PPG1000 and castor oil were added to a reactor, stirred and heated to 50°C;

[0105] (2) Add A-link35 according to the recipe and slowly raise the temperature to 90°C;

[0106] (3) After reacting for 2 h at 90°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0107] (4) Cool down to below 50°C, add MDI according to the formula, and slowly raise the temperature to 90°C;

[0108] (5) After reacting for 2 h at 90°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0109] (6) Discharge the material after the hydroxyl value is qualified.

[0110] Table 7 Silane modified polyurethane resin 3# composition and weight parts are as follows:

[0111]

[0112] The preparation method of the above-mentioned low-temperature resistant polyurethane toughened modified epoxy mortar has the following steps, and the amounts of the raw materials used are shown in Tables 8 and 9:

[0113] (1) Bisphenol A epoxy resin, silane-modified polyurethane resin 3#, heavy calcium carbonate, 1,4-butanediol diglycidyl ether, fumed silica, and C.I Pigment Green were added to a reaction kettle in sequence, heated to 60°C, mixed and stirred for 1 hour, and dispersed four times on a three-roll mill before discharging to obtain component A;

[0114] (2) polyamide resin, N-aminoethylpiperazine, heavy calcium carbonate and methanol were added to a reaction kettle in sequence, heated to 50°C, mixed and stirred for 1 hour, dispersed four times on a three-roll mill and then discharged to obtain component B;

[0115] (3) Component A of step (1) and component B of step (2) are mixed uniformly in a weight ratio of 1:0.9 to obtain a low-temperature resistant polyurethane toughened modified epoxy putty.

[0116] The composition and weight parts of the components in Table 8A are as follows:

[0117]

[0118]

[0119] Table 9B components and weight parts are as follows:

[0120] raw material Active hydrogen equivalent g / eq Number of copies polyamide resin 240 40 Heavy calcium carbonate 55 N-Aminoethylpiperazine 3 Methanol 2

[0121] Example 4

[0122] The preparation method of silane-modified polyurethane resin 4# is as follows. The amounts of the raw materials used are shown in Table 10:

[0123] (7) PPG1000 and castor oil were added to the reactor, stirred and heated to 60°C;

[0124] (8) Add A-link35 according to the recipe and slowly raise the temperature to 86°C;

[0125] (9) After reacting for 2 h at 86°C, measure the NCO value every 0.5 h until the NCO value is less than 0.02%, and then measure the hydroxyl value of the resin;

[0126] (10) Cool down to below 50°C, add MDI according to the formula, and slowly raise the temperature to 86°C;

[0127] (11) After reacting for 2 h at 86°C, the NCO value was measured every 0.5 h until the NCO value was <0.02%, and the hydroxyl value of the resin was measured;

[0128] (12) Discharge the material after the hydroxyl value is qualified.

[0129] Table 10 Silane modified polyurethane resin 4# composition and weight parts

[0130]

[0131] The preparation method of the above-mentioned low-temperature resistant polyurethane toughened modified epoxy mortar has the following steps, and the amounts of the raw materials used are shown in Table 11 and Table 12:

[0132] (1) Bisphenol A epoxy resin, silane-modified polyurethane resin 4#, heavy calcium carbonate, 1,4-butanediol diglycidyl ether, fumed silica, and C.I Pigment Green were added to a reactor in sequence, heated to 55°C, mixed and stirred for 1 hour, and dispersed four times on a three-roll mill before discharging to obtain component A;

[0133] (2) polyamide resin, N-aminoethylpiperazine, heavy calcium carbonate and methanol were added to a reaction kettle in sequence, heated to 55°C, mixed and stirred for 1 hour, dispersed four times on a three-roll mill, and then discharged to obtain component B;

[0134] (3) Component A of step (1) and component B of step (2) are mixed uniformly in a weight ratio of 1:1 to obtain a low-temperature resistant polyurethane toughened modified epoxy putty.

[0135] The composition and weight parts of the components in Table 11A are as follows:

[0136] raw material Epoxy equivalent eq / 100g Hydroxyl value mgKOH / g Number of copies Bisphenol A epoxy resin 0.49 40 Heavy calcium carbonate 50 Silane modified polyurethane resin 4# 120 15 1,4-Butanediol diglycidyl ether 5 Fumed silica 2 C.IPigment Green 0.5

[0137] Table 12B components and weight parts are as follows:

[0138] raw material Active hydrogen equivalent g / eq Number of copies polyamide resin 240 40 Heavy calcium carbonate 50 N-Aminoethylpiperazine 3 Benzyl alcohol 2

[0139] Example 5

[0140] The same preparation method as Example 1 is used, with the only difference being that: (3) component A of step (1) and component B of step (2) are uniformly mixed in a weight ratio of 1:0.6 to obtain a low-temperature resistant polyurethane toughened modified epoxy putty.

