CN115232505B - Self-repairing anti-cracking putty and preparation method thereof - Google Patents
Self-repairing anti-cracking putty and preparation method thereof Download PDFInfo
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Abstract
The invention provides self-repairing anti-cracking putty and a preparation method thereof, wherein the self-repairing anti-cracking putty comprises a component A and a component B, and the preparation raw materials of the component A comprise the following components in percentage by weight: 15-35% of white cement, 60-85% of heavy calcium carbonate, 0.3-0.5% of nano cellulose and 1-5% of microcapsule; the preparation raw materials of the component B comprise the following components in percentage by weight: 40-60% of modified polyurethane emulsion, 5-10% of auxiliary agent and 30-55% of water. When the self-repairing anti-cracking putty is acted by external force, the liquid in the microcapsule can be released, wherein olefin and conjugated double bonds in the modified polyurethane emulsion undergo cycloaddition reaction under the action of a heated environment and a catalyst, so that the self-repairing anti-cracking putty has self-repairing and anti-cracking performances.
Description
Technical Field
The invention belongs to the technical field of putty, and relates to self-repairing anti-cracking putty and a preparation method thereof.
Background
There are a number of reasons for cracking the putty. For newly constructed systems, there is still a drying and curing process after the putty is applied to the wall, which may be locally restrained, and the restraining effect causes pores or gaps to be generated at the restrained position; another cause of cracking is plastic shrinkage, which occurs when the moisture on the surface of the putty quickly volatilizes in the presence of low ambient humidity, high temperature and wind. For systems that are under construction for a period of time, dry shrinkage is a common cause of cracking, and moreover, temperature, weathering, etc. can cause cracking in the system. How to reduce or prevent cracking of the putty is a technical problem to be solved by the person skilled in the art.
At present, various anti-cracking putty is available at home and abroad, for example, CN110408257A discloses that the high cellulose is processed by adding a resin matrix composite material of a fiber reinforcement, so that the anti-cracking performance and durability of the putty are improved; CN110305515a discloses that the inclusion of the putty is improved by adding sodium alginate/HCl mixed solution, thereby improving the cracking resistance of the putty.
However, in the prior art, anti-cracking materials are added in the early stage, so that the toughness of the putty is enhanced, and although a plurality of problems are solved, once the putty cracks in the curing process due to poor construction, no redundant means are needed to make up.
Accordingly, in the art, it is desirable to develop an anti-crack putty with a self-repairing function, which can be polished by a polisher if cracks are found during curing, and then repaired.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide self-repairing anti-cracking putty and a preparation method thereof.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides self-repairing anti-cracking putty, which comprises an A component and a B component, wherein the A component comprises the following preparation raw materials in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
40-60% of modified polyurethane emulsion
5-10% of auxiliary agent
30-55% of water.
In the invention, the microcapsules in the self-repairing anti-cracking putty contain diene substances, the modified polyurethane emulsion is polyurethane dispersion with olefin end sealing groups, the nanocellulose can play a part of thickening role, and the modified polyurethane emulsion has a catalytic addition effect on Diels-Alder reaction in a heated environment (polishing). When the self-repairing anti-cracking putty is acted by external force, the liquid in the microcapsule can be released, wherein olefin and conjugated double bonds in the modified polyurethane emulsion undergo cycloaddition reaction under the action of a catalyst (nanocellulose can play a role in catalysis) in a heated environment, so that the self-repairing anti-cracking putty has self-repairing and anti-cracking performances. Namely, in the invention, the microcapsule, the modified polyurethane emulsion and the nanocellulose are synergistic, so that the putty has self-repairing and crack-resisting properties.
In addition, compared with the prior art, the self-repairing anti-cracking putty has good application value, is simple to operate and has visual results.
In the invention, the raw materials for preparing the component A comprise 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33% or 35% of white cement by weight percent.
In the invention, the raw materials for preparing the component A comprise 60%, 63%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83% or 85% of heavy calcium carbonate by weight.
In the invention, the raw materials for preparing the component A comprise 0.3 percent, 0.4 percent or 0.5 percent of nanocellulose in percentage by weight.
In the invention, the preparation raw materials of the component A comprise 1%, 2%, 3%, 4% or 5% of microcapsules by weight.
