CN110066371A - A kind of polyhydroxy anacardol benzoxazine resin and preparation method thereof - Google Patents
A kind of polyhydroxy anacardol benzoxazine resin and preparation method thereof Download PDFInfo
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- CN110066371A CN110066371A CN201910439683.3A CN201910439683A CN110066371A CN 110066371 A CN110066371 A CN 110066371A CN 201910439683 A CN201910439683 A CN 201910439683A CN 110066371 A CN110066371 A CN 110066371A
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- anacardol
- polyhydroxy
- benzoxazine
- benzoxazine resin
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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
- C08G14/06—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 and monomers containing hydrogen attached to nitrogen
Abstract
The invention discloses a kind of polyhydroxy anacardol benzoxazine resins and preparation method thereof.Using anacardol, alkamine compound and formaldehyde in 90~110 DEG C of 4~6h of reaction；Through alkali cleaning, water washing to neutrality after reactant is cooling；Organic phase is evaporated under reduced pressure to obtain hydroxyl anacardol benzoxazine monomer；The monomer obtains polyhydroxy anacardol benzoxazine resin then at 200~220 DEG C of 1~2h of solidification in 150~180 DEG C of 2~5h of solidification.The method of the present invention is easy, environmentally protective；Compared with similar benzoxazine monomer, the ring-opening polymerisation temperature of hydroxyl anacardol benzoxazine monomer is substantially reduced；Prepared polyhydroxy anacardol benzoxazine resin heat resistance with higher, can be used for composite material, coating and adhesive etc..
Description
Technical field
The present invention relates to a kind of biomass-based and oxazines resin and preparation method thereof more particularly to a kind of polyhydroxy anacardols
Benzoxazine resin and preparation method thereof.
Background technique
Benzoxazine is miscellaneous containing N, O through one kind made from condensation reaction as phenolic compound, primary amino-compound and formaldehyde
The compound of ring structure.The compound can the ring-opening polymerisation under heat treatment or catalyst action, generate a kind of nitrogenous and similar
In polymer-polybenzoxazine resin of phenolic resin.Benzoxazine resin while keeping traditional phenolic resin advantage,
Also there is flexible MOLECULE DESIGN, release without small molecule in solidification process and is solidfied material heat resistance with higher, excellent
The advantages that mechanical performance and low water absorbable, application field is extensive.
Currently, being mostly petroleum-based compounds for synthesizing the raw material of benzoxazine.Anacardol is one kind C containing unsaturation15It is long
The natural phenolic compound of side chain not only with the high temperature resistance of aromatic compound, but also has aliphatic compound good
Flexibility, excellent hydrophobicity, low-permeability and from performances such as stemness.It is prepared using anacardol substitution petroleum base phenolic compound
Benzoxazine, the defects of petroleum base benzoxazine resin brittleness can be overcome big, while assigning resin superior mechanical performance
And biodegradability.Yan Zengyang etc. utilizes anacardol benzoxazine compounds and polyurethane resin containing carboxylic acid, multifunctional ring
The compoundings such as oxygen resin, amine curing agent and phosphonium flame retardant are prepared for a kind of with excellent heat resistance, flexibility, peel strength
With the Halogen resin covering film (number of patent application 201710816678.0) of anti-flammability.
Under heating or catalyst action, oxygen-carbon fracture in the oxazines hexa-member heterocycle of benzoxazine monomer, and can be with ortho position
Monomer addition polymerization generates polybenzoxazine resin.However benzoxazine monomer usually requires to open at 200 DEG C or more
Cyclopolymerization, and curing time is longer.Gu Yi etc. has synthesized a kind of cashew nut phenolic benzoxazine with anacardol, aniline and formaldehyde, point
Analysis determines that the initial temperature at the benzoxazine Unit heating polymerization exotherm peak is 243 DEG C, summit temperature is 262 DEG C.Li et al. with
Anacardol has synthesized a kind of anacardol bisphenol derivative with phenol reactant, then reacts with aniline and furfuramide synthesized two kinds respectively
Bisphenol type cashew nut phenolic group benzoxazine piperazine monomer (CBB and CBF).Two kinds of benzoxazine lists are had studied using differential scanning calorimetry
The heat polymerization process of body, the results showed that the initial temperature of CBB and CBF exothermic peak is respectively 214 DEG C and 219 DEG C, summit temperature is
Respectively in 242 DEG C and 253 DEG C.Rao etc. has synthesized a kind of anacardol benzoxazine using anacardol, formaldehyde and aniline, using difference
Show scanning calorimetry analysis shows, the heat curing temperature range of the monomer is 225 DEG C~291 DEG C, and summit temperature is 272.3 DEG C.
