CN115651594B - Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof - Google Patents

Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof Download PDF

Info

Publication number
CN115651594B
CN115651594B CN202211334715.1A CN202211334715A CN115651594B CN 115651594 B CN115651594 B CN 115651594B CN 202211334715 A CN202211334715 A CN 202211334715A CN 115651594 B CN115651594 B CN 115651594B
Authority
CN
China
Prior art keywords
component
curing
mixture
antioxidant
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211334715.1A
Other languages
Chinese (zh)
Other versions
CN115651594A (en
Inventor
崔涛
张继清
齐春雨
刘锦春
王达麟
宋乐阳
许耘赫
董子辉
李闯
苏威铭
林勇威
徐振艳
宋冉
刘惠敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University of Science and Technology
China Railway Design Corp
Original Assignee
Qingdao University of Science and Technology
China Railway Design Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University of Science and Technology, China Railway Design Corp filed Critical Qingdao University of Science and Technology
Priority to CN202211334715.1A priority Critical patent/CN115651594B/en
Publication of CN115651594A publication Critical patent/CN115651594A/en
Application granted granted Critical
Publication of CN115651594B publication Critical patent/CN115651594B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a quick-curing double-component polyurethane water-swelling sealant and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a first polyether polyol, a chain extender and a catalyst, dehydrating under the condition of stirring at 100-120 ℃ and a vacuum degree of 0.05-0.10 Mpa for 1-2 hours until the moisture content is below 0.05wt% to obtain a curing agent component, drying a plasticizer, a filler, a thixotropic agent, a super absorbent resin and a first epoxy resin at 100-120 ℃ for 3-5 hours, cooling to 30-50 ℃, adding the curing agent component, stirring uniformly, adding a water scavenger and a tackifier under the protection of nitrogen, continuing mixing and stirring at 25-45 ℃ for 1-1.5 hours to obtain a component A, and mixing the component B and the component A to obtain the quick-curing double-component polyurethane water-swelling sealant.

