CN107916089B - Slow-expansion type water-swelling polyurethane sealant and preparation method thereof - Google Patents

Slow-expansion type water-swelling polyurethane sealant and preparation method thereof Download PDF

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CN107916089B
CN107916089B CN201711207406.7A CN201711207406A CN107916089B CN 107916089 B CN107916089 B CN 107916089B CN 201711207406 A CN201711207406 A CN 201711207406A CN 107916089 B CN107916089 B CN 107916089B
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slow
block polyether
swelling
water
expansion
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CN107916089A (en
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李浩治
詹锋
张志文
黄淑坚
张志军
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Guangdong Pustar Adhesives & Sealants Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Inorganic Chemistry (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of sealants, in particular to a slow-expansion water-swelling polyurethane sealant and a preparation method thereof. This slowly expand type water-swelling polyurethane sealant includes: the slow-swelling polyurethane prepolymer comprises a slow-swelling polyurethane prepolymer, a plasticizer, a filler, an adhesion promoter, a thixotropic agent, a high water-absorbent resin, a catalyst, an antioxidant and a water removal agent; the slow-swelling type polyurethane prepolymer comprises: random block polyether diol, isotactic block polyether diol, random block polyether triol, isotactic block polyether triol, polyisocyanate, plasticizer and catalyst. The preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps: firstly, preparing a slow-swelling polyurethane prepolymer; secondly, stirring in vacuum; thirdly, drying and mixing; and fourthly, mixing and stirring. The sealant has good slow expansion effect, and is particularly suitable for sealing and waterproofing irregular gaps, such as deformation joints and post-cast strips of underground construction engineering, water supply dam construction, urban pipe gallery engineering and the like.

Description

Slow-expansion type water-swelling polyurethane sealant and preparation method thereof
Technical Field
The invention relates to the technical field of sealants, in particular to a slow-expansion water-swelling polyurethane sealant and a preparation method thereof.
Background
The water-swellable material has dual functions of elastic sealing and water swelling, is widely applied to anti-seepage projects such as tunnel construction, house construction, dam construction and the like, and is generally divided into water-swellable rubber and water-swellable sealant. The water-swellable sealant is generally a polyurethane paste, is used for sealing an amorphous joint, does not need to be precisely cut, does not have the problem of poor matching between the product size and a construction joint, is convenient to construct and is more and more widely applied. The water-swellable sealant reacts with water vapor in the air after being applied to form a polyurethane elastomer, and because the molecular main chain structure contains the ethylene ether (-CH2-CH2-O-) hydrophilic group, the water-swellable sealant can be associated with water in a hydrogen bond mode to swell to play a role in waterproof sealing. In Chinese patent CN102408866B, random block polyether and water-absorbent resin are adopted to prepare an expanded single-component polyurethane sealant, the maximum volume expansion ratio can reach 400%, but the slow expansion effect cannot be reached. In the engineering application process, the colloid is usually constructed in a water state in the early stage, if the material expands in the early stage, great inconvenience is brought to construction operation, a water-based water-swelling elastomer slow-swelling treating agent is prepared by taking styrene-acrylic emulsion as matrix resin in Chinese patent CN104177941A, the water-swelling elastomer slow-swelling treating agent is coated on the surface of the water-swelling elastomer, a complete and continuous compact waterproof isolation layer is formed after a coating film is dried, and the elastomer slow-swelling effect is controlled by adjusting the thickness of the water-based waterproof isolation layer and the soaking failure time. The method is only suitable for prefabricating the water-swellable sealing strip and is not suitable for the paste-shaped water-swellable sealant. The water-swelling polyurethane sealant has the important function of slow swelling. However, the slow expansion type water-swelling polyurethane sealant has not been available in the prior art.
Disclosure of Invention
The invention aims to provide a slow-expansion type water-swelling polyurethane sealant aiming at the defects of the prior art.
The second purpose of the invention is to provide a preparation method of the slow-expansion type water-swelling polyurethane sealant aiming at the defects of the prior art.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
the slow-expansion water-swelling polyurethane sealant is prepared from the following components in percentage by weight:
Figure BDA0001483961080000021
the slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
Figure BDA0001483961080000022
the NCO content of the slow-swelling polyurethane prepolymer is 0.5-3.5%.