In the invention, the preparation raw materials of the component B comprise 40%, 43%, 45%, 48%, 50%, 53%, 55%, 58% or 60% of modified polyurethane emulsion by weight percent.
In the invention, the preparation raw materials of the component B comprise 5%, 6%, 7%, 8%, 9% or 10% of auxiliary agents by weight percent.
In the invention, the raw materials for preparing the component B comprise, by weight, 30%, 33%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 53% or 55% of water.
Preferably, the mass ratio of the A component to the B component is 1 (2-3), such as 1:2, 1:2.5 or 1:3.
If the mass ratio of the component A to the component B is less than 1:3, namely the content of the component B is too much, the effective content of the nanocellulose in the component A is too little, and the cycloaddition reaction cannot be fully performed, so that the repair and anti-cracking effects of the putty are affected, and if the mass ratio of the component A to the component B is more than 1:2, namely the content of the component A is too much, the effective content of the nanocellulose in the component A is too much, the cycloaddition reaction can be fully performed, but the cellulose content in the system is too much and the emulsion content of the putty is too little, so that the initial strength and flexibility of the putty system can be reduced.
Preferably, the nanocellulose is an anionic modified nanocellulose, including NFC-5L1.
Preferably, the microcapsules are prepared by the following preparation method:
will beEP MA 120 is diluted with water, beta-cyclodextrin is added, dispersed and dried to obtain the microcapsule.
Preferably, the aqueous diluent is diluted to a water diluentEP MA 120 is diluted to an aqueous solution with a mass percentage of 8-12% (e.g. 8%, 9%, 10%, 11% or 12%, etc.).
Preferably, the saidThe mass ratio of EP MA 120 to beta-cyclodextrin is 1 (3-4), e.g. 1:3, 1:3.2, 1:3.3, 1:3.5, 1:3.8 or 1:4, etc.
Preferably, the dispersing comprises ultrasonic dispersing.
Preferably, the ultrasonic dispersion is performed in an ultrasonic shaker.
Preferably, the temperature of the ultrasonic dispersion is 40-60 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or the like, the time of the ultrasonic dispersion is 20-40min, such as 20min, 25min, 30min, 35min or 40min or the like, and the frequency of the ultrasonic dispersion is 30-50Hz, such as 30Hz, 35Hz, 40Hz, 45Hz or 50Hz or the like.
Preferably, the modified polyurethane emulsion is prepared by the following preparation method:
adding isocyanate into maleic anhydride Modified Castor Oil (MCO), adding a catalyst, reacting, sequentially adding polyol and a chain extender solution, heating, continuously reacting, cooling, adding a first neutralizing agent, stirring, adding a second neutralizing agent, and continuously stirring to obtain the modified polyurethane emulsion.
Preferably, the maleic anhydride modified castor oil is dehydrated before use, and specifically comprises the following steps: the maleic anhydride-modified castor oil is heated to 110-130 ℃, e.g., 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, etc., and vacuum dehydrated for 1-3 hours, e.g., 1 hour, 2 hours, 3 hours, etc.
Preferably, the isocyanate is added to the maleic anhydride modified castor oil such that n (-NCO): n (-OH) = (1.1-1.3): 1, e.g., 1.1:1, 1.15:1, 1.2:1, or 1.3:1, etc. N (-NCO): n (-OH) = (1.1-1.3): 1 means that the molar ratio of-NCO to-OH is (1.1-1.3): 1.
Preferably, the isocyanate comprises isophorone diisocyanate (IPDI).
Preferably, the catalyst comprises dibutyltin Dilaurate (DBT).
The amount of the catalyst to be added in the present invention is not particularly limited, and preferably not more than 1% by mass of the system.
Preferably, the polyol comprises tetrahydrofuran-propylene oxide copolyglycol (Ng 210).
Preferably, the mass ratio of maleic anhydride modified castor oil to polyol is (0.9-1.1): 1, e.g. 0.9:1, 1:1 or 1.1:1, etc.
Preferably, the chain extender in the chain extender solution comprises dimethylolpropionic acid (DMPA) and/or 1, 4-Butanediol (BD), and the solvent comprises N-methyl-2-pyrrolidone (NMP).
Preferably, the chain extender solution is 1-2% by mass of the system, for example 1%, 1.5% or 2% by mass, etc.
Preferably, the mass ratio of the N-methyl-2-pyrrolidone, the dimethylolpropionic acid and the 1, 4-butanediol in the chain extender solution is 1:2:2.