Description

Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane sealants, and particularly relates to a quick-curing double-component polyurethane water-swelling sealant and a preparation method thereof.
Background
With the increase of the investment of the national infrastructure construction such as subways, tunnels, highways and the like, the waterproof problem of the building engineering is also more important, because the life of the building engineering is ensured, and protecting the building from water is a very important part of engineering construction and maintenance. The water-swelling polyurethane material is a novel functional polymer material with double functions of water swelling and elastic sealing, and is widely applied to civil engineering, sewer and water-sealingThe dam caulking field has the characteristics of no toxicity, no smell, medium resistance, good repeated expansion performance and the like. The water-swellable polyurethane sealant is a paste, can be used for sealing a non-sizing joint, does not need to be precisely cut, and has good matching performance between the product size and a construction joint and convenient construction. Polyether polyol as main material of water-swelling polyurethane sealant has longer ethylene ether chain segment (-CH) 2 -CH 2 -O-), which has excellent flexibility, usually in a folded state, and when water is encountered, the ether bond (-O-) can be connected with hydrogen atoms in water molecules to form a large number of hydrogen bond associations, and due to the formation of hydrogen bonds, the polyethylene oxide molecular chain changes from zigzag to zigzag, the hydrophobic 1, 2-ethylene is located at the inner side of the chain, and the oxygen atoms in the hydrophilic ether bond are located at the outer side of the chain, so that the polymer chain becomes easy to combine with water, and the material undergoes volume expansion with the gradual combination and entry of water molecules.
In the Chinese patent publication No. CN 102408866A, a single-component water-absorbent expansion polyurethane sealant is prepared by adopting water-absorbent resin and polyether polyol, the maximum volume expansion rate can reach 439%, but the initial curing speed is 2.1h, the actual curing time is longer, the quick curing effect cannot be achieved, and under the condition of larger addition of the super-absorbent resin, the risk of precipitation is caused when the super-absorbent resin is in contact with water for a long time, the expansion rate is reduced, and the sealing waterproof performance is affected.
In the construction application process, the colloid is often required to be quickly solidified at normal temperature and normal pressure so as to improve the construction efficiency and meet the requirements of actual working conditions. Under the condition of meeting various physical and mechanical properties and water-swelling properties, the two-component water-swelling polyurethane sealant is crucial in realizing the function of rapid curing, however, the rapidly-curable water-swelling polyurethane sealant is not found in the prior art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a fast-curing double-component polyurethane water-swelling sealant.
The invention also aims to provide the quick-curing double-component polyurethane water-swelling sealant obtained by the preparation method, which is pasty, has the characteristics of good bonding performance with a sealing interface, convenient construction and quick curing at room temperature after being beaten out, thereby playing a role in waterproof sealing.
The aim of the invention is achieved by the following technical scheme.
A preparation method of a fast-curing two-component polyurethane water-swellable sealant comprises the following steps:
1) Mixing a first polyether polyol, a chain extender and a catalyst, and dehydrating for 1-2 hours under the conditions of stirring at 100-120 ℃ and a vacuum degree of 0.05-0.10 Mpa until the moisture content is below 0.05wt%, thereby obtaining a curing agent component, wherein the ratio of the first polyether polyol to the chain extender to the catalyst is (65-75) in parts by weight: (10-15): (0.1-0.3), wherein the catalyst is one or more of dibutyl tin dilaurate, potassium isooctanoate, triethylenediamine, dibutyl tin diacetate, stannous octoate, lead isooctanoate and phenylmercury acetate, and the chain extender is one or more of 1, 4-butanediol, 3, 5-dimethyl thiotoluenediamine and 3, 5-diethyl toluenediamine;
2) Drying a plasticizer, a filler, a thixotropic agent, a super absorbent resin and a first epoxy resin for 3-5 hours at 100-120 ℃, cooling to 30-50 ℃, adding the curing agent component obtained in the step 1), stirring uniformly, adding a water removing agent and a tackifier under the protection of nitrogen, and continuously mixing and stirring for 1-1.5 hours at 25-45 ℃ to obtain a component A, wherein the ratio of the plasticizer, the filler, the thixotropic agent, the super absorbent resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is (2-10) according to parts by weight: (10-30): (0.1-10): (2-10): (5-15): (40-55): (0.1-3): (2-5); the plasticizer is one or a mixture of more than two of dioctyl phthalate, dinonyl phthalate, dioctyl adipate and didecyl adipate, the filler is one or a mixture of more than two of active calcium carbonate, carbon black, titanium white powder, silica micropowder, hollow glass microsphere, talcum powder, kaolin and diatomite, the thixotropic agent is one or a mixture of more than two of nano active calcium carbonate, nano light calcium, hydrogenated castor oil, weather white carbon black and nano silicon dioxide, and the super absorbent resin is one or a mixture of more than two of acrylic acid or methacrylic acid salts, hydrophilic vinyl compounds, acrylic acid hydroxy esters, acrylamide and derivatives thereof; the water scavenger is one or a mixture of more than two of p-methylsulfonyl isocyanate, calcium oxide, trimethyl orthoformate and a hydrolyzable silane coupling agent, and the tackifier is one or a mixture of more than two of gamma-glycidoxypropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-phenyl gamma-aminopropyl trimethoxysilane and gamma- (2, 3-epoxypropyl) propyl trimethoxysilane;
