CN112979924A - Low-molecular-weight polyamide curing agent, and preparation method and application thereof - Google Patents
Low-molecular-weight polyamide curing agent, and preparation method and application thereof Download PDFInfo
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- CN112979924A CN112979924A CN202110267242.7A CN202110267242A CN112979924A CN 112979924 A CN112979924 A CN 112979924A CN 202110267242 A CN202110267242 A CN 202110267242A CN 112979924 A CN112979924 A CN 112979924A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 56
- 229920002647 polyamide Polymers 0.000 title claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003292 glue Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 23
- 239000000539 dimer Substances 0.000 claims description 22
- 150000004985 diamines Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 230000008439 repair process Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 description 8
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 6
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006335 epoxy glue Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002636 imidazolinyl group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- HFBHOAHFRNLZGN-LURJTMIESA-N (2s)-2-formamido-4-methylpentanoic acid Chemical compound CC(C)C[C@@H](C(O)=O)NC=O HFBHOAHFRNLZGN-LURJTMIESA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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
- C08G59/44—Amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/21—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to an acyclic carbon atom of an unsaturated carbon skeleton containing rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the field of thermosetting resin materials, and particularly relates to a low-molecular-weight polyamide curing agent, and a preparation method and application thereof. According to the low molecular weight polyamide curing agent provided by the invention, an ether bond structure is introduced into the molecules of the low molecular weight polyamide curing agent, so that the flexibility of polyamide molecules is greatly improved, and the low molecular weight polyamide curing agent has good technological properties such as low viscosity; after the epoxy resin is reacted and cured, the cured product has the advantages of high strength and high flexibility, and the comprehensive performance is further enhanced. The concrete crack repairing glue has the characteristics of low viscosity, high strength and high flexibility, and has remarkable advantages in application to concrete crack repairing glue.
Description
Technical Field
The invention relates to the field of thermosetting resin materials, in particular to a low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity, a preparation method and application thereof.
Background
The thermosetting epoxy resin material has the advantages of special mechanical property, adhesive property and aging resistance, so that the thermosetting epoxy resin material has wide application in the fields of concrete structure reinforcement and crack repair such as buildings, roads and bridges and the like. Because the concrete structure of the road usually works under dynamic load, higher requirements are put on the flexibility and elasticity of the reinforcing glue and the crack repairing glue. One of the ideas for improving the flexibility of the epoxy glue is to select a special epoxy resin or a flexibility modifier with high flexibility, such as dimer acid type epoxy resin, an organic silicon-epoxy block copolymer, a terminal active liquid nitrile rubber and the like, wherein the materials can obviously change key performances such as curing rate and the like while improving the flexibility of the epoxy glue, cause adverse effects on the technological properties of the epoxy glue and are expensive; the other idea is to select a high-flexibility curing agent, wherein the polyether amine curing agent has excellent high flexibility and elasticity, but can only be used for epoxy systems cured at medium and high temperatures and cannot be used in outdoor fields such as buildings, roads and bridges, and the like, and the low-molecular-weight polyamide curing agent has proper curing rate and toughness and can be widely applied to room-temperature curing epoxy adhesives. However, the existing low molecular weight polyamide has high viscosity and few selectable high-flexibility varieties, and cannot meet the requirements of the concrete crack repair adhesive on high flexibility and low viscosity.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
In order to solve the problems, the invention aims to provide a low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity, a preparation method and application thereof. According to the low molecular weight polyamide curing agent provided by the invention, ether bonds are introduced into the molecular structure of the low molecular weight polyamide curing agent, so that the flexibility of polyamide is greatly improved; and it has a low viscosity. After the epoxy resin is reacted and cured, the cured material has higher mechanical strength, bonding strength and elongation at break, and has remarkable advantages when being applied to concrete crack repair glue.
Solution scheme
In order to realize the purpose of the invention, the invention is realized by the following technical scheme:
a low molecular weight polyamide curing agent has a structure shown in formula I:
wherein: r1Is selected from-CH2CH2CH2OCH2CH2OCH2CH2CH2-、-CH2CH2OCH2CH2OCH2CH2-or-CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2-；
R2Selected from H or dimer acid.
Further preferably, the compound of formula 1 is selected from the following table 1:
table 1 Compounds
| Compound numbering | R1 | R2 |
| 1 | -CH2CH2CH2OCH2CH2OCH2CH2CH2- | H |
| 2 | -CH2CH2CH2OCH2CH2OCH2CH2CH2- | Dimer acid |
| 3 | -CH2CH2OCH2CH2OCH2CH2- | H |
| 4 | -CH2CH2OCH2CH2OCH2CH2- | Dimer acid |
| 5 | -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2- | H |
| 6 | -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2- | Dimer acid |
The invention also provides a preparation method of the low molecular weight polyamide curing agent, which comprises the following steps: the dimer acid and the oligoether diamine are subjected to polycondensation reaction under the heating condition to prepare the polyether diamine.
Preferably, the preparation method of the low molecular weight polyamide curing agent comprises the following steps: under the protection of inert gas, heating dimer acid and oligoether diamine, stirring them to make polycondensation reaction so as to obtain the invented product.
The preparation method of the low molecular weight polyamide curing agent provided by the invention is characterized in that the molar ratio of oligoether diamine to dimer acid is (1.5-3.5): 1; preferably (2.0-3.0): 1; preferably 2.5: 1.
according to the preparation method of the low molecular weight polyamide curing agent, the oligoether diamine contains 2 or 3 ether bonds.
Preferably, the structural general formula of the oligoether diamine is H2N-R1-NH2(ii) a Wherein: r1Is selected from-CH2CH2CH2OCH2CH2OCH2CH2CH2-、-CH2CH2OCH2CH2OCH2CH2-or-CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2-。
According to the preparation method of the low molecular weight polyamide curing agent, after the reaction material dimer acid is heated to be more than or equal to 100 ℃, oligoether diamine is added into a reaction system in a dropwise manner.
Preferably, heating to 100-250 ℃; more preferably, to 120-.
More preferably, in the preparation method of the low molecular weight polyamide curing agent, the polycondensation reaction adopts a temperature programming mode, and the temperature is raised to between 15 and 25 ℃ and the final temperature is 200-250 ℃ every 20 to 30 minutes; preferably, the temperature is raised to 20 ℃ to 200 ℃ every 30 minutes.
According to the preparation method of the low molecular weight polyamide curing agent, after the polycondensation reaction reaches the final temperature, the stirring reaction is carried out for 1-5 hours; preferably, stirring for 2-3 h; preferably, stirring is carried out for 2 h.
The preparation method of the low molecular weight polyamide curing agent further comprises the steps of cooling the reaction materials after the polycondensation reaction is completed, then distilling under reduced pressure to remove water in the system, and cooling to obtain the low molecular weight polyamide.
The temperature is reduced to 100-120 ℃; preferably, the temperature is reduced to 100 ℃.
The cooling is carried out to 10-40 ℃; preferably, cooling to 20-30 ℃.
The inert gas for the above preparation method of the present invention includes at least one of nitrogen or argon, preferably nitrogen.
The invention also provides application of the low molecular weight polyamide curing agent in concrete crack repair glue. Preferably, the low molecular weight polyamide curing agent is used in combination with high-flexibility epoxy resin or concrete for application in the field of crack repair.
The invention also provides a concrete crack repairing adhesive which comprises 50-100 parts of the low molecular weight polyamide curing agent, 100 parts of epoxy resin, 5-10 parts of the diluent, 10-40 parts of the filler and 1 part of carbon black.
Such fillers include, but are not limited to, quartz powder, talc, calcium carbonate, silica, and the like.
The dimer acid CAS 6144-28-1 has the structure shown in the formula II:
ethylene glycol di (3-aminopropyl) ether:
CAS 2997-01-5；H2N-CH2CH2CH2OCH2CH2OCH2CH2CH2-NH2。
ethylene glycol di (2-aminoethyl) ether:
CAS 929-59-9；H2N-CH2CH2OCH2CH2OCH2CH2-NH2。
diethylene glycol bis (3-aminopropyl) ether:
CAS 4246-51-9；H2N-CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2-NH2。
advantageous effects
(1) In the existing low molecular weight polyamide curing agent, polyamine is small molecular aliphatic amine, such as diethylenetriamine, triethylenetetramine and the like; the invention provides a new concept of introducing an ether bond structure into a polyamide molecule. The low molecular weight polyamide provided by the invention has high strength, high flexibility and low viscosity. By selecting the low molecular weight diamine containing ether bonds and introducing an ether bond structure into polyamide molecules, the flexibility of the polyamide curing agent is greatly improved because the ether bonds are easy to rotate, and finally the elongation at break and the flexibility of the cured epoxy resin are improved. In addition, the selected oligoether diamine has low molecular weight and active terminal group, so that the reaction activity of the oligoether diamine and the obtained polyamide curing agent is higher than that of the commercially available polyether amine curing agent (such as D230, D400 and the like), and the oligoether diamine can be cured at room temperature.
(2) After the low molecular weight polyamide curing agent provided by the invention is cured by reacting with epoxy resin, a cured product has good mechanical strength, bonding strength and elongation at break, namely, high strength and high flexibility.
(3) The concrete crack repair adhesive prepared by compounding the low molecular weight polyamide curing agent with epoxy resin and the like has the advantages of low viscosity, high strength and high adhesion. One example post mix viscosity 477cP, tensile strength 25.1MPa, elongation at break 8.9%, and steel-to-steel tensile shear strength 27.4 MPa.
(4) The preparation method has simple process and high yield, and forms imidazoline ring structure in the product by strictly gradient temperature rise and slowly dripping oligoether diamine, thereby greatly improving the compatibility of the polyamide curing agent and the epoxy resin, and further improving the curing speed and the comprehensive performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
In the following examples, dimer acid, reference YD-29A, was obtained from Yuanchun Daihong chemical Co., Ltd, Yichun, Jiangxi, CAS number 6144-28-1, acid number 190-;
ethylene glycol bis (3-aminopropyl) ether was purchased from alatin, molecular weight 176.26, CAS number 2997-01-5;
ethylene glycol bis (2-aminoethyl) ether available from Hensman under the designation EDR-148, molecular weight 148;
diethylene glycol bis (3-aminopropyl) ether was purchased from alatin with a molecular weight of 220.31 and a CAS number of 4246-51-9.
Example 1
A low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity is prepared by the following steps:
adding 56.1g (0.1mol) of dimer acid YD-29A into a 250mL four-neck flask, setting up a stirrer, a reflux condenser and a thermometer, and slowly heating to 120 ℃ under the protection of nitrogen;
26.4g (0.15mol) of ethylene glycol di (3-aminopropyl) ether is put into a constant pressure dropping funnel and slowly dropped into a flask under stirring, and the mixture is light yellow uniform transparent liquid after dropping;
heating by program, raising the temperature by 20 ℃ every half hour until the temperature reaches 200 ℃, keeping the temperature at 200 ℃ for 2 hours, and finishing the reaction;
cooling to 100 ℃, then removing water in the system through reduced pressure distillation, cooling to obtain a product which is yellow transparent viscous liquid, and pouring the yellow transparent viscous liquid into a sample bottle for later use.
The molecular weight and the distribution of the product were determined by Gel Permeation Chromatography (GPC), with a number average molecular weight (Mn) of 3320 and a Polydispersity (PDI) of 1.06.
The viscosity of the product was measured by a rotational viscometer method and at 25 ℃ the viscosity was 39600 cP.
The amine number of the product was determined by perchloric-glacial acetic acid titration and found to be 106 mg/KOH/g.
The infrared spectrum of the structure of the product is characterized, and the length of the infrared spectrum is 3296cm-11648cm from the stretching vibration absorption peak of the amino group-1The absorption peak of C ═ O stretching vibration of amide appears at 1100cm-1Is the absorption peak of C ═ N bond in imidazoline ring.
Examples 2 to 5
A low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity is prepared by the following steps: the procedure is the same as in example 1, except that the molar ratio of ethylene glycol di (3-aminopropyl) ether to dimer acid (i.e., the molar ratio of amino groups to carboxyl groups) is different, and the specific amounts added are shown in Table 1.
TABLE 1
Examples 6 to 10
A low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity is prepared by the following steps: the procedure is as in example 1 except that diethylene glycol bis (3-aminopropyl) ether is replaced by diethylene glycol bis (3-aminopropyl) ether, and the specific amounts are shown in Table 2.
TABLE 2
Examples 11 to 12
A low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity is prepared by the following steps: the procedure is as in example 1, except that ethylene glycol di (3-aminopropyl) ether is replaced by ethylene glycol di (2-aminoethyl) ether, and the specific amounts are shown in Table 3.