Preferably, the first neutralizing agent comprises Triethylamine (TEA).
The amount of the neutralizing agent I added is not particularly limited, and preferably not more than 1% by mass of the system.
Preferably, the neutralizing agent comprises Ethylenediamine (EDA).
The addition amount of the second neutralizing agent is not particularly limited, and preferably not more than 1% by mass of the system.
Preferably, the temperature of the reaction is 50-70 ℃, e.g., 50 ℃, 55 ℃, 60 ℃, 65 ℃, or 70 ℃, and the like, and the reaction time is 0.5-1h, e.g., 0.5h, 0.6h, 0.8h, or 1h, and the like.
Preferably, the reaction is carried out under inert gas.
Preferably, the inert gas comprises nitrogen.
Preferably, the temperature is raised to 60-70 ℃, e.g., 60 ℃, 63 ℃, 65 ℃, 68 ℃, or 70 ℃, etc.
Preferably, the time to continue the reaction is from 0.5 to 1h, such as 0.5h, 0.6h, 0.8h, 1h, or the like.
Preferably, the temperature is reduced to 40-50deg.C, such as 40deg.C, 43deg.C, 45deg.C, 48deg.C or 50deg.C, etc.
Preferably, the stirring time is 20-40min, such as 20min, 25min, 30min, 35min or 40min, etc.
Preferably, the stirring is continued for a period of time ranging from 1 to 2 hours, such as 1 hour, 1.5 hours, 2 hours, etc.
Preferably, the content of the effective matter in the modified polyurethane emulsion is 18-22%, for example 18%, 19%, 20%, 21% or 22%, etc. The content of the effective substance in the modified polyurethane emulsion refers to the content of-NH-COO-generated by the reaction of-NCO and-OH.
As a preferred technical scheme of the invention, the modified polyurethane emulsion is prepared by the following preparation method:
under the protection of inert gas, adding isophorone diisocyanate into dehydrated maleic anhydride Modified Castor Oil (MCO), adding dibutyltin dilaurate, reacting for 0.5-1h at 50-70 ℃, adding tetrahydrofuran-propylene oxide copolymer glycol with the same mass as the maleic anhydride modified castor oil, dropwise adding dimethylolpropionic acid and 1, 4-butanediol dissolved by N-methyl-2-pyrrolidone, heating to 60-70 ℃, continuously reacting for 0.5-1h, cooling to 40-50 ℃, adding triethylamine for neutralization, rapidly stirring for 20-40min, adding ethylenediamine, and continuously stirring for 1-2h to obtain the modified polyurethane emulsion.
Preferably, the auxiliary comprises any one or a combination of at least two of a film forming auxiliary, a dispersing agent or a wetting agent.
In a second aspect, the present invention provides a method for preparing the self-repairing anti-cracking putty according to the first aspect, the method comprising the following steps:
(1) Mixing white cement, heavy calcium carbonate, nanocellulose and microcapsules according to the formula amount to obtain a component A;
(2) Mixing the modified polyurethane emulsion, the auxiliary agent and water according to the formula amount to obtain a component B;
(3) And mixing the component A and the component B to obtain the self-repairing anti-cracking putty.
Compared with the prior art, the invention has at least the following beneficial effects:
in the invention, the microcapsules in the self-repairing anti-cracking putty contain diene substances, the modified polyurethane emulsion is polyurethane dispersion with olefin end sealing groups, the nanocellulose can play a part of thickening role, and the modified polyurethane emulsion has a catalytic addition effect on Diels-Alder reaction in a heated environment (polishing). When the self-repairing anti-cracking putty is acted by external force, the liquid in the microcapsule can be released, wherein olefin and conjugated double bonds in the modified polyurethane emulsion undergo cycloaddition reaction under the action of a heated environment (polishing) and a catalyst (nano cellulose can play a role in catalysis), so that the self-repairing anti-cracking putty has self-repairing and anti-cracking performances.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw material information used in the preparation example of the invention is as follows:
maleic anhydride Modified Castor Oil (MCO): hydroxyl value 112 mgKOH.g -1 Acid value of 42 mgKOH.g -1 ；
Tetrahydrofuran-propylene oxide copolyglycol (Ng 210): mn=1000±100Hydroxyl value=102-104 mg koh·g -1 Dehydrating under vacuum for 48h before use, and cutting off the waste water;
isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA): zhejiang Dongbao chemical Co., ltd;
triethylamine (TEA): shanghai Sanyi reagent Co., ltd;
n-methyl-2-pyrrolidone (NMP), 1, 4-Butanediol (BD), ethylenediamine (EDA): national pharmaceutical group chemical agents, inc;
dibutyl tin Dilaurate (DBT): shanghai reagent is a factory.
