CN113416511B

CN113416511B - MS sealant for assembled concrete and preparation method thereof

Info

Publication number: CN113416511B
Application number: CN202110641026.4A
Authority: CN
Inventors: 王洪波; 林展鹏
Original assignee: Guangdong Engineering Polytechnic
Current assignee: Guangdong Engineering Polytechnic
Priority date: 2021-06-09
Filing date: 2021-06-09
Publication date: 2023-09-26
Anticipated expiration: 2041-06-09
Also published as: CN113416511A

Abstract

The application discloses a novel MS sealant for assembled concrete and a preparation method thereof. According to the application, through the hydrogen bonding effect and the steric hindrance effect formed by the dispersing agent, the viscosity of the system is greatly reduced, the uniform arrangement property of the filler is improved, so that a more compact three-dimensional interpenetrating body structural adhesive is formed, the cohesiveness and the storage stability of the MS sealant are improved, the particle problem of the MS sealant is solved, meanwhile, the thixotropic agent endows the MS sealant with good thixotropic property, the industry common problem of poor extrusion property after storage is eliminated, and the MS sealant is easier to construct in the construction process.

Description

MS sealant for assembled concrete and preparation method thereof

Technical Field

The application relates to MS sealant, in particular to MS sealant for assembled concrete and a preparation method thereof.

Background

The structural joint refers to a joint arranged between two adjacent buildings or two parts of the buildings for avoiding temperature expansion and contraction, foundation settlement, earthquake collision and the like, and comprises a construction joint, an expansion joint, a settlement joint, a shockproof joint and the like. In order to prevent corrosion between the structural joints, a sealant is poured between the structural joints.

The assembled concrete structure sealant is a cross-linked polymer based on silane end-capped polyether, and is mainly a single-component or double-component elastic sealant which is prepared by taking an MS polymer as a base polymer and matching with a filler, a plasticizer and other functional additives, and is also called MS sealant. MS sealants achieve crosslinking or curing by continuous exposure to moisture, mainly from air or the adhered substrate itself.

At present, because the MS sealant has higher viscosity of MS resin, the adding proportion and the dispersing uniformity of the filled calcium powder are limited, and each performance of the sealant is further limited, and the unilateral improvement of the proportion of the filled calcium powder can lead to the problems of high viscosity, low extrusion rate, low construction efficiency, low bonding strength of the sealant, short storage period and the like, and secondly, the MS sealant has higher specific gravity, the shape retention is possibly poor during the vertical construction, the thickness and the position of the colloid are offset, and the construction effect is influenced.

Disclosure of Invention

Aiming at the problems, one of the purposes of the application is to provide an MS sealant for assembled concrete, which can effectively reduce solid particle accumulation with high specific gravity and improve the uniformity of particle dispersion through a high molecular polyamide dispersing agent and a polyamide thixotropic agent with a certain proportion, thereby improving the cohesiveness and storage stability of the sealant, and being easier to glue and having good shape retention in the construction process.

The technical aim of the application is realized by the following technical scheme, namely the MS sealant for the fabricated concrete comprises the following components in parts by weight:

in the application, the dispersing agent is a high molecular weight polyamide dispersing agent selected from Guangzhou core new material science and technology Co-Ltd, and comprises the following components: polyimide, solvation chain and anchoring group, the polyimide has two symmetrical hydroxyl groups, the solvation chain is solvation chain, caprolactone or ethylene oxide with carboxyl, the hydroxyl on the polyimide is combined with the solvation chain, caprolactone or ethylene oxide with carboxyl, and the anchoring group is formed by grafting the polyimide on the solvation chain and then reacting with phosphate or anhydride.

The polyimide with hydroxyl is obtained after the reaction by mixing hydroxy carboxylic acid and polyvinyl amine, the polyimide is used as a framework of a dispersant to be prepared, then the obtained polyimide is subjected to solvated chain grafting, and the grafted polymer is mixed with phosphate or anhydride for reaction to prepare the dispersant.