TABLE 3
Example 13
The application method of the low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity comprises the following steps: the polyamide and the epoxy resin are uniformly mixed in proportion, and the mixture can be completely cured after being placed at room temperature for 3 days, wherein the curing performance and the mechanical performance test results are shown in table 4. It can be seen that the polyamide products of examples 9 and 10 cured epoxy resin E51, which had a tensile strength of about 30MPa and an elongation at break of more than 20%, exhibited the most outstanding properties in terms of high strength and high flexibility. On the other hand, after all the polyamide curing agents of the invention cure the epoxy resin E51, the elongation at break is higher than 10%, and the whole is superior to the polyamide curing agents (650, 651 and 140) commonly used in the market and also superior to the polyether amine curing agents (D230 and D400).
TABLE 4
Example 14
The application method of the low molecular weight polyamide curing agent with high strength, high flexibility and low viscosity comprises the following steps: 100g of epoxy resin E51, 70g of polyamide of example 5, 8g of diluent 692, 20g of quartz powder and 1g of carbon black are weighed in a 500mL plastic bucket, and are primarily mixed by a putty knife and ground three times on a three-roll grinder to obtain the pourable crack repair adhesive.
The viscosity of the crack repair paste was measured with a rotational viscometer and found to be 477 cP.
The mechanical properties of the crack repair adhesive are performed according to GB/T2567-.
The adhesive property of the crack repair adhesive is carried out according to GB/T7124-.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A low molecular weight polyamide curing agent is characterized in that: the structure is shown as formula 1
Wherein: r1Is selected from-CH2CH2CH2OCH2CH2OCH2CH2CH2-、-CH2CH2OCH2CH2OCH2CH2-or-CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2-；
R2Selected from H or dimer acid.
2. The low molecular weight polyamide curative of claim 1 wherein the compound of formula 1 is selected from the following table:
。
3. The method for preparing a low molecular weight polyamide curing agent according to claim 1 or 2, characterized by comprising the steps of: the dimer acid and the oligoether diamine are subjected to polycondensation reaction under the heating condition to obtain the dimer acid and the oligoether diamine; preferably, the dimer acid and the oligoether diamine are heated and stirred under the condition of inert gas to carry out polycondensation reaction.
4. The method of claim 3, wherein the molar ratio of oligoether diamine to dimer acid is (1.5-3.5): 1; alternatively (2.0-3.0): 1; alternatively 2.5: 1.
5. the method of claim 3, wherein the oligoetherdiamine contains 2 or 3 ether linkages; preferably, the structural general formula of the oligoether diamine is H2N-R1-NH2(ii) a Wherein: r1Is selected from-CH2CH2CH2OCH2CH2OCH2CH2CH2-、-CH2CH2OCH2CH2OCH2CH2-or-CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2CH2-。
6. The preparation method of the low molecular weight polyamide curing agent according to claim 3, wherein after the reaction material dimer acid is heated to more than or equal to 100 ℃, oligoether diamine is added dropwise into the reaction system; preferably, heating to 100-250 ℃; further optionally, heating to 120-; more preferably, the polycondensation reaction adopts a temperature programming mode, and the temperature is raised to between 15 and 25 ℃ and the final temperature of 200 and 250 ℃ every 20 to 30 minutes; preferably, the temperature is raised to 20 ℃ to 200 ℃ every 30 minutes.
7. The method for preparing a low molecular weight polyamide curing agent according to claim 6, characterized in that: stirring and reacting for 1-5h after the final temperature is reached; optionally, stirring for 2-3 h; optionally, stirring for 2 h.
8. The method for preparing a low molecular weight polyamide curing agent according to claim 3, characterized in that: cooling the reaction material after the polycondensation reaction, then distilling under reduced pressure to remove water in the system, and cooling to obtain low molecular weight polyamide; optionally, cooling to 100-120 ℃; further optionally, cooling to 100 ℃; the cooling is carried out to 10-40 ℃; further optionally, cooling to 20-30 ℃.
9. Use of the low molecular weight polyamide curing agent according to claim 1 or 2 in concrete crack repair cement.
10. The concrete crack repairing glue is characterized in that: comprising 50-100 parts of the low molecular weight polyamide curing agent as defined in claim 1 or 2, 100 parts of epoxy resin, 5-10 parts of diluent, 10-40 parts of filler and 1 part of carbon black.
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Application publication date: 20210618 |