The disadvantage that temperature is high when to overcome benzoxazine heat cure, the time is long, usually draws in benzoxazine molecular structure
Benzoxazine ring-opening polymerization temperature can be reduced by entering special chemical group, shorten the reaction time.Such as in benzoxazine knot
Electron-withdrawing group is introduced in structure can be improved the concentration and stability for solidifying intermediate, accelerate benzoxazine polymerization, and then reduce and open
Cyclopolymerization reaction temperature.The benzoxazine monomer and its polymer resin for researching and developing low-temperature setting not only facilitate understanding benzo
Oxazines ring-opening polymerization mechanism, while also there is good application value.
Summary of the invention
The purpose of the present invention is to provide a kind of polyhydroxy anacardol benzoxazine resins and preparation method thereof.This method with
Anacardol, formaldehyde react first synthesis hydroxyl anacardol benzoxazine monomer with alkamine compound, then obtain through heat polymerization
To polyhydroxy anacardol benzoxazine resin.Method of the invention is easy, and environmentally protective, reaction condition is mild；Prepared contains
Hydroxyl anacardol benzoxazine monomer ring-opening polymerisation temperature is lower, the polyhydroxy anacardol benzoxazine resin tool formed after solidification
Have the advantages that excellent high temperature resistant and biodegradable, can composite material, coating and in terms of apply.
Technical solution
A kind of polyhydroxy anacardol benzoxazine resin, chemical structural formula are as follows:
Wherein, R=-C15H31-2x, x=0~3；R'=-CH2CH2OH ,-CH2CH2CH2OH ,-CH2CHOHCH3,-
CH2CH2CH2CH2OH ,-CH2CH2CH2CH2CH2OH or-CH2CH2CH2CH2CH2CH2OH, n=2~12.
A kind of preparation method of polyhydroxy anacardol benzoxazine resin, preparation route are as follows:
Wherein, R=-C15H31-2x, x=0~3；R'=-CH2CH2OH ,-CH2CH2CH2OH ,-CH2CHOHCH3,-
CH2CH2CH2CH2OH ,-CH2CH2CH2CH2CH2OH or-CH2CH2CH2CH2CH2CH2OH, n=2~12.
The preparation method of the polyhydroxy anacardol benzoxazine resin, specific preparation process is as follows:
(1) it prepares anacardol hydroxyl benzoxazine monomer: being reacted by anacardol, formaldehyde with alkamine compound heating；
After reaction, it is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation obtains hydroxyl anacardol benzo evil
Piperazine monomer.
(2) polyhydroxy anacardol benzoxazine resin is prepared: above-mentioned hydroxyl anacardol benzoxazine monomer is first pre- solid
Change, resolidification obtains polyhydroxy anacardol benzoxazine resin.
Heating reaction temperature is 90~110 DEG C in step (1), and the reaction time is 4~6h.
Step (2) precuring temperature is 150~180 DEG C, and pre-cure time is 2~5h.
Step (2) solidification temperature is 200~220 DEG C, and curing time is 1~2h.
The formaldehyde is paraformaldehyde, any one in formalin, dosage be the amount of anacardol substance 2.0~
2.1 again.
The amino alcohol is ethanol amine, 3- amino -1- propyl alcohol, 1- amino -2- propyl alcohol, 4- amino-n-butyl alcohol, 5- ammonia
Any one in the alkamine compounds such as base -1- amylalcohol and 6- amino -1- hexanol, dosage are the 1.0 of the amount of anacardol substance
~1.1 times.
Beneficial effect
(1) the method for the present invention is easy, has many advantages, such as that reaction condition is mild, preparation process is environmentally protective.
(2) the primary raw material anacardol used in the present invention is a kind of reproducible natural resources, the polyhydroxy benzo of preparation
Oxazines resin has many advantages, such as green low toxicity and biodegradable is good, glass transition temperature also with higher, good heat
Stability.
(3) contain hydroxyl reactive group in polyhydroxy benzoxazine resinous molecular structure prepared by the present invention, it can be with epoxy
Group, isocyanate group reaction, can be used for modified epoxy, polyurethane etc..
