CN112898538A - Thick-coatable modified ketimine curing agent and preparation method and application thereof - Google Patents
Thick-coatable modified ketimine curing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN112898538A CN112898538A CN201911227776.6A CN201911227776A CN112898538A CN 112898538 A CN112898538 A CN 112898538A CN 201911227776 A CN201911227776 A CN 201911227776A CN 112898538 A CN112898538 A CN 112898538A
- Authority
- CN
- China
- Prior art keywords
- component
- curing agent
- ketimine
- modified
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a modified ketimine curing agent capable of being coated thickly, a preparation method and application thereof, which is prepared by the reaction of a component a) modified amine containing a polyester chain segment and a component b) polyalcohol aminal ketone.
Description
Technical Field
The invention belongs to the field of curing agents, and particularly relates to a modified ketimine curing agent capable of being coated thickly, a preparation method and application thereof, which can be used for curing epoxy resin under underwater conditions.
Technical Field
Epoxy resin is widely applied to various fields, especially the field of adhesives, because of excellent cohesiveness, low shrinkage, dielectricity and chemical stability, wherein the application in the field of building adhesives accounts for a large proportion. The epoxy resin curing agent specifically comprises a steel adhesive, an anchoring adhesive, a carbon fiber reinforced adhesive, a grouting reinforced adhesive, an underwater reinforced building epoxy adhesive and other traditional amine curing agents which are melted in water and cannot completely cure the epoxy resin, so that the amine curing agents need to be modified to meet the use requirements. The adhesive has better mechanical strength under moist water, higher bonding strength to a bonded structure, and smaller performance difference compared with bonding under a dry condition. The curing agents commonly used for the underwater building epoxy adhesive include ketimine, modified amine and the like. The ketimine is used as a single-component latent curing agent and is prepared by condensation reaction of ketone and polyamine, the ketimine generates reverse reaction after absorbing moisture to generate polyamine, and then the polyamine and an epoxy compound react to cure, so that the epoxy resin can be cured in moisture or underwater. However, the ketimine underwater curing agent generally has a thin coating to ensure the performance thereof, because the ketimine can only contact with water to generate reverse reaction, and when the ketimine underwater curing agent is used, if the coating is too thick, the inside of the curing agent can not contact with water, so that the inside can not generate reverse reaction to generate polyamine, the epoxy curing is incomplete, and the performance of the ketimine underwater curing agent is affected.
Patent CN105308145 provides a ketimine curing agent of polyoxyalkylene containing hydrolyzable silyl group, which can ensure the adhesion performance with the adhesive surface even under low temperature or alkaline condition by the water absorption crosslinking effect of the silyl group, i.e. enhance the adhesion ability with the adhesive surface. However, the curing agent is mainly used for the reaction of the surface layer in contact with water, and the problem that the polyamine curing epoxy resin cannot be decomposed in the coating layer which is too thick is not solved. Some patents, such as CN103193959, etc., improve the degradability of the cured epoxy resin by introducing hydrolyzable groups into the main chain of the polyamine. However, in such patents, the hydrolyzable group is mostly in the main chain structure of the curing agent, and if the group is hydrolyzed and the two amino groups are separated, the whole cured product cannot be completely crosslinked and cured, and the cured resin starts to be gradually degraded. The method can only be used for recycling and degrading the cured epoxy resin, and cannot ensure that a resin system is completely cured and has enough performance to be continuously used after partial hydrolysis.
The invention content is as follows:
the invention aims to provide a modified ketimine curing agent capable of being coated thickly and a preparation method thereof.
The invention also aims to provide application of the thick-coating modified ketimine curing agent.
The technical scheme of the invention is as follows:
a modified ketimine curing agent has a structural formula as follows:
wherein R is1Is one of substituted or non-substituted ethyl, propyl and butyl, R2Is any one of alkylene, alicyclic group or arylene, preferably alicyclic group, wherein n is 1-5, R3Is one of H, methyl, ethyl and propyl, and is preferably H.
Further, the modified ketimine is prepared by adopting the reaction of the following components,
a) a modified amine containing a polyester segment, wherein the modified amine contains a polyester segment,
b) a polyalcohol amine ketone;
preferably, the modified amine containing the polyester chain segment of the component a) is prepared by the reaction of a polycyclic ester of the component a1) and a primary diamine of the component a2),
the component b) polyalcohol amine ketone is prepared by the reaction of polyalcohol amine containing a component b1) and halogenated dihydric alcohol containing a component b 2).
