CN113121814A - Polyether amine modification method - Google Patents
Polyether amine modification method Download PDFInfo
- Publication number
- CN113121814A CN113121814A CN201911409919.5A CN201911409919A CN113121814A CN 113121814 A CN113121814 A CN 113121814A CN 201911409919 A CN201911409919 A CN 201911409919A CN 113121814 A CN113121814 A CN 113121814A
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- CN
- China
- Prior art keywords
- polyether amine
- polyetheramine
- mixture obtained
- tetrabromobisphenol
- epoxy
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- 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.)
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- 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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Abstract
The invention relates to a polyether amine modification method, which is characterized by comprising the following steps: s1, mixing tetrabromobisphenol A and an epoxy active diluent according to the mass ratio of 1: 1-2, and heating to 65-75 ℃ under a stirring state until the tetrabromobisphenol A is dissolved in the epoxy active diluent; s2, adding polyether amine into the mixture obtained in the S1, wherein the added polyether amine accounts for 1-2 wt% of the mixture; s3, reacting the mixture obtained in the step S2 at a constant temperature of 65-75 ℃ for 2-4 hours; s4, uniformly mixing the mixture obtained in the step S3 and polyether amine according to the mass part ratio of 1: 1-2, and reacting at the constant temperature of 85-95 ℃ for 3-5 hours.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a polyether amine modification method.
Background
The epoxy resin has the characteristics of mild curing, low viscosity, good color and luster, no whitening, tough cured material, high insulating strength and impact resistance, and is particularly suitable for electronic casting, potting and the like. However, epoxy resins have a low oxygen index and poor flame retardancy, and thus the applicability of epoxy resins is reduced.
The invention provides a method for modifying polyether amine, which is characterized in that tetrabromobisphenol A is used for modifying polyether amine, and the modified polyether amine is used as a curing agent to be applied to epoxy resin, so that the flame retardance of the epoxy resin is improved.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the following technical scheme: a method for modifying polyetheramines, comprising the steps of:
s1, mixing tetrabromobisphenol A and an epoxy active diluent according to the mass ratio of 1: 1-2, and heating to 65-75 ℃ under a stirring state until the tetrabromobisphenol A is dissolved in the epoxy active diluent;
s2, adding polyether amine into the mixture obtained in the S1, wherein the added polyether amine accounts for 1-2 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at a constant temperature of 65-75 ℃ for 2-4 hours;
s4, uniformly mixing the mixture obtained in the step S3 and polyether amine according to the mass part ratio of 1: 1-2, and reacting at the constant temperature of 85-95 ℃ for 3-5 hours.
Further, the epoxy reactive diluent contains an ether bond and an epoxy group.
Preferably, the epoxy reactive diluent is Butyl Glycidyl Ether (BGE) or 1, 4-butanediol diglycidyl ether.
Further, the polyetheramine in step S2 is one of polyetheramine D230, polyetheramine D400, or polyetheramine D403.
Further, the polyetheramine in step S4 is one of polyetheramine D230, polyetheramine D400, or polyetheramine D403.
Tetrabromobisphenol A has good compatibility with epoxy active diluent, and tetrabromobisphenol A can be easily dissolved in epoxy active diluent by heating and stirring. In step S2, a small amount of polyetheramine is added dropwise to promote the reaction of tetrabromobisphenol A and the epoxy reactive diluent to form the brominated epoxy diluent. In the step S4, the brominated epoxy diluent and the polyetheramine are mixed according to different mass ratios, the polyetheramine with different bromine contents can be formed through addition reaction, and the modified polyetheramine is used as a curing agent to be applied to the epoxy resin, so that the flame retardance of the cured epoxy resin can be improved.
The modified polyether amine is used as a curing agent to be applied to epoxy resin, and the adding method is consistent with the technical method of applying the unmodified polyether amine to the epoxy resin disclosed in the prior art.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
This example provides a method for modifying polyetheramine, comprising the steps of:
s1, mixing tetrabromobisphenol A and butyl glycidyl ether according to the mass part ratio of 1:1, heating to 70 ℃ under the stirring state until tetrabromobisphenol A is dissolved in butyl glycidyl ether;
s2, adding the polyether amine D230 into the mixture obtained in the S1, wherein the added polyether amine D230 accounts for 1 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at a constant temperature of 70 ℃ for 3 hours;
s4, uniformly mixing the mixture obtained in the step S3 and the polyether amine D230 in a mass portion ratio of 1:1, and reacting at the constant temperature of 90 ℃ for 4 hours to obtain the modified polyether amine D230 with the bromine content of 14.5%.
Example 2
This example provides a method for modifying polyetheramine, comprising the steps of:
s1, mixing tetrabromobisphenol A and 1, 4-butanediol diglycidyl ether according to the mass part ratio of 1:1, heating to 65 ℃ under the stirring state until the tetrabromobisphenol A is dissolved in the 1, 4-butanediol diglycidyl ether;
s2, adding the polyether amine D400 into the mixture obtained in the S1, wherein the added polyether amine D400 accounts for 2 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at a constant temperature of 65 ℃ for 4 hours;
s4, uniformly mixing the mixture obtained in the step S3 and the polyether amine D400 according to the mass portion ratio of 1:1, and reacting at the constant temperature of 85 ℃ for 5 hours to obtain the modified polyether amine D400 with the bromine content of 14.5%.
Example 3
This example provides a method for modifying polyetheramine, comprising the steps of:
s1, mixing tetrabromobisphenol A and butyl glycidyl ether according to the mass part ratio of 1:2, heating to 75 ℃ under the stirring state until tetrabromobisphenol A is dissolved in butyl glycidyl ether;
s2, adding the polyether amine D403 into the mixture obtained in the S1, wherein the added polyether amine D403 accounts for 2 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at the constant temperature of 75 ℃ for 2 hours;
s4, uniformly mixing the mixture obtained in the step S3 and the polyether amine D403 in a mass part ratio of 1:2, and reacting at the constant temperature of 95 ℃ for 3 hours to obtain the modified polyether amine D403 with the bromine content of 7.4%.
Example 4
This example provides a method for modifying polyetheramine, comprising the steps of:
s1, mixing tetrabromobisphenol A and 1, 4-butanediol diglycidyl ether according to the mass part ratio of 1:1, heating to 68 ℃ under the stirring state until the tetrabromobisphenol A is dissolved in the 1, 4-butanediol diglycidyl ether;
s2, adding the polyether amine D230 into the mixture obtained in the S1, wherein the added polyether amine D230 accounts for 1.6 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at a constant temperature of 72 ℃ for 3 hours;
s4, uniformly mixing the mixture obtained in the step S3 and the polyether amine D403 in a mass portion ratio of 1:1.6, and reacting at the constant temperature of 92 ℃ for 5 hours to obtain the modified polyether amine D403 with the bromine content of 10.4%.
Example 5
This example provides a method for modifying polyetheramine, comprising the steps of:
s1, mixing tetrabromobisphenol A and butyl glycidyl ether according to the mass part ratio of 1:1.5, heating to 68 ℃ under the stirring state until the tetrabromobisphenol A is dissolved in the butyl glycidyl ether;
s2, adding the polyether amine D400 into the mixture obtained in the S1, wherein the added polyether amine D400 accounts for 1.5 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at a constant temperature of 65 ℃ for 4 hours;
s4, uniformly mixing the mixture obtained in the step S3 and the polyether amine D230 according to the mass part ratio of 1:1.5, and reacting at the constant temperature of 95 ℃ for 3 hours to obtain the modified polyether amine D230 with the bromine content of 12.6%. .
Comparative example 1
The modified polyetheramine D230 prepared in example 1 and the modified polyetheramines D230, D400 and D403 were added as curing agents to epoxy resins, respectively, and after the epoxy resins were cured, the flame retardancy of the cured epoxy resins was measured by the horizontal flame test method of UL94HB in the fire rating of UL94, and the results were as follows:
the modified polyether amine is added into the epoxy resin, so that the flame retardance is remarkably improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (5)
1. A polyether amine modification method is characterized by comprising the following steps:
s1, mixing tetrabromobisphenol A and an epoxy active diluent according to the mass ratio of 1: 1-2, and heating to 65-75 ℃ under a stirring state until the tetrabromobisphenol A is dissolved in the epoxy active diluent;
s2, adding polyether amine into the mixture obtained in the S1, wherein the added polyether amine accounts for 1-2 wt% of the mixture;
s3, reacting the mixture obtained in the step S2 at a constant temperature of 65-75 ℃ for 2-4 hours;
s4, uniformly mixing the mixture obtained in the step S3 and polyether amine according to the mass part ratio of 1: 1-2, and reacting at the constant temperature of 85-95 ℃ for 3-5 hours.
2. The method for modifying polyether amine according to claim 1, wherein: the epoxy reactive diluent comprises an ether linkage and an epoxy group.
3. The method for modifying polyether amine according to claim 2, wherein: the epoxy reactive diluent is butyl glycidyl ether or 1, 4-butanediol diglycidyl ether.
4. The method for modifying polyether amine according to claim 3, wherein: the polyetheramine in the step S2 is one of polyetheramine D230, polyetheramine D400, or polyetheramine D403.
5. The method for modifying polyether amine according to claim 4, wherein: the polyetheramine in the step S4 is one of polyetheramine D230, polyetheramine D400, or polyetheramine D403.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911409919.5A CN113121814A (en) | 2019-12-31 | 2019-12-31 | Polyether amine modification method |
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| CN201911409919.5A CN113121814A (en) | 2019-12-31 | 2019-12-31 | Polyether amine modification method |
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| CN113121814A true CN113121814A (en) | 2021-07-16 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803882A (en) * | 2005-11-24 | 2006-07-19 | 武汉理工大学 | Alpha, omega end amino polyether used as epoxy resin curing agent and method for preparing the same |
| TW201037010A (en) * | 2009-04-01 | 2010-10-16 | Univ Nat Taiwan | Polyoxyalkylene-amine phosphorous based flame retardant and polymer material applying the same |
| US20150259466A1 (en) * | 2012-09-28 | 2015-09-17 | Dow Global Technologies Llc | Adduct compositions |
-
2019
- 2019-12-31 CN CN201911409919.5A patent/CN113121814A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803882A (en) * | 2005-11-24 | 2006-07-19 | 武汉理工大学 | Alpha, omega end amino polyether used as epoxy resin curing agent and method for preparing the same |
| TW201037010A (en) * | 2009-04-01 | 2010-10-16 | Univ Nat Taiwan | Polyoxyalkylene-amine phosphorous based flame retardant and polymer material applying the same |
| US20150259466A1 (en) * | 2012-09-28 | 2015-09-17 | Dow Global Technologies Llc | Adduct compositions |
Non-Patent Citations (1)
| Title |
|---|
| 陈红等: "磷系阻燃环氧树脂与固化剂", 《热固性树脂》 * |
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Application publication date: 20210716 |
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