3) Mixing the component B with the component A to obtain the fast-curing double-component polyurethane water-swelling sealant, wherein the ratio of the component B to the component A is 1 (1-2) in parts by volume, and the method for preparing the component B comprises the following steps: mixing a second polyether polyol and an antioxidant, dehydrating for 1-2 hours under the condition of stirring at 100-120 ℃ and a vacuum degree of 0.05-0.10 Mpa until the moisture content is below 0.05%, cooling to 60 ℃, adding isocyanate, reacting for 1-2 hours at 80 ℃, adding a second epoxy resin, and continuously stirring for 1 hour to obtain a component B, wherein the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is (90-110) in parts by weight: (0.3-0.6): (25-45): (5-10), wherein the isocyanate is diisocyanate,
in the step 3), the diisocyanate is toluene diisocyanate, 4' -diphenylmethane diisocyanate or hexamethylene diisocyanate.
In the step 3), the antioxidant is one or a mixture of more than two of antioxidant 1010, antioxidant 245, antioxidant 1076, antioxidant 1035, antioxidant 626 and antioxidant 1010.
In the above technical scheme, the first polyether polyol and the second polyether polyol are the same, and are propylene oxide ring-opening polymerization polyol or ethylene oxide ring-opening polymerization polyol.
In the above technical scheme, the number average molecular weight of the first polyether polyol and the second polyether polyol is 1000-5000.
In the above technical scheme, the first polyether polyol is ethylene oxide polyether polyol or propylene oxide ethylene oxide copolyether glycol.
The quick-curing double-component polyurethane water-swelling sealant obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The main chain of the quick-curing double-component polyurethane water-swelling sealant contains hydrophilic groups, and the quick-curing double-component polyurethane water-swelling sealant has stable performance after swelling in water, few educts, high and adjustable expansion multiplying power and good water pressure resistance.
(2) The quick-curing double-component polyurethane water-swelling sealant disclosed by the invention can be used together with the lead isooctanoate and phenylmercuric acetate catalysts insensitive to water due to the fact that the organotin catalysts with high catalytic activity and the diamine chain extenders with high reaction rate are used in the formula, so that the two components of the sealant are mixed and then quickly react and are quickly cured, and the sealant can be cured and formed at about 5 minutes at room temperature, and has the advantages of simplicity in operation, convenience, strong universality and high practical application value in engineering application.
(3) The quick-curing double-component polyurethane water-swelling sealant of the invention synthesizes the component B and the component A by a two-step method, and the method has the advantages that the viscosity of the two components is lower through appearance, the fluidity is good, and the two components are easy to mix uniformly.
(4) The quick-curing double-component polyurethane water-swelling sealant is paste, so that the quick-curing double-component polyurethane water-swelling sealant is particularly suitable for sealing the surface of a waterproof substrate or performing construction in irregular gaps, such as engineering deformation joints, construction joints, various pipeline joint seals, dam caulking joints and the like.
(5) The epoxy resin and the tackifier are added into the formula of the quick-curing two-component polyurethane water-swelling sealant, the polyurethane is modified, the epoxy resin has the advantages of good adhesiveness, corrosion resistance, high strength and the like, the epoxy group is introduced into a polyurethane system to obtain a product with better performance, and the main purpose of adding the epoxy resin is to improve the adhesive force of the sealant to concrete.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The drug purchase sources involved in the following examples are as follows:
polyether polyol
Polyoxypropylene diol CHE-203 Mn =3000 changhua chemical technologies inc;
polyoxypropylene triol CHE-304 Mn =4000 changhua chemical technologies inc;
polyoxyethylene glycol CHPEG2500 mn=2500 changhua chemical technologies inc;
isocyanate:
4,4' -dimethylmethane diisocyanate (MDI), vancomic chemical group inc;
toluene diisocyanate (TDI-100), BAYER, germany;
chain extender:
1, 4-Butanediol (BDO), mitsubishi Kabushiki Kaisha;
3, 5-Dimethylthiotoluenediamine (DMTDA), a chemical Co., ltd;
3, 5-Diethyltoluenediamine (DETDA) was prepared from the chemical Co., ltd
And (3) a plasticizer:
dioctyl phthalate (DOP), shandong-Bos plasticizer works;