[0141] Example 6

[0142] The same preparation method as Example 1 is used, with the only difference being that: (3) component A of step (1) and component B of step (2) are uniformly mixed in a weight ratio of 1:1.3 to obtain a low-temperature resistant polyurethane toughened modified epoxy putty.

[0143] Comparative Example 1

[0144] The same preparation method as Example 1 is used, except that no silane-modified polyurethane resin is added.

[0145] The mechanical properties and adhesive properties test results of the two-component epoxy mortar obtained in the above embodiments according to the corresponding test standards and methods are shown in the following table:

[0146]

[0147]

[0148] By comparing the results of Example 1 of the present invention with those of Comparative Example 1, it can be seen that the elongation at break of the epoxy putty of Comparative Example 1 is relatively small at both low temperature (-40°C) and room temperature (23°C), indicating that the unmodified epoxy putty is extremely brittle at low temperatures and cannot withstand deformation. The elongation at break of the epoxy putties of Examples 1-6 is significantly improved (7.2% to 11.8%), indicating that the silane-modified polyurethane resin prepared by the present invention effectively suppresses low-temperature brittleness and imparts ductility to the material. In particular, the present invention effectively improves the low-temperature flexibility of the epoxy putty without substantially sacrificing strength.

[0149] In summary, the present invention successfully achieved a balance between high toughness and strength of epoxy putty at -40°C through molecular design and process optimization of silane-modified polyurethane resin, and exhibited excellent tensile strength, elongation at break and shear strength at both low and room temperatures, indicating that its comprehensive performance is optimal and solves the low-temperature brittleness problem of traditional epoxy putty.

[0150] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

[0151] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of conflict, the definitions in this specification shall prevail.

[0152] When this specification uses the prefix "well known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, the objects introduced by the prefix include those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become generally recognized in the art to be suitable for similar purposes.

[0153] In the context of this specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

Claims

1. A silane-modified polyurethane resin, characterized in that: The silane-modified polyurethane resin is prepared from raw materials including hydroxyl components, monofunctional NCO-based silane substances and multifunctional NCO components.

2. The silane-modified polyurethane resin according to claim 1, wherein: The hydroxyl component is selected from at least one of polyether, polybutylene adipate, castor oil or soybean oil; preferably, the polyether is selected from at least one of polypropylene glycol, polyethylene glycol or polybutylene glycol; and / or, The monofunctional NCO-based silane substance is selected from NCO-terminated silanes; preferably, the monofunctional NCO-based silane substance is selected from at least one of 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane; and / or, The multifunctional NCO component is selected from at least one of diisocyanate and a polymer formed with diisocyanate as a raw material; preferably, the diisocyanate is selected from at least one of TDI, MDI-50, MDI, IPDI and HDI.

3. The silane-modified polyurethane resin according to claim 1, wherein: In parts by weight, The hydroxyl component is 30-150 parts; preferably 30-135 parts; The monofunctional NCO-based silane substance is 6-12 parts, preferably 6-10 parts; The polyfunctional NCO component is 9-15 parts; preferably 11-13 parts.

4. A method for preparing a silane-modified polyurethane resin according to any one of claims 1 to 3, characterized in that: The following steps are involved: The hydroxyl component first reacts with a monofunctional NCO-based silane substance and then a multifunctional NCO component is added to react to obtain a silane-modified polyurethane resin; Preferably, (1) After heating the hydroxyl component with stirring, add a monofunctional NCO-based silane substance and continue to heat the reaction until the NCO value is less than 0.02%; (2) Cooling, adding multifunctional NCO components, raising the temperature to react until the NCO value is less than 0.02%, measuring the hydroxyl value of the resin, and discharging the material after the hydroxyl value is qualified.

5. The method for preparing a silane-modified polyurethane resin according to claim 4, wherein: In step (1), the heating temperature is 50-60°C; Continue to heat the reaction to a temperature of 80-90°C; Continue heating the reaction for ≥ 2 hours. Preferably, after 2 hours of reaction, measure the NCO value every 0.5 hours until the NCO value is less than 0.02%; In step (2), the cooling temperature is below 50°C; The temperature of the temperature-raising reaction is 80-90°C; The temperature-raising reaction time is ≥ 2 hours. Preferably, after 2 hours of reaction, the NCO value is measured every 0.5 hours until the NCO value is less than 0.02%.

