CN113583172B - Long-chain polyether amine hydrophilic low-molecular-weight polymer and preparation method thereof - Google Patents
Long-chain polyether amine hydrophilic low-molecular-weight polymer and preparation method thereof Download PDFInfo
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- CN113583172B CN113583172B CN202110849556.8A CN202110849556A CN113583172B CN 113583172 B CN113583172 B CN 113583172B CN 202110849556 A CN202110849556 A CN 202110849556A CN 113583172 B CN113583172 B CN 113583172B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- 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
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Abstract
The invention discloses a long-chain polyether amine hydrophilic low molecular weight polymer and a preparation method thereof, wherein 102-118 parts of carboxylic acid monomer, 87-105 parts of amine monomer and 0.1-0.2 part of polymerization inhibitor are added into a reaction kettle provided with a stirrer; heating to 90-95 ℃ by adopting an oil bath, and reacting for 1-2h to obtain an amide monomer; then adding 189-223 parts of prepared amide monomer and 95-107 parts of ether alcohol head into a reaction kettle with a stirrer, and heating to 80-85 ℃ in a water bath; preparing 100-116 parts of ether alcohol head and 130-155 parts of water into solution A, preparing 2.01-3.32 parts of initiator, 5-12 parts of chain transfer agent and part of water into solution B, and dripping A, B into the reaction kettle by using a dripping pump; and (3) preserving the heat for 1-2 hours after the dripping is finished to prepare a polyetheramine solution, and supplementing water to 1000 parts to obtain the long-chain polyetheramine hydrophilic low-molecular-weight polymer. The polyether amine molecule with the amide group and the ether bond on the molecular side chain is prepared in two steps, the prepared polyether amine has a good curing effect on epoxy resin, and the properties of the epoxy resin such as viscosity, durability and the like can be improved.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a long-chain polyether amine hydrophilic low-molecular-weight polymer and a preparation method thereof.
Background
The polyether amine curing agent is an internal toughening type amino-terminated curing agent and contains a soft polyether framework. Such curing agents are widely used in recent years because they are transparent and colorless, have low viscosity and low heat generation during curing, have good compatibility with epoxy resins, and the cured products are colorless and transparent, and have good flexibility and low-temperature properties.
The patent CN106117557A discloses a method for efficiently preparing polythioetherimide, and the invention relates to a method for preparing polythioetherimide, which comprises the following steps: monosubstituted phthalic anhydride and organic diamine are used as raw materials to react to synthesize disubstituted phthalimide, and anhydrous alkali metal hydrosulfide, a catalyst and an auxiliary agent are added into the reaction system to react with the synthesized disubstituted phthalimide to generate polythioetherimide. The polythioetherimide prepared by the method of the invention simplifies the process flow, shortens the reaction period, reduces the equipment and production cost and improves the production efficiency; and the prepared polythioetherimide has excellent mechanical property and processability.
The invention discloses a polyether amine modified polycarboxylic acid superplasticizer and a preparation method thereof, and discloses a polyether amine modified polycarboxylic acid superplasticizer and a preparation method thereof, wherein the dispersant is a polycarboxylic acid copolymer which contains a polyether group structural unit I, a carboxylic group structural unit II and an amide polyether structural unit III and has the weight-average molecular weight of 10000-120000; the preparation method comprises the following steps: firstly, copolymerizing an unsaturated polyether monomer A and an unsaturated carboxylic acid monomer B in an aqueous solution at 50-100 ℃ in the presence of an initiator and a chain transfer agent to obtain a carboxylic acid-based polymer with the molecular weight of 5000-30000; and then carrying out amidation reaction on the carboxylic group polymer and a polyether amine monomer C at the temperature of 80-200 ℃ to obtain the carboxylic group polymer. The polyether amine modified polycarboxylic acid superplasticizer still has high concrete water reducing rate under the condition of low doping amount, and simultaneously has good concrete slump retention.
The patent CN109897227A discloses a polyether amine modified graphene oxide and an epoxy nanocomposite thereof, and the invention provides a polyamino polyether amine modified graphene oxide, which is obtained by replacing-OH groups on carboxyl groups on the surface of graphene oxide with A groups. And further preparing to obtain the polyamino polyether amine modified graphene oxide/TDE-85 epoxy nano composite material system. The polyamino polyether amine modified graphene oxide can effectively improve the mechanical property of epoxy resin, and particularly when m (GO) and n (T5000) are 1:7, the mechanical property of the composite material with the grafting amount reaches the best, so that the composite material has a good application prospect.
Different from the patents, the invention aims to prepare the long-chain polyether amine hydrophilic low-molecular-weight polymer. The invention firstly carries out condensation reaction on polyamine and organic acid to prepare amide molecules containing double bonds, and then the amide monomers react with ether alcohol heads containing double bonds to prepare the long-chain polyether amine polymer. The long-chain polyether amine polymer has a flexible polyether framework, the whole molecular chain has higher flexibility, and the long-chain polyether amine polymer has a good modification effect on substances such as epoxy resin and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a long-chain polyether amine hydrophilic low-molecular-weight polymer. The preparation method has the advantages of simple preparation process, excellent product performance, good stability and wide adaptability.
The invention discloses a long-chain polyether amine polymer, which is prepared by taking a carboxylic acid monomer and an amine monomer as raw materials and a polymerization inhibitor as an auxiliary material to prepare an amide monomer with double bonds, and polymerizing the amide monomer and an unsaturated polyether alcohol head to prepare a polyether amine polymer containing ether bonds and amide groups.
The technical scheme of the invention is as follows:
the preparation method of the long-chain polyether amine hydrophilic low-molecular-weight polymer is characterized by sequentially comprising the following operation steps of:
the method comprises the following steps: adding 102-118 parts of carboxylic acid monomer, 87-105 parts of amine monomer and 0.1-0.2 part of polymerization inhibitor into a reaction kettle with a stirrer in parts by mass; heating to 90-95 ℃ by adopting an oil bath, and reacting for 1-2h to obtain an amide monomer;
step two: adding the amide monomer prepared in the step one and 95-107 parts of ether alcohol head into a reaction kettle provided with a stirrer, and heating in water bath to 80-85 ℃; preparing 100-116 parts of ether alcohol head and 130-155 parts of water into solution A, preparing 2.01-3.32 parts of initiator, 5-12 parts of chain transfer agent and water into solution B, dripping A, B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is performed for 1-1.5 hours, and the dripping of the solution B is performed for 1-2 hours; and (3) after the A, B solution is dripped, preserving the heat for 1-2 hours to prepare a polyetheramine solution, and replenishing water to 1000 parts to obtain the long-chain polyetheramine hydrophilic low-molecular-weight polymer.
Preferably, the carboxylic acid monomer is acrylic acid.
Preferably, the amine monomer is 3-methyl-2-butene-1-amine or 3-butene-1-amine.
Preferably, the ether alcohol head is allyloxypropanol, CAS number: 6180-67-2.
Preferably, the polymerization inhibitor is any one or more of hydroquinone, paragazel quinone, p-benzoquinone, p-tert-butyl catechol, 2, 6-di-tert-butyl-p-methylphenol, 4' -bis-menthyl biphenyl and 1, 1-diphenyl-2-trinitrophenylhydrazine. A composition of p-benzoquinone and 4,4' -dialkylbiphenyl in a mass ratio of 1:2 is preferred.
Preferably, the initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate, Benzoyl Peroxide (BPO), di-tert-butyl peroxide (DTBP) and dicyclohexyl peroxydicarbonate. Preferably a combination of benzoyl peroxide and di-t-butyl peroxide in a mass ratio of 1: 2.
Preferably, the chain transfer agent is any one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol. Preferably a composition of thioglycolic acid and mercaptopropanol in a mass ratio of 5: 3.
The invention also provides a long-chain polyether amine hydrophilic low-molecular weight polymer which is prepared from the following components: 102-118 parts of carboxylic acid monomer, 87-105 parts of amine monomer, 195-223 parts of ether alcohol head, 2.01-3.32 parts of initiator, 5-12 parts of chain transfer agent, 0.4-0.8 part of polymerization inhibitor and the balance of water, and the total mass is 1000 parts. The solid content of the prepared finished product is 35-45%.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the long-chain polyether amide polymer prepared by the invention has the characteristics of relatively large molecular weight, good molecular chain flexibility and the like, can effectively toughen epoxy resin when participating in epoxy resin curing, and improves the elongation at break and the impact toughness of the epoxy resin.
2. According to the invention, a polymerization inhibitor is added during the preparation of an amide monomer, so that the acrylic acid with higher activity is prevented from generating self-polymerization reaction to form polyacrylic acid with large molecular weight, so that the groups in the molecular chain of the synthesized polyether amine are not uniformly distributed, and the related performance is influenced.
3. According to the invention, ethers with hydroxyl are used as raw materials, and hydroxyl groups with good hydrophilicity are introduced into polyether amine molecules, so that the hydrophilicity of the epoxy resin can be improved when the epoxy resin is cured and modified, the epoxy resin is conveniently modified into a water-based epoxy resin, water can be used as a solvent, the use of organic solvents is reduced, and the effect of avoiding environmental pollution is achieved.
Detailed Description
The technical solutions and advantages of the present invention are further described in detail with reference to the following specific examples, but it should be understood that the following examples should not be construed as limiting the scope of the claims of the present application in any way.
Example 1
The long-chain polyether amine hydrophilic low-molecular-weight polymer is polymerized from the following components in parts by weight, wherein the total mass of the raw materials is 1000 parts, and the components comprise:
109 parts of acrylic acid;
95 parts of 3-methyl-2-butene-1-amine;
212 parts of allyloxypropanol;
0.6 part of composition of p-benzoquinone and 4,4' -dialkylbiphenyl in a mass ratio of 1: 2;
2.79 parts of a composition of benzoyl peroxide and di-tert-butyl peroxide in a mass ratio of 1: 2;
8 parts of a composition of thioglycolic acid and mercaptopropanol in a mass ratio of 5: 3;
the balance of water.
The preparation method of the long-chain polyether amine hydrophilic low-molecular-weight polymer comprises the following operation steps:
the method comprises the following steps: a reaction vessel equipped with a stirrer was charged with 109 parts of acrylic acid, 95 parts of 3-methyl-2-buten-1-amine and 0.1 part of a composition of p-benzoquinone and 4,4' -dialkylbiphenyl in a mass ratio of 1: 2. Heating to 94 ℃ by adopting an oil bath, and reacting for 1h to obtain the amide monomer.
Step two: all of the amide monomers from step one were charged with 100 parts allyloxypropanol to a reaction vessel equipped with a stirrer and heated to 83 ℃ in a water bath. Preparing 112 parts of allyloxypropanol and water into solution A, preparing 2.79 parts of a composition of benzoyl peroxide and di-tert-butyl peroxide in a mass ratio of 1:2, 8 parts of a composition of thioglycolic acid and mercaptopropanol in a mass ratio of 5:3 and water into solution B, and dropwise adding A, B into the reaction kettle by using a dropwise adding pump, wherein the solution A is dropwise added for 1.5 hours, and the solution B is dropwise added for 2 hours. And after the A, B liquid is added, keeping the temperature for 2 hours to prepare the polyether amine solution. And (5) supplementing water to 1000 parts to obtain the long-chain polyether amine hydrophilic low-molecular-weight polymer.
Examples 2-6 were prepared in the same manner as in example 1, with the component differences and process parameter differences being detailed in tables 1 and 2.
Table 1 shows the difference between the components of the production methods of examples 1 to 6 of the present invention
Table 2 shows the difference between the process parameters of the preparation methods of examples 1 to 6 of the present invention
And (3) detection data:
the epoxy resin is cured by using the polyether amine curing agent prepared by the embodiment of the invention, and the performance of the cured epoxy resin is detected to obtain the following table (the corresponding indexes of the epoxy resin are detected according to the standard of GB/T2567-2008)
Table 3 shows the properties of the cured epoxy resins of examples 1 to 6 of the present invention
As can be seen from the table, the curing agent prepared by the embodiment of the invention can play a good curing role when being used in epoxy resin, and improves the mechanical properties of the epoxy resin, such as tensile strength, elastic modulus and the like, which shows that the curing agent improves the stability of the internal three-dimensional structure of the epoxy resin and has better curing effect.
The above embodiments are only for illustrating the present invention and are not to be construed as limiting the present invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (5)
1. The preparation method of the long-chain polyether amine hydrophilic low-molecular-weight polymer is characterized by sequentially comprising the following operation steps of:
the method comprises the following steps: adding 102-118 parts of carboxylic acid monomer, 87-105 parts of amine monomer and 0.1-0.2 part of polymerization inhibitor into a reaction kettle with a stirrer in parts by mass; heating to 90-95 ℃ by adopting an oil bath, and reacting for 1-2h to obtain an amide monomer;
step two: adding all the amide monomers prepared in the step one and 95-107 parts of ether alcohol heads into a reaction kettle provided with a stirrer, and heating in a water bath to 80-85 ℃; preparing 100-116 parts of ether alcohol head and 130-155 parts of water into solution A, preparing 2.01-3.32 parts of initiator, 5-12 parts of chain transfer agent and water into solution B, dripping A, B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is performed for 1-1.5 hours, and the dripping of the solution B is performed for 1-2 hours; after the A, B solution is dripped, the temperature is kept for 1 to 2 hours to prepare a polyetheramine solution, and water is supplemented to 1000 parts to obtain a long-chain polyetheramine hydrophilic low molecular weight polymer;
the carboxylic acid monomer is acrylic acid; the amine monomer is 3-methyl-2-butene-1-amine; the ether alcohol head is allyloxypropanol, CAS number: 6180-67-2.
2. The method for preparing the long-chain polyether amine hydrophilic low-molecular weight polymer as claimed in claim 1, wherein the method comprises the following steps: the polymerization inhibitor is any one or more of hydroquinone, p-gao quinone, p-benzoquinone, p-tert-butyl catechol, 2, 6-di-tert-butyl-p-methylphenol and 1, 1-diphenyl-2-trinitrophenylhydrazine.
3. The method for preparing a long-chain polyether amine hydrophilic low-molecular weight polymer according to claim 1, wherein the method comprises the following steps: the initiator is any one or more of ammonium persulfate, azodiisobutyronitrile, diisopropyl peroxydicarbonate, benzoyl peroxide, di-tert-butyl peroxide and dicyclohexyl peroxydicarbonate.
4. The preparation method of the long-chain polyether amine hydrophilic low molecular weight polymer as claimed in claim 1, wherein the preparation method comprises the following steps: the chain transfer agent is any one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol.
5. A long-chain polyether amine hydrophilic low molecular weight polymer is characterized in that: prepared by the preparation method of any one of claims 1 to 4.
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| US7399818B2 (en) * | 2004-03-16 | 2008-07-15 | Rohm And Haas Company | Curable composition and use thereof |
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