catalyst:
dibutyl tin dilaurate, jilin pan stone, field chemical auxiliary research institute;
phenylmercuric acetate, smoke desk sunlight plastic
Lead isooctanoate, smoke desk sunlight plastic
Thixotropic agent: meteorological white carbon black Germany winning company
Nano calcium carbonate Shandong midday mineral Co.Ltd
Epoxy resin Baling petrochemical Limited liability company
The high water absorption resin is acrylic acid, and sodium polyacrylate is specifically adopted.
Sag resistance was measured according to GB/T1723-1993, tack free time was measured according to GB/T13477-2002, tensile strength was measured according to GB/T528-2009, tear strength was measured according to GB/T529-2008, hardness was measured according to GB/T5311-2008, and water absorption capacity was measured according to GB/T18173-2002.
Example 1
A preparation method of a fast-curing two-component polyurethane water-swellable sealant comprises the following steps:
1) Mixing the first polyether polyol, the chain extender and the catalyst in a three-neck flask with a thermometer and a stirring paddle, and dehydrating for 1.5 hours under the stirring condition at 120 ℃ and under the vacuum degree of 0.05Mpa until the moisture content is below 0.05wt% to obtain a curing agent component, wherein the ratio of the first polyether polyol to the chain extender to the catalyst is 70 in parts by weight: 10:0.2, the catalyst is dibutyl tin dilaurate, the chain extender is a mixture of 1, 4-butanediol and 3, 5-diethyl toluenediamine, and the ratio of the 1, 4-butanediol to the 3, 5-diethyl toluenediamine is 6:4 in parts by weight;
2) Drying a plasticizer, a filler, a thixotropic agent, a high-hydroscopicity resin and a first epoxy resin at 100 ℃ for 3 hours, cooling to 50 ℃, adding the curing agent component obtained in the step 1), stirring for 2 hours uniformly in a double-planetary stirrer of a high-speed dispersion disc, adding a water removing agent and a tackifier under the protection of nitrogen, and continuously mixing and stirring for 1.5 hours at 40 ℃ to obtain a component A, wherein the weight ratio of the plasticizer, the filler, the thixotropic agent, the high-hydroscopicity resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is 5:15:5:8:8:50:1:2; the plasticizer is dioctyl phthalate, the filler is carbon black, the thixotropic agent is weather white carbon black, and the super absorbent resin is acrylic acid; the water scavenger is p-methylsulfonyl isocyanate and the tackifier is gamma-glycidol ether oxygen propyl trimethoxy silane.
3) 50mL of the component B and 50mL of the component A are mixed to obtain the fast-curing double-component polyurethane water-swelling sealant, wherein the ratio of the component B to the component A is 1:1 by volume, and the method for preparing the component B comprises the following steps: mixing a second polyether polyol and an antioxidant in a three-neck flask with a thermometer and a stirring paddle, dehydrating for 1.5 hours under the stirring condition at 120 ℃ and under the vacuum degree of 0.05Mpa until the moisture content is below 0.05%, cooling to 60 ℃, adding isocyanate into the three-neck flask, reacting for 2 hours at 80 ℃, adding a second epoxy resin, and continuing stirring for 1 hour to obtain a component B, wherein the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is 100:0.5:28 in parts by weight: 5, isocyanate is toluene diisocyanate, and antioxidant is antioxidant 1010.
The first polyether polyol and the second polyether polyol are the same, and are a mixture of polyoxypropylene diol with a number average molecular weight of 3000, polyoxypropylene triol with a number average molecular weight of 4000 and polyoxyethylene diol with a number average molecular weight of 2500, and the ratio of the polyoxypropylene diol, the polyoxypropylene triol and the polyoxyethylene diol is 6:2:2 in parts by weight.
Example 2
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the embodiment 1, and the only difference is that: the ratio of the polyoxypropylene glycol, the polyoxypropylene triol and the polyoxyethylene glycol is 4:2:2 in parts by weight.
The fast curing two-component polyurethane water-swellable sealants prepared in examples 1 and 2 were tested and the test results were as follows:
content of test Example 1 Example 2
Sag resistance, um 175 175
Time of surface drying, min 4 4
Tensile strength, MPa 6.20 4.77
Tear Strength, kN/m 31.17 23.63
Hardness (Shore A) 45 48
Rate of volume expansion of 2 h% 356% 392%
Volume expansion rate of 24h,% 436% 445%
Mass loss rate -2.86% -1.48%
As shown in the table, the polypropylene oxide glycol has a large part and excellent mechanical properties; the polyethylene glycol oxide has a large number of parts and excellent water swelling performance. Therefore, the polyol with proper proportion can be added according to the actual use requirement.
Example 3
A preparation method of a fast-curing two-component polyurethane water-swellable sealant comprises the following steps:
1) Mixing the first polyether polyol, the chain extender and the catalyst in a three-neck flask with a thermometer and a stirring paddle, and dehydrating for 1.5 hours under the stirring condition at 120 ℃ and under the vacuum degree of 0.05Mpa until the moisture content is below 0.05wt% to obtain a curing agent component, wherein the ratio of the first polyether polyol to the chain extender to the catalyst is 70 in parts by weight: 13:0.1, the catalyst is phenylmercuric acetate, and the chain extender is 3, 5-dimethyl thiotoluene diamine.