In some embodiments of the present invention, the molar ratio of the modified amine containing polyester segment of component a) to the polyalcohol amine ketone of component b) is 1 to 3: 1;
the molar ratio of the added polycyclic ester of the component a1) to the added diamine of the component a2) is 1-5: 1, preferably 1 to 1.5: 1;
the molar ratio of the component b1) polyalcohol amine to the component b2) halogenated diol is 2-3: 1.
in some embodiments of the present invention, the component b1) polyalcohol amine and the component b2) halogenated diol are reacted under acidic catalyst conditions.
Preferably, the acidic catalyst is one or a combination of more than two of hydrochloric acid, sulfuric acid, nitric acid and Lewis acid.
Further, the component a1) polycyclic ester contains at least one ester group cyclic structure, including but not limited to one or more of butyrolactone, lactide, valerolactone and caprolactone.
Further, the primary diamine of component a2) is preferably one or two or more of aliphatic primary diamine, alicyclic primary diamine, and aromatic primary diamine, such as ethylenediamine, propylenediamine, butylenediamine, m-xylylenediamine, m-phenylenediamine, 4' -diaminodicyclohexylmethane, isophoronediamine, and more preferably 4,4' -diaminodicyclohexylmethane and isophoronediamine, such as 4,4' -diaminodicyclohexylmethane and isophoronediamine of Waals chemical
Further, the halogenated diol is one or more than two of 1, 3-chlorodiol, 2, 4-chlorodiol, 1, 3-fluorodiol, 2, 4-fluorodiol, 1, 3-bromodiol and 2, 4-bromodiol, and 1, 3-chlorodiol is further preferable.
Further, the polyalcohol amine is one or more of diethanolamine, di-n-propanolamine and di-n-butanolamine, and further preferably diethanolamine.
Further, the preparation method of the modified amine containing the polyester chain segment of the component a) comprises the following steps:
adding a certain amount of a1) polycyclic ester, a component a2) primary diamine and an organic solvent into a dry reactor, heating under the protection of nitrogen atmosphere, reacting for 4-5 hours at 40-80 ℃, and adding hydrochloric acid to terminate the reaction to obtain a modified amine product containing a polyester chain segment.
Further, precipitating and drying the reaction solution generated after the reaction in a precipitating agent, wherein the precipitating agent is: one or more of petroleum ether, diethyl ether and ethyl acetate.
Hydrochloric acid is added into the system as a terminator, the addition amount of the hydrochloric acid is 0.1-0.5% of the total mass of reactants, and the concentration of the hydrochloric acid is between 40% and 50%.
The preparation method of the component b) polyalcohol amine ketone comprises the following steps: adding a certain amount of component b1) polyalcohol amine and component b2) halogenated dihydric alcohol into a dry reactor, reacting for 3-4 hours at 60-100 ℃, adding an acid catalyst, raising the temperature of the system to 120-140 ℃, and reacting for 3-4 hours to prepare the polyalcohol keton.
The adding amount of the acid catalyst accounts for 1-0.01%, preferably 0.5-0.1% of the total mass of the reactants.
Further, the organic solvent includes, but is not limited to, one or a combination of two or more of toluene, dimethyl sulfoxide, cyclohexane and tetrahydrofuran.
The invention also provides a preparation method of the modified ketimine curing agent, which comprises the following steps:
adding the modified amine containing the polyester chain segment of the component a) and the polyalcohol amine ketone of the component b) into a dry reactor, heating, reacting for 2-4 hours at the temperature of 100-130 ℃, and removing water by a condensing device while reacting to prepare the modified ketimine.
The reaction scheme is shown by taking the component a1) as lactide and the component b1) as diethanol amine as an example:
the modified ketimine can be mixed with epoxy resin to prepare a curing agent, and can also be independently used as an epoxy curing agent; the epoxy resin is bisphenol A type epoxy resin.
In some preferred embodiments of the present invention, the epoxy resin, curing agent and curing accelerator are mixed in the following ratio: curing agent 100: (25-125) stirring uniformly, sealing and packaging, and avoiding contact with water in the placing process. The mixing of the epoxy resin with the curing agent can also be selected by the person skilled in the art on the basis of practice.