6. A low-temperature resistant polyurethane toughened modified epoxy putty, characterized by: The cement is prepared from raw materials including component A and component B; Component A comprises, by weight: 15-50 parts of epoxy resin, 5-30 parts of silane-modified polyurethane resin, 1-10 parts of diluent, 40-75 parts of filler, 0.5-5 parts of thixotropic agent, and 0.1-1 parts of pigment; The silane-modified polyurethane resin is selected from the silane-modified polyurethane resin according to any one of claims 1 to 3 or the silane-modified polyurethane resin prepared by the method according to any one of claims 4 to 5; Calculated by weight, component B includes: 30-50 parts of amine curing agent, 0.5-5 parts of curing accelerator, 40-65 parts of filler, and 0.5-5 parts of diluent; The mass ratio of component A to component B is 1:(0.5-1.5).

7. The low-temperature resistant polyurethane toughened modified epoxy mortar according to claim 6, characterized in that: Component A comprises 30-45 parts of epoxy resin, 5-20 parts of silane-modified polyurethane resin, 3-8 parts of diluent, 50-65 parts of filler, 1-3 parts of thixotropic agent, and 0.1-1 part of pigment; and / or In component A, The epoxy resin is a bisphenol A epoxy resin; preferably, the epoxy equivalent of the epoxy resin is 0.13-0.56 eq / 100 g and the viscosity is 8000-20000 mPa·s; and / or, The diluent is selected from at least one of C2-C16 glycidyl ethers; preferably, the diluent is selected from at least one of dodecyl glycidyl ether, ethylene glycol glycidyl ether, and 1,4-butanediol diglycidyl ether; and / or, The filler is selected from at least one of inorganic fillers; preferably, the filler is selected from at least one of fumed silica, wollastonite, heavy calcium carbonate, light calcium carbonate or quartz powder; and / or, The thixotropic agent is selected from at least one of hydrogenated castor oil, polyamide wax, fumed silica or light calcium carbonate; and / or, The pigment is selected from at least one azo pigment, and preferably, the pigment is selected from dioxazine pigments.

8. The low-temperature resistant polyurethane toughened modified epoxy mortar according to claim 6, characterized in that: In component B, 35-45 parts of amine curing agent, 1-4 parts of curing accelerator, 45-60 parts of filler, and 1-4 parts of diluent; and / or, In component B, The amine curing agent is selected from at least one of polyamide curing agents; preferably, the active hydrogen equivalent of the amine curing agent is 90-250 g / eq and the viscosity is 100-4000 mPa·s; and / or, The curing accelerator is selected from at least one of small molecule amines or piperazine accelerators; preferably, the curing accelerator is selected from at least one of triethanolamine, N-aminoethylpiperazine, 2-ethyl-4-methylimidazole, benzoyl peroxide, and nonylphenol; and / or, The filler is selected from at least one of inorganic fillers; preferably, the filler is selected from at least one of fumed silica, wollastonite, heavy calcium carbonate, light calcium carbonate or quartz powder; and / or, The diluent is selected from at least one low-volatile organic solvent; preferably, the diluent is selected from at least one alcohol solvent; further preferably, the diluent is selected from at least one of benzyl alcohol, n-butanol or methanol.

9. A method for preparing the low-temperature resistant polyurethane toughened modified epoxy mortar according to any one of claims 6 to 8, characterized in that: The following steps are involved: The raw materials in component A are heated and mixed; the raw materials in component B are heated and mixed, and then components A and B are mixed evenly to obtain the low-temperature resistant polyurethane toughened modified epoxy putty; Preferably, When the raw materials in component A and component B are heated and mixed, the heating and mixing temperature is independently selected from 30-80° C.; the mixing and stirring time is independently selected from 1-2 hours, and the materials are independently dispersed 2-4 times by a three-roll mill before being discharged.

10. Use of the low-temperature resistant polyurethane toughened modified epoxy putty as described in any one of claims 6 to 8 as an adhesive; preferably, use as an adhesive for transportation and storage devices of clean energy; further preferably, use as an adhesive for bonding metal and wood materials in liquefied oil and gas ships, shore tanks, and shore station liquid cargo containment systems.

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