CN110684193A - Polyurea compound and process for producing the same - Google Patents
Polyurea compound and process for producing the same Download PDFInfo
- Publication number
- CN110684193A CN110684193A CN201911105197.4A CN201911105197A CN110684193A CN 110684193 A CN110684193 A CN 110684193A CN 201911105197 A CN201911105197 A CN 201911105197A CN 110684193 A CN110684193 A CN 110684193A
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- formula
- diamine
- alkene
- alkane
- urea
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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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a polyurea compound and a preparation method thereof, wherein the polyurea compound is prepared from a.urea and b.diamine or polyamine through amine exchange reaction. The polyurea structure in the compound can fully improve the polarity in an epoxy system, so that the adhesive force and the strength of the product are improved, and meanwhile, the stability of the polyurea group is favorable for the water resistance, chemical resistance, heat resistance, cold resistance, light resistance and other properties of the product.
Description
Technical Field
The present invention relates to a polyurea compound and a method for producing the same.
Background
The amine is one of important raw materials of epoxy resin materials, and relates to the industries and fields of coatings, adhesives, composite materials and the like. Small molecular amines used in daily life in the industry have inconvenience in application due to the problems of low boiling point, large odor, high moisture tendency and the like, and conventional modified amines such as polyurea, phenol aldehyde amine and epoxy addition amine are difficult to accurately control the molecular weight, the molecular structure and the purity, so that the performance of epoxy products is adversely affected.
Disclosure of Invention
The object of the present invention is to provide a novel polyurea compound and a method for preparing the same.
The polyurea compound is prepared by the amine exchange reaction of a, urea and b, diamine or polyamine,
the urea: the molar ratio of diamine or polyamine is 3: 1-1.01: 1,
the diamine is a compound with a structure shown in a formula I,
wherein R in the formula I is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
the structure of the poly-teleamine is selected from formulas II to II:
r in the formula II is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
r in the formula III is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
wherein x in the formula IV is 1-20,
wherein x + y + z in the formula V is 1-40,
in the formula VI, R is the structure of any one of alkane, alkene and benzene series substances of C2-C15, and x + y + z is 1-40.
Further, the amine exchange reaction step comprises: and (2) putting the urea and the diamine or polyamine into a reaction kettle, heating under the protection of nitrogen until the raw materials are melted to perform amine exchange reaction, wherein the reaction time is 0.5-48 h, the amine value of the system is continuously reduced in the reaction process, sampling and detecting until the actually measured amine value is close to or equal to the theoretical value, and cooling and discharging.
The invention also relates to a two-component coating which contains the polyurea compound.
The invention prepares a novel material with controllable molecular weight and structure and low free amine through the amine exchange reaction between amine and urea, and the novel material can be matched with common amine in epoxy products or used independently. The polyurea structure in the compound can fully improve the polarity in an epoxy system, so that the adhesive force and the strength of the product are improved, and meanwhile, the stability of the polyurea group is favorable for the water resistance, chemical resistance, heat resistance, cold resistance, light resistance and other properties of the product.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
The reaction principle and steps of the invention are as follows.
The urea structure is carbamide, and the amide group of the carbamide can perform amine exchange reaction with primary amine or secondary amine under proper conditions to generate new carbamide and ammonia gas.
When urea is used to react with diamines, the two carboxamides of urea can react simultaneously to produce the following structures, such as:
by adjusting the ratio of urea to diamine, binary linear polyurea compounds of different molecular weights can be obtained, such as:
when more than two polyamines are used, the reaction product is a dendritic or steric structure such as:
the preparation process mainly comprises the steps of putting a, urea and b, diamine or polyamine into a reaction kettle, heating the mixture under the protection of nitrogen until the raw materials are molten to carry out amine exchange reaction, wherein the reaction time is 0.5-48 h, the amine value of the system is continuously reduced in the reaction process, sampling and detecting until the actually measured amine value is close to or equal to the theoretical value, and cooling and discharging.
Example 1, preparation of polyurea compound 1:
in a reaction kettle, the materials are fed according to the following mixture ratio:
| raw materials | Dosage (kg) |
| Hexamethylene diamine | 232 |
| Diethylenetriamine | 103.2 |
| D400 (polyether amine) | 862.5 |
| Urea | 240.1 |
After feeding, introducing nitrogen, heating to 120 ℃, and controlling condensation reflux so that the raw material amine cannot be blown out by the nitrogen. Continuously reacting under heating and stirring until the amine value is reduced to below 140mgKOH, adding 300kg of propylene glycol methyl ether and 350kg of diacetone alcohol to dilute the product, and discharging after cooling.
The polyurea compound 1 thus obtained was provided with an inner finish of a water-based paint for containers according to the following formulation:
component A
Component B
| Polyurea compound 1 | 273.91 |
| Propylene glycol butyl ether | 27.08 |
| Rust inhibitor | 3.32 |
| ANCAMINE K54 | 2.21 |
And mixing the AB components according to the total mass, spraying the AB components in an airless manner, wherein the thickness of a wet film is 20-35 mu m, and curing the AB components for 20min at 70 ℃ after drying.
And (3) placing the cured coating for 24h for testing, wherein the adhesive force is grade 1, the impact resistance is more than 50cm/kg, the coating has no bubbles and corrosion after being subjected to a damp-heat test for 240h, and the corrosion width of salt spray for 480h is less than 2 mm. The performances of the epoxy inner finish paint are far superior to those of the conventional waterborne epoxy inner finish paint.
Example 2 preparation of polyurea compound 2:
in a reaction kettle, the materials are fed according to the following mixture ratio:
| raw materials | Dosage (kg) |
| DDM | 396.1 |
| T403 (polyether amine) | 452.2 |
| Hexamethylene diamine | 232 |
| Urea | 240.1 |
After feeding, introducing nitrogen, heating to 140 ℃, and controlling condensation reflux so that the raw material amine cannot be blown out by the nitrogen. Continuously reacting under heating and stirring until the amine value is reduced to below 150mgKOH, adding 270kg of ethylene glycol propyl ether and 330kg of dimethylbenzene to dilute the product, and discharging after cooling.
The polyurea compound 2 obtained was formulated into a high-solid epoxy coating for containers according to the following formulation:
component A
Component B
| Raw materials | Dosage (kg) |
| Polyurea compound 2 | 33.5 |
| Auxiliary agent | 6 |
| Others | 44 |
And (3) mixing the component A and the component B according to the total mass, spraying the mixture in an airless manner, wherein the thickness of a wet film is 30-50 mu m, and curing the mixture at room temperature.
And (3) performing a performance test after curing for 3 days, wherein the adhesive force is grade 1, the positive and negative impact resistance is greater than 40cm/kg, the damp-heat test is carried out for 360h, no bubbles and no corrosion are generated, and the salt spray corrosion width is less than 2mm after 1000 h. The performances of the coating far exceed those of the conventional high-solid epoxy coating.
Claims (4)
1. A polyurea compound is prepared by amine exchange reaction of a, urea and b, diamine or polyamine, and is characterized in that:
the urea: the molar ratio of diamine or polyamine is 3: 1-1.01: 1,
the diamine is a compound with a structure shown in a formula I,
wherein R in the formula I is the structure of any one of alkane, alkene and benzene series substances of C2-C40, and the structure of the poly-teleamine is selected from the formulas II-II:
r in the formula II is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
r in the formula III is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
wherein x in the formula IV is 1-20,
wherein x + y + z in the formula V is 1-40,
in the formula VI, R is the structure of any one of alkane, alkene and benzene series substances of C2-C15, and x + y + z is 1-40.
2. A process for the preparation of a polyurea compound comprising the step of an amine exchange reaction from a. urea and b. a diamine or polyamine, characterized in that:
the urea: the molar ratio of diamine or polyamine is 3: 1-1.01: 1,
the diamine is a compound with a structure shown in a formula I,
wherein R in the formula I is the structure of any one of alkane, alkene and benzene series substances of C2-C40, and the structure of the poly-teleamine is selected from the formulas II-II:
r in the formula II is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
r in the formula III is the structure of any one of alkane, alkene and benzene series substances of C2-C40,
wherein x in the formula IV is 1-20,
wherein x + y + z in the formula V is 1-40,
in the formula VI, R is the structure of any one of alkane, alkene and benzene series substances of C2-C15, and x + y + z is 1-40.