The dispersing agent is adsorbed on the surfaces of pigment and filler particles such as calcium powder through anchoring groups carried by the dispersing agent, and a good steric hindrance effect is formed through solvation chain segments, so that the viscosity of the system is greatly reduced, the uniformity of the pigment and filler particles and the uniformity of dispersion are improved, and a more compact three-dimensional interpenetrating network structure adhesive can be formed, so that the dispersing agent is applicable to different solution systems, and meanwhile, the wettability and the adsorptivity of the dispersing agent are improved.

The thixotropic agent is a polyamide thixotropic agent, is selected from Guangzhou core new material science and technology Co., ltd, and comprises the following preparation steps:

step (1): heating and mixing the component A containing carboxyl, the component B containing amino and the catalyst for a certain time, and vacuumizing to enable the carboxyl to react with the amino to generate polyamide; the component A is hydroxycarboxylic acid or a mixture of hydroxycarboxylic acid and alkyl carboxylic acid, specifically, the hydroxycarboxylic acid is ricinoleic acid or dodecahydroxystearic acid, the alkyl carboxylic acid is lauric acid, the mixture of hydroxycarboxylic acid and alkyl carboxylic acid is a mixture of dodecahydroxystearic acid and lauric acid, the catalyst is dibutyl tin oxide or monobutyl tin oxide, and the structural formula of the component B is: h- (NH-CH 2) n-NH 2, n=1-5;

step (2): mixing the polyamide obtained in the step (alpha) with a polymer with epoxy groups or isocyanate groups, and heating to enable active hydrogen on the polyamide to react with the epoxy groups or isocyanate groups, wherein the polymer with epoxy groups is polyethylene glycol diglycidyl ether with an average molecular weight of 500 or terminal single epoxy end-capped polybutyl acrylate with an average molecular weight of 1000; the polymer with isocyanate groups is: 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate, and finally preparing the modified polyamide structural rheological agent used in the application.

The modified polyamide structural rheological agent has wide applicable systems and good compatibility in various systems such as low-polarity, medium-polarity and high-polarity systems; meanwhile, OH or urethane bonds are added on a molecular chain of the modified polyamide rheological agent, nitrogen or oxygen in the molecular chain and hydrogen in self or other hydrocarbon form a hydrogen bond with a space network structure, the speed and the number of the hydrogen bonds formed in the system are improved, when the hydrogen bonds with the space network structure are damaged by shearing force, good construction performance is provided by viscosity reduction, and when the shearing force is removed, the hydrogen bonds are reformed, so that the modified polyamide rheological agent has good thixotropic, anti-sinking and anti-sagging effects.

Further, MS sealant used for the fabricated concrete comprises the following components in parts by weight:

in the application, the dispersing agent is polyamide dispersing agent with molecular weight more than 6000.

Further, the dispersing agent is selected from Guangzhou core new material science and technology limited company, and the product is at least one of DISPUPER S35, DISPUPER S9500 and DISPUPER S9300.

In the application, the thixotropic agent is a powdery polyamide thixotropic agent.

Further, the thixotropic agent is selected from Guangzhou core New Material technologies Co., ltd, and the product is at least one of PAMID D680, PAMID D520 and PAMID D580.

In the application, the calcium powder filling material comprises heavy calcium carbonate and light calcium carbonate.

In the application, the plasticizer is at least one of diisononyl phthalate and dioctyl phthalate.

In the application, the coupling agent is an aminosilane coupling agent, and the water scavenger is a vinyl silane water scavenger.

The application further aims at providing a preparation method of MS sealant for assembled concrete, which comprises the following steps:

(1) The calcium powder filling material is dehydrated in a blast electric heating oven and then is uniformly mixed with pigment to be used as pigment filling material;

(2) Adding plasticizer, dispersant and thixotropic agent into a dispersing cylinder of a planetary vacuum stirrer, and regulating a co-rotating disc and a gear disc to carry out dispersing stirring at 10-20 Hz;

(3) Adding pigment and filler after stirring uniformly, starting vacuum, regulating the common turntable and gear disc to be 30-40Hz, raising the temperature to 70-90 ℃, maintaining for 30-60min, enabling the thixotropic agent to be completely activated and dissolved, then continuously stirring and dispersing for 1-2h at 110-130 ℃, controlling the humidity of the obtained viscous colloid to be less than 800PPM, and removing the moisture and the activated thixotropic agent in the materials;