Preparation example 1
In the preparation example, a modified polyurethane emulsion is provided, and the preparation method comprises the following steps:
adding MCO into a dry three-port bottle, heating to 120 ℃, vacuum dehydrating for 2 hours, introducing nitrogen, cooling to 60 ℃, dropwise adding metered IPDI according to n (-NCO): n (-OH) =1.15, adding DBT (the adding amount is 0.8 per mill of the mass of the system), reacting for 0.5 hours, adding Ng210 with the same mass as MCO into the system, dropwise adding DMPA and BD (the total mass of NMP, DMPA and BD is 1.5 per mill of the system, the mass ratio of NMP, DMPA and BD is 1:2:2), heating to 65 ℃, continuing to react for 0.5 hours, cooling to 50 ℃, adding TEA (the adding amount is 0.8 per mill of the mass of the system), neutralizing, rapidly stirring for 30 minutes, then dropwise adding EDA (the adding amount is 0.8 per mill of the mass of the system) into the reaction material under high-speed stirring, and continuously stirring for 1 hour to obtain the modified polyurethane emulsion with the effective matter content of 20%.
Preparation example 2
In the preparation example, a modified polyurethane emulsion is provided, and the preparation method comprises the following steps:
adding MCO into a dry three-port bottle, heating to 120 ℃, vacuum dehydrating for 2 hours, heating to 60 ℃, cooling to 60 ℃, dropwise adding metered IPDI according to n (-NCO): n (-OH) =1.1, adding DBT (the adding amount is 0.8 per mill of the mass of the system), reacting for 1 hour, adding Ng210 with the same mass as MCO into the system, dropwise adding DMPA and BD (the total mass of NMP, DMPA and BD is 1.5 per mill of the system, the mass ratio of NMP, DMPA and BD is 1:2:2), heating to 60 ℃, continuing to react for 0.5 hour, then cooling to 40 ℃, adding TEA (the adding amount is 0.8 per mill of the mass of the system) for neutralization, then dropwise adding EDA (the adding amount is 0.8 per mill of the mass of the system) into the reaction material under high-speed stirring, and continuing stirring for 1 hour to obtain the modified polyurethane emulsion with the effective matter content of 18%.
Preparation example 3
In the preparation example, a modified polyurethane emulsion is provided, and the preparation method comprises the following steps:
adding MCO into a dry three-port bottle, heating to 120 ℃, vacuum dehydrating for 2 hours, heating to 70 ℃, cooling to 60 ℃, dropwise adding metered IPDI according to n (-NCO): n (-OH) =1.3, adding DBT (the adding amount is 0.8 per mill of the mass of the system), reacting for 1 hour, adding Ng210 with the same mass as MCO into the system, dropwise adding DMPA and BD (the total mass of NMP, DMPA and BD is 1.5 per mill of the system, the mass ratio of NMP, DMPA and BD is 1:2:2), heating to 70 ℃, continuing to react for 0.5 hour, then cooling to 50 ℃, adding TEA (the adding amount is 0.8 per mill of the mass of the system) for neutralization, then dropwise adding EDA (the adding amount is 0.8 per mill of the mass of the system) into the reaction material under high-speed stirring, and continuing to stir for 2 hours to obtain the modified polyurethane emulsion with the effective content of 22%.
The raw material information used in the embodiment of the invention is as follows:
white cement: P.W 32.5.5 Jiangxi silver fir white cement Co., ltd;
heavy calcium carbonate: :200 mesh, changxing Huayuan powder materials limited company;
nanocellulose: anionic modified nanocellulose NFC-5L1 (san spa group);
film forming auxiliary agent: texanol, eastmann chemical;
dispersing agent: 1134, a dow chemical;
wetting agent: ANTI-tera-204, pick chemistry.