2) Drying a plasticizer, a filler, a thixotropic agent, a high-hydroscopicity resin and a first epoxy resin at 100 ℃ for 3 hours, cooling to 50 ℃, adding the curing agent component obtained in the step 1), stirring for 2 hours uniformly in a double-planetary stirrer of a high-speed dispersion disc, adding a water removing agent and a tackifier under the protection of nitrogen, and continuously mixing and stirring for 1.5 hours at 40 ℃ to obtain a component A, wherein the weight ratio of the plasticizer, the filler, the thixotropic agent, the high-hydroscopicity resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is 5:15:5:8:8:50:1:2; the plasticizer is dioctyl phthalate, the filler is carbon black, the thixotropic agent is weather white carbon black, and the super absorbent resin is acrylic acid; the water scavenger is p-methylsulfonyl isocyanate and the tackifier is gamma-glycidol ether oxygen propyl trimethoxy silane.
3) 50mL of the component B and 50mL of the component A are mixed to obtain the fast-curing double-component polyurethane water-swelling sealant, wherein the ratio of the component B to the component A is 1:1 by volume, and the method for preparing the component B comprises the following steps: mixing a second polyether polyol and an antioxidant in a three-neck flask with a thermometer and a stirring paddle, dehydrating for 1.5 hours under the stirring condition at 120 ℃ and under the vacuum degree of 0.05Mpa until the moisture content is below 0.05%, cooling to 60 ℃, adding isocyanate into the three-neck flask, reacting for 2 hours at 80 ℃, adding a second epoxy resin, and continuing stirring for 1 hour to obtain a component B, wherein the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is 100 in parts by weight: 0.5:28:5, isocyanate is toluene diisocyanate, and antioxidant is antioxidant 1010.
The first polyether polyol and the second polyether polyol are the same, and are a mixture of polyoxypropylene diol with a number average molecular weight of 3000, polyoxypropylene triol with a number average molecular weight of 4000 and polyoxyethylene diol with a number average molecular weight of 2500, and the ratio of the polyoxypropylene diol, the polyoxypropylene triol and the polyoxyethylene diol is 5:2:3.
example 4
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically consistent with the embodiment 3, and the only difference is that: the isocyanate in this example is 4,4' -diphenylmethane diisocyanate.
The fast curing two-component polyurethane water-swellable sealants prepared in examples 3 and 4 were tested and the test results were as follows:
content of test Example 3 Example 4
Sag resistance, um 175 175
Time of surface drying, min 4 3’30
Tensile strength, MPa 5.23 5.18
Tear Strength, kN/m 30.4 30.2
Hardness (Shore A) 43 45
Rate of volume expansion of 2 h% 320% 300%
Volume expansion rate of 24h,% 403% 386%
The rate of mass loss is determined by the method, -1.96% -1.88%
as can be seen from the table, when the isocyanate is 4,4' -dimethylmethane diisocyanate, the curing time is shorter than that of the sample in which the isocyanate is toluene diisocyanate, but the mechanical properties and the water swelling property are slightly lower. Suitable isocyanates can therefore be added according to the actual use requirements.
Example 5
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the embodiment 1, and the only difference is that: the 1, 4-butanediol of example 1 was replaced with "3, 5-dimethylthiotoluenediamine".
Example 6
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the embodiment 1, and the only difference is that: the 1, 4-butanediol of example 1 was replaced with "3, 5-diethyltoluenediamine".
The fast curing two-component polyurethane water-swellable sealants prepared in examples 5 and 6 were tested and the test results were as follows:
content of test Example 1 Example 5 Example 6
Sag resistance, um 175 175 175
Time of surface drying, min 4 3 1
Tensile strength, MPa 6.20 6.32 4.25
Tear Strength, kN/m 31.17 35.93 21.22
Hardness (Shore A) 45 47 47
Rate of volume expansion of 2 h% 356% 318% 309%
Volume expansion rate of 24h,% 436% 400% 402%
The rate of mass loss is determined by the method, -2.86% -2.80% -2.92%
it can be seen from the table that 3, 5-diethyltoluenediamine is superior to 3, 5-dimethylthiotoluenediamine to 1, 4-butanediol in terms of curing time and speed; in terms of strength, 3, 5-dimethylthiotoluene diamine is superior to 1, 4-butanediol and 3, 5-diethyltoluene diamine; 1, 4-butanediol is superior to 3, 5-dimethyl thiotoluene diamine in water swelling property, and 3, 5-diethyl toluene diamine. Therefore, the chain extender can be added according to the actual use requirement.
Example 7
A preparation method of a fast-curing two-component polyurethane water-swellable sealant comprises the following steps:
1) Mixing the first polyether polyol, the chain extender and the catalyst in a three-neck flask with a thermometer and a stirring paddle, and dehydrating for 1.5 hours under the stirring condition at 120 ℃ and under the vacuum degree of 0.05Mpa until the moisture content is below 0.05wt% to obtain a curing agent component, wherein the ratio of the first polyether polyol to the chain extender to the catalyst is 70 in parts by weight: 13:0.1, the catalyst is dibutyl tin dilaurate, and the chain extender is 3, 5-dimethyl thiotoluene diamine.
