CN116239757A - Brominated epoxy resin bio-based derivative and preparation method and application thereof - Google Patents
Brominated epoxy resin bio-based derivative and preparation method and application thereof Download PDFInfo
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- CN116239757A CN116239757A CN202310250781.9A CN202310250781A CN116239757A CN 116239757 A CN116239757 A CN 116239757A CN 202310250781 A CN202310250781 A CN 202310250781A CN 116239757 A CN116239757 A CN 116239757A
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention provides a brominated epoxy resin bio-based derivative, a preparation method and application thereof, which solve the problem that the existing brominated epoxy resin is completely derived from petroleum base and depends on nonrenewable petroleum resources, and synthesize the brominated epoxy resin bio-based derivative containing Br and P synergistic carbon-containing fifteen flexible groups, and the brominated epoxy resin bio-based derivative has the structural formula shown in the following formula (I):
wherein R is 1 、R 2 The structure is independently a bond wire structure shown in any one of the following formulas (II), (III), (IV) and (V): alternatively, R 1 、R 2 Independently is a bond line type structure shown in any one of the following formulas (V), (VII), (VIII) and (IX):
the invention also discloses a preparation method and application of the brominated epoxy resin bio-based derivative, and the brominated epoxy resin bio-based derivative can be widely applied to the technical field of high polymer materials.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a brominated epoxy resin bio-based derivative, a preparation method and application thereof.
Background
The brominated epoxy resin is an epoxy resin material containing bromine in a molecular structure, has excellent electrical insulation property and adhesion property of common epoxy resin, has excellent self-flame retardance, and is widely applied to various flame-retardant electronic elements.
The brominated epoxy resin is prepared by a substitution reaction of tetrabromobisphenol A and epichlorohydrin, and although the brominated epoxy resin has the excellent performance, the production of the epoxy monomer mainly depends on non-renewable petroleum resources, is not beneficial to limiting the emission of greenhouse gases, and does not meet the requirement of green sustainable development. Therefore, the development of bio-based epoxy resins is of great importance.
Disclosure of Invention
The invention aims to solve the defects of the technology and provides a brominated epoxy resin bio-based derivative, a preparation method and application thereof.
To this end, the present invention provides a brominated epoxy resin bio-based derivative having the structural formula (I):
wherein R is 1 、R 2 The structure is independently a bond line type structure shown in any one of the following formulas (II), (III), (IV) and (V); alternatively, R 1 、R 2 Independently is a bond line type structure shown in any one of the following formulas (V), (VII), (VIII) and (IX):
the invention also provides a preparation method of the brominated epoxy resin bio-based derivative, which comprises the following steps: brominated epoxy treeReacting the fat with cardanol under the action of a catalyst to obtain cardanol modified brominated epoxy resin; then epoxidation reaction is carried out to obtain the epoxidized cardanol modified brominated epoxy resin, namely the brominated epoxy resin bio-based derivative which has the structural formula as shown in the formula (I), wherein R 1 、R 2 The structure is independently a bond line structure shown in any one of a formula (V), a formula (VII), a formula (VIII) and a formula (IX).
Cardanol has reactive phenolic hydroxyl groups and unsaturated long alkyl chains, is extracted from natural cashew nut shell oil as an agricultural byproduct, and has the advantages of rich sources, low price and reproducibility. Typically cardanol is a mixture of four alkylphenols with different degrees of saturation, respectively 3% saturated alkyl cardanol, 42% mono-olefin cardanol, 17% di-alkyl cardanol and 38% tri-olefin cardanol. The structure is schematically as follows:
it can be seen that the cardanol modified brominated epoxy resin is epoxidized substantially on the carbon pentadecyl side chain of cardanol.
And (3) performing addition reaction on the epoxidized cardanol modified brominated epoxy resin and DOPO to obtain the brominated epoxy resin bio-based derivative shown in the structural formula. Wherein:
the DOPO as the raw material is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for short, and compared with halogen flame retardant, the novel reactive phosphorus-containing flame retardant has the structure containing P-H bond, has activity on olefin, epoxy bond and carbonyl base, and participates in the synthesis of phosphorus-containing epoxy resin, and has the advantages of no halogen, no smoke, no toxicity, no migration and lasting flame retardant property.
Preferably, the preparation method of the cardanol modified brominated epoxy resin comprises the following steps: and heating the brominated epoxy resin and excessive cardanol to 95-105 ℃, adding a catalyst, stirring and dissolving, continuously heating to 170-190 ℃, and obtaining the cardanol modified brominated epoxy resin after the reaction is completed.
Preferably, the molar ratio of the brominated epoxy resin to the cardanol is 1:2-1:2.1.
Preferably, the catalyst is triphenylphosphine, and the addition amount of the triphenylphosphine is 0.1-0.5% of the total mass. The total mass refers to the sum of the weights of all raw materials added in the preparation of the cardanol modified brominated epoxy resin by using the cardanol and the brominated epoxy resin under the action of a catalyst.
Preferably, the preparation method of the epoxidized cardanol modified brominated epoxy resin comprises the following steps: and (3) dissolving the cardanol modified brominated epoxy resin in an organic solvent, adding m-chloroperoxybenzoic acid (preferably added in batches) at the temperature of 25-30 ℃, filtering after the reaction is finished, washing filtrate to be neutral, and then distilling to remove the organic solvent to obtain the epoxidized cardanol modified brominated epoxy resin.
Preferably, the organic solvent is one or more of dichloromethane, dichloroethane, dichloropropane, trichloroethane and trichloromethane.
Preferably, the method for washing the filtrate to neutrality is as follows: the filtrate is washed with sodium bisulphite solution, excess m-chloroperoxybenzoic acid is removed, washing with sodium carbonate is continued, excess sodium bisulphite is neutralized, and finally water washing is carried out until neutrality.
Preferably, the flame retardant has Br and P synergistic flame retardant effect; it comprises the following steps: subjecting the obtained epoxidized cardanol-modified brominated epoxy resin to addition reaction with DOPO at 140-180 ℃ to obtain the brominated epoxy resin bio-based derivative as defined in claim 1, which has a structural formula as shown in formula (I), wherein R 1 、R 2 The structure is independently a bond wire structure shown in any one of a formula (II), a formula (III), a formula (IV) and a formula (V).
Preferably, the epoxidized cardanol modified brominated epoxy resin is reacted with DOPO in an amount such that the molar ratio of epoxy groups to DOPO is =1:1.
The brominated epoxy resin bio-based derivative with the chemical formula is used as a high-molecular flame retardant to be applied to flame-retardant epoxy high-molecular materials.
The beneficial effects of the invention are as follows: the invention provides a brominated epoxy resin bio-based derivative, a preparation method and application thereof, wherein the brominated epoxy resin bio-based derivative is used as a high polymer flame retardant to be applied to flame-retardant epoxy high polymer materials, and the limitation that the brominated epoxy resin is entirely derived from petroleum groups is changed. The raw material cardanol is the main component of cashew nut shell liquid, and the cashew nut shell liquid is an important agricultural and sideline product in cashew nut production, has wide sources and huge reserves, so that abundant and low-cost natural compounds are adopted as raw materials to synthesize brominated epoxy resin bio-based derivatives, thereby being beneficial to reducing the consumption of petroleum-based raw materials in the products and conforming to the definition of green chemistry.
In addition, the brominated epoxy resin bio-based derivative effectively combines higher flame retardant effect of brominated flame retardants, better toughening effect of cardanol, active reactive groups and DOPO reactive phosphorus-containing flame retardants, combines brominated epoxy resins, cardanol and DOPO, effectively improves the mechanical properties of flame-retarded resins, and synthesizes a novel polymer flame retardant for flame-retarded epoxy polymer materials.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required for the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a cardanol-modified brominated epoxy resin prepared in example 2, an epoxidized cardanol-modified brominated epoxy resin prepared in example 3;
FIG. 2 is an infrared spectrum of DOPO, and the brominated epoxy resin biobased derivative produced in example 4.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application. The method used in the invention is a conventional method unless specified otherwise; the raw materials and devices used, unless otherwise specified, are all conventional commercial products. Wherein cardanol is purchased from the chemical industry company of the white pharmaceutical industry of the Wuhan and has the purity of more than 99 percent; epoxy E51 was purchased from eastern jufeng chemical company, inc; curing agent C19 was purchased from Kagaku chemical Co., ltd.
Examples
Example 1:
preparation of brominated epoxy resin:
410g of epichlorohydrin and 400g of tetrabromobisphenol A are weighed and added into a four-necked flask, a reflux condenser and a thermometer are installed, heating is started, 1.2g of benzyl triethyl ammonium chloride is added, stirring and heating are carried out to 90 ℃, reaction is carried out for 2.5h, and excessive epichlorohydrin is removed by reduced pressure distillation; cooling to 60 ℃, adding 100g of toluene as a solvent, uniformly stirring, uniformly adding 25% sodium hydroxide solution in 1h, uniformly stirring, and reacting for 5h; then adding 300g of solvent toluene for extraction, adding 400g of water for washing while the solvent toluene is hot, washing off generated sodium chloride, and separating liquid; then 400g of hot water with the temperature of 60 ℃ is added for washing twice continuously, and liquid separation is carried out; as the solvent toluene was distilled off under reduced pressure, a brominated epoxy resin was obtained.
The resultant brominated epoxy resin is free of flow at room temperature and exists in a form close to a solid to the extent that it cannot be tested by a viscometer. Further, it was found from the experimental test (hydrochloric acid-acetone method) that the epoxy equivalent of the brominated epoxy resin was 350 g/equivalent (epoxy value was 0.286), and that the average molecular weight of the brominated epoxy resin prepared in example 1 was 700.
It should be noted that:
(1) Epoxy equivalent refers to the gram of epoxy resin containing one equivalent of epoxy groups in [ grams per equivalent ], i.e., the average molecular weight of the epoxy resin divided by the number of epoxy groups contained per molecule. Thus, the epoxy equivalent of the brominated epoxy resin has a value of 1/2 of the average molecular weight of the brominated epoxy resin.
(2) As the quaternary ammonium salt catalyst, tetrabutylammonium bisulfate can be used, or benzyltriethylammonium chloride and tetrabutylammonium bisulfate can be used together instead.
Example 2
Preparing cardanol modified brominated epoxy resin:
175.50g (0.25 mol) of the brominated epoxy resin prepared in example 1 and 154.87g (0.51 mol) of cardanol were weighed into a four-necked flask, heated to 100℃and stirred to dissolve, 1.32g of triphenylphosphine catalyst was added into the reaction flask, and the temperature was further raised to 180℃to react for 90min. After the reaction is finished, the cardanol modified brominated epoxy resin in a flowing state can be obtained.
The cardanol-modified brominated epoxy resin synthesized in example 2 was measured by the hydrochloric acid-acetone method to have an epoxy equivalent of 2941 g/equivalent (the epoxy value was 0.034, and the epoxy functional group of the brominated epoxy resin was considered to have reacted substantially completely.)
To further verify the successful synthesis of cardanol modified brominated epoxy resin, the cardanol modified brominated epoxy resin obtained in example 2 was subjected to infrared characterization, and the infrared spectrum formed is shown in fig. 1.
As can be seen from the infrared spectrum of example 2 in FIG. 1, the spectrum is between 1600 and 1447cm -1 The absorption bands at the sites are C=C stretching vibration peaks on the aromatic ring skeleton and unsaturated double bond, 3008, 911 and 871cm -1 The presence of the above functional groups, which are the C-H stretching vibration peak and the out-of-plane bending vibration absorption peak on c=c, indicates the synthesis of cardanol-modified brominated epoxy resin.
Example 3
Preparing an epoxidized cardanol modified brominated epoxy resin:
53.91g of the cardanol-modified brominated epoxy resin prepared in example 2 and 320g of methylene chloride were weighed into a three-necked flask, and 25.98g of m-chloroperoxybenzoic acid was added in portions at 26℃to supplement 130g of methylene chloride during the process, followed by stirring at 30℃for 3 hours. After the reaction is finished, carrying out suction filtration, washing filtrate with sodium bisulphite solution with the mass fraction of 5% for 2 times, washing filtrate with sodium carbonate solution with the mass fraction of 5% for 3 times, and finally washing filtrate with pure water to be neutral. And distilling dichloromethane at 50 ℃ to obtain brown-black viscous epoxidized cardanol modified brominated epoxy resin.
Example 3 the epoxy equivalent weight of the epoxidized cardanol-modified brominated epoxy resin was 537.6 g/equivalent (epoxy value 0.186, calculated to have about 2.46 moles of double bonds oxidized to epoxide groups per 1 mole of cardanol-modified brominated epoxy resin) as measured by the hydrochloric acid-acetone method.
To further verify that the cardanol-modified brominated epoxy resin was epoxidized, the epoxidized cardanol-modified brominated epoxy resin obtained in example 3 was subjected to infrared characterization, and the infrared spectrum formed was shown in fig. 1.
As can be seen from FIG. 1, example 3 compares with the infrared spectrum of example 2 at 914cm -1 Is end ring oxygen absorption peak, 848cm -1 The absorption peak of the epoxy group of the fatty chain is 3008cm -1 The C-H absorption peak on the side chain disappears, and the change of the functional groups indicates that the double bond on the side chain of the cardanol modified brominated epoxy resin undergoes epoxidation reaction.
Example 4
Preparation of brominated epoxy resin biobased derivatives:
26.5g of the epoxidized cardanol-modified brominated epoxy resin prepared in example 3, 10.68g of DOPO were weighed into a three-necked flask and reacted at 160℃for 6 hours. After the reaction was completed, a yellow transparent solid was obtained.
To further verify the successful synthesis of epoxidized cardanol-modified brominated epoxy resin with DOPO, the sample obtained in example 4 was subjected to infrared characterization, resulting in an infrared spectrum as shown in fig. 2.
As can be seen from FIG. 2, example 4 compares 1156cm with the infrared spectrum of DOPO -1 P-O-C stretching vibration peak at 1585cm -1 The P-Ph stretching vibration peak at this point is still present in the infrared spectrum of example 4, while the characteristic peak of DOPO is a P-H bond of 2385cm -1 The absorption peak of (2) was disappeared in example 4, demonstrating that DOPO reacted with the epoxidized brominated epoxy resin to synthesize a brominated epoxy resin biobased derivative.
In this example 4, the P-H bond in DOPO is linked to the strong electron withdrawing group P-0, so that DOPO has a certain activity, and DOPO can form a phosphorus anion to undergo nucleophilic reaction as a nucleophile. The epoxy gene has high ternary ring tension and thus high activity, and is easy to open, and carbon atoms in the ring are attacked by nucleophilic reagents to form stable compounds.
Application examples
The cardanol modified brominated epoxy resin prepared in example 2 and the brominated epoxy resin bio-based derivative prepared in example 4 are respectively used as high molecular flame retardants to be applied to flame-retardant epoxy high molecular materials, and the physical properties of the flame-retardant epoxy high molecular materials are tested by tensile and non-notch impact tests.
Application example 1
(1) Weighing 20.0g of cardanol modified brominated epoxy resin prepared in example 2, mixing with 100.0g of epoxy resin E51, adding 0.2g of defoamer B-459 into the mixture, and heating the mixture in a water bath at 80 ℃ for 30min to obtain an epoxy resin mixed solution for later use;
(2) Placing 50.0g of curing agent C19 into a water bath kettle at 80 ℃ and heating for 30min for later use;
(3) Placing the stainless steel die into a drying oven to be preheated to 80 ℃ for standby;
(4) Pouring the curing agent C19 heated in the water bath in the step (2) into the epoxy resin mixture in the step (1), fully stirring, pouring into the stainless steel die in the step (3), putting the die into an oven at 80 ℃ for 2 hours, taking out, standing and curing for 4 hours at room temperature, and demoulding and taking out after the cured product in the die is slowly cooled to room temperature to obtain a tensile test sample and a notch-free impact test sample.