Example 1
The self-repairing anti-cracking putty provided in the embodiment comprises a component A and a component B, wherein the raw materials for preparing the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
50% of the modified polyurethane emulsion obtained in preparation example 1
Auxiliary agent 8%
Water 42%.
Wherein the mass ratio of the component A to the component B is 1:2.5, the auxiliary agent is a film forming auxiliary agent, a dispersing agent and a wetting agent with the mass ratio of 2:1:1, and the microcapsule is prepared by the following preparation method: will beDiluting EPMA 120 (Yingchuang) with water to obtain 10% solution, and adding beta-cyclodextrin>The mass ratio of the EP MA 120 to the beta-cyclodextrin is 1:3.5), dispersing for 30min in an ultrasonic oscillator, controlling the temperature to be 50 ℃, controlling the frequency to be 40Hz, and drying to obtain the microcapsule.
The preparation method of the self-repairing anti-cracking putty comprises the following steps:
(1) Mixing white cement, heavy calcium carbonate, nanocellulose and microcapsules according to the formula amount to obtain a component A;
(2) Mixing the modified polyurethane emulsion, the auxiliary agent and water according to the formula amount to obtain a component B;
(3) And mixing the component A and the component B according to the formula amount to obtain the self-repairing anti-cracking putty.
Example 2
The self-repairing anti-cracking putty provided in the embodiment comprises a component A and a component B, wherein the raw materials for preparing the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
60% of modified polyurethane emulsion obtained in preparation example 1
Auxiliary agent 8%
Water 32%.
Wherein the mass ratio of the component A to the component B is 1:2, and the auxiliary agent is a film forming auxiliary agent, a dispersing agent and a wetting agent with the mass ratio of 2:1:1, and the preparation method of the microcapsule is the same as that of the example 1.
The preparation method of the self-repairing anti-cracking putty is the same as in example 1.
Example 3
The self-repairing anti-cracking putty provided in the embodiment comprises a component A and a component B, wherein the raw materials for preparing the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
40% of modified polyurethane emulsion obtained in preparation example 1
Auxiliary agent 8%
52% of water.
Wherein the mass ratio of the component A to the component B is 1:3, and the auxiliary agent is a film forming auxiliary agent, a dispersing agent and a wetting agent with the mass ratio of 2:1:1, and the preparation method of the microcapsule is the same as that of the example 1.
The preparation method of the self-repairing anti-cracking putty is the same as in example 1.
Example 4
The self-repairing anti-cracking putty provided in the embodiment comprises a component A and a component B, wherein the raw materials for preparing the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
45% of modified polyurethane emulsion obtained in preparation example 1
Auxiliary agent 10%
45% of water.
Wherein the mass ratio of the component A to the component B is 1:2.5, and the auxiliary agent is a film forming auxiliary agent, a dispersing agent and a wetting agent with the mass ratio of 2:1:1, and the preparation method of the microcapsule is the same as that of the example 1.
The preparation method of the self-repairing anti-cracking putty is the same as in example 1.
Example 5
The self-repairing anti-cracking putty provided in the embodiment comprises a component A and a component B, wherein the raw materials for preparing the component A comprise the following components in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
55% of modified polyurethane emulsion obtained in preparation example 1
Auxiliary agent 5%
40% of water.
Wherein the mass ratio of the component A to the component B is 1:2.5, and the auxiliary agent is a film forming auxiliary agent, a dispersing agent and a wetting agent with the mass ratio of 2:1:1, and the preparation method of the microcapsule is the same as that of the example 1.
The preparation method of the self-repairing anti-cracking putty is the same as in example 1.
Example 6
This example differs from example 1 only in that the modified polyurethane emulsion obtained in preparation example 1 was replaced with the modified polyurethane emulsion obtained in preparation example 2 in an equivalent amount.
Example 7
This example differs from example 1 only in that the modified polyurethane emulsion obtained in preparation example 1 was replaced with the modified polyurethane emulsion obtained in preparation example 3 in an equivalent amount.
Comparative example 1
This comparative example differs from example 1 only in that the modified polyurethane emulsion obtained in preparation example 1 was replaced with an equivalent amount of a conventional emulsion (Z30R, polymer mortar emulsion, tianjin lucky science and technology Co., ltd.).
Comparative example 2
This comparative example differs from example 1 only in that the microcapsules are not included in the a-component, the weight percentage of ground calcium carbonate being 74.6%.