The polyisocyanate is one or a composition of more than two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate or 1, 6-hexamethylene diisocyanate.
The random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol are block copolymers of propylene oxide, ethylene oxide and tetrahydrofuran, wherein the EO content of the random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol is 30-75%;
the molecular weight of the random block polyether diol and the molecular weight of the isotactic block polyether diol are both 2000-6000, and the molecular weight of the random block polyether triol and the molecular weight of the isotactic block polyether triol are both 5000-6000.
The plasticizer is one or a composition of more than two of phthalic acid esters, alkyl sulfonate or chlorinated paraffin; the phthalate is one or a composition of more than two of dibutyl phthalate, diisononyl phthalate, dioctyl phthalate or diisodecyl phthalate;
the catalyst is one or a composition of more than two of dibutyltin dilaurate, stannous octoate, triethylenediamine or dimorpholinyl diethyl ether;
the filler is one or a composition of more than two of heavy calcium carbonate, light calcium carbonate, hollow glass microspheres, talcum powder, rutile titanium dioxide, silica micropowder, calcined kaolin, diatomite, PVC paste resin or attapulgite;
the adhesion promoter is one or a composition of more than two of silane coupling agents, gamma-aminopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane or gamma- (2, 3-epoxypropyl) propyltrimethoxysilane;
the thixotropic agent is one or a composition of more than two of nano active calcium carbonate, hydrogenated castor oil, fumed silica, carbon black or polyamide wax;
the super absorbent resin is one or a composition of more than two of copolymerized acrylic acid or methacrylate, acrylate, acrylamide and derivatives thereof and hydrophilic vinyl compounds;
the antioxidant is one or a composition of more than two of an antioxidant 1010, an antioxidant 1076, an antioxidant 168 or an antioxidant 626;
the water removing agent is one or a composition of more than two of trimethyl orthoformate, oxazolidine water removing agents or toluene sulfonyl isocyanate.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding the random block polyether diol, the isotactic block polyether diol, the random block polyether triol, the isotactic block polyether triol and the plasticizer into a vacuum reaction kettle according to the formula, dehydrating for a certain time under the vacuum condition of a certain temperature, controlling the water content of the mixture, cooling to a certain temperature, adding the polyisocyanate and the catalyst according to the formula under the nitrogen protection condition, and reacting for a certain time to obtain the slow-expansion polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for a certain time under a vacuum condition and at a certain temperature;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant at a certain temperature, cooling to a certain temperature, and adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for a certain time;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water scavenger in a formula amount under the protection of nitrogen, and continuously mixing and stirring for a certain time at a certain temperature to obtain the slow-expansion water-swelling polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
In the technical scheme, in the first step, the preparation of the slow swelling type polyurethane prepolymer comprises the following steps: adding the random block polyether diol, the isotactic block polyether diol, the random block polyether triol, the isotactic block polyether triol and the plasticizer into a vacuum reaction kettle according to the formula, dehydrating for 2-4 h under the vacuum condition of 100-110 ℃, controlling the water content of the mixture to be 10-100 ppm, cooling to 50-80 ℃, adding the polyisocyanate and the catalyst according to the formula under the nitrogen protection condition, and reacting for 1-4 h to obtain the slow-swelling polyurethane prepolymer.
In the above technical solution, the second step, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1-1.5 h under the vacuum condition of 0.05-0.10 MPa and at the temperature of 25-45 ℃.
In the above technical solution, the third step, drying and mixing: the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant in the formula amount are dried for 5min to 20min at 105 ℃ to 120 ℃, cooled to 30 ℃ to 50 ℃, and then added into the slow-expansion polyurethane prepolymer in the second step to be mixed and stirred for 1h to 1.5 h.