2) Drying a plasticizer, a filler, a thixotropic agent, a high-hydroscopicity resin and a first epoxy resin at 100 ℃ for 3 hours, cooling to 50 ℃, adding the curing agent component obtained in the step 1), stirring for 2 hours uniformly in a double-planetary stirrer of a high-speed dispersion disc, adding a water removing agent and a tackifier under the protection of nitrogen, and continuously mixing and stirring for 1.5 hours at 40 ℃ to obtain a component A, wherein the weight ratio of the plasticizer, the filler, the thixotropic agent, the high-hydroscopicity resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is 5:15:5:8:8:50:1:2; the plasticizer is dioctyl phthalate, the filler is carbon black, the thixotropic agent is weather white carbon black, and the super absorbent resin is acrylic acid; the water scavenger is p-methylsulfonyl isocyanate and the tackifier is gamma-glycidol ether oxygen propyl trimethoxy silane.
3) 50mL of the component B and 50mL of the component A are mixed to obtain the fast-curing double-component polyurethane water-swelling sealant, wherein the ratio of the component B to the component A is 1:1 by volume, and the method for preparing the component B comprises the following steps: mixing a second polyether polyol and an antioxidant in a three-neck flask with a thermometer and a stirring paddle, dehydrating for 1.5 hours under the stirring condition at 120 ℃ and under the vacuum degree of 0.05Mpa until the moisture content is below 0.05%, cooling to 60 ℃, adding isocyanate into the three-neck flask, reacting for 2 hours at 80 ℃, adding a second epoxy resin, and continuing stirring for 1 hour to obtain a component B, wherein the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is 100:0.5:43.6 in parts by weight: the isocyanate is 4,4' -dimethyl methane diisocyanate, and the antioxidant is antioxidant 1010.
The first polyether polyol and the second polyether polyol are the same, and are a mixture of polyoxypropylene diol with a number average molecular weight of 3000, polyoxypropylene triol with a number average molecular weight of 4000 and polyoxyethylene diol with a number average molecular weight of 2500, and the ratio of the polyoxypropylene diol, the polyoxypropylene triol and the polyoxyethylene diol is 5:2:3 in parts by weight.
Example 8
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the example 7, and the only difference is that: the catalyst in example 7 was replaced with "a mixture of dibutyltin dilaurate and lead isooctanoate", in parts by mass, the ratio of dibutyltin dilaurate to lead isooctanoate being 1:1.
Example 9
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the example 7, and the only difference is that: the catalyst in example 7 was replaced with "a mixture of dibutyltin dilaurate and phenylmercuric acetate", and the ratio of dibutyltin dilaurate to phenylmercuric acetate was 1:1 in parts by mass.
The fast-curing two-component polyurethane water-swellable sealants prepared in examples 7 to 9 were tested and the test results were as follows:
as is clear from the table, the catalyst dibutyl tin dilaurate has a faster curing speed when used alone, and the catalyst dibutyl tin dilaurate is used together with lead isooctanoate and phenylmercuric acetate in a ratio of 1 to 1, so that the curing time is prolonged, and the mechanical and water absorption properties are slightly better but approximate to those of the catalyst dibutyl tin dilaurate. So that a suitable catalyst can be added according to the actual use requirements.
Example 10
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the embodiment 1, and the only difference is that: the thixotropic agent in example 1 was replaced with "nano-active calcium carbonate".
The fast curing two-component polyurethane water-swellable sealant prepared in example 10 was tested and the test results were as follows:
content of test Example 1 Example 10
Sag resistance, um 175 210
Viscosity, mPas 3500 2100
Time of surface drying, min 4 4
Tensile strength, MPa 6.20 5.23
Tear Strength, kN/m 31.17 22.67
Hardness (Shore A) 45 46
The volume expansion rate is 2 hours, %356% 344%
the volume expansion rate of the material is 24 hours, 436% 418%
mass loss rate -2.86% -3.33%
Example 11
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the embodiment 1, and the only difference is that: in the component A, the ratio of the plasticizer, the filler, the thixotropic agent, the super absorbent resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is 5:15:5:8:12:50:1:2. In the component B, the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is 100:0.5:28:8.
example 12
The preparation method of the quick-curing two-component polyurethane water-swellable sealant is basically the same as that of the embodiment 1, and the only difference is that: in the component A, the ratio of the plasticizer, the filler, the thixotropic agent, the super absorbent resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is 5:15:5:8:15:50:1:2. In the component B, the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is 100:0.5:28:10.
the quick-setting two-component polyurethane water-swelling sealant prepared in examples 11 and 12 was tested and the test results were as follows:
as shown in the table, after the part of the epoxy resin is increased, the sagging resistance of the material is improved, the viscosity is increased, and the adhesive property of the material is improved. But the mechanical properties and the water-swelling properties are reduced. Therefore, the epoxy resin can be added in proper parts according to the actual use requirement.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.