Further, the curing accelerator is one of tertiary amine, imidazole and organophosphorus compounds.
After the modified ketimine is in contact with water, in addition to reverse reaction on the normal surface, the polyester structure in the modified ketimine is hydrolyzed to ensure that the crosslinking degree is reduced, and water in the environment can enter the system to further initiate the reverse reaction. When the internal reverse reaction is fully initiated, the original hydrolysis part is further reacted by a diamine curing agent, and the system can recover and completely cure and crosslink to meet the use requirement, so that the whole thick coating resin system can be completely cured.
The invention also provides application of the modified ketimine curing agent, and the modified ketimine curing agent can be used for underwater adhesives, coatings and other application fields needing curing under humid and water conditions.
The invention has the beneficial effects that:
1. the polyester chain segment is hydrolyzed to reduce the curing degree in a short time on the premise of not influencing the whole curing capability of the polyamine curing agent, so that water in the external environment can enter the system. Meanwhile, the inside ketimine is decomposed under the combined action of water generated in the hydrolysis process, the system continues to be crosslinked and cured after the ketimine is completely decomposed into polyamine, and the hydrolyzed part of the system forms a crosslinked network structure again along with the enhancement of the reaction degree of the polyamine and the epoxy curing, so that the service performance of the final cured product is not influenced, and the epoxy cured product capable of meeting the use requirement is finally formed. The ketimine curing agent solves the problem that the conventional ketimine curing agent cannot be used in a thick coating mode, and overcomes the defects that the traditional ketimine curing agent is limited in water contact surface, the interior ketimine cannot be decomposed, the epoxy resin cannot be cured completely, and only a thin layer can be used.
2. The ketone used for synthesizing the ketimine in the invention is alkaline novel-structure polyalcohol aminal ketone, which is released into a system along with the decomposition reaction of the ketimine, and an alkaline condition capable of promoting polyester hydrolysis is formed near a polyester chain segment, so that the latent directional catalysis of the polyester hydrolysis can be realized by promoting the polyester chain segment hydrolysis.
3. The modified ketimine curing agent can be independently cured with epoxy resin, and can also be used in combination with other curing agents, so that the effect of fully curing the epoxy resin under humid underwater conditions is mainly achieved.
Drawings
FIG. 1 is an IR spectrum of the polyethanolaminone prepared in example 1.
wherein-OH characteristic peak is3342cm-1The characteristic peak of N-H is 3364cm-1，3218cm-1C-O characteristic peak is 1081cm-1，1038cm-1Therefore, the infrared characteristic peak of each characteristic functional group of the polyethanolamine can be obviously identified, and the polyethanolamine with the required structure is obtained.
FIG. 2 is an IR spectrum of a modified ketimine prepared in example 1.
The modified ketimine is 1736cm-1The infrared characteristic peak of the polyester chain segment is increased, and the polyester chain segment is added in the structure, so that the required modified ketimine is obtained.
FIG. 3 is a diagram of the polyethanolaminone prepared in example 11H-NMR spectrum.
Wherein the characteristic peak of-OH is 43, and the characteristic peak of N-H is 43. From these results, it is clear that the characteristic functional groups of the polyethanolamine1The characteristic peak of H-NMR can be obviously identified, namely the polyalcohol amine with the required structure is obtained.
FIG. 4 shows a modified ketimine prepared in example 11H-NMR spectrum.
Compared with pure polyalcohol amine ketone, the ketimine modified by the ketone increases polyester chain segments at 1.6 and 5.31H-NMR characteristic peaks prove that the polyester chain segment is added in the structure, and the required modified ketimine is obtained.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The test method comprises the following steps: the method for testing the tensile shear strength of the sample comprises the following steps: GB T7124-.
The degree of polymerization of the polyester segment was determined by GPC analysis
Reagent manufacturers: butyrolactone: guangzhou City information source chemical Co., Ltd; diisopropanolamine: (ii) the chemistry of the dow; ketimine DA-134 epoxy curing agent: guangzhou Wei Li Na chemical Co., Ltd; 40-50% of hydrochloric acid solution and Shandong Kunbao chemical industry.