(4) Heating, regulating the revolution disc and the gear disc to 10-20Hz, closing vacuum and heating, opening the cooling device to cool the dispersion cylinder to room temperature, adding a water removing agent and silane modified resin into the dispersion cylinder, opening the vacuum, dispersing for 40-60min at 10-20Hz, adding a coupling agent and a water removing agent, filling nitrogen for protection, dispersing for 50-60min under vacuum, stirring and cooling to room temperature, and discharging by using an extruder.

The application has the following beneficial effects:

1. according to the application, the high molecular polyamide dispersing agent is added into the MS sealing colloid system, and is adsorbed on the surfaces of pigment and filler particles such as calcium powder through anchoring groups carried by the high molecular polyamide dispersing agent, and a good steric hindrance effect is formed through solvation chain segments, so that the viscosity of the system is greatly reduced, the particle uniformity and dispersion uniformity of pigment and filler are improved, and pigment and filler with more proportions can be added;

2. according to the application, the polyamide thixotropic agent is added into the MS sealing colloid system, so that the completely melted and activated thixotropic agent can uniformly form a space reticular structure through the action of hydrogen bonds, and meanwhile, the fiber reticular structure is bridged again to endow colloid thixotropic property, thereby improving sagging of the high specific gravity pigment and filler sealing colloid in the construction process, ensuring good gumming property and greatly improving shape retention;

3. the MS sealant prepared by the application improves pigment and filler particle dispersibility by adding the high molecular polyamide dispersing agent, so that pigment and filler with more proportion can be added, and the MS sealant has more excellent heat aging fixed elongation retention time, wherein the fixed elongation retention time after heat aging is 7d and longer than the fixed elongation retention time of a commercial product;

4. the MS sealant prepared by the application has more excellent tensile bonding performance, and the tensile strength and the maximum tensile force of the MS sealant are higher than those of other MS sealants in the market.

Detailed Description

Example 1

25 parts of STP silane modified polyether resin, 5 parts of pigment, 45 parts of calcium powder filler, 0.6 part of dispersing agent, 0.6 part of thixotropic agent, 22.6 parts of plasticizer, 0.6 part of coupling agent and 0.6 part of water scavenger.

Wherein the STP silane modified polyether resin is selected from Jiangsu Ruiyan Antai New Material technology Co., ltd, and the product trade name is 30000T.

Wherein the pigment comprises carbon black and titanium dioxide.

Wherein, the calcium powder filling material is selected from the Colon powder limited company in Guangxi He, and comprises 800-mesh heavy calcium carbonate and 1300-mesh light calcium carbonate, and the proportion of the heavy calcium carbonate to the light calcium carbonate is as follows: 1:1.

Wherein the dispersing agent is a high molecular polyamide dispersing agent, which is selected from Guangzhou core new material science and technology Co., ltd, the product brand is DISPUPER S35, and the molecular weight is 6500.

The preparation method of the dispersing agent comprises the following steps:

step (1): mixing 536-656 g of ricinoleic acid, 130-160 g of triethylene tetramine and 18-22 g of dibutyl tin oxide, and reacting to obtain polyimide; or mixing 540-660 g of dodecahydroxystearic acid, 170-206 g of tetraethylenepentamine and 18-22 g of monobutyl tin oxide, and reacting to obtain polyimide;

step (2): 126 to 154 g of polyimide, 270 to 330 g of caprolactone, 270 to 330 g of dodecahydroxy stearic acid and 18 to 22 g of diisobutyltin dilaurate are mixed to graft solvated chains of the obtained polyimide; or mixing 126-154 g of polyimide and 450-550 g of carboxyl-terminated polymethyl methacrylate for reaction, and then adding 270-330 g of caprolactone and 18-22 g of diisobutyltin dilaurate to graft solvated chains of the obtained polyimide;

step (3): and mixing the grafted polymer with phosphate or anhydride to react so as to prepare the dispersing agent.

Wherein the thixotropic agent is a powdery polyamide thixotropic agent and is selected from Guangzhou core new material technology Co., ltd, and the product brand is PAMID D680.

The preparation method of the thixotropic agent comprises the following steps:

step (1): mixing the component A containing carboxyl, the component B containing amino and the catalyst at 150-230 ℃ for 4-10 hours, and vacuumizing at 180-230 ℃ for 1 hour after the reaction to enable the carboxyl and the amino to react to generate polyamide; wherein the molar ratio of the component A to the component B is 2:1, the catalyst accounts for 1.4 to 1.7 percent of the mass of the component A and the component B, and active hydrogen is hydrogen on secondary amine in polyamide; wherein the component A is hydroxycarboxylic acid or a mixture of hydroxycarboxylic acid and alkyl carboxylic acid, specifically, the hydroxycarboxylic acid is ricinoleic acid or dodecahydroxystearic acid, the alkyl carboxylic acid is lauric acid, the mixture of hydroxycarboxylic acid and alkyl carboxylic acid is a mixture of dodecahydroxystearic acid and lauric acid, and the ratio of the amount of the dodecahydroxystearic acid to the amount of lauric acid substances in the mixture is 1:1, the catalyst is dibutyl tin oxide or monobutyl tin oxide, and the structural formula of the component B is as follows: h- (NH-CH 2) n-NH 2, n=1-5;

step (2): mixing the polyamide obtained in the step (1) with a polymer with epoxy groups or isocyanate groups at the temperature of 80-85 ℃ for 2-4 hours, so that active hydrogen on the polyamide reacts with the epoxy groups or isocyanate groups, wherein the polymer with epoxy groups is polyethylene glycol diglycidyl ether with the average molecular weight of 500 or terminal single epoxy end-capped polybutyl acrylate with the average molecular weight of 1000; the polymers with isocyanate groups are: 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate, and finally preparing the modified polyamide structural rheological agent.

Wherein the plasticizer is DINP diisononyl phthalate.

Wherein the coupling agent is an aminosilane coupling agent selected from the German winning Industrial group (Evonik IndustriesAG), and the product brand is Dynasylan DAMO.

The water scavenger is vinyl silane water scavenger selected from the American Maifanitum high new material group (MomentivePerformance Materials) with product name of SILQUEST A171.

The preparation method of the embodiment comprises the following steps:

(1) Removing water from the calcium powder filling material in a blast electrothermal oven at 120 ℃ for 24 hours; uniformly mixing the calcium powder filling material and pigment to obtain pigment filling material;

(2) Adding a plasticizer, a dispersing agent and a thixotropic agent into a dispersing cylinder of five liters of a planetary vacuum stirrer, closing the dispersing cylinder and a stirring disc, and adjusting a co-rotating disc and a gear disc to carry out dispersing stirring at 15 Hz;

(3) Adding pigment and filler after stirring uniformly, closing a dispersing agent, continuously stirring uniformly, scraping powder attached to a dispersing disc and a dispersing cylinder while the dispersing agent is hot to fully mix, starting vacuum after the mixing, regulating a common rotating disc and a gear disc to 34Hz, raising the temperature to 70-90 ℃, maintaining for 30-60min to fully activate and dissolve the thixotropic agent, continuously stirring and dispersing for 1.5h at 120 ℃, controlling the humidity of the obtained viscous colloid to be less than 800PPM, and removing water and activating the thixotropic agent in the materials;

(4) And (3) regulating the revolution disc and the gear disc to 15Hz after heating, closing vacuum and heating, starting to cool the dispersion cylinder to room temperature, adding a water removing agent and silane modified resin into the dispersion cylinder, starting vacuum, dispersing for 50min at 15Hz, adding a coupling agent and a water removing agent, filling nitrogen for protection, dispersing for 55min under vacuum, stirring and cooling to room temperature, and discharging by using an extruder.

Example 2

This embodiment differs from embodiment 1 in that:

23 parts of STP silane modified polyether resin, 10 parts of pigment, 45 parts of calcium powder filler, 0.3 part of dispersing agent, 0.7 part of thixotropic agent, 20 parts of plasticizer, 0.5 part of coupling agent and 0.5 part of water scavenger.

The dispersing agent is a high molecular polyamide dispersing agent, and is selected from Guangzhou core new material science and technology Co., ltd, the product brand is DISPUPER S9500, and the molecular weight is 15000.

The thixotropic agent is a powdery polyamide thixotropic agent and is selected from Guangzhou core new material technology Co., ltd, and the product brand is PAMID D520.

The plasticizer is dioctyl phthalate.

The preparation method of this example differs from example 1 in that: in the step (2), the common turntable and the gear disc are regulated to be dispersed and stirred at 10 Hz; in the step (3), the common turntable and the gear disc are adjusted to be 30Hz, and then stirring and dispersing are continued for 1h at 110 ℃; in the step (4), the revolution disc and the gear disc are regulated to 10Hz, vacuum is started, the dispersion is carried out for 40min under 10Hz, then the coupling agent and the water removing agent are added, and then nitrogen is filled for protection, and the dispersion is carried out for 50min under vacuum.

Example 3

This embodiment differs from embodiment 1 in that:

30 parts of STP silane modified polyether resin, 1 part of pigment, 50 parts of calcium powder filler, 1 part of dispersing agent, 1 part of thixotropic agent, 25 parts of plasticizer, 1 part of coupling agent and 1 part of water scavenger.

The dispersing agent is a high molecular polyamide dispersing agent, and is selected from Guangzhou core new material science and technology Co., ltd, the product brand is DISPUPER S9300, and the molecular weight is 16000.

The thixotropic agent is a powdery polyamide thixotropic agent and is selected from Guangzhou core new material technology Co., ltd, and the product brand is PAMID D580.

The preparation method of this example differs from example 1 in that: in the step (2), the common turntable and the gear disc are regulated to be dispersed and stirred at 20 Hz; in the step (3), the common turntable and the gear disc are adjusted to 40Hz, and then stirring and dispersing are continued for 2 hours at 130 ℃; in the step (4), the revolution disc and the gear disc are regulated to 20Hz, vacuum is started, the dispersion is carried out for 60min under 20Hz, then the coupling agent and the water removing agent are added, and then nitrogen is filled for protection, and the dispersion is carried out for 60min under vacuum.

Example 4

This embodiment differs from embodiment 1 in that:

30 parts of STP silane modified polyether resin, 10 parts of pigment, 35 parts of calcium powder filler, 0.2 part of dispersing agent, 0.2 part of thixotropic agent, 15 parts of plasticizer, 0.2 part of coupling agent and 0.2 part of water scavenger.

The MS sealant product prepared in example 1 was tested

1. And (3) testing the stretching adhesion:

comparing the fixed extension adhesion of the common building assembly sealant and the novel MS sealant on different base materials in the market, testing and referring to the standard of the test method of building sealing materials, namely, the test of the fixed extension adhesion of GB/T13477.10-2017, wherein the test principle is to bond the sealing materials to be tested between the surfaces of two parallel base materials to prepare a test piece, stretching the test piece to a specified width, keeping the stretching state under the specified width, and recording the cohesive or cohesive failure mode of the sealing materials.

The test and record data include eight contents of test temperature, tensile speed, initial width, tensile elongation, fixed elongation retention time, breaking depth and tensile result, and the test is performed on two substrates of cement substrate and aluminum alloy substrate by using the method A (standard test condition placement 28 d), and the specific test data and results are as follows:

TABLE 1

The data in Table 1 shows that the MS sealant prepared by the application meets the requirement of stretching adhesion on different base materials and has the performance similar to that of products on the market.

2. And (3) after soaking, stretching adhesion test:

the test is based on the test of the adhesion/cohesion performance of MS sealant in a fixed elongation state, part 11 of the test method for building sealant, the test is based on the standard of the test GB/T13477.11-2017 for the fixed elongation adhesion after soaking, the test principle is that a to-be-tested sealant is adhered between the surfaces of two parallel substrates to prepare a test piece and a reference test piece, the test piece is soaked under the specified conditions, the test piece and the reference test piece are stretched to the specified width, and after the stretched state is maintained for the specified time, the adhesion or cohesion failure form of the test piece is measured and recorded.