Detailed description of the invention
Fig. 1 is hydroxyl anacardol benzoxazine monomer (B) prepared by anacardol (A) and embodiment 11H NMR light
Spectrogram.There is the characteristic peak of oxazines ring at δ 4.82,3.62ppm in hydroxyl anacardol benzoxazine monomer, goes out at δ 3.96ppm
Show the absorption peak of alcoholic extract hydroxyl group, connects the absorption peak of the methine of hydroxyl at δ 3.53ppm out, N- occur at δ 2.72,2.82ppm
CH2Absorption peak.
Fig. 2 is hydroxyl anacardol benzoxazine monomer (B) prepared by anacardol (A) and embodiment 113C NMR light
Spectrogram.Hydroxyl anacardol benzoxazine monomer is the absorption peak of oxazines ring at δ 82.3,51.5ppm, is at δ 63.0ppm
The absorption peak of the methine of hydroxyl is connected, is N-CH at δ 50.3ppm2Absorption peak.
Fig. 3 is the thermogravimetric curve of polyhydroxy anacardol benzoxazine resin prepared by embodiment 1.Polyhydroxy anacardol benzene
And the initial decomposition temperature of oxazines resin is 434.5 DEG C, temperature T when decomposition rate maximumpCarbon residue when being 449.6 DEG C, 650 DEG C
Rate is 11.34%.
Fig. 4 be embodiment 1 prepared by polyhydroxy anacardol benzoxazine resin storage modulus (G', a) and medium damage
Consume the factor (tan δ, b) curve.There are two glass transition temperatures for polyhydroxy anacardol benzoxazine resin tool, respectively
72.93℃、207.23℃。
Specific embodiment
The present invention is reacted by anacardol with formaldehyde, alkamine compound under solvent-free conditions first synthesizes hydroxyl anacardol
Benzoxazine monomer, then polyhydroxy anacardol benzoxazine resin is prepared through heat polymerization.The polyhydroxy waist invented
Fruit phenol benzoxazine resin have excellent thermal stability and mechanical property, can composite material, coating and in terms of
Using.
The raw materials used in the present invention is technical grade anacardol (cashew nut phenol content is not less than 85%), includes four kinds of molecular structures:
The technical solution of the present invention is as follows:
Wherein, R=-C15H31-2x, x=0~3；R'=-CH2CH2OH ,-CH2CH2CH2OH ,-CH2CHOHCH3,-
CH2CH2CH2CH2OH ,-CH2CH2CH2CH2CH2OH or-CH2CH2CH2CH2CH2CH2OH, n=2~12.
The first step, anacardol, formaldehyde and alkamine compound are in 90~110 DEG C of 4~6h of reaction；After reaction, cooling
To room temperature, alkali cleaning, then it is washed to neutrality；Organic phase vacuum distillation, obtains hydroxyl anacardol benzoxazine monomer.Wherein, ammonia
Base alcoholic compound be ethanol amine, 3- amino -1- propyl alcohol, 1- amino -2- propyl alcohol, 4- amino-n-butyl alcohol, 5- amino -1- amylalcohol and
Any one in the amino alcohols such as 6- amino -1- hexanol, dosage are 1.0~1.1 times of the amount of anacardol substance；Formaldehyde is poly
Any one in formaldehyde, formalin, dosage are 2.0~2.1 times of the amount of anacardol substance.
Second step, by hydroxyl anacardol benzoxazine monomer in 150~180 DEG C of 2~5h of solidification, then at 200~220 DEG C
Solidify 1~2h, obtains polyhydroxy anacardol benzoxazine resin.
Embodiment 1
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 29.7g paraformaldehyde and 37.9g 5- amino -1- amylalcohol are heated to 110 DEG C under stiring, react 4h；Reaction knot
Shu Hou is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzene
And oxazines monomer, yield 86.5%.
(2) the resulting hydroxyl benzoxazine monomer of step (1) is placed in air dry oven, in 150 DEG C of solidification 4h, then
In 220 DEG C of solidification 1h, polyhydroxy anacardol benzoxazine resin is obtained.
Embodiment 2
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 21.5g paraformaldehyde and 22.4g ethanol amine are heated to 100 DEG C under stiring, react 4h；After reaction, cold
But to room temperature, alkali cleaning, then it is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzoxazine
Monomer, yield 89.1%.
(2) the resulting hydroxyl anacardol benzoxazine monomer of step (1) is placed in air dry oven, it is solid in 150 DEG C
Change 4h and obtains polyhydroxy anacardol benzoxazine resin then at 210 DEG C of solidification 1h.
Embodiment 3
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 29.7g paraformaldehyde and 27.6g 3- amino -1- propyl alcohol are heated to 110 DEG C under stiring, react 4h；Reaction knot
Shu Hou is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzene
And oxazines monomer, yield 84.3%.
(2) the resulting hydroxyl anacardol benzoxazine monomer of step (1) is placed in air dry oven, it is solid in 180 DEG C
Change 2h and obtains polyhydroxy anacardol benzoxazine resin then at 220 DEG C of solidification 1h.
Embodiment 4
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 21.5g paraformaldehyde and 27.6g 1- amino -2- propyl alcohol are heated to 100 DEG C under stiring, react 4h；Reaction knot
Shu Hou is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzene
And oxazines monomer, yield 81.6%.
(2) the resulting hydroxyl anacardol benzoxazine monomer of step (1) is placed in air dry oven, it is solid in 170 DEG C
Change 5h and obtains polyhydroxy anacardol benzoxazine resin then at 220 DEG C of solidification 1h.
Embodiment 5
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 29.7g paraformaldehyde and 32.7g 4- amino-n-butyl alcohol are heated to 110 DEG C under stiring, react 4h；Reaction knot
Shu Hou is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzene
And oxazines monomer, yield 83.6%.
(2) the resulting hydroxyl anacardol benzoxazine monomer of step (1) is placed in air dry oven, it is solid in 150 DEG C
Change 4h and obtains polyhydroxy anacardol benzoxazine resin then at 220 DEG C of solidification 1h.
Embodiment 6
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 29.7g paraformaldehyde and 43.0g 6- amino -1- hexanol are heated to 110 DEG C under stiring, react 4h；Reaction knot
Shu Hou is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzene
And oxazines monomer, yield 89.1%.
(2) the resulting hydroxyl anacardol benzoxazine monomer of step (1) is placed in air dry oven, it is solid in 150 DEG C
5h obtains polyhydroxy anacardol benzoxazine resin then at 220 DEG C of solidification 1h.
Embodiment 7
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 37% formalin of 59.6g and 28.9g 3- amino -1- propyl alcohol are heated to 90 DEG C under stiring, react 6h；Instead
It after answering, is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl cashew nut
Phenol benzoxazine monomer, yield 85.3%.
(2) the resulting hydroxyl anacardol benzoxazine monomer of step (1) is placed in air dry oven, it is solid in 150 DEG C
Change 4h and obtains polyhydroxy anacardol benzoxazine resin then at 220 DEG C of solidification 1h.
Embodiment 8
(1) in the 500mL four round flask with blender, thermometer and reflux condenser, 105.0g waist is added
Fruit phenol, 37% formalin of 59.6g and 23.5g ethanol amine are heated to 110 DEG C under stiring, react 4h；Reaction terminates
Afterwards, it is cooled to room temperature, alkali cleaning, then is washed to neutrality；Organic phase vacuum distillation, obtains rufous liquid hydroxyl anacardol benzo
Oxazines monomer, yield 89.2%.
(2) the resulting benzoxazine monomer of step (1) is placed in air dry oven, in 150 DEG C of solidification 4h, then at 220
DEG C solidification 1h, obtain polyhydroxy anacardol benzoxazine resin.
Claims (8)
1. a kind of polyhydroxy anacardol benzoxazine resin, which is characterized in that the change of the polyhydroxy anacardol benzoxazine resin
Learn structural formula are as follows:
Wherein, R=-C15H31-2x, x=0~3；R'=-CH2CH2OH ,-CH2CH2CH2OH ,-CH2CHOHCH3,-
CH2CH2CH2CH2OH ,-CH2CH2CH2CH2CH2OH or-CH2CH2CH2CH2CH2CH2OH, n=2~12.
2. a kind of preparation method of polyhydroxy anacardol benzoxazine resin described in claim 1, which is characterized in that the polyhydroxy
The preparation route of base anacardol benzoxazine resin is as follows:
Wherein, R=-C15H31-2x, x=0~3；R'=-CH2CH2OH ,-CH2CH2CH2OH ,-CH2CHOHCH3,-
CH2CH2CH2CH2OH ,-CH2CH2CH2CH2CH2OH or-CH2CH2CH2CH2CH2CH2OH, n=2~12.