1, 3-dichloroethylene glycol: shanghai super research Biotech Co., Ltd
1, 3-dibromopropanediol, Chengdu pure science and technology Co., Ltd
1, 3-difluoroethylene glycol, Jiangsu Wide area chemistry
1, 3-dibromoethylene glycol, Alatin
Example 1
(1) Adding 258g (3mol) of butyrolactone, 170g (1mol) of isophorone diamine and 100ml of dimethyl sulfoxide into a dry reactor, heating and reacting for 4 hours at 60 ℃ under the protection of nitrogen atmosphere, dripping 0.5g of hydrochloric acid to terminate the reaction, pouring the product into petroleum ether for precipitation, putting the precipitate into a 50 ℃ oven for drying, and obtaining diamine A with a polyester chain segment, wherein the polymerization degree is 3 by analysis.
(2) 315g (3mol) of diethanolamine and 131g (1mol) of 1, 3-dichloroethylene glycol are added into a dry reactor, the mixture is heated and reacted for 3 hours at the temperature of 90 ℃, 4.4g of hydrochloric acid is dripped, the mixture is heated to 120 ℃, the reaction is continued for 3 hours, and the polyethanolamine ketone A is prepared, and the nuclear magnetic analysis result shows that the content of the polyethanolamine ketone A is 85 percent.
(3) Adding diamine A214g with polyester chain segments (with polymerization degree n of 3) and the polyethanolamine ketone A52.6g prepared in the step (2), namely the molar ratio of 3:1, into a dry reactor, heating to 100 ℃, reacting for 3 hours, and removing water through a condensation system while reacting to prepare the modified ketimine A.
(4) Drying the curing agent: the modified ketimine A and epoxy resin E51 are mixed according to the mass ratio of 100:100, then are uniformly mixed by a stirrer, and are cured under the humid underwater condition, so that a cured ketimine epoxy resin capable of being coated thickly is obtained. The mixture was coated on a standard size test specimen with a thickness of 4mm according to the national standard GB T7124-. The sample is put into a humid condition with the temperature of 15 ℃ for curing for 48 hours, and then is tested in a breaking time range required by national standards by a universal tensile machine, and the tensile shear strength of the sample can reach 10.4 Mpa.
Example 2
(1) 130g (1.3mol) of valerolactone, 210g (1mol) of 4,4' -diaminodicyclohexylmethane and 100ml of cyclohexane were charged into a dry reactor, and the mixture was heated and reacted at 60 ℃ for 4 hours under a nitrogen atmosphere. And 1.0g of hydrochloric acid was added dropwise to terminate the reaction. And pouring the product into ether for precipitation, and putting the precipitate into a 50 ℃ oven for drying to obtain diamine B with a polyester chain segment, wherein the polymerization degree n is 1.3 through testing.
(2) 332.5g (2.5mol) of diisopropanolamine and 234g (1mol) of 1, 3-dibromopropylene glycol are added into a dry reactor, heated to react for 3 hours at 90 ℃, then 0.56g of hydrochloric acid is dripped into the reactor, heated to 120 ℃, and continuously reacted for 3 hours to prepare the poly (propanolamine) ketone B. The nuclear magnetic analysis result shows that the content of the poly (propanolamine) ketone B is 90%.
(3) Diamine B165g having a polyester segment (degree of polymerization n of 1.3) and polypropanolone B93.9g, i.e.in a molar ratio of 2:1, were mixed and introduced into a dry reactor. Heating to 100 ℃, reacting for 3 hours, and removing water by a condensing system while reacting to prepare the modified ketimine B. The infrared test result shows that the ketimine B is 1736cm-1The infrared characteristic peak of the polyester chain segment exists, and the polyester chain segment exists in the structure. Meanwhile, the nuclear magnetic results show that a-OH characteristic peak and an N-H characteristic peak exist at the position 43, and the generated product is proved to be a ketimine structural substance containing a polyester chain segment.
(4) The curing agent is dried. Modified ketimine B and epoxy resin E51 were mixed in a ratio of 120g to 100g, and then mixed uniformly with a stirrer. And then curing under the humid underwater condition to obtain the cured product of the ketimine epoxy resin capable of being thickly coated. The mixture was coated on a standard size test specimen with a thickness of 4mm according to the national standard GB T7124-. The sample is put into a humid condition with the temperature of 15 ℃ for curing for 48 hours, and then is tested in a breaking time range required by national standards by a universal tensile machine, and the tensile shear strength of the sample can reach 9.8 Mpa.
Example 3
(1) 720g (5mol) of lactide, 210g (1mol) of 4,4' -diaminodicyclohexylmethane and 100ml of cyclohexane are added into a dry reactor, the mixture is heated and reacted for 2 hours at 80 ℃ under the protection of nitrogen atmosphere, then 4.6g of hydrochloric acid is dropped to stop the reaction, the product is poured into ethyl acetate for precipitation, the precipitate is put into a 50 ℃ oven for drying, diamine C with polyester chain segments is prepared, and the polymerization degree n is tested to be 5.
(2) 330g (2mol) of di-n-butanol amine and 98g (1mol) of 1, 3-difluoroethylene glycol are added into a dry reactor, heated to 110 ℃ for reaction for 3 hours, then 1.326g of hydrochloric acid is dripped, heated to 120 ℃, and continuously reacted for 3 hours to prepare the poly-butanol amine ketone C. The result of nuclear magnetic analysis shows that the content of the polybutaminoketone C is 88%.
(3) Diamine C186g with polyester chain segment (polymerization degree n is 5) and polybutaminone C86g are mixed according to the molar ratio of 1:1, and then are added into a dry reactor, heated to 120 ℃, reacted for 3 hours, and water is removed by a condensation system while reacting to prepare the modified ketimine C. According to the infrared test result, the ketimine C is 1738cm-1The infrared characteristic peak of the polyester chain segment exists, and the polyester chain segment exists in the structure. Meanwhile, the nuclear magnetic results show that a-OH characteristic peak and an N-H characteristic peak exist at the position 43, and the generated product is proved to be a ketimine structural substance containing a polyester chain segment.
(4) The curing agent is dried. The modified ketimine C and epoxy resin E51 were mixed in a ratio of 105g to 100g, and then mixed uniformly with a stirrer. And then curing under a humid condition to obtain the cured product of the ketimine epoxy resin capable of being coated thickly. The mixture was coated on a standard size test specimen with a thickness of 4mm according to the national standard GB T7124-. The sample is put into a humid condition with the temperature of 15 ℃ for curing for 48 hours, and then is tested in a breaking time range required by national standards by a universal tensile machine, and the tensile shear strength of the sample can reach 9.7 Mpa.
Example 4
(1) 200g (2.0mol) of valerolactone, 210g (1mol) of 4,4' -diaminodicyclohexylmethane and 100ml of tetrahydrofuran were charged into a dry reactor, and the reaction was terminated by heating at 70 ℃ for 4 hours under a nitrogen atmosphere and dropping 2.05g of hydrochloric acid. And pouring the product into petroleum ether for precipitation, putting the precipitate into a 50 ℃ oven for drying to prepare diamine D with a polyester chain segment, and analyzing and testing to obtain the diamine with the polymerization degree n of 2.
(2) 359.1g (2.7mol) of diisopropanolamine and 220g (1mol) of 1, 3-dibromoethylene glycol are added into a dry reactor, heated to react for 3 hours at 90 ℃, then 1.8g of hydrochloric acid is dripped into the reactor, heated to 120 ℃, and continuously reacted for 3 hours to prepare the poly (propanolamine) ketone D. The nuclear magnetic analysis result shows that the content of the poly (propanolamine) D is 83 percent.
(3) Adding diamine D102.5g with a polyester chain segment (the polymerization degree n is 2) and poly-propanolamine ketone D54g into a dry reactor according to the molar ratio of about 1.8:1, heating to 100 ℃, reacting for 3 hours, and removing water through a condensation system while reacting to prepare modified ketimine D. According to the infrared test result, the ketimine D is 1737cm-1The infrared characteristic peak of the polyester chain segment exists, and the polyester chain segment exists in the structure. Meanwhile, the nuclear magnetic results show that a-OH characteristic peak and an N-H characteristic peak exist at the position 43, and the generated product is proved to be a ketimine structural substance containing a polyester chain segment.
(4) Drying the curing agent, mixing the modified ketimine D and the epoxy resin E51 in a wet water ratio of 115g to 100g, and uniformly mixing by using a stirrer. And then curing under the condition to obtain a cured ketimine epoxy resin capable of being thickly coated, and coating the mixture on a standard-size test sample according to the national standard GB T7124-2008, wherein the thickness of the test sample is 4 mm. The sample is put into a humid condition with the temperature of 15 ℃ for curing for 48 hours, and then is tested in a breaking time range required by national standards by a universal tensile machine, and the tensile shear strength of the sample can reach 10.4 Mpa.
Example 5
(1) 144g (1.0mol) of lactide, 210g (1mol) of 4,4' -diaminodicyclohexylmethane and 120ml of toluene were charged into a dry reactor, and the reaction was stopped by heating at 70 ℃ for 4 hours under a nitrogen atmosphere and dropping 0.5g of hydrochloric acid. The product is poured into ether for precipitation, and the precipitate is put into a 50 ℃ oven for drying. To obtain diamine E with polyester chain segment.
(2) 210g (2mol) of diethanolamine and 234g (1mol) of 1, 3-dibromopropanediol are added into a dry reactor, heated to react for 3 hours at 95 ℃, then 2.7g of hydrochloric acid is added dropwise, heated to 120 ℃, and continuously reacted for 3 hours to obtain the polyethanolamine ketone E. The result of nuclear magnetic analysis showed that the content of the polyethanolamine ketone E was 85%.
(3) Adding 88.5g of diamine with a polyester chain segment (with the polymerization degree n of 1) and 66.4g of polypropanolone into a dry reactor according to the mol ratio of 1.25:1, heating to 100 ℃, reacting for 2.5 hours, and removing water by a condensation system while reacting to prepare the modified ketimine E. The infrared test result shows that the ketimine E is 1740cm-1The infrared characteristic peak of the polyester chain segment exists, and the polyester chain segment exists in the structure. Meanwhile, the nuclear magnetic results show that a-OH characteristic peak and an N-H characteristic peak exist at the position 43, and the generated product is proved to be a ketimine structural substance containing a polyester chain segment.
(4) Drying the curing agent, mixing the curing agent with epoxy resin E51 according to the proportion of 110g to 100g, uniformly mixing by using a stirrer, and curing under the humid underwater condition to obtain the cured ketimine epoxy resin capable of being coated thickly. The mixture was coated on a standard size test specimen with a thickness of 4mm according to the national standard GB T7124-. The sample is put into a humid condition with the temperature of 15 ℃ for curing for 48 hours, and then is tested in a breaking time range required by national standards by a universal tensile machine, and the tensile shear strength of the sample can reach 10.9 Mpa.
Comparative example
The performance test and the comparison of the examples are carried out on the ketimine DA-134 epoxy curing agent which is simply synthesized by common ketone and amine monomers. Under the condition of room temperature of 25 ℃, curing agent of ketimine DA-134 epoxy curing agent is prepared by the following components in mass ratio: after mixing the resin 40:100, and after rapid stirring, test samples were prepared according to the national standard, except that a 4mm thick mixture was applied to an aluminum sample sheet of the same specification as in example 1. The sample is put into a humid condition of 15 ℃ for curing to prepare a sample, after curing for 48 hours, the sample is taken out and is respectively subjected to tensile shear strength test on a universal tensile machine, and the shear strength of the ketimine in the comparative example is only 2.4 Mpa. The modified novel ketimine curing agent can be fully decomposed under the thick coating condition to initiate the curing of the epoxy resin and meet the use requirements.
Claims (10)
1. A modified ketimine curing agent capable of being thickly coated is characterized by comprising the following structural formula:
wherein R is1Is one of substituted or non-substituted ethyl, propyl and butyl, R2Is any one of alkylene, alicyclic group or arylene, preferably alicyclic group, wherein n is 1-5, R3Is one of H, methyl, ethyl and propyl, and is preferably H.
2. The ketimine curing agent according to claim 1, characterized in that the modified ketimine is produced by a reaction comprising,
a) a modified amine containing a polyester segment, wherein the modified amine contains a polyester segment,
b) a polyalcohol amine ketone;
preferably, the modified amine containing the polyester chain segment of the component a) is prepared by the reaction of a polycyclic ester of the component a1) and a primary diamine of the component a2),
the component b) polyalcohol amine ketone is prepared by the reaction of polyalcohol amine containing a component b1) and halogenated dihydric alcohol containing a component b 2).
3. The ketimine curing agent according to claim 2, characterized in that the molar ratio of said modified amine containing polyester segments of component a) to said polyalcohol aminone of component b) is 1-3: 1;
preferably, the molar ratio of the component a1) polycyclic ester to the component a2) primary diamine is 1-5: 1, more preferably 1-1.5: 1;
the molar ratio of the component b1) polyalcohol amine to the component b2) halogenated dihydric alcohol is 2-3: 1.
4. the ketimine curing agent according to claim 2 or 3, characterized in that the component b1) polyalcohol amine and the component b2) halogenated diol are reacted under acidic catalyst condition,
preferably, the acidic catalyst is one or more than two of hydrochloric acid, sulfuric acid, nitric acid and Lewis acid.
5. The ketimine curing agent according to any one of claims 2 to 4, wherein the component a1) polycycloester comprises a cyclic structure of at least one ester group, including but not limited to one or more of butyrolactone, lactide, valerolactone, caprolactone;
the binary primary amine of the component a2) comprises one or more than two of aliphatic primary diamine, alicyclic primary diamine and aromatic primary diamine, preferably ethylenediamine, propylenediamine, butylenediamine, m-xylylenediamine, m-phenylenediamine, 4 '-diaminodicyclohexylmethane and isophorone diamine, and further preferably 4,4' -diaminodicyclohexylmethane and isophorone diamine;
the halogenated dihydric alcohol is one or more than two of 1, 3-chlorodihydric alcohol, 2, 4-chlorodihydric alcohol, 1, 3-fluorodihydric alcohol, 2, 4-fluorodihydric alcohol, 1, 3-bromodihydric alcohol and 2, 4-bromodihydric alcohol, and 1, 3-chlorodihydric alcohol is further preferable;
the polyalcohol amine comprises one or more of diethanolamine, diisopropanolamine, di-n-propanolamine and di-n-butanolamine, and further preferably diethanolamine.
6. The ketimine curing agent according to any one of claims 2 to 5, characterized in that the modified amine containing a polyester segment of component a) is prepared by:
adding a certain amount of a1) polycyclic ester, a component a2) primary diamine and an organic solvent into a dry reactor, heating under the protection of nitrogen atmosphere, reacting for 4-5 hours at 40-80 ℃, and adding hydrochloric acid to terminate the reaction to obtain a modified amine product containing a polyester chain segment;
preferably, the reaction solution generated after the reaction is precipitated and dried in a precipitating agent, wherein the precipitating agent is: one or more of petroleum ether, diethyl ether and ethyl acetate;
preferably, the amount of hydrochloric acid added for terminating the reaction is 0.1 to 0.5% by mass of the total mass of the reactants.
7. The ketimine curing agent according to any one of claims 2 to 6, characterized in that the component b), the polyalcohol aminones, is prepared by: adding a certain amount of component b1) polyalcohol amine and component b2) halogenated dihydric alcohol into a dry reactor, reacting for 3-4 hours at 60-100 ℃, adding an acid catalyst, raising the temperature of the system to 120-140 ℃, and reacting for 3-4 hours to prepare polyalcohol amine ketone;
preferably, the amount of the acidic catalyst added is 1 to 0.01%, preferably 0.5% to 0.1% of the total mass of the reactants.
8. The ketimine curing agent according to claim 6, wherein the organic solvent includes one or more of but not limited to toluene, dimethylsulfoxide, cyclohexane, and tetrahydrofuran.
9. A method for preparing the ketimine curing agent according to any one of claims 1 to 8, characterized by comprising the steps of:
adding the modified amine containing the polyester chain segment of the component a) and the polyalcohol amine ketone of the component b) into a dry reactor, and heating and reacting for 2-4 hours at the temperature of 100-130 ℃ to prepare the modified ketimine.