In the above technical solution, the fourth step is mixing and stirring: adding the adhesion promoter, the catalyst and the water removal agent in the formula amount under the protection of nitrogen, and continuously mixing and stirring for 1-1.5 h at the temperature of 25-45 ℃ to obtain the slow-expansion water-swellable polyurethane sealant.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the slow-expansion water-swelling polyurethane sealant provided by the invention, as the random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol in the formula components are hydrophilic polyethers, the random block polyether diol and the random block polyether triol have high expansion rate and high expansion speed, and the maximum expansion rate can be reached in a short time; the isotactic block polyether dihydric alcohol and the isotactic block polyether trihydric alcohol have regular structures and high crystallization degrees, have poor expansion effect when being used independently, can reach the maximum expansion rate only after being soaked in water for a long time, and have expansion rate which can not meet the engineering use requirements.
(2) The main chain of the slow-expansion water-swelling polyurethane sealant provided by the invention contains hydrophilic groups, the slow-expansion water-swelling polyurethane sealant has stable performance after water expansion and can resist water pressure for a long time, random block polyether (random block polyether diol and random block polyether triol) and isotactic block polyether (isotactic block polyether diol and isotactic block polyether triol) and super absorbent resin are adopted to adjust the expansion rate to be high, and meanwhile, isotactic block polyether diol and isotactic block polyether triol are adopted to adjust the slow-expansion effect, so that the subsequent construction can be facilitated, and the engineering quality is improved.
(3) According to the slow-expansion water-swelling polyurethane sealant provided by the invention, as the formula components contain the thixotropic agent, the prepared slow-expansion water-swelling polyurethane sealant can be constructed on both a horizontal plane and a vertical plane and has the advantage of short drawn wires; in addition, as the components of the formula contain the water removing agent, the prepared slow-expansion type water-swelling polyurethane sealant has long product quality guarantee period and stable quality.
(4) The slow-expansion water-swelling polyurethane sealant provided by the invention is paste, so that the slow-expansion water-swelling polyurethane sealant is particularly suitable for sealing and waterproofing irregular gaps, such as deformation joints and post-pouring belts of underground construction engineering, water supply dam construction, urban pipe gallery engineering and the like.
(5) The preparation method of the slow-expansion water-swelling polyurethane sealant provided by the invention has the characteristics of simple preparation method and suitability for industrial large-scale production.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The NCO referred to herein is an isocyanate group. EO as referred to herein represents ethylene oxide.
Example 1.
A slow-expansion water-swelling polyurethane sealant is prepared from the following components in parts by weight:
Figure BDA0001483961080000051
Figure BDA0001483961080000061
the slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
Figure BDA0001483961080000062
wherein, the NCO content of the slow-swelling type polyurethane prepolymer is 0.5-3.5%.
Wherein the polyisocyanate is one or a composition of more than two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate or 1, 6-hexamethylene diisocyanate.
Wherein the random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol are block copolymers of propylene oxide, ethylene oxide and tetrahydrofuran, and the EO content of the random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol is 30-75%;
the molecular weight of the random block polyether diol and the molecular weight of the isotactic block polyether diol are both 2000-6000, and the molecular weight of the random block polyether triol and the molecular weight of the isotactic block polyether triol are both 5000-6000.
Wherein the plasticizer is one or a composition of more than two of phthalic acid esters, alkyl sulfonic acid esters or chlorinated paraffin; the phthalate is one or a composition of more than two of dibutyl phthalate, diisononyl phthalate, dioctyl phthalate or diisodecyl phthalate;
the catalyst is one or the composition of more than two of dibutyltin dilaurate, stannous octoate, triethylenediamine or dimorpholinyl diethyl ether;
the filler is one or a composition of more than two of heavy calcium carbonate, light calcium carbonate, hollow glass microspheres, talcum powder, rutile titanium dioxide, silicon micropowder, calcined kaolin, diatomite, PVC paste resin or attapulgite;
the adhesion promoter is one or the composition of more than two of silane coupling agent, gamma-aminopropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, N-phenyl-gamma-aminopropyl trimethoxy silane or gamma- (2, 3-epoxypropyl) propyl trimethoxy silane;
the thixotropic agent is one or the composition of more than two of nano active calcium carbonate, hydrogenated castor oil, fumed silica, carbon black or polyamide wax;
the high water absorption resin is one or a composition of more than two of copolymerized acrylic acid or methacrylate, acrylate, acrylamide and derivatives thereof and hydrophilic vinyl compounds;
the antioxidant is one or a composition of more than two of antioxidant 1010, antioxidant 1076, antioxidant 168 or antioxidant 626;
the water removing agent is one or a composition of more than two of trimethyl orthoformate, oxazolidine water removing agents or toluene sulfonyl isocyanate.
The preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding random block polyether diol, isotactic block polyether diol, random block polyether triol, isotactic block polyether triol and plasticizer in the formula amount into a vacuum reaction kettle, dehydrating for 2-4 h under the vacuum condition of 100-110 ℃, controlling the water content of the mixture to be 10-100 ppm, cooling to 50-80 ℃, adding polyisocyanate and catalyst in the formula amount under the nitrogen protection condition, and reacting for 1-4 h to obtain the slow-swelling polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1-1.5 h under the vacuum condition of 0.05-0.10 MPa and at the temperature of 25-45 ℃;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant according to the formula ratio at 105-120 ℃ for 5-20 min, cooling to 30-50 ℃, and adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for 1-1.5 h;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water removal agent in a formula amount under the protection of nitrogen, and continuously mixing and stirring for 1-1.5 h at 25-45 ℃ to obtain the slow-expansion water-swellable polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
Example 2.
Figure BDA0001483961080000081
The slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
Figure BDA0001483961080000082
wherein, the NCO content of the slow-swelling polyurethane prepolymer is 1.76%.
Wherein, the EO content of the random block polyether diol is 70 percent, and the molecular weight is 4000; the isotactic block polyether dihydric alcohol EO content is 70 percent, and the molecular weight is 4000; the EO content of the random block polyether triol is 70 percent, and the molecular weight is 6000; the isotactic block polyether triol EO content is 70%, and the molecular weight is 6000.
The preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding random block polyether diol, isotactic block polyether diol, random block polyether triol, isotactic block polyether triol and plasticizer in the formula amount into a vacuum reaction kettle, dehydrating for 3 hours at 105 ℃, controlling the water content of the mixture to be 50ppm, cooling to 65 ℃, adding polyisocyanate and catalyst in the formula amount under the protection of nitrogen, and reacting for 2.5 hours to obtain the slow-expansion polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1.3h under the vacuum condition of 0.08MPa and at the temperature of 35 ℃;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant in a formula ratio at 110 ℃ for 10min, cooling to 40 ℃, and then adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for 1.3 h;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water scavenger in a formula amount under the protection of nitrogen, and continuously mixing and stirring for 1.3 hours at 35 ℃ to obtain the slow-expansion water-swellable polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
Example 3.
Figure BDA0001483961080000091
The slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
Figure BDA0001483961080000092
Figure BDA0001483961080000101
wherein, the NCO content of the slow-swelling polyurethane prepolymer is 1.48 percent.
Wherein, the content of EO in the regular block polyether diol is 37 percent, and the molecular weight is 4000; the isotactic block polyether dihydric alcohol EO content is 37 percent, and the molecular weight is 4000; the content of EO in the random block polyether triol is 70 percent, and the molecular weight is 5000; the isotactic block polyether triol EO content is 70%, and the molecular weight is 5000.
The preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding random block polyether diol, isotactic block polyether diol, random block polyether triol, isotactic block polyether triol and plasticizer in a formula ratio into a vacuum reaction kettle, dehydrating for 2-4 h under the vacuum condition of 100 ℃, controlling the water content of the mixture to be 10ppm, cooling to 50 ℃, adding polyisocyanate and catalyst in the formula ratio under the nitrogen protection condition, and reacting for 1h to obtain the slow-swelling polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1h under the vacuum condition of 0.05MPa and at the temperature of 25 ℃;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant in a formula ratio at 105 ℃ for 5min, cooling to 30 ℃, and then adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for 1 h;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water removal agent in a formula amount under the protection of nitrogen, and continuously mixing and stirring for 1h at 25 ℃ to obtain the slow-expansion water-swelling polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
Example 4.
Figure BDA0001483961080000102
Figure BDA0001483961080000111
The slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
Figure BDA0001483961080000112
wherein, the NCO content of the slow-swelling polyurethane prepolymer is 1.88%.
Wherein, the EO content of the random block polyether diol is 37 percent, and the molecular weight is 2000; the isotactic block polyether dihydric alcohol EO content is 37 percent, and the molecular weight is 2000; the content of EO in the random block polyether triol is 70 percent, and the molecular weight is 5000; the isotactic block polyether triol EO content is 70%, and the molecular weight is 5000.
The preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding random block polyether diol, isotactic block polyether diol, random block polyether triol, isotactic block polyether triol and plasticizer in the formula amount into a vacuum reaction kettle, dehydrating for 4 hours at the temperature of 110 ℃, controlling the water content of the mixture to be 100ppm, cooling to 80 ℃, and adding polyisocyanate and catalyst in the formula amount to react for 4 hours under the nitrogen protection condition to obtain the slow-expansion polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1.5h under the vacuum condition of 0.10MPa and at the temperature of 45 ℃;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant in a formula ratio at 120 ℃ for 20min, cooling to 50 ℃, and then adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for 1.5 h;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water removal agent in a formula amount under the protection of nitrogen, and continuously mixing and stirring for 1.5 hours at the temperature of 45 ℃ to obtain the slow-expansion water-swelling polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
Example 5.
Figure BDA0001483961080000121
The slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
Figure BDA0001483961080000122
wherein, the NCO content of the slow-swelling polyurethane prepolymer is 2.13 percent.
Wherein, the EO content of the random block polyether diol is 37 percent, and the molecular weight is 2000; the isotactic block polyether dihydric alcohol EO content is 37 percent, and the molecular weight is 2000; the EO content of the random block polyether triol is 70 percent, and the molecular weight is 6000; the isotactic block polyether triol EO content is 70%, and the molecular weight is 6000.
The preparation method of the slow-expansion water-swelling polyurethane sealant comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding random block polyether diol, isotactic block polyether diol, random block polyether triol, isotactic block polyether triol and plasticizer in a formula ratio into a vacuum reaction kettle, dehydrating for 2-4 h under the vacuum condition of 108 ℃, controlling the water content of the mixture to be 80ppm, cooling to 70 ℃, adding polyisocyanate and catalyst in the formula ratio under the nitrogen protection condition, and reacting for 3h to obtain the slow-swelling polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1.4h under the vacuum condition of 0.09MPa and at the temperature of 30 ℃;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant in a formula ratio at 110 ℃ for 15min, cooling to 45 ℃, and then adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for 1.1 h;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water removal agent in a formula amount under the protection of nitrogen, and continuously mixing and stirring for 1.1h at 40 ℃ to obtain the slow-expansion water-swelling polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
Comparative example:
comparative example 1.
The polyurethane sealant comprises the following raw materials in percentage by mass:
Figure BDA0001483961080000131
Figure BDA0001483961080000141
the polyurethane prepolymer comprises the following raw materials in percentage by mass:
Figure BDA0001483961080000142
the NCO content of the polyurethane prepolymer is 1.76%, and the mass ratio of the atactic polyether to the isotactic polyether is 1: 0. The EO content of the random block polyether diol is 70 percent, and the molecular weight is 4000; the EO content of the random block polyether triol is 70 percent, and the molecular weight is 6000. The preparation method of the polyurethane prepolymer comprises the following steps: adding random block polyether diol, random block polyether triol and plasticizer into a vacuum reaction kettle, dehydrating for 1.5h at the temperature of 110 ℃ under the vacuum condition, controlling the water content of the mixture to be less than or equal to 100ppm, cooling to 65 ℃, and adding polyisocyanate and catalyst to react for 2.5h under the nitrogen protection condition to obtain the polyurethane prepolymer.
The preparation method of the polyurethane sealant in this example is the same as that of example 2.
Comparative example 2.
The polyurethane sealant comprises the following raw materials in percentage by mass:
Figure BDA0001483961080000143
Figure BDA0001483961080000151
the polyurethane prepolymer comprises the following raw materials in percentage by mass:
Figure BDA0001483961080000152
the NCO content of the polyurethane prepolymer is 1.76%, and the mass ratio of the atactic polyether to the isotactic polyether is 0: 1. The isotactic block polyether dihydric alcohol EO content is 70 percent, and the molecular weight is 4000; the isotactic block polyether triol EO content is 70%, and the molecular weight is 6000. The preparation method of the polyurethane prepolymer comprises the following steps: adding isotactic block polyether dihydric alcohol, isotactic block polyether trihydric alcohol and a plasticizer into a vacuum reaction kettle, dehydrating for 1.5h at the temperature of 110 ℃ under the vacuum condition, controlling the water content of the mixture to be less than or equal to 100ppm, cooling to 65 ℃, and adding polyisocyanate and a catalyst to react for 2.5h under the nitrogen protection condition to obtain the polyurethane prepolymer.
The preparation method of the polyurethane sealant in this example is the same as that of example 2.
And (3) comparative analysis:
the performance of the sealants obtained in examples 2 to 5, and comparative examples 1 and 2 were compared and shown in Table 1.
Table 1 table of properties of examples 2 to 5 and comparative examples 1 to 2
Figure BDA0001483961080000153
Figure BDA0001483961080000161
As can be seen from the performance test data in Table 1, the swelling effect is poor when isotactic block polyether is singly adopted, and the slow swelling effect cannot be achieved when random block polyether is singly adopted; the isotactic block polyether and the random strength polyether can achieve good slow expansion effect by compounding.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The slow-expansion water-swelling polyurethane sealant is characterized in that: the paint is prepared from the following components in percentage by weight:
40-60% of slow-swelling polyurethane prepolymer
1-10% of plasticizer
10-50% of filler
0.01-2% of adhesion promoter
0.01% -10% of thixotropic agent
1-10% of high water-absorbing resin
0.01 to 2 percent of catalyst
0.1 to 2.5 percent of antioxidant
0.1% -3% of a water removing agent;
the slow-swelling polyurethane prepolymer is prepared from the following components in percentage by weight:
5-15% of random block polyether diol
5-15% of isotactic block polyether diol
5-30% of random block polyether triol
5-30% of isotactic block polyether triol
5-15% of polyisocyanate
20-50% of plasticizer
0.1% -1% of catalyst.
2. The slow-expansion water-swelling polyurethane sealant according to claim 1, characterized in that: the NCO content of the slow-swelling polyurethane prepolymer is 0.5-3.5%.
3. The slow-expansion water-swelling polyurethane sealant according to claim 1, characterized in that: the polyisocyanate is one or a composition of more than two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate or 1, 6-hexamethylene diisocyanate.
4. The slow-expansion water-swelling polyurethane sealant according to claim 1, characterized in that: the random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol are block copolymers of propylene oxide, ethylene oxide and tetrahydrofuran, wherein the EO content of the random block polyether diol, the isotactic block polyether diol, the random block polyether triol and the isotactic block polyether triol is 30-75%;
the molecular weight of the random block polyether diol and the molecular weight of the isotactic block polyether diol are both 2000-6000, and the molecular weight of the random block polyether triol and the molecular weight of the isotactic block polyether triol are both 5000-6000.
5. The slow-expansion water-swelling polyurethane sealant according to claim 1, characterized in that: the plasticizer is one or a composition of more than two of phthalic acid esters, alkyl sulfonate or chlorinated paraffin; the phthalate is one or a composition of more than two of dibutyl phthalate, diisononyl phthalate, dioctyl phthalate or diisodecyl phthalate;
the catalyst is one or a composition of more than two of dibutyltin dilaurate, stannous octoate, triethylenediamine or dimorpholinyl diethyl ether;
the filler is one or a composition of more than two of heavy calcium carbonate, light calcium carbonate, hollow glass microspheres, talcum powder, rutile titanium dioxide, silica micropowder, calcined kaolin, diatomite, PVC paste resin or attapulgite;
the adhesion promoter is one or the composition of more than two of gamma-aminopropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, N-phenyl-gamma-aminopropyl trimethoxy silane or gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane;
the thixotropic agent is one or a composition of more than two of nano active calcium carbonate, hydrogenated castor oil, fumed silica or polyamide wax, or the thixotropic agent is a composition of fumed silica and carbon black;
the super absorbent resin is one or a composition of more than two of copolymerized acrylic acid or methacrylate, acrylate, acrylamide and derivatives thereof and hydrophilic vinyl compounds;
the antioxidant is one or a composition of more than two of an antioxidant 1010, an antioxidant 1076, an antioxidant 168 or an antioxidant 626;
the water removing agent is one or a composition of more than two of trimethyl orthoformate, oxazolidine water removing agents or toluene sulfonyl isocyanate.
6. The preparation method of the slow-expansion water-swelling polyurethane sealant as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps: it comprises the following steps:
step one, preparing a slow swelling type polyurethane prepolymer: adding the random block polyether diol, the isotactic block polyether diol, the random block polyether triol, the isotactic block polyether triol and the plasticizer into a vacuum reaction kettle according to the formula, dehydrating for a certain time under the vacuum condition of a certain temperature, controlling the water content of the mixture, cooling to a certain temperature, adding the polyisocyanate and the catalyst according to the formula under the nitrogen protection condition, and reacting for a certain time to obtain the slow-expansion polyurethane prepolymer;
step two, vacuum stirring: adding the slow-expansion type polyurethane prepolymer prepared in the first step into a mixer, and stirring for a certain time under a vacuum condition and at a certain temperature;
third, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant at a certain temperature, cooling to a certain temperature, and adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for a certain time;
step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water scavenger in a formula amount under the protection of nitrogen, and continuously mixing and stirring for a certain time at a certain temperature to obtain the slow-expansion water-swelling polyurethane sealant; wherein the prepared slow-expansion water-swelling polyurethane sealant is a paste.
7. The preparation method of the slow-expansion water-swelling polyurethane sealant according to claim 6, which is characterized by comprising the following steps: the first step is to prepare a slow swelling type polyurethane prepolymer: adding the random block polyether diol, the isotactic block polyether diol, the random block polyether triol, the isotactic block polyether triol and the plasticizer into a vacuum reaction kettle according to the formula, dehydrating for 2-4 hours at the temperature of 100-110 ℃, controlling the water content of the mixture to be 10-100 ppm, cooling to 50-80 ℃, adding the polyisocyanate and the catalyst according to the formula under the nitrogen protection condition, and reacting for 1-4 hours to obtain the slow-expansion polyurethane prepolymer.
8. The preparation method of the slow-expansion water-swelling polyurethane sealant according to claim 6, which is characterized by comprising the following steps: the second step, vacuum stirring: and adding the slow-expansion polyurethane prepolymer prepared in the first step into a mixer, and stirring for 1-1.5 h at 25-45 ℃ under the vacuum condition of 0.05-0.10 MPa.
9. The preparation method of the slow-expansion water-swelling polyurethane sealant according to claim 6, which is characterized by comprising the following steps: the third step, drying and mixing: drying the plasticizer, the filler, the thixotropic agent, the super absorbent resin and the antioxidant according to the formula ratio at 105-120 ℃ for 5-20 min, cooling to 30-50 ℃, and adding the mixture into the slow-expansion polyurethane prepolymer in the second step to mix and stir for 1-1.5 h.
10. The preparation method of the slow-expansion water-swelling polyurethane sealant according to claim 6, which is characterized by comprising the following steps: and step four, mixing and stirring: adding an adhesion promoter, a catalyst and a water removal agent in a formula amount under the protection of nitrogen, and continuously mixing and stirring for 1-1.5 h at the temperature of 25-45 ℃ to obtain the slow-expansion water-swellable polyurethane sealant.
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