Description: the stainless steel die is internally provided with a cavity matched with the shape and the size of a tensile test sample and a non-notch impact test sample.
Application example 2
The difference from application example 2 is only that 20.0g of the cardanol-modified brominated epoxy resin prepared in example 2 was replaced with 20.0g of the brominated epoxy resin bio-based derivative prepared in example 4, and the other matters are exactly the same as those of application example 2, and will not be described again.
Tensile test specimens and unnotched impact test specimens prepared in application examples 1 and 2 were subjected to tensile test and unnotched impact test, respectively. Wherein:
(1) Tensile test
Tensile test standard: determination of the tensile Properties of plastics (GB/T2567-2021).
Sample size: according to GB/T2567-2021, the sample is required to be made into a dumbbell shape.
The testing method comprises the following steps: the sample is clamped, the long axis of the sample is consistent with the pulling force direction of the center lines of the upper clamp and the lower clamp, the sample is continuously loaded to damage at a certain speed, and the damage loading value is read. The loading speed is 2mm/min, each group of samples is not less than 5, and if the breaking point of the samples is not in the middle parallel part, the samples are invalidated. The average of all test data is the final test result. The test results are shown in Table 1 below.
Table 1: application of tensile test results of examples 1 and 2
| Application examples | Tensile Strength/MPa | Elongation at break/% |
| Application example 1 | 34.37 | 5 |
| Application example 2 | 36.68 | 4.84 |
(2) Notch-free impact test
Test standard for notched impact test: GB/T1043.1-2008 "determination of impact Property of Plastic simple corbel".
Sample specification: the length (80+/-2) mm, the width (10+/-0.2) mm, the thickness (4+/-0.2) mm and the span (60) mm.
The testing method comprises the following steps: the test is symmetrically and vertically clung to the support, the impact speed of the pendulum bob is 2.9m/s, the pendulum bob is steadily released, and the energy absorbed by the punching section test is read. And each group of samples is not less than 5. The average of all test data is the final test result. The test results are shown in Table 2 below.
Table 2: application examples 1, 2 results of the unnotched impact test
| Application examples | Impact Strength/KJ/m 2 |
| Application example 1 | 9.85 |
| Application example 2 | 11.87 |
From the test data in tables 1 and 2, it can be seen that the synthesized brominated epoxy resin bio-based derivative has better tensile property and impact property than cardanol modified brominated epoxy resin due to the introduction of DOPO group with rigid structure. The brominated epoxy resin bio-based derivative effectively combines the flame retardant effect of the brominated flame retardant, the better toughening effect of cardanol and the DOPO reactive phosphorus-containing flame retardant, and the mechanical property of the flame-retardant resin is improved.
It should be noted that:
(1) In the preparation process of the cardanol modified brominated epoxy resin, the addition amount, the reaction time, the catalyst dosage and the like of the brominated epoxy resin and excessive cardanol can be adjusted according to practical conditions. In the actual production process, the reaction time is usually 1-3 h; the mol ratio of the brominated epoxy resin to the cardanol is 1:2-1:2.1; the catalyst uses triphenylphosphine, and the addition amount of the triphenylphosphine is 0.1-0.5% of the total mass.
(2) In the preparation process of the epoxidized cardanol modified brominated epoxy resin, the addition amount of raw materials, the reaction time, the types of organic solvents, the mass fraction of washing liquid, the washing times and the like can be adjusted according to actual conditions. In the actual production process, the reaction time is usually 2-4 hours; the organic solvent adopts dichloromethane, dichloroethane, dichloropropane, trichloroethane, trichloromethane and the like; washing the filtrate with sodium bisulphite solution with the mass fraction of 5% for 2-3 times, continuously washing with sodium carbonate with the mass fraction of 5% for 3 times, and finally washing with water for 3-5 times until the filtrate is neutral.
(3) In the preparation process of the brominated epoxy resin bio-based derivative, the addition amount of raw materials, the reaction time and the like can be adjusted according to actual conditions. Typically the molar ratio of epoxidized cardanol modified brominated epoxy resin to DOPO is 1:1; the reaction time is 5 to 8 hours; the reaction vessel is preferably a flask with stirring means, thermometer and condensation collection means.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (10)
1. A brominated epoxy resin bio-based derivative, characterized in that it has the structural formula (I):
wherein R is 1 、R 2 The structure is independently a bond line type structure shown in any one of the following formulas (II), (III), (IV) and (V); alternatively, R 1 、R 2 Independently is a bond line type structure shown in any one of the following formulas (V), (VII), (VIII) and (IX):
2. a method for preparing a brominated epoxy resin bio-based derivative, comprising the steps of: reacting the brominated epoxy resin with cardanol under the action of a catalyst to obtain cardanol modified brominated epoxy resin; then epoxidation reaction is carried out to obtain epoxidized cardanol modified brominated epoxy resin, namely the brominated epoxy resin bio-based derivative as shown in claim 1, which has the structural formula shown in formula (I), wherein R 1 、R 2 The structure is independently a bond line structure shown in any one of a formula (V), a formula (VII), a formula (VIII) and a formula (IX).
3. The method for preparing the brominated epoxy resin bio-based derivative according to claim 2, wherein the method for preparing the cardanol modified brominated epoxy resin comprises the following steps: and heating the brominated epoxy resin and excessive cardanol to 95-105 ℃, adding a catalyst, stirring and dissolving, continuously heating to 170-190 ℃, and obtaining the cardanol modified brominated epoxy resin after the reaction is completed.
4. The method for preparing a brominated epoxy resin bio-based derivative according to claim 3, wherein the molar ratio of the brominated epoxy resin to cardanol is 1:2-1:2.1.
5. The method for preparing a brominated epoxy resin bio-based derivative according to claim 2, wherein the catalyst is triphenylphosphine, and the addition amount of the triphenylphosphine is 0.1-0.5% of the total mass.
6. The method for preparing the brominated epoxy resin bio-based derivative according to claim 2, wherein the method for preparing the epoxidized cardanol-modified brominated epoxy resin comprises the following steps: dissolving the cardanol modified brominated epoxy resin in an organic solvent, adding m-chloroperoxybenzoic acid at the temperature of 25-30 ℃, filtering after the reaction is finished, washing filtrate to be neutral, and then distilling to remove the organic solvent to obtain the epoxidized cardanol modified brominated epoxy resin.
7. The method for preparing a brominated epoxy resin bio-based derivative according to claim 6, wherein the organic solvent is one or more of dichloromethane, dichloroethane, dichloropropane, trichloroethane and trichloromethane.
8. The method for preparing a brominated epoxy resin bio-based derivative according to claim 6, wherein the method for washing the filtrate to neutrality is as follows: the filtrate is washed with sodium bisulphite solution, excess m-chloroperoxybenzoic acid is removed, washing with sodium carbonate is continued, excess sodium bisulphite is neutralized, and finally water washing is carried out until neutrality.
9. The method for preparing the brominated epoxy resin bio-based derivative according to claim 2, which is characterized by having Br and P synergistic flame retardant effect; it comprises the following steps: subjecting the obtained epoxidized cardanol-modified brominated epoxy resin to addition reaction with DOPO at 140-180 ℃ to obtain the brominated epoxy resin bio-based derivative as defined in claim 1, which has a structural formula as shown in formula (I), wherein R 1 、R 2 Independent and independentThe structure is a bond line structure shown in any one of a formula (II), a formula (III), a formula (IV) and a formula (V).
10. The application of the brominated epoxy resin bio-based derivative is characterized in that the brominated epoxy resin bio-based derivative as claimed in claim 1 is used as a high polymer flame retardant for flame-retardant epoxy high polymer materials.
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2023
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