Claims (4)

1. The preparation method of the fast-curing bi-component polyurethane water-swellable sealant is characterized by comprising the following steps of:
1) Mixing a first polyether polyol, a chain extender and a catalyst, and dehydrating for 1-2 hours under the conditions of stirring at 100-120 ℃ and a vacuum degree of 0.05-0.10 Mpa until the moisture content is below 0.05wt%, thereby obtaining a curing agent component, wherein the ratio of the first polyether polyol to the chain extender to the catalyst is (65-75) in parts by weight: (10-15): (0.1-0.3), wherein the catalyst is one or a mixture of more than two of dibutyl tin dilaurate, lead isooctanoate and phenylmercuric acetate, the chain extender is a mixture of 1, 4-butanediol and 3, 5-diethyl toluenediamine or a mixture of 3, 5-dimethyl thiotoluenediamine and 3, 5-diethyl toluenediamine or 3, 5-dimethyl thiotoluenediamine, the first polyether polyol is a mixture of polyoxypropylene glycol, polyoxypropylene triol and polyoxyethylene glycol, and the ratio of the polyoxypropylene glycol, the polyoxypropylene triol and the polyoxyethylene glycol is 6:2:2 or 5:2:3 in parts by weight;
2) Drying a plasticizer, a filler, a thixotropic agent, a super absorbent resin and a first epoxy resin for 3-5 hours at 100-120 ℃, cooling to 30-50 ℃, adding the curing agent component obtained in the step 1), stirring uniformly, adding a water removing agent and a tackifier under the protection of nitrogen, and continuously mixing and stirring for 1-1.5 hours at 25-45 ℃ to obtain a component A, wherein the ratio of the plasticizer, the filler, the thixotropic agent, the super absorbent resin, the first epoxy resin, the curing agent component, the water removing agent and the tackifier is (2-10) according to parts by weight: (10-30): (0.1-10): (2-10): (5-15): (40-55): (0.1-3): (2-5); the plasticizer is one or a mixture of more than two of dioctyl phthalate, dinonyl phthalate, dioctyl adipate and didecyl adipate, the filler is one or a mixture of more than two of active calcium carbonate, carbon black, titanium white powder, silica micropowder, hollow glass microsphere, talcum powder, kaolin and diatomite, the thixotropic agent is one or a mixture of more than two of nano active calcium carbonate, nano light calcium, hydrogenated castor oil and gas-phase white carbon black, and the super absorbent resin is one or a mixture of more than two of copolymerized acrylic acid or methacrylic acid salts, acrylic acid hydroxy esters, acrylamide and derivatives thereof; the water scavenger is one or a mixture of more than two of p-methylsulfonyl isocyanate, calcium oxide and trimethyl orthoformate, and the tackifier is one or a mixture of more than two of gamma-glycidol ether oxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane and N-phenyl-gamma-aminopropyl trimethoxy silane;
3) Mixing the component B with the component A to obtain the fast-curing bi-component polyurethane water-swelling sealant, wherein the ratio of the component B to the component A is 1 (1-2) in parts by volume, and the method for preparing the component B comprises the following steps: mixing a second polyether polyol and an antioxidant, dehydrating for 1-2 hours under the condition of stirring at 100-120 ℃ and a vacuum degree of 0.05-0.10 Mpa until the moisture content is below 0.05%, cooling to 60 ℃, adding isocyanate, reacting for 1-2 hours at 80 ℃, adding a second epoxy resin, and continuously stirring for 1 hour to obtain a component B, wherein the ratio of the second polyether polyol to the antioxidant to the isocyanate to the second epoxy resin is (90-110): (0.3-0.6): (25-45): (5-10), wherein the isocyanate is diisocyanate, the diisocyanate is toluene diisocyanate, 4' -diphenylmethane diisocyanate or hexamethylene diisocyanate, the second polyether polyol is polyoxypropylene glycol, a mixture of polyoxypropylene glycol and polyoxyethylene glycol, and the ratio of the polyoxypropylene glycol, the polyoxypropylene glycol and the polyoxyethylene glycol is 6:2:2 or 5:2:3 in parts by weight.
2. The method of claim 1, wherein in step 3), the antioxidant is one or a mixture of more than two of antioxidant 1010, antioxidant 245, antioxidant 1076, antioxidant 1035, and antioxidant 626.
3. The method of claim 1, wherein the first and second polyether polyols have a number average molecular weight of 1000 to 5000.
4. A fast curing two-component polyurethane water-swellable sealant obtained by the method of any one of claims 1-3.
CN202211334715.1A 2022-10-28 2022-10-28 Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof Active CN115651594B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211334715.1A CN115651594B (en) 2022-10-28 2022-10-28 Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211334715.1A CN115651594B (en) 2022-10-28 2022-10-28 Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115651594A CN115651594A (en) 2023-01-31
CN115651594B true CN115651594B (en) 2024-04-16

Family

ID=84993290

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211334715.1A Active CN115651594B (en) 2022-10-28 2022-10-28 Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115651594B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885957A (en) * 2010-07-09 2010-11-17 山东北方现代化学工业有限公司 Room-temperature moisture cured one-component water-expansion polyurethane sealant
CN111484730A (en) * 2020-06-18 2020-08-04 中电保力(北京)科技有限公司 Bi-component fast-curing plastic daub and preparation method thereof
CN111944470A (en) * 2020-08-20 2020-11-17 中电保力(北京)科技有限公司 Bi-component water-absorbing expansion daub and application thereof
KR102289659B1 (en) * 2021-03-24 2021-08-17 케이엘건설 주식회사 Polyurethane composition with water expansion and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885957A (en) * 2010-07-09 2010-11-17 山东北方现代化学工业有限公司 Room-temperature moisture cured one-component water-expansion polyurethane sealant
CN111484730A (en) * 2020-06-18 2020-08-04 中电保力(北京)科技有限公司 Bi-component fast-curing plastic daub and preparation method thereof
CN111944470A (en) * 2020-08-20 2020-11-17 中电保力(北京)科技有限公司 Bi-component water-absorbing expansion daub and application thereof
KR102289659B1 (en) * 2021-03-24 2021-08-17 케이엘건설 주식회사 Polyurethane composition with water expansion and manufacturing method thereof

Also Published As

Publication number Publication date
CN115651594A (en) 2023-01-31

Similar Documents

Publication Publication Date Title
CN108531120B (en) High-elasticity low-modulus single-component silane modified polyether sealant and preparation method thereof
CN110172323B (en) Solvent-resistant epoxy modified polyurethane sealant and preparation method thereof
US8609800B2 (en) Curable compositions containing silylated polyurethanes
US6762270B2 (en) Polyurethane prepolymers with reduced functionality having terminal alkoxysilane and OH groups, a method of preparing them and their use
US8431675B2 (en) Curable compound comprising silylated polyurethane
CN102816549B (en) Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof
CN105176439A (en) Adhesive used adhesion promoter, and synthetic method and applications thereof
CN109575870B (en) Modified siloxane-terminated polyurethane sealant and preparation method thereof
KR101148418B1 (en) Prepolymer compositions and sealants made therefrom
RU2690688C2 (en) Silylated polyurethanes, production and use thereof
CN104177819B (en) A kind of ballastless track of high-speed railway polyurethane caulking material interfacial agents and preparation method thereof
CN103897652A (en) Environment-friendly high-strength polyurethane adhesive sealant and preparation method thereof
CN107033827B (en) Single-component silane modified polyether sealant for building and preparation method thereof
CN109777338A (en) High-intensitive high elongation at tear monocomponent polyurethane adhesive and preparation method
JP2009132832A (en) One-component type polyurethane-based curable composition and adhesive using this
CN108949090B (en) Solvent-free two-component polyurethane sealant and preparation method thereof
CN101245182B (en) Fire resistant water resistant polyurethane composition for fluid sealant and manufacture method thereof
CN111978912A (en) Organic silicon modified polyurethane sealing material and preparation method thereof
JP4800653B2 (en) One-component urethane sealant composition for construction working joint and its construction method
CN105176479A (en) High-strength silicone rubber and preparation method therefor
CN105504787B (en) A kind of silane end capped polyurethane composition and its preparation method and application
EP2183332A2 (en) Hydrophilic sealants
CN105199653A (en) High-strength low-viscosity island modified polyurethane resin
CN115651594B (en) Rapid-curing two-component polyurethane water-swelling sealant and preparation method thereof
CN115160914B (en) Single-component polyurethane waterproof coating special for waterproof repairing engineering of back water surface

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant