CN109265634B - Linseed oil modified waterborne benzoxazine resin and preparation method thereof - Google Patents
Linseed oil modified waterborne benzoxazine resin and preparation method thereof Download PDFInfo
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- CN109265634B CN109265634B CN201811292907.4A CN201811292907A CN109265634B CN 109265634 B CN109265634 B CN 109265634B CN 201811292907 A CN201811292907 A CN 201811292907A CN 109265634 B CN109265634 B CN 109265634B
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- linseed oil
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20
Abstract
The invention discloses a linseed oil modified water-based benzoxazine resin and a preparation method thereof, wherein the linseed oil modified water-based benzoxazine resin is prepared from six components of formaldehyde, ethylenediamine, bisphenol A, a silane coupling agent, linseed oil and a water-based functional monomer substance, and the weight ratio of the formaldehyde, the ethylenediamine, the bisphenol A, the silane coupling agent, the linseed oil and the water-based functional monomer substance is (6), (1-2): (0.5-3):(0-2):(0-3):(1-4). In the preparation process, water is used as a dispersion medium, no toxic solvent is used, the preparation process is environment-friendly and pollution-free, and the prepared linseed oil modified waterborne benzoxazine resin has good water solubility, does not need to be added with an organic solvent in the use process, can be applied to a waterborne system, and is healthy and environment-friendly.
Description
Technical Field
The invention relates to the field of fine chemical engineering, and particularly relates to linseed oil modified waterborne benzoxazine resin and a preparation method thereof.
Background
Benzoxazine resin is a new-developed phenolic resin, and is generally prepared by condensation reaction of phenolic compounds, primary amine compounds and formaldehyde. The benzoxazine resin has the advantages of flame retardance, high curing speed, high hardness, high heat resistance level, excellent dielectric property and the like, and can be widely applied to the fields of civil use, aviation, military industry and the like as other resin curing agents or composite material resin matrixes. Because of the hydrophobicity of the oxazine ring structure, organic solvents such as benzene, toluene and the like are generally selected as diluents for benzoxazine resins. The existence of the organic solvent can cause the problems of environmental pollution, harm to human health and the like. Meanwhile, most of the existing benzoxazine resins have the problems of high brittleness and poor flexibility, so that the application of the benzoxazine resins in various fields is greatly limited.
Regarding the water-based benzoxazine resin, patent CN 103951808B discloses a "water-soluble benzoxazine resin and a preparation method thereof", and the prepared benzoxazine resin has good water solubility and can be rapidly cured at a lower temperature. However, the properties of the prepared water-soluble benzoxazine, including film-forming properties, flame retardancy and the like, are not specifically described.
Disclosure of Invention
The invention aims to provide a benzoxazine resin capable of having water solubility under the condition of keeping high flame retardance and a preparation method thereof.
The above purpose is realized by the following technical scheme:
the linseed oil modified water-based benzoxazine resin is prepared from six components of formaldehyde, ethylenediamine, bisphenol A, a silane coupling agent, linseed oil and a water-based functional monomer substance, wherein the weight ratio of the formaldehyde, the ethylenediamine, the bisphenol A, the silane coupling agent, the linseed oil and the water-based functional monomer substance is 6 (1-2): (0.5-3):(0-2):(0-3):(1-4).
The silane coupling agent is 3-aminopropyl trimethoxy silane and 3-aminopropyl dimethylethoxy silane.
The water-based functional monomer is 1, 4-butanediol-2-sodium sulfonate and N-methyldiethanolamine.
The preparation method of the linseed oil modified waterborne benzoxazine resin comprises the following steps:
(1) at room temperature, putting 37 wt% of formaldehyde aqueous solution into a reactor, and adjusting the pH value to 8-10 by using triethylamine;
(2) adding ethylenediamine, heating to 40 ℃, and stirring for reaction for 10-60 min;
(3) adding bisphenol A, and violently stirring and heating to 80-90 ℃;
(4) adding a silane coupling agent, and stirring for reacting for 2-4 h;
(5) adding linseed oil, heating to 100 ℃, and continuing to react for 1-2 h;
(6) adding water-based functional monomer, and reacting for 0.5-2h at the temperature of 95 ℃ with stirring; distilling under reduced pressure for 0.5-2h, cooling to 30 deg.C, and discharging to obtain viscous dark yellow liquid, i.e. linseed oil modified water-based benzoxazine resin.