3. the preparation method of polyhydroxy anacardol benzoxazine resin as claimed in claim 2, which is characterized in that specific preparation
Steps are as follows:
(1) it prepares hydroxyl anacardol benzoxazine monomer: being reacted by anacardol, formaldehyde with alkamine compound heating；Reaction
After, it is cooled to room temperature, alkali cleaning, then be washed to neutrality；Organic phase vacuum distillation, obtains anacardol hydroxyl benzoxazine list
Body.
(2) polyhydroxy anacardol benzoxazine resin is prepared: by the precuring of above-mentioned hydroxyl anacardol benzoxazine monomer elder generation, then
Solidification, obtains polyhydroxy anacardol benzoxazine resin.
4. the preparation method of polyhydroxy anacardol benzoxazine resin as claimed in claim 3, which is characterized in that step (1)
Middle heating reaction temperature is 90~110 DEG C, and the reaction time is 4~6h.
5. the preparation method of polyhydroxy anacardol benzoxazine resin as claimed in claim 3, which is characterized in that step (2)
Precuring temperature is 150~180 DEG C, and pre-cure time is 2~5h.
6. the preparation method of polyhydroxy anacardol benzoxazine resin as claimed in claim 3, which is characterized in that step (2)
Solidification temperature is 200~220 DEG C, and curing time is 1~2h.
7. the preparation method of the polyhydroxy anacardol benzoxazine resin as described in claim 2 and 3, which is characterized in that described
Formaldehyde be paraformaldehyde, any one in formalin, dosage is 2.0~2.1 times of the amount of anacardol substance.
8. the preparation method of the polyhydroxy anacardol benzoxazine resin as described in claim 2 and 3, which is characterized in that described
Amino alcohol be ethanol amine, 3- amino -1- propyl alcohol, 1- amino -2- propyl alcohol, 4- amino-n-butyl alcohol, 5- amino -1- amylalcohol and 6-
Any one in the alkamine compounds such as amino -1- hexanol, dosage are 1.0~1.1 times of the amount of anacardol substance.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248675A (en) * | 2021-04-20 | 2021-08-13 | 中国林业科学研究院林产化学工业研究所 | Cardanol-based self-repairing shape memory polymer and preparation method and application thereof |
| CN113292691A (en) * | 2021-04-20 | 2021-08-24 | 中国林业科学研究院林产化学工业研究所 | Cardanol-based benzoxazine resin and preparation method and application thereof |
| CN113416289A (en) * | 2021-07-15 | 2021-09-21 | 中国科学院宁波材料技术与工程研究所 | Bio-based benzoxazine organic phase change material and preparation method and application thereof |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
| CN115010679A (en) * | 2022-07-22 | 2022-09-06 | 濮阳市恩赢高分子材料有限公司 | Synthetic method of water-soluble benzoxazine |
| CN114573842B (en) * | 2022-03-14 | 2023-09-26 | 山东大学 | High-temperature-resistant reworkable benzoxazine thermosetting resin and synthetic method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248675A (en) * | 2021-04-20 | 2021-08-13 | 中国林业科学研究院林产化学工业研究所 | Cardanol-based self-repairing shape memory polymer and preparation method and application thereof |
| CN113292691A (en) * | 2021-04-20 | 2021-08-24 | 中国林业科学研究院林产化学工业研究所 | Cardanol-based benzoxazine resin and preparation method and application thereof |
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| CN113416289A (en) * | 2021-07-15 | 2021-09-21 | 中国科学院宁波材料技术与工程研究所 | Bio-based benzoxazine organic phase change material and preparation method and application thereof |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
| CN114573842B (en) * | 2022-03-14 | 2023-09-26 | 山东大学 | High-temperature-resistant reworkable benzoxazine thermosetting resin and synthetic method and application thereof |
| CN115010679A (en) * | 2022-07-22 | 2022-09-06 | 濮阳市恩赢高分子材料有限公司 | Synthetic method of water-soluble benzoxazine |
| CN115010679B (en) * | 2022-07-22 | 2024-01-23 | 濮阳市恩赢高分子材料有限公司 | Synthesis method of water-soluble benzoxazine |
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Application publication date: 20190730 |