3. The method of claim 2, wherein the step of amine exchange comprises: and (2) putting the urea and the diamine or polyamine into a reaction kettle, heating under the protection of nitrogen until the raw materials are melted to perform amine exchange reaction, wherein the reaction time is 0.5-48 h, the amine value of the system is continuously reduced in the reaction process, sampling and detecting until the actually measured amine value is close to or equal to the theoretical value, and cooling and discharging.
4. A two-component coating material characterized by containing the polyurea compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911105197.4A CN110684193A (en) | 2019-11-13 | 2019-11-13 | Polyurea compound and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911105197.4A CN110684193A (en) | 2019-11-13 | 2019-11-13 | Polyurea compound and process for producing the same |
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| Publication Number | Publication Date |
|---|---|
| CN110684193A true CN110684193A (en) | 2020-01-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911105197.4A Pending CN110684193A (en) | 2019-11-13 | 2019-11-13 | Polyurea compound and process for producing the same |
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| CN (1) | CN110684193A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662447A (en) * | 2020-05-28 | 2020-09-15 | 天津大学 | Method for synthesizing porous functional ion polyurea material by solvothermal method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3763106A (en) * | 1969-11-28 | 1973-10-02 | Atlas Chem Ind | Polymers prepared by reacting urea with an amino alcohol or diamine followed by methylolation with formaldehyde |
| CN1101413C (en) * | 1996-04-12 | 2003-02-12 | 住友化学工业株式会社 | Water soluble resins and application thereof to paper coating |
| CN1918212A (en) * | 2004-02-09 | 2007-02-21 | 巴斯福股份公司 | Highly functional, highly branched polyureas |
| CN103436148A (en) * | 2013-08-01 | 2013-12-11 | 中山市明日涂料材料有限公司 | Polyurea paint formula and polyurea paint prepared by polyurea paint formula |
| CN109504234A (en) * | 2018-11-11 | 2019-03-22 | 中海油常州涂料化工研究院有限公司 | A kind of chemicals-resistant epoxy inside liner coating and preparation method thereof |
| CN110437658A (en) * | 2019-08-19 | 2019-11-12 | 浩力森化学科技（江苏）有限公司 | A kind of anti-corrosive aids and preparation method and the electrophoretic coating with highly corrosion resistant |
-
2019
- 2019-11-13 CN CN201911105197.4A patent/CN110684193A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3763106A (en) * | 1969-11-28 | 1973-10-02 | Atlas Chem Ind | Polymers prepared by reacting urea with an amino alcohol or diamine followed by methylolation with formaldehyde |
| CN1101413C (en) * | 1996-04-12 | 2003-02-12 | 住友化学工业株式会社 | Water soluble resins and application thereof to paper coating |
| CN1918212A (en) * | 2004-02-09 | 2007-02-21 | 巴斯福股份公司 | Highly functional, highly branched polyureas |
| CN103436148A (en) * | 2013-08-01 | 2013-12-11 | 中山市明日涂料材料有限公司 | Polyurea paint formula and polyurea paint prepared by polyurea paint formula |
| CN109504234A (en) * | 2018-11-11 | 2019-03-22 | 中海油常州涂料化工研究院有限公司 | A kind of chemicals-resistant epoxy inside liner coating and preparation method thereof |
| CN110437658A (en) * | 2019-08-19 | 2019-11-12 | 浩力森化学科技（江苏）有限公司 | A kind of anti-corrosive aids and preparation method and the electrophoretic coating with highly corrosion resistant |
Non-Patent Citations (1)
| Title |
|---|
| JOSEPH M.DENNIS等: ""Synthesis and characterization of isocyanate-free polyureas"", 《GREEN CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662447A (en) * | 2020-05-28 | 2020-09-15 | 天津大学 | Method for synthesizing porous functional ion polyurea material by solvothermal method |
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Application publication date: 20200114 |
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