Comparative example 3
This comparative example differs from example 1 only in that nanocellulose was replaced with an equivalent amount of plain cellulose (brand number HPK40M, shandongherda).
Comparative example 4
This comparative example differs from example 1 only in that the mass ratio of the A component and the B component is 1:1.
Comparative example 5
This comparative example differs from example 1 only in that the mass ratio of the A component and the B component is 1:4.
Comparative example 6
This comparative example differs from example 1 only in that the weight percent of the modified polyurethane emulsion in the B component is 35% and the weight percent of water is 57%.
Comparative example 7
This comparative example differs from example 1 only in that the weight percent of the modified polyurethane emulsion in the B component is 65% and the weight percent of water is 27%.
Comparative example 8
The comparative example differs from example 1 only in that the weight percentage of nanocellulose in the a-component is 0.2% and the weight percentage of ground calcium carbonate is 72.8%.
Comparative example 9
The comparative example differs from example 1 only in that the weight percentage of nanocellulose in the a-component is 0.6% and the weight percentage of ground calcium carbonate is 72.4%.
Comparative example 10
This comparative example differs from example 1 only in that the weight percentage of microcapsules in the a-component is 6% and the weight percentage of ground calcium carbonate is 68.6%.
The putty prepared in the examples and comparative examples was subjected to performance testing as follows:
(1) Bond strength (standard state): testing according to JG/T157-2009 putty for building exterior wall;
(2) Bond strength (heat aging): sample preparation is carried out according to JG/T157-2009 putty for building exterior wall 6.13.1, the sample is cured for 7d under the standard environment with the temperature of 23+/-2 ℃ and the relative humidity of 50+/-5 ℃, then is placed for 7d in an air circulation oven with the temperature of 70+/-2 ℃, and finally is cured for 1d under the standard environment with the temperature of 23+/-2 ℃ and the relative humidity of 50+/-5%, and then the test is carried out;
(3) Putty film flexibility (standard state) and putty film flexibility (5 times of cold and hot cycles): the testing is carried out according to the standard of GB/T23455-2009 Flexible putty for external wall.
The results of the performance test are shown in Table 1.
TABLE 1
Note that: the bonding strength (standard state) is more than or equal to 0.6MPa, the bonding strength (heat aging) is more than or equal to 0.6MPa, the flexibility (standard state) of the putty film meets the requirement of no crack with the diameter of 50mm, and the flexibility (5 times of cold and hot circulation) of the putty film meets the requirement of no crack with the diameter of 100mm, so that the putty film is qualified.
As can be seen from Table 1, the self-repairing anti-cracking putty prepared in examples 1 to 7 of the present invention has a high bonding strength (standard state): 0.9 to 1.2MPa and bonding strength (heat aging): 0.7 to 1.0 MPa) both in the standard state and after heat and cold cycles for 5 times, and has excellent flexibility (putty film flexibility (standard state): diameter 50mm without cracks, putty film flexibility (heat and cold cycles for 5 times): diameter 80mm without cracks or diameter 90mm without cracks), which indicates that the putty provided by the present invention has both self-repairing and anti-cracking properties.
The putty provided in comparative examples 1 to 10 showed a significant decrease in bonding strength both in the standard state and after heat aging treatment, and a significant decrease in flexibility both in the standard state and after 5 times of cooling and heating cycles, as compared with example 1.
The applicant states that the self-repairing anti-crack putty and the preparation method thereof are described by the above examples, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (23)
1. The self-repairing anti-cracking putty is characterized by comprising a component A and a component B, wherein the component A comprises the following preparation raw materials in percentage by weight:
the preparation raw materials of the component B comprise the following components in percentage by weight:
40-60% of modified polyurethane emulsion
5-10% of auxiliary agent
30-55% of water;
the microcapsule is prepared by the following preparation method:
will beDiluting EP MA 120 with water, adding beta-cyclodextrin, dispersing, and drying to obtain the microcapsule;
the modified polyurethane emulsion is a polyurethane dispersion with an olefin end-capping group;
the mass ratio of the component A to the component B is 1 (2-3).
2. The self-repairing anti-crack putty according to claim 1, wherein the nanocellulose is an anionically modified nanocellulose, comprising NFC-5L1.