The test and record data includes eight contents of test temperature, tensile speed, initial width, tensile elongation, fixed elongation retention time, breaking depth and tensile result, and the test is performed on the cement substrate by using the method A (standard test condition placement 28 d), and the specific test data and results are as follows:

TABLE 2

The data in Table 2 shows that the MS sealant prepared by the application meets the requirement of stretching adhesion after soaking, and has the performance similar to that of products on the market.

3. Post heat aging elongation adhesion test at 70 DEG C

And testing the stretching adhesion of the MS sealant after heat aging at 70 ℃ and heat aging at 70 ℃ for 7 days, wherein the testing is in accordance with the stretching adhesion according to the testing principle of the standard GB/T13477.10-2017 for testing the stretching adhesion of the building sealing material test method part 10.

Test and record data the A method (standard test condition set 28 d) was used to perform the test on the cement substrate, and the specific test data and results are as follows:

TABLE 3 Table 3

The data in Table 3 shows that the post-immersion elongation adhesion of the MS sealant prepared according to the application is close to that of the commercial product.

4. Elastic recovery test

The elastic recovery rate of a commercially available sample and a novel MS sealant is tested and compared, the test is referred to the standard of the building sealing material test method 17 part 17, namely, the measurement of the stretching adhesion GB/T13477.17-2017, and the test principle is that a test piece is stretched to a specified width, kept in a stretched state for a specified time and then released. The elastic recovery (expressed as a percentage of elongation) was calculated as the change in width of the test piece before and after stretching.

TABLE 4 Table 4

The data in Table 4 illustrates that the elastic recovery rate of the MS sealant prepared by the application is close to that of the product on the market.

5. Stretch-bond test

The MS sealant is tested for tensile adhesion, and the test is based on the test principle that a sealing material to be tested is adhered between the surfaces of two parallel base materials to prepare a test piece according to the standard of the test GB/T13477.8-2017 of the tensile adhesion of the building sealing material test method part 8. The test piece was stretched to failure, and a force value-elongation value curve was drawn to express the tensile adhesion property of the sealing material in terms of the calculated secant tensile modulus, maximum tensile strength, and elongation at break.

Test and record data the A method (standard test condition set 28 d) was used to test on cement and aluminum alloy substrates, the specific test data and results were as follows:

TABLE 5

The data in Table 5 shows that the MS sealant prepared by the application has better tensile bonding performance than the product on the market, and has higher maximum tensile force and tensile strength.

The foregoing examples are illustrative only and are provided to illustrate some of the features of the methods of the present application. The claims that follow are intended to claim the broadest possible scope as conceivable and the embodiments presented herein are demonstrated for the applicant's true test results. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the application. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.

Claims

1. The MS sealant for the fabricated concrete is characterized by comprising the following components in parts by weight:

the STP silane modified polyether resin is selected from Jiangsu Ruiyan Antai New Material technology Co., ltd, and the product trade name is 30000T;

the molecular weight of the dispersing agent is more than 6000 and is selected from Guangzhou core new material science and technology Co., ltd, and the product is DISPUPER S35;

the thixotropic agent is selected from Guangzhou core new material science and technology limited company, and the product is PAMID D680;

the preparation method of the MS sealant comprises the following steps:

2. The MS sealant for the fabricated concrete according to claim 1, which is characterized by comprising the following components in parts by weight:

3. an MS sealer for use in fabricated concrete according to claim 1, wherein the calcium powder filler comprises heavy calcium carbonate and light calcium carbonate.

4. An MS sealer for use in fabricated concrete according to claim 1, wherein the plasticizer is at least one of diisononyl phthalate and dioctyl phthalate.

5. The MS sealer for fabricated concrete according to claim 1, wherein the coupling agent is an aminosilane coupling agent, and the water scavenger is a vinyl silane water scavenger.