10. Use of the curing agent according to claims 1-8 or the curing agent prepared by the process according to claim 9 in underwater adhesives, coatings and applications requiring curing under wet and aqueous conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911227776.6A CN112898538B (en) | 2019-12-04 | 2019-12-04 | Thick-coatable modified ketimine curing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911227776.6A CN112898538B (en) | 2019-12-04 | 2019-12-04 | Thick-coatable modified ketimine curing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112898538A true CN112898538A (en) | 2021-06-04 |
| CN112898538B CN112898538B (en) | 2022-04-19 |
Family
ID=76110755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911227776.6A Active CN112898538B (en) | 2019-12-04 | 2019-12-04 | Thick-coatable modified ketimine curing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112898538B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001529A1 (en) * | 1995-06-28 | 1997-01-16 | Minnesota Mining And Manufacturing Company | Ketimine curing agents and rapidly curing magnetic recording media and films prepared with ketimines |
| CN103193959A (en) * | 2013-04-18 | 2013-07-10 | 艾达索高新材料无锡有限公司 | Degradable hydrazide latent epoxy resin curing agent and application thereof |
| CN105308145A (en) * | 2013-06-14 | 2016-02-03 | 积水富乐株式会社 | Adhesive composition |
| CN110128376A (en) * | 2019-05-09 | 2019-08-16 | 万华化学集团股份有限公司 | A kind of compound and preparation method and its purposes as resting form epoxy hardener |
| CN111909359A (en) * | 2020-07-17 | 2020-11-10 | 广东省石油与精细化工研究院 | Curing agent and preparation method and application thereof |
-
2019
- 2019-12-04 CN CN201911227776.6A patent/CN112898538B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001529A1 (en) * | 1995-06-28 | 1997-01-16 | Minnesota Mining And Manufacturing Company | Ketimine curing agents and rapidly curing magnetic recording media and films prepared with ketimines |
| CN103193959A (en) * | 2013-04-18 | 2013-07-10 | 艾达索高新材料无锡有限公司 | Degradable hydrazide latent epoxy resin curing agent and application thereof |
| CN105308145A (en) * | 2013-06-14 | 2016-02-03 | 积水富乐株式会社 | Adhesive composition |
| CN110128376A (en) * | 2019-05-09 | 2019-08-16 | 万华化学集团股份有限公司 | A kind of compound and preparation method and its purposes as resting form epoxy hardener |
| CN111909359A (en) * | 2020-07-17 | 2020-11-10 | 广东省石油与精细化工研究院 | Curing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112898538B (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114163645A (en) | Anchoring agent and preparation method and application thereof | |
| CA3119870A1 (en) | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof | |
| CN109776804B (en) | Cross-linkable POSS reinforced polyurethane nano hybrid material and preparation method thereof | |
| CN111662675B (en) | Mural and colored drawing cultural relic reinforcing agent with self-healing function and preparation method thereof | |
| WO2011142468A1 (en) | Curable composition, method for manufacturing an epoxy resin/inorganic polymer composite material using said curable composition, and epoxy resin/inorganic polymer composite material | |
| CN114940651A (en) | Wet bonding curing agent and preparation method and application thereof | |
| CN112898538B (en) | Thick-coatable modified ketimine curing agent and preparation method and application thereof | |
| CN113912840B (en) | Preparation method and application of hollow glass bead modified polyaspartic acid ester | |
| KR20090094451A (en) | Method for coating metal bands | |
| KR20170082973A (en) | Aryl compound and making method | |
| CN109851758B (en) | Degradable recyclable hyperbranched epoxy resin and preparation method and application thereof | |
| US20180179416A1 (en) | Coating composition and method of preparing the same | |
| Sun et al. | Catechol-modified epoxy coatings with high adhesive strength on saturated concrete substrate | |
| KR101578636B1 (en) | The method of manufacturing watersoluble ceramic paint composition having waterproof quality | |
| CN115505239B (en) | Preparation method of polysiloxane modified epoxy resin material | |
| CN109468058B (en) | Ultrathin weather-resistant anti-cracking organic silicon fireproof coating | |
| JP3681582B2 (en) | Epoxy group-containing silicone resin | |
| CN114933882A (en) | Durable sealant with ultrahigh elongation, high adhesion and high toughness and preparation method thereof | |
| CN113831571A (en) | Preparation method of PC glass plate for shielding door | |
| JP6801480B2 (en) | Infrared shielding film forming paint | |
| CN114057671B (en) | Diepoxyaromatic phenol and preparation method thereof, hyperbranched phenolic amine epoxy curing agent and preparation method thereof | |
| JPH08209069A (en) | Coating fluid and its production | |
| CN116135935B (en) | High-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection and preparation method thereof | |
| CN114806478B (en) | Anticorrosive monocomponent silane modified polyether sealant and preparation method thereof | |
| JPH02132174A (en) | Production of tacky product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |