CN107573334B - Monofunctional benzoxazine containing alicyclic hydrocarbon imide group and preparation method thereof - Google Patents
Monofunctional benzoxazine containing alicyclic hydrocarbon imide group and preparation method thereof Download PDFInfo
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- CN107573334B CN107573334B CN201710229092.4A CN201710229092A CN107573334B CN 107573334 B CN107573334 B CN 107573334B CN 201710229092 A CN201710229092 A CN 201710229092A CN 107573334 B CN107573334 B CN 107573334B
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- aminophenol
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Abstract
The invention provides a monofunctional benzoxazine containing alicyclic hydrocarbon imide group and a preparation method thereof. The preparation method consists of two steps. The first step is as follows: reacting to synthesize a phenolic compound containing an alicyclic hydrocarbon imide structure; the second step is that: the method is characterized in that a monofunctional benzoxazine monomer of alicyclic hydrocarbon imide groups is synthesized by reacting phenolic compounds containing alicyclic hydrocarbon imide, amine compounds and paraformaldehyde as raw materials. The invention has the advantages that: the six-membered alicyclic hydrocarbon imide group is adopted, the processability of imide benzoxazine resin is effectively improved, and part of alicyclic hydrocarbon contains a carbon-carbon double bond structure, so that the benzoxazine ring is subjected to ring opening crosslinking and the end sealing group can be subjected to secondary crosslinking when the benzoxazine is heated and cured, and the thermal stability of the resin is greatly improved. The processing temperature window of the resin obtained by the invention is widened, and the processing and forming are facilitated. The method has simple preparation process and low requirement on equipment, and can be used for industrial production.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin and preparation thereof, and particularly relates to monofunctional benzoxazine containing alicyclic hydrocarbon imide groups and a preparation method thereof.
Background
The traditional phenolic resin has the advantages of easily available raw materials, low price, simple production process and equipment, and wide application because the prepared product has excellent mechanical property, weather resistance, cold resistance, heat resistance and dimensional stability. However, with the increasing application fields and performance requirements, the phenolic resin does not meet the requirements of some fields. To meet the requirements of higher decomposition temperature, good heat recovery, sufficient coefficient of friction, better wear resistance and lower noise, benzoxazines were unexpectedly discovered by Holly and Cope. Benzoxazine compound is an intermediate containing heterocyclic structure, is generally prepared by condensation reaction of phenolic compound, primary amine compound and formaldehyde, and then is subjected to ring opening polymerization under the action of heating or catalyst to generate a nitrogen-containing network structure similar to phenolic resin, which is called polybenzoxazine.
There are a number of patents directed to benzoxazines containing imide or amide structures. For example, Chinese patent invention No. 2009100975549.6, Bibenzoxazine containing imide Structure and its preparation method (No. CN 101857592A), discloses a Bibenzoxazine containing imide Structure and its preparation method, which introduces imide structure into the molecular chain of benzoxazine compound, increases the heat resistance and mechanical property of polymer, has excellent comprehensive properties, and is suitable for resin matrix of high-performance composite material; the invention patent with application number 200610020900.8, namely 'benzoxazine containing maleimide and allyl ether and preparation method thereof', discloses benzoxazine containing maleimide and allyl ether, and the benzoxazine prepared by the invention patent has the advantages of greatly improved thermal stability, few reaction steps of the preparation method and low production cost.
These patents improve the heat resistance of the polymer by modifying the structure of the benzoxazine monomer, but are not ideal enough, and especially the processing window of the resin monomer is often only fifty degrees or more, which is not favorable for molding processing. In addition, the benzoxazine monomer prepared by adopting a phenol source containing a six-membered alicyclic hydrocarbon and imide connecting structural group and performance are not reported at present.
Disclosure of Invention
Aiming at the existing defects of benzoxazine resin, the invention introduces six-membered alicyclic hydrocarbon structure to simplify the synthesis process of benzoxazine, and the introduced six-membered alicyclic hydrocarbon structure makes up the performance defects caused by low molecular weight and high molecular rigidity of the traditional imide benzoxazine monomer, improves the processability of the benzoxazine resin and endows the benzoxazine resin with specific performance.
The molecular formula of the benzoxazine which achieves the performance is as follows:
wherein R is1-is one of the following:
R1in the ortho, meta or para position to the oxygen atom;
to achieve another object of the present invention, there is provided a method for preparing monofunctional benzoxazine containing alicyclic hydrocarbon imide group, comprising the steps of:
(1) the method takes one of o-aminophenol, m-aminophenol and p-aminophenol and an anhydride compound as raw materials to react and synthesize the phenolic compound containing the alicyclic hydrocarbon imide structure, and the reaction equation is as follows:
wherein R is one of the following:
R1-is one of the following:
R1at the ortho, meta or para position relative to the phenolic hydroxyl group.
(2) Taking a phenolic compound containing alicyclic hydrocarbon imide, an amine compound and paraformaldehyde as raw materials, and reacting to synthesize the monofunctional benzoxazine of the alicyclic hydrocarbon imide group, wherein the reaction equation is as follows:
wherein R is1-is one of the following:
R1in the ortho, meta or para position to the oxygen atom;
the specific operation steps are as follows:
(1) one of o-aminophenol, m-aminophenol and p-aminophenol and an anhydride compound are mixed according to a proper molar ratio, added into a reaction system with glacial acetic acid as a solvent, then the reaction system is filled with nitrogen or other inert protective gases, the temperature of the system is raised to 100-120 ℃ from room temperature, and the total reaction time is 6-8 hours. After the reaction is stopped, precipitating the reaction solution by deionized water, washing, filtering and drying to obtain the phenolic compound containing alicyclic hydrocarbon imide groups.
One of o-aminophenol, m-aminophenol and p-aminophenol and the acid anhydride compound are mixed according to a molar ratio of 1: 1-1: 1.3; the preferred ratio is 1: 1.1.
(2) mixing phenolic compounds containing imide alicyclic hydrocarbon, amine compounds and paraformaldehyde according to a proper molar ratio, adding the mixture into a low-polarity solvent, heating to raise the temperature, reacting the reaction system at 100-120 ℃ for 8-12 hours, washing the reaction solution with alkali liquor A for 2-3 times after the reaction is stopped, and suspending and evaporating the solvent to obtain a precipitate to obtain the monofunctional benzoxazine.
The molar ratio of the alicyclic hydrocarbon imide phenol compound containing to the amine compound containing to the paraformaldehyde is 1:1: 2-1: 1:2.2, and the preferable ratio is 1:1:2.1.
The low-polarity solvent is toluene or xylene.
The alkali liquor A is one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
Compared with the prior art, the invention has the advantages that: the six-membered alicyclic hydrocarbon imide group is adopted, the processability of imide benzoxazine resin is effectively improved, and part of alicyclic hydrocarbon contains a carbon-carbon double bond structure, so that the benzoxazine ring is subjected to ring opening crosslinking and the end sealing group can be subjected to secondary crosslinking when the benzoxazine is heated and cured, and the thermal stability of the resin is greatly improved. The processing temperature window of the resin obtained by the invention is widened, and the processing and forming are facilitated. The method has simple preparation process and low requirement on equipment, and can be used for industrial production.
Drawings
FIG. 1 is an infrared spectrum of a benzoxazine monomer obtained in example 1;
FIG. 2 is a DSC chart of the benzoxazine resin obtained in example 1.
Detailed Description
The present invention is further described below with reference to specific examples. It is to be noted that: the following examples are intended to illustrate the invention further and are not intended to limit the scope of the invention. After reading the present invention, those skilled in the art can make various improvements and modifications without departing from the spirit of the present invention, and such improvements and modifications are within the scope of the present invention as claimed.
Example one
10.91g of 2-aminophenol, 15.22g of tetrahydrophthalic anhydride and 250.00ml of acetic acid are added into a reaction bottle containing a stirrer, a thermometer and a condenser tube, the reaction device is vacuumized by a vacuum pump, and then nitrogen is filled into the reaction bottle for three times. Under the protection of nitrogen gas, the temperature is gradually increased to 120 ℃ for reaction for 6 hours. Then 300ml of deionized water was added to obtain a large amount of precipitate. After suction filtration, washing three times with a large amount of water and ethanol, and drying in a vacuum oven at 50 ℃ to obtain 21.63g of the product with a yield of 89%. The reaction equation is as follows:
12.16g of the alicyclic hydrocarbon imide group-containing phenolic compound obtained in the above step, 4.66g of aniline, 3.13g of paraformaldehyde and 100ml of xylene were weighed and charged into a reaction flask equipped with a stirrer, a thermometer and a condenser, and heated to 120 ℃ at a rate of 10 ℃/h to react for 8 hours. After the reaction was completed, the solution was cooled to room temperature, washed 3 times with a 5% by mass sodium bicarbonate solution, and then dried by evaporation to obtain 16.38g of a product with a yield of 91%. The reaction equation is as follows:
the Fourier infrared spectrum, differential scanning calorimetry and the thermal weight loss characterization results of the cured resin of the product are shown in the attached figures 1 and 2. FIG. 1 is an infrared spectrum of 935cm-1The peak is the characteristic peak of oxazine ring. FIG. 2 is a DSC chart obtained by differential scanning calorimetry, and it can be seen that the maximum curing peak temperature of the resin is 249.8 ℃.
After the benzoxazine obtained in the embodiment is subjected to thermal ring-opening curing, the glass transition temperature of the benzoxazine is 278 ℃, the 5% thermal weight loss temperature of the benzoxazine is 368 ℃, and the carbon residue rate of the benzoxazine at 800 ℃ is 55%.
Example two
The tetrahydrophthalic anhydride was replaced with 1, 2-cyclohexanedianhydride, the aniline was replaced with m-fluoroaniline in example 1, the amounts of the reactants were varied accordingly, and the other procedures were the same as in example 1.
Wherein, the specific structural formula of the 1, 2-cyclohexanedianhydride is as follows:
the specific structural formula of the m-fluoroaniline is as follows:
in the first reaction step, the amounts of reactants were changed to: 15.42g of 1, 2-cyclohexanedicarboxylic anhydride, 10.91g of 2-aminophenol and 250.00ml of acetic acid are used to obtain 20.85g of a product with the yield of 85%.
In the second reaction step, the amounts of reactants were changed to: the amount of phenol obtained by the above reaction was 12.26g, that of paraformaldehyde was 3.13g, and that of m-fluoroaniline was 4.66g, to obtain 1.77g of a product with a yield of 83%.
The structural formula of the obtained oxazine monomer is as follows:
after the benzoxazine obtained in the example is subjected to ring-opening thermal curing, the glass transition temperature is 267 ℃, the 5% thermal weight loss temperature is 359 ℃, and the carbon residue rate at 800 ℃ is 51%.
EXAMPLE III
The tetrahydrophthalic anhydride of example 1 was replaced with 3-methyltetrahydrophthalic anhydride, the amounts of reactants were varied accordingly, and the other procedures were the same as those of example 1.
Wherein, the specific chemical structural formula of the 3-methyl tetrahydrophthalic anhydride is as follows:
in the first reaction step, the amounts of reactants were changed to: 16.62g of 3-methyltetrahydrophthalic anhydride, 10.91g of 2-aminophenol and 250.00ml of acetic acid were added to obtain 23.67g of a product with a yield of 92%.
In the second reaction step, the amounts of reactants were changed to: the amount of phenol obtained in the previous reaction was 12.86g, that of paraformaldehyde was 3.13g, and that of aniline was 5.56g, to obtain 16.47g of a product with a yield of 88%.
The structural formula of the obtained product is as follows:
after the benzoxazine obtained in the embodiment is subjected to thermal ring-opening curing, the glass transition temperature is 289 ℃, the 5% thermal weight loss temperature is 379 ℃, and the carbon residue rate at 800 ℃ is 60%.
Claims (9)
1. A monofunctional benzoxazine containing alicyclic hydrocarbon imide groups characterized in that: the molecular formula of the monofunctional benzoxazine is as follows:
wherein R is1-is one of the following:
R1in the ortho, meta or para position to the oxygen atom;
2. the method for preparing monofunctional benzoxazine containing alicyclic hydrocarbon imide group according to claim 1, comprising the steps of:
(1) the method takes one of o-aminophenol, m-aminophenol and p-aminophenol and an anhydride compound as raw materials to react and synthesize the phenolic compound containing the alicyclic hydrocarbon imide structure, and the reaction equation is as follows:
wherein R is one of the following:
R1-is one of the following:
R1at the ortho, meta or para position of the phenolic hydroxyl group;
(2) taking a phenolic compound containing alicyclic hydrocarbon imide, an amine compound and paraformaldehyde as raw materials, and reacting to synthesize the monofunctional benzoxazine of the alicyclic hydrocarbon imide group, wherein the reaction equation is as follows:
wherein R is1-is one of the following:
R1in the ortho, meta or para position to the oxygen atom;
3. the preparation method according to claim 2, characterized by the following specific steps:
(1) mixing one of o-aminophenol, m-aminophenol and p-aminophenol and an anhydride compound according to a proper molar ratio, adding the mixture into a reaction system taking glacial acetic acid as a solvent, filling nitrogen or other inert protective gases into the reaction system, heating the system from room temperature to 100-120 ℃, wherein the total reaction time is 6-8 hours, stopping the reaction, and precipitating, washing, filtering and drying the reaction solution by deionized water to obtain the phenolic compound containing the alicyclic hydrocarbon imide group;
(2) mixing phenolic compounds containing imide alicyclic hydrocarbon, amine compounds and paraformaldehyde according to a proper molar ratio, adding the mixture into a low-polarity solvent, heating to raise the temperature, reacting the reaction system at 100-120 ℃ for 8-12 hours, washing the reaction solution with alkali liquor A for 2-3 times after the reaction is stopped, and suspending and evaporating the solvent to obtain a precipitate to obtain the monofunctional benzoxazine.
4. The production method according to claim 3, characterized in that: in the step (1), the molar ratio of one of o-aminophenol, m-aminophenol and p-aminophenol to the acid anhydride compound is 1: 1-1: 1.3.
5. the method of claim 4, wherein: the molar ratio of one of o-aminophenol, m-aminophenol and p-aminophenol to the acid anhydride compound is 1: 1.1.
6. the production method according to claim 3, characterized in that: in the step (2), the molar ratio of the alicyclic hydrocarbon imide phenol compound and the amine compound to the paraformaldehyde is 1:1: 2-1: 1: 2.2.
7. The method of claim 6, wherein: the molar ratio of the alicyclic hydrocarbon imide phenol compound containing to the amine compound to the paraformaldehyde is 1:1:2.1.
8. The production method according to claim 3, characterized in that: in the step (2), the low-polarity solvent is toluene or xylene; the alkali liquor A is one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
9. Use of a monofunctional benzoxazine containing alicyclic hydrocarbon imide group according to claim 1 as a polymer-based matrix material in automotive, aerospace and electronic packaging applications.
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| CN111269395A (en) * | 2020-04-14 | 2020-06-12 | 镇江利德尔复合材料有限公司 | Benzoxazine epoxy resin copolymer containing phenolic hydroxyl and preparation method thereof |
| CN114195803B (en) * | 2021-08-24 | 2024-04-02 | 镇江利德尔复合材料有限公司 | Difunctional benzoxazine resin based on coumarin bio-base and preparation method thereof |
| CN117362285B (en) * | 2023-12-06 | 2024-02-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
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| CN106220620A (en) * | 2016-08-30 | 2016-12-14 | 常州市宏发纵横新材料科技股份有限公司 | A kind of ortho position maleimide monofunctional benzoxazine monomer and preparation method thereof |
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| Synthesis of High Thermal Stability Polybenzoxazoles via Ortho-Imide-Functional Benzoxazine Monomers;Kan Zhang etal.;《JOURNAL OF POLYMER SCIENCE，PART A: POLYMER CHEMISTRY》;20151231;1-9 * |
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