3. The self-repairing anti-crack putty according to claim 1, wherein said water is diluted to a predetermined extentEP MA 120 is diluted into an aqueous solution with the mass percentage of 8-12%.
4. The self-repairing anti-crack putty according to claim 1, wherein said putty comprisesThe mass ratio of the EP MA 120 to the beta-cyclodextrin is 1 (3-4).
5. The self-repairing anti-crack putty according to claim 1 wherein said dispersion comprises ultrasonic dispersion.
6. The self-repairing anti-cracking putty according to claim 1, wherein the modified polyurethane emulsion is prepared by the following preparation method:
adding isocyanate into maleic anhydride modified castor oil, adding a catalyst, reacting, sequentially adding a polyol and a chain extender solution, heating, continuing the reaction, cooling, adding a first neutralizing agent, stirring, adding a second neutralizing agent, and continuing stirring to obtain the modified polyurethane emulsion.
7. A self-repairing crack-resistant putty according to claim 6 characterised in that said isocyanate is added to the maleic anhydride modified castor oil such that n (-NCO): n (-OH) = (1.1-1.3): 1.
8. A self-repairing crack-resistant putty according to claim 6 characterised in that said isocyanate comprises isophorone diisocyanate.
9. A self-repairing crack-resistant putty according to claim 6 wherein said catalyst comprises dibutyl tin dilaurate.
10. A self-repairing anti-crack putty according to claim 6 wherein said polyol comprises tetrahydrofuran-propylene oxide copolyol.
11. A self-repairing crack-resistant putty according to claim 6 characterized in that the mass ratio of maleic anhydride modified castor oil to polyol is (0.9-1.1): 1.
12. A self-repairing anti-crack putty according to claim 6 characterized in that the chain extender in the chain extender solution comprises dimethylolpropionic acid or the chain extender in the chain extender solution comprises dimethylolpropionic acid and 1, 4-butanediol and the solvent comprises N-methyl-2-pyrrolidone.
13. The self-repairing anti-crack putty according to claim 6, wherein said neutralizing agent one comprises triethylamine.
14. The self-repairing anti-crack putty according to claim 6, wherein said neutralizing agent comprises ethylenediamine.
15. The self-repairing crack-resistant putty according to claim 6, wherein the reaction temperature is 50-70 ℃ and the reaction time is 0.5-1h.
16. The self-repairing anti-crack putty according to claim 6, wherein the reaction is performed under inert gas protection.
17. A self-repairing crack-resistant putty according to claim 6 characterised in that the temperature rise is to 60-70 ℃.
18. A self-repairing crack-resistant putty according to claim 6 characterised in that the time to continue the reaction is 0.5-1h.
19. A self-repairing crack-resistant putty according to claim 6 characterised in that the temperature reduction is to 40-50 ℃.
20. A self-repairing crack-resistant putty according to claim 1 characterised in that the content of actives in the modified polyurethane emulsion is 18-22%.
21. The self-repairing anti-cracking putty according to claim 1, wherein the modified polyurethane emulsion is prepared by the following preparation method:
under the protection of inert gas, adding isophorone diisocyanate into dehydrated maleic anhydride modified castor oil, adding dibutyl tin dilaurate, reacting for 0.5-1h at 50-70 ℃, adding tetrahydrofuran-propylene oxide copolyglycol with the same mass as the maleic anhydride modified castor oil, dropwise adding dimethylolpropionic acid and 1, 4-butanediol dissolved by N-methyl-2-pyrrolidone, heating to 60-70 ℃, continuously reacting for 0.5-1h, cooling to 40-50 ℃, adding triethylamine for neutralization, stirring for 20-40min, then adding ethylenediamine, and continuously stirring for 1-2h to obtain the modified polyurethane emulsion.
22. A self-repairing anti-crack putty according to claim 1 characterised in that said auxiliary agent comprises any one or a combination of at least two of a film forming auxiliary agent, a dispersing agent or a wetting agent.
23. The method of preparing a self-repairing anti-crack putty according to any one of claims 1 to 22, characterized in that the method of preparing comprises the steps of:
(1) Mixing white cement, heavy calcium carbonate, nanocellulose and microcapsules according to the formula amount to obtain a component A;
(2) Mixing the modified polyurethane emulsion, the auxiliary agent and water according to the formula amount to obtain a component B;
(3) And mixing the component A and the component B to obtain the self-repairing anti-cracking putty.
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