The vacuum degree of the reduced pressure distillation under certain pressure is 0.05-0.09 MPa.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the invention relates to a linseed oil modified waterborne benzoxazine resin and a preparation method thereof. The prepared linseed oil modified waterborne benzoxazine resin has good water solubility, does not need to add an organic solvent in the use process, can be applied to a waterborne system, and is healthy and environment-friendly;
2. the linseed oil modified waterborne benzoxazine resin prepared by the method introduces linseed oil soft segment, has good flexibility, and obviously improves the film forming property of the conventional benzoxazine resin;
3. the linseed oil modified waterborne benzoxazine resin prepared by the method introduces the siloxane coupling agent, improves the crosslinking density of the resin and the adhesive force with a base material, has good flame retardance, does not contain halogen and phosphorus elements, does not release harmful gas in the combustion process, and has good environmental protection performance;
4. the linseed oil modified waterborne benzoxazine resin prepared by the method has good water solubility, so that the linseed oil modified waterborne benzoxazine resin can be used as a curing agent of a waterborne system, does not generate any small molecular substance in the curing process, and has good environmental protection property. Belongs to green environment-friendly materials;
5. the linseed oil modified waterborne benzoxazine resin prepared by the method has good film forming property, and can be used as a single film forming substance to be applied to waterborne coatings.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the technical scheme in the embodiment of the invention will be clearly and completely described in the following with the embodiment of the invention.
Example one
At room temperature, putting 37 wt% of formaldehyde aqueous solution into a reactor, adjusting the pH value to 8 with triethylamine, adding ethylenediamine, heating to 40 ℃, stirring for reaction for 10min, adding bisphenol A, violently stirring, heating to 80 ℃, adding 3-aminopropyltrimethoxysilane serving as a silane coupling agent, stirring for reaction for 2h, adding linseed oil, heating to 100 ℃, continuing to react for 2h, adding 1, 4-butanediol-2-sodium sulfonate serving as a water-based functional monomer, and keeping the temperature and stirring for reaction for 1h at 95 ℃; carrying out reduced pressure distillation for 2h under the vacuum degree of 0.05MPa, cooling to 30 ℃, discharging to obtain a viscous dark yellow liquid, namely linseed oil modified water-based benzoxazine resin, namely resin A, wherein the ratio of the amount of formaldehyde, ethylenediamine, bisphenol A, silane coupling agent, linseed oil and water-based functional monomer substances is 6:1:1:1: 2.
Example two
At room temperature, putting 37 wt% of formaldehyde aqueous solution into a reactor, adjusting the pH value to 10 with triethylamine, adding ethylenediamine, heating to 40 ℃, stirring and reacting for 30min, adding bisphenol A, violently stirring and heating to 90 ℃, adding 3-aminopropyl dimethyl ethoxy silane serving as a silane coupling agent, stirring and reacting for 2h, adding linseed oil, heating to 100 ℃, continuing to react for 1h, adding 1, 4-butanediol-2-sodium sulfonate serving as a water-based functional monomer, and keeping the temperature and stirring and reacting for 1h at 95 ℃; carrying out reduced pressure distillation for 1h under the vacuum degree of 0.09MPa, cooling to 30 ℃, discharging to obtain a viscous dark yellow liquid, namely linseed oil modified water-based benzoxazine resin named as resin B, wherein the ratio of the amount of formaldehyde, ethylenediamine, bisphenol A, silane coupling agent, linseed oil and water-based functional monomer substances is 6:1: 1.5:1.5: 3.
EXAMPLE III
At room temperature, putting 37 wt% of formaldehyde aqueous solution into a reactor, adjusting the pH value to 10 with triethylamine, adding ethylenediamine, heating to 40 ℃, stirring and reacting for 60min, adding bisphenol A, violently stirring and heating to 90 ℃, adding 3-aminopropyl dimethyl ethoxy silane serving as a silane coupling agent, stirring and reacting for 2h, adding linseed oil, heating to 100 ℃, continuing to react for 1h, adding an aqueous functional monomer N-methyldiethanolamine, and keeping the temperature and stirring and reacting for 1h at 95 ℃; carrying out reduced pressure distillation for 2h under the vacuum degree of 0.06MPa, cooling to 30 ℃, discharging to obtain a viscous dark yellow liquid, namely linseed oil modified water-based benzoxazine resin named as resin C, wherein the ratio of the amount of formaldehyde, ethylenediamine, bisphenol A, silane coupling agent, linseed oil and water-based functional monomer substances is 6:1: 1.5:1.5: 3.
Example four
At room temperature, putting 37 wt% of formaldehyde aqueous solution into a reactor, adjusting the pH value to 8 with triethylamine, adding ethylenediamine, heating to 40 ℃, stirring and reacting for 10min, adding bisphenol A, violently stirring and heating to 80 ℃, adding 3-aminopropyltrimethoxysilane serving as a silane coupling agent, stirring and reacting for 2h, adding linseed oil, heating to 100 ℃, continuing to react for 2h, adding N-methyldiethanolamine serving as a water-based functional monomer, and keeping the temperature and stirring and reacting for 1h at 95 ℃; carrying out reduced pressure distillation for 1h under the vacuum degree of 0.08MPa, cooling to 30 ℃, discharging to obtain a viscous dark yellow liquid, namely linseed oil modified water-based benzoxazine resin named as resin D, wherein the ratio of the amount of formaldehyde, ethylenediamine, bisphenol A, silane coupling agent, linseed oil and water-based functional monomer substances is 6:1:1:1: 2.
Summary of the invention
1. Water solubility testing of the products
At room temperature of 25 ℃, 100g of distilled water is taken into a beaker under the standard atmospheric pressure, 0.1g of the waterborne benzoxazine resin synthesized in the first to fourth examples is dripped into the beaker each time, and the mixture is stirred until the waterborne benzoxazine resin is completely dissolved. And repeating the operation until the aqueous benzoxazine resin can not be completely dissolved after continuous stirring, recording the mass of the aqueous benzoxazine resin which is dropwise stirred until the aqueous benzoxazine resin is completely dissolved, and calculating the solubility of the embodiment.
The solubility of the resin A, B, C, D in water is 18g, 20g, 12g and 14g respectively, which shows that the prepared linseed oil modified water-based benzoxazine resin has good water solubility.
2. Flame retardancy test of the product
The linseed oil modified waterborne benzoxazine resin A, B, C, D obtained in the first to fourth examples was added to an epoxy resin, acetone was added to the epoxy resin and the mixture was stirred uniformly, and then the mixture was put into a vacuum drying oven to remove air bubbles in the epoxy resin, wherein the addition amount of the benzoxazine resin was 20 wt%. Finally, the liquid is poured into a mould and is cured for 2h at 120 ℃ and is continuously cured for 2h at 180 ℃. After curing, the cured product was cooled to room temperature, and the samples were subjected to a Limiting Oxygen Index (LOI) test using a JF-3 type oxygen index tester, and the results are shown in the following table.
3. Product flexibility testing
The flexibility of the linseed oil modified waterborne benzoxazine resin is tested according to the national standard GB/T7193-2008, and the results are shown in the following table.
As can be seen from the data in the table above, the synthesized linseed oil modified aqueous benzoxazine resin exhibits good flexibility.
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 skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; 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 (2)
1. The linseed oil modified water-based benzoxazine resin is characterized by being prepared from six components of formaldehyde, ethylenediamine, bisphenol A, a silane coupling agent, linseed oil and a water-based functional monomer substance, wherein the weight ratio of the formaldehyde, the ethylenediamine, the bisphenol A, the silane coupling agent, the linseed oil and the water-based functional monomer substance is (6), (1-2): (0.5-3): (0-2): 0-3): 1-4);
the silane coupling agent is 3-aminopropyl trimethoxy silane and 3-aminopropyl dimethylethoxy silane;
the water-based functional monomer is 1, 4-butanediol-2-sodium sulfonate and N-methyldiethanolamine;
the preparation method of the linseed oil modified waterborne benzoxazine resin comprises the following steps:
(1) at room temperature, putting 37 wt% of formaldehyde aqueous solution into a reactor, and adjusting the pH value to 8-10 by using triethylamine;
(2) adding ethylenediamine, heating to 40 ℃, and stirring for reaction for 10-60 min;
(3) adding bisphenol A, and violently stirring and heating to 80-90 ℃;
(4) adding a silane coupling agent, and stirring for reacting for 2-4 h;
(5) adding linseed oil, heating to 100 ℃, and continuing to react for 1-2 h;
(6) adding water-based functional monomer, and reacting for 0.5-2h at the temperature of 95 ℃ with stirring; distilling under reduced pressure for 0.5-2h, cooling to 30 deg.C, and discharging to obtain viscous dark yellow liquid, i.e. linseed oil modified water-based benzoxazine resin.
2. The linseed oil modified water-based benzoxazine resin according to claim 1, wherein the vacuum degree of vacuum distillation under a certain pressure is 0.05-0.09 MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811292907.4A CN109265634B (en) | 2018-11-01 | 2018-11-01 | Linseed oil modified waterborne benzoxazine resin and preparation method thereof |
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| CN201811292907.4A CN109265634B (en) | 2018-11-01 | 2018-11-01 | Linseed oil modified waterborne benzoxazine resin and preparation method thereof |
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| CN109265634A CN109265634A (en) | 2019-01-25 |
| CN109265634B true CN109265634B (en) | 2021-05-18 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999050352A1 (en) * | 1998-04-01 | 1999-10-07 | Borden Chemical, Inc. | A benzoxazine polymer composition |
| CN1259530A (en) * | 1999-01-06 | 2000-07-12 | 四川联合大学 | Vegetable oil modified benzoxazine intermediate product and its prepn. method and use |
| JP3550814B2 (en) * | 1995-08-21 | 2004-08-04 | 日立化成工業株式会社 | Thermosetting resin, cured product thereof, and method for producing this thermosetting resin |
| CN102584884A (en) * | 2011-12-19 | 2012-07-18 | 中科院广州化学有限公司 | Benzoxazine monomer, benzoxazine precursor and low-dielectric benzoxazine resin |
| CN103951808A (en) * | 2014-01-21 | 2014-07-30 | 哈尔滨理工大学 | Water-soluble benzoxazine resin and preparation method thereof |
-
2018
- 2018-11-01 CN CN201811292907.4A patent/CN109265634B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3550814B2 (en) * | 1995-08-21 | 2004-08-04 | 日立化成工業株式会社 | Thermosetting resin, cured product thereof, and method for producing this thermosetting resin |
| WO1999050352A1 (en) * | 1998-04-01 | 1999-10-07 | Borden Chemical, Inc. | A benzoxazine polymer composition |
| CN1259530A (en) * | 1999-01-06 | 2000-07-12 | 四川联合大学 | Vegetable oil modified benzoxazine intermediate product and its prepn. method and use |
| CN102584884A (en) * | 2011-12-19 | 2012-07-18 | 中科院广州化学有限公司 | Benzoxazine monomer, benzoxazine precursor and low-dielectric benzoxazine resin |
| CN103951808A (en) * | 2014-01-21 | 2014-07-30 | 哈尔滨理工大学 | Water-soluble benzoxazine resin and preparation method thereof |
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