CN108250382A - Biomass diphenolic acid-chaff amine type benzoxazine colophony and preparation method thereof - Google Patents
Biomass diphenolic acid-chaff amine type benzoxazine colophony and preparation method thereof Download PDFInfo
- Publication number
- CN108250382A CN108250382A CN201810013847.1A CN201810013847A CN108250382A CN 108250382 A CN108250382 A CN 108250382A CN 201810013847 A CN201810013847 A CN 201810013847A CN 108250382 A CN108250382 A CN 108250382A
- Authority
- CN
- China
- Prior art keywords
- chaff amine
- biomass
- diphenolic acid
- amine type
- type benzoxazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 biomass diphenolic acid chaff amine type benzoxazine colophonies and preparation method thereof, and step includes：Solution is formed with solvent dissolving chaff amine, formaldehyde and diphenolic acid respectively first, then formalin is transferred in reactor and is stirred, chaff amine aqueous solution is added dropwise into reactor, bis-phenol acid solution is added dropwise after dripping off again；Then it is stirred and heated to reflux state and reacts 10~15h；Extra solvent is removed after the completion of reaction, with ether dissolution, washing, drying, ether is removed, is dried to obtain biomass diphenolic acid chaff amine type benzoxazine monomer；Biomass diphenolic acid chaff amine type benzoxazine monomer obtained by step (1) is placed in mold, it is then staged curing, obtain biomass diphenolic acid chaff amine type benzoxazine colophony.Synthesis technology advantages of simple, purity are high, yield is high and cost is relatively low.The structural formula of the resin is as follows.
Description
Technical field
The present invention relates to a kind of thermosetting resin and its preparation technical field more particularly to a kind of biomass diphenolic acid-
Chaff amine type benzoxazine colophony and preparation method thereof.
Background technology
Benzoxazine colophony is a kind of novel hot setting engineering plastics, compared with traditional phenolic resin, is had preferably resistance to
Hot property, electrical property, low-surface-energy, low water absorption and dimensional stability, it be suitable for prepare low porosity, high-performance, it is low into
This composite material.The resin is to react generation monomer by phenolic compound, primary amine compound and formaldehyde, is then being heated
And/or crosslinking curing is made under the action of catalyst.Most benzoxazine colophonies are all with fossil resource currently on the market
For raw material production, but as people are higher and higher to the attention rate of environment and energy sustainable development, in addition fossil resource with
The use for people is fewer and fewer, and find new renewable resource has more become the research emphasis of researcher.Therefore,
Biomass benzoxazine colophony has become the big hot spot in thermosetting resin research field as a kind of new material.
Contain in diphenolic acid (DPA) molecule there are two phenolic hydroxyl group and a carboxyl functional group, have similar with bisphenol-A (BPA)
As structure, polycondensation reaction easily occurs, is a kind of important from the organic synthesis intermediate of biomass and the list of high polymer
Body.Meanwhile DPA is also the derivative of this biology base platform chemicals of levulic acid, it is more environmentally friendly, more using diphenolic acid as raw material
It is healthy and safe.Since DPA has the structure similar with BPA, so DPA is as a kind of polymer list that can be reused
Body, completely can replace synthesis benzoxazine colophony bisphenol-A (bisphenol-A very likely causes brokenly the internal system of human body
It is bad), for the preparation of the high molecular materials such as benzoxazine colophony.Meanwhile in DPA molecular structures also contain there are one carboxyl (-
COOH), the curing reaction reaction of meeting Dui benzoxazine colophony Jie Gou Zhong oxazine rings produces a very large impact, while also in the molecule
The group that some functionalization can be introduced provides good approach, and then can assign benzoxazine colophony more fully performance.
Therefore, it is skyrocketed through recently as oil, the decline of coal reserves and oil price, as various countries' environmental pollution is asked
The growing interest of topic and attention, the application of the regenerated resources of this sustainable developments of DPA are increasingly taken seriously.Chaff amine is also one
The common biomass fine chemistry industry of the plant materials production such as corncob, cotton seed hulls and the bagasse of kind in nature is former
Material.For the present invention using diphenolic acid as phenol source, chaff amine is amine source, prepares a kind of benzoxazine colophony of biomass source, breaks away from tradition
Excessive dependence of the benzoxazine colophony to oil product.
Invention content
The technical problems to be solved by the invention are for the prior art, provide a kind of biomass benzoxazine colophony ---
Diphenolic acid-chaff amine type benzoxazine colophony and preparation method thereof.
The technical solution adopted in the present invention is：
A kind of biomass diphenolic acid-chaff amine type benzoxazine colophony, structural formula are as follows：
The biomass diphenolic acid of above structure of the present invention-chaff amine type benzoxazine colophony, by the monomer of following general structure
Synthesis：
The monomer structure Han You oxazine rings of the above-mentioned benzoxazine of the present invention, therefore, under conditions of heating or adding catalyst
The reticular structure of the nitrogenous and similar phenolic resin of polymerisation generation can occur.
The step of preparation method of the above-mentioned biomass diphenolic acid-chaff amine type benzoxazine colophony of the present invention, this method, includes：
(1) solution is formed with solvent dissolving chaff amine, formaldehyde and diphenolic acid respectively first, is then transferred to formalin instead
It answers in device and stirs, chaff amine aqueous solution is added dropwise into reactor, bis-phenol acid solution is added dropwise after dripping off again；Then it is stirred and heated to reflux shape
State reacts 10~15h；Extra solvent is removed after the completion of reaction, with ether dissolution, washing, drying, ether is removed, is dried to obtain
Biomass diphenolic acid-chaff amine type benzoxazine monomer；
(2) the biomass diphenolic acid obtained by step (1)-chaff amine type benzoxazine monomer is placed in mold, then ladder
Curing, obtains biomass diphenolic acid-chaff amine type benzoxazine colophony.
Solvent in above-mentioned steps (1) of the present invention is dioxane, one kind in dimethyl sulfoxide (DMSO), toluene.
Formaldehyde in above-mentioned steps (1) of the present invention is paraformaldehyde, one kind of formalin.
In above-mentioned steps (1) of the present invention the time for adding of chaff amine aqueous solution be 10~30min, the time for adding of bis-phenol acid solution
For 20~40min.
Diphenolic acid in above-mentioned steps (1) of the present invention, chaff amine, paraformaldehyde and solvent proportioning be followed successively by 0.03~
0.10mol：0.06~0.20mol：0.132~0.44mol：60~240ml.Said ratio is not limited by concrete unit,
Scaled down or increase are thought to fall into the range of aforementioned proportion on the basis of above-mentioned numerical scale.
Staged curing (stage curing) is in above-mentioned steps (2) of the present invention：130-150 DEG C, 0.5-1.5h, 160-180 DEG C,
1.5-2.5h, 180-200 DEG C, 0.5-1.5h, 200-220 DEG C, 1.5-2.5h, 230-250 DEG C, 0.5-1.5h.Preferably, step
(2) ladder is cured as 140 DEG C, 1h, 170 DEG C, 2h, 190 DEG C, 1h, 210 DEG C, 2h, 240 DEG C, 1h in.Compared with prior art, originally
Invention has following remarkable advantage and advantageous effect：
(1) biomass benzoxazine colophony of the present invention is to use diphenolic acid as phenol source, and chaff amine is amine source, both substances are all
It is environmentally protective from biomass.
(2) the synthesis technology advantages of simple of biomass diphenolic acid of the present invention-chaff amine type benzoxazine colophony, purity are high, produce
Rate is high and cost is relatively low；
(3) biomass diphenolic acid-chaff amine type benzoxazine colophony prepared by the method for the present invention has good low-temperature setting
Characteristic is suitable for preparing the Green Composites of natural fiber enhancing.
(4) biomass diphenolic acid-chaff amine type benzoxazine colophony prepared by the method for the present invention has higher heat resistance
And carbon yield, it is suitable for preparing some high-performance, heat safe material.
(5) bisphenol-A-aniline type benzo of diphenolic acid-chaff amine type benzoxazine colophony of the invention and comparative example, that is, traditional
The TG spectrograms of oxazine resin are relatively understood：Diphenolic acid-chaff amine type benzoxazine colophony (Bio-PolyBoz-DF) of the present invention
Initial decomposition temperature (T5%) 340 DEG C are up to, and carbon residue retention rate is up to 50% at 800 DEG C.And traditional bisphenol-A-aniline type benzene
Initial decomposition temperature (the T of Bing oxazines resin (PolyBoz-BA)5%) it is 343 DEG C, but carbon residue retention rate only has at 800 DEG C
34%.It can be seen that though Bio-PolyBoz-PF is compared than PolyBoz-BA has similar initial decomposition temperature, 800
DEG C when carbon residue retention rate improve 16%.It is good can to illustrate that the biomass benzoxazine colophony of the present invention has by TG results
Heat resistance, particularly hot stage have slower decomposition rate and higher carbon residue retention rate.
Description of the drawings
Shown in FIG. 1 is the FTIR spectrograms of biomass diphenolic acid of the present invention-chaff amine type benzoxazine monomer；
Shown in Fig. 2 is biomass diphenolic acid of the present invention-chaff amine type benzoxazine monomer1H NMR spectras；
Shown in Fig. 3 is biomass diphenolic acid-chaff amine type benzoxazine monomer and comparative example tradition bisphenol-A-benzene of the present invention
The DSC spectrograms of amine type benzoxazine monomer；
Shown in Fig. 4 is biomass diphenolic acid-chaff amine type benzoxazine colophony and comparative example tradition bisphenol-A-benzene of the present invention
The TG spectrograms of amine type benzoxazine colophony；
Specific embodiment
The present invention is further described in detail with reference to embodiments.It is noted that detailed description below is all to illustrate
Property, it is intended to provide further instruction to the present invention.Unless otherwise indicated, all scientific and technical terms that the present invention uses
With with the normally understood identical meanings of the technical field of the invention personnel.
Comparative example：
Directly commodity bisphenol-A-aniline type benzoxazine monomer is placed in the mold prepared in advance, is subsequently placed in air blast
It is staged curing in drying box：Then 140 DEG C of maintenance 1h are warming up to 170 DEG C of maintenance 2h, be then warming up to 190 DEG C of maintenance 1h, then
210 DEG C of maintenance 2h are warming up to, 240 DEG C of maintenance 1h is then warming up to, obtains thermosetting property tradition bisphenol-A-aniline type benzoxazine tree
Fat.
Embodiment 1：
The preparation method of the present embodiment biomass benzoxazine colophony, includes the following steps：
(1) equipped with magnetic stirring apparatus, spherical condensation tube, thermometer, constant pressure addition funnel four round flask in, add
Enter 1, the 2- dioxane of 24ml as solvent and the formaldehyde of 0.132mol, be stirred at room temperature, 6ml 1 is added dropwise, 2- dioxane is made
For the 0.06mol chaff amine aqueous solutions of solvent, its time for adding 10min or so is controlled.60ml 1,2- dioxane is added dropwise again as molten
The 0.03mol bis-phenol acid solutions of agent control its time for adding then to be heated to flow back to mixed solution in 20min or so, constant temperature
Reaction 14 hours.Revolving removes extra solvent, and then with ether dissolution, deionization washing three times, then anhydrous sodium sulfate is done
Dry, revolving removes ether, is placed on vacuum drying chamber drying for 24 hours, obtains brownish-yellow powder, i.e. diphenolic acid-chaff amine type benzoxazine
Monomer, yield 86.05%.
(2) the diphenolic acid chaff amine type benzoxazine monomer obtained by step (1) is placed in the mold prepared in advance, then
(the staged curing same comparative example of temperature) staged curing in air dry oven is placed in, obtains thermosetting property biomass diphenolic acid-chaff amine type
Benzoxazine colophony.
Embodiment 2：
The preparation method of the present embodiment biomass benzoxazine colophony, includes the following steps：
(1) equipped with magnetic stirring apparatus, spherical condensation tube, thermometer, constant pressure addition funnel four round flask in, add
Enter formalin of the toluene of 32ml as solvent and 0.22mol, be stirred at room temperature, 0.10mol of the 8ml toluene as solvent is added dropwise
Chaff amine aqueous solution controls its time for adding 20min or so.0.05mol bis-phenol acid solution of the 80ml toluene as solvent is added dropwise again, controls
Its time for adding 30min or so is made, then mixed solution is heated to flow back, isothermal reaction 11 hours.It is extra that revolving removes
Solvent, then with ether dissolution, deionization washes three times, and then anhydrous sodium sulfate is dried, and revolving removes ether, is placed on vacuum
Drying box is dried for 24 hours, obtains brownish-yellow powder, i.e. diphenolic acid-chaff amine type benzoxazine monomer, yield 83.25%.
(2) the diphenolic acid chaff amine type benzoxazine monomer obtained by step (1) is placed in the mold prepared in advance, then
(the staged curing same comparative example of temperature) staged curing in air dry oven is placed in, obtains thermosetting property biomass diphenolic acid-chaff amine type
Benzoxazine colophony.
Embodiment 3：
The preparation method of the present embodiment biomass benzoxazine colophony, includes the following steps：
(1) equipped with magnetic stirring apparatus, spherical condensation tube, thermometer, constant pressure addition funnel four round flask in, add
Enter the dimethyl sulfoxide (DMSO) of 96ml as solvent and the paraformaldehyde of 0.44mol, be stirred at room temperature, 24ml dimethyl sulfoxide (DMSO) conducts are added dropwise
The 0.20mol chaff amine aqueous solutions of solvent, control its time for adding 30min or so.240ml dimethyl sulfoxide (DMSO)s are added dropwise afterwards as solvent
Then 0.10mol bis-phenol acid solutions, control time for adding are heated to flow back in 40min or so to mixed solution, isothermal reaction 15
Hour.Revolving removes extra solvent, then with ether dissolution, deionization washing three times, then anhydrous sodium sulfate drying, revolving
Ether is removed, vacuum drying chamber drying is placed on for 24 hours, obtains brownish-yellow powder, i.e. diphenolic acid-chaff amine type benzoxazine monomer, produce
Rate 81.46%.
(2) the diphenolic acid chaff amine type benzoxazine monomer obtained by step (1) is placed in the mold prepared in advance, then
(the staged curing same comparative example of temperature) staged curing in air dry oven is placed in, obtains thermosetting property biomass diphenolic acid-chaff amine type
Benzoxazine colophony.
Embodiment 4：
Biomass diphenolic acid-chaff amine type the benzoxazine colophony and intermediate product benzoxazine monomer obtained to embodiment 1
The traditional bisphenol-A obtained with comparative example-aniline type benzoxazine colophony carries out index of correlation detection, as a result as shown in Figs 1-4.
Fig. 1 is the FTIR spectrograms of biomass diphenolic acid-chaff amine type benzoxazine monomer.It can be seen from the figure that Ben Bing Evil
The characteristic absorption peak of piperazine structure appears in：3449cm-1A neighbouring broad peak is the characteristic peak of carboxylic acid, 1715cm-1It is in carboxylic acid
The vibration peak of carbonyl, 1232cm-1It is the symmetrical stretching vibration of Ar-O-C, 1011cm-1It is the asymmetric vibration peak of Ar-O-C,
1499cm-1And 937cm-1The characteristic peak of Shi oxazine rings.
Fig. 2 is biomass diphenolic acid-chaff amine type benzoxazine monomer1H NMR spectras.As can be seen from the figure：Oxazine
Hydrogen Proton chemical shift in ring appears in 3.89ppm and 4.77ppm, is respectively belonging to-Ar-CH2- N- and-O-CH2-N-；N with
The methylene Hydrogen Proton chemical shift of furan nucleus connection appears in 3.82ppm；The steamed bun peak that 11.99ppm occurs is carboxyl
The characteristic peak of middle Hydrogen Proton；Area ratio is 1.55：1.77：1.70：0.41, close to 4：4：4：1 and target product in Hydrogen Proton
Number ratio it is consistent.
Therefore, from FTIR and1It is seen in H NMR spectras, the structure of prepared product and target product is consistent, i.e.,
The structure of biomass diphenolic acid-chaff amine type benzoxazine monomer.
Fig. 3 is biomass diphenolic acid-chaff amine type benzoxazine monomer and comparative example tradition bisphenol-A-aniline type benzoxazine
The DSC spectrograms of the DSC spectrograms of monomer.As can be seen from the figure：Biomass diphenolic acid-chaff amine type benzoxazine monomer (Bio-
Boz-DF curing peak) is bimodal, and initial cure temperature is 125 DEG C, and the first cure peak temperature is 179 DEG C, the second curing peak
It is 223 DEG C to be worth temperature.And the curing peak of traditional bisphenol-A-aniline type benzoxazine monomer (Boz-BA) is unimodal, initial cure temperature
Degree and cure peak temperature are respectively 212.0 DEG C and 252.4 DEG C.It can be seen that Bio-Boz-DF, compared with Boz-BA, starting is solid
Changing temperature reduces 87 DEG C, while curing exotherm rate is also very slow.It can illustrate that this novel biomass is double by DSC results
Phenolic acid-chaff amine type benzoxazine has good low-temperature setting characteristic.
Fig. 4 is the biomass diphenolic acid-chaff amine type benzoxazine colophony and comparative example tradition bisphenol-A-aniline type after curing
The TG spectrograms of benzoxazine colophony.As can be seen from the figure：Novel biomass diphenolic acid-chaff amine type benzoxazine colophony (Bio-
PolyBoz-DF initial decomposition temperature (T)5%) 340 DEG C are up to, and carbon residue retention rate is up to 50% at 800 DEG C.It is and traditional
Initial decomposition temperature (the T of bisphenol-A-aniline type benzoxazine colophony (PolyBoz-BA)5%) it is 343 DEG C, but residual at 800 DEG C
Charcoal retention rate only has 34%.It can be seen that though Bio-PolyBoz-PF is compared than PolyBoz-BA with similar starting point
Temperature is solved, but carbon residue retention rate improves 16% at 800 DEG C.This novel biomass benzoxazine can be illustrated by TG results
There is resin good heat resistance, particularly hot stage to have slower decomposition rate and higher carbon residue retention rate.
Embodiment 5：
Biomass diphenolic acid-chaff amine type the benzoxazine colophony and intermediate product benzoxazine monomer obtained to embodiment 2
Index of correlation detection is carried out, it is as a result similar to Example 4, therefore be just not repeated to enumerate here.
Embodiment 6：
Biomass diphenolic acid-chaff amine type the benzoxazine colophony and intermediate product benzoxazine monomer obtained to embodiment 3
Index of correlation detection is carried out, it is as a result similar to Example 4, therefore be just not repeated to enumerate here.
The present embodiments relate to material, reagent and experimental facilities, be to meet thermosetting property tree unless otherwise instructed
The commercial product of fat preparing technical field.
The above is merely a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise of the core technology for not departing from the present invention, improvements and modifications can also be made, these improvements and modifications also should
Belong to the scope of patent protection of the present invention.With any change in the comparable meaning and scope of claims of the present invention, all
It is considered as being included within the scope of the claims.
Claims (9)
1. a kind of biomass diphenolic acid-chaff amine type benzoxazine colophony, it is characterised in that：The structural formula of the resin is as follows：
2. biomass diphenolic acid according to claim 1-chaff amine type benzoxazine colophony, it is characterised in that：The life
Substance diphenolic acid-chaff amine type benzoxazine colophony is synthesized by the monomer of following general structure：
3. the preparation method of biomass diphenolic acid according to claim 1 or 2-chaff amine type benzoxazine colophony, feature
It is：Preparation process includes：
(1) solution is formed with solvent dissolving chaff amine, formaldehyde and diphenolic acid respectively first, formalin is then transferred to reactor
Chaff amine aqueous solution is added dropwise into reactor, bis-phenol acid solution is added dropwise after dripping off again for middle stirring；Then it is anti-to be stirred and heated to reflux state
Answer 10~15h；Extra solvent is removed after the completion of reaction, with ether dissolution, washing, drying, ether is removed, is dried to obtain biology
Matter diphenolic acid-chaff amine type benzoxazine monomer；
(2) the biomass diphenolic acid obtained by step (1)-chaff amine type benzoxazine monomer is placed in mold, it is then staged curing,
Obtain biomass diphenolic acid-chaff amine type benzoxazine colophony.
4. the preparation method of biomass diphenolic acid according to claim 3-chaff amine type benzoxazine colophony, feature exist
In：Solvent in step (1) is dioxane, one kind in dimethyl sulfoxide (DMSO), toluene.
5. the preparation method of biomass diphenolic acid according to claim 3-chaff amine type benzoxazine colophony, feature exist
In：Formaldehyde in step (1) is paraformaldehyde, one kind of formalin.
6. the preparation method of biomass diphenolic acid according to claim 3-chaff amine type benzoxazine colophony, feature exist
In：The time for adding of chaff amine aqueous solution is 10~30min in step (1), and the time for adding of bis-phenol acid solution is 20~40min.
7. the preparation method of biomass diphenolic acid according to claim 3-chaff amine type benzoxazine colophony, feature exist
In：Diphenolic acid in step (1), chaff amine, paraformaldehyde and solvent proportioning be followed successively by 0.03~0.10mol：0.06~
0.20mol：0.132~0.44mol：60~240ml.
8. the preparation method of biomass diphenolic acid according to claim 3-chaff amine type benzoxazine colophony, feature exist
In：Ladder is cured as in step (2)：130-150 DEG C, 0.5-1.5h, 160-180 DEG C, 1.5-2.5h, 180-200 DEG C, 0.5-
1.5h, 200-220 DEG C, 1.5-2.5h, 230-250 DEG C, 0.5-1.5h.
9. the preparation method of biomass diphenolic acid according to claim 8-chaff amine type benzoxazine colophony, feature exist
In：Ladder is cured as 140 DEG C, 1h, 170 DEG C, 2h, 190 DEG C, 1h, 210 DEG C, 2h, 240 DEG C, 1h in step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810013847.1A CN108250382B (en) | 2018-01-08 | 2018-01-08 | Biomass diphenolic acid-furfuryl amine type benzoxazine resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810013847.1A CN108250382B (en) | 2018-01-08 | 2018-01-08 | Biomass diphenolic acid-furfuryl amine type benzoxazine resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108250382A true CN108250382A (en) | 2018-07-06 |
| CN108250382B CN108250382B (en) | 2020-06-02 |
Family
ID=62725917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810013847.1A Active CN108250382B (en) | 2018-01-08 | 2018-01-08 | Biomass diphenolic acid-furfuryl amine type benzoxazine resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108250382B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180889A (en) * | 2018-08-31 | 2019-01-11 | 淮北绿洲新材料有限责任公司 | A kind of preparation method and applications of full biological source benzoxazine resin |
| CN111057050A (en) * | 2019-12-20 | 2020-04-24 | 浙江大学宁波理工学院 | Monomer of bio-based benzoxazine resin, benzoxazine resin and preparation method thereof |
| CN111138423A (en) * | 2019-12-20 | 2020-05-12 | 浙江大学宁波理工学院 | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof |
| CN113149856A (en) * | 2021-01-13 | 2021-07-23 | 浙江理工大学 | Amide-containing bio-based benzoxazine resin and preparation method thereof |
| CN113881009A (en) * | 2021-10-28 | 2022-01-04 | 青岛卓英社科技股份有限公司 | High-density microporous polyurethane foam and preparation method thereof |
| CN114933685A (en) * | 2022-04-13 | 2022-08-23 | 衡水学院 | Benzoxazine resin with self-repairing performance and preparation method and application thereof |
| CN115449045A (en) * | 2022-10-14 | 2022-12-09 | 四川金象赛瑞化工股份有限公司 | Synthesis of melamine modified bisphenol-furan benzoxazine resin and preparation method of composite material thereof |
| CN116836350A (en) * | 2023-06-26 | 2023-10-03 | 苏州大学 | Heat-resistant bio-based benzoxazine resin and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516537A (en) * | 2011-12-09 | 2012-06-27 | 浙江大学宁波理工学院 | Aromatic diamine type cyano group-containing benzoxazine resin and its preparation method |
| CN106079723A (en) * | 2016-06-24 | 2016-11-09 | 浙江大学宁波理工学院 | Flame-retardant modified ramie fabric/benzoxazine resins laminate and preparation method thereof |
| CN105085910B (en) * | 2015-08-25 | 2017-08-15 | 浙江大学宁波理工学院 | Inherent flame retardant bio-based benzoxazine colophony and preparation method thereof |
-
2018
- 2018-01-08 CN CN201810013847.1A patent/CN108250382B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516537A (en) * | 2011-12-09 | 2012-06-27 | 浙江大学宁波理工学院 | Aromatic diamine type cyano group-containing benzoxazine resin and its preparation method |
| CN105085910B (en) * | 2015-08-25 | 2017-08-15 | 浙江大学宁波理工学院 | Inherent flame retardant bio-based benzoxazine colophony and preparation method thereof |
| CN106079723A (en) * | 2016-06-24 | 2016-11-09 | 浙江大学宁波理工学院 | Flame-retardant modified ramie fabric/benzoxazine resins laminate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGQIANG YAN: "Synthesis of anintrinsically flameretardant bio-based benzoxazine resin", 《POLYMER》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180889A (en) * | 2018-08-31 | 2019-01-11 | 淮北绿洲新材料有限责任公司 | A kind of preparation method and applications of full biological source benzoxazine resin |
| CN109180889B (en) * | 2018-08-31 | 2021-11-12 | 淮北绿洲新材料有限责任公司 | Preparation method and application of benzoxazine resin with full biological sources |
| CN111057050A (en) * | 2019-12-20 | 2020-04-24 | 浙江大学宁波理工学院 | Monomer of bio-based benzoxazine resin, benzoxazine resin and preparation method thereof |
| CN111138423A (en) * | 2019-12-20 | 2020-05-12 | 浙江大学宁波理工学院 | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof |
| CN111138423B (en) * | 2019-12-20 | 2022-12-20 | 浙江大学宁波理工学院 | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof |
| CN113149856A (en) * | 2021-01-13 | 2021-07-23 | 浙江理工大学 | Amide-containing bio-based benzoxazine resin and preparation method thereof |
| CN113881009A (en) * | 2021-10-28 | 2022-01-04 | 青岛卓英社科技股份有限公司 | High-density microporous polyurethane foam and preparation method thereof |
| CN113881009B (en) * | 2021-10-28 | 2022-04-19 | 青岛卓英社科技股份有限公司 | High-density microporous polyurethane foam and preparation method thereof |
| CN114933685A (en) * | 2022-04-13 | 2022-08-23 | 衡水学院 | Benzoxazine resin with self-repairing performance and preparation method and application thereof |
| CN115449045A (en) * | 2022-10-14 | 2022-12-09 | 四川金象赛瑞化工股份有限公司 | Synthesis of melamine modified bisphenol-furan benzoxazine resin and preparation method of composite material thereof |
| CN116836350A (en) * | 2023-06-26 | 2023-10-03 | 苏州大学 | Heat-resistant bio-based benzoxazine resin and preparation method and application thereof |
| CN116836350B (en) * | 2023-06-26 | 2024-04-05 | 苏州大学 | Heat-resistant bio-based benzoxazine resin and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108250382B (en) | 2020-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108250382A (en) | Biomass diphenolic acid-chaff amine type benzoxazine colophony and preparation method thereof | |
| CN105085910B (en) | Inherent flame retardant bio-based benzoxazine colophony and preparation method thereof | |
| CN102558507B (en) | Raw material of biomass epoxy resin and preparation method of biomass epoxy resin | |
| CN110128611B (en) | Low-temperature curing bio-based benzoxazine resin and preparation method thereof | |
| CN106750289B (en) | A kind of benzoxazine oligomer of maleimide base group end-sealed type and preparation method thereof | |
| CN108192078A (en) | A kind of preparation method of biology base fire retarding epoxide resin and its biology base fire retarding epoxide resin obtained | |
| CN111205437B (en) | Preparation method of biological basic characteristic type flame-retardant epoxy resin | |
| CN109734684B (en) | Bio-based flame-retardant epoxy resin precursor based on natural phenolic monomers, and preparation method and application thereof | |
| CN107459512A (en) | A kind of benzoxazine of bio-based active function groups containing double bond and preparation method thereof | |
| CN103936686B (en) | N-semiaromatic alkyl diamine-bisphenol type four degree of functionality fluorenyl benzoxazine and preparation methods | |
| CN110951018A (en) | Apigenin-based bio-based benzoxazine resin and preparation method thereof | |
| CN111138423B (en) | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof | |
| CN115260425B (en) | Main chain type bio-based benzoxazine resin and preparation method thereof | |
| CN111057050B (en) | Monomer of bio-based benzoxazine resin, benzoxazine resin and preparation method thereof | |
| CN110358055A (en) | The method that one kettle way prepares lignin acid anhydride curable epoxy resin | |
| CN110240692B (en) | Bio-based flame-retardant furan epoxy resin and preparation method thereof | |
| CN102250318A (en) | Full-rosinyl epoxy resin composite and condensate thereof | |
| He et al. | Curing characteristics, kinetics, and thermal properties of multifunctional fluorene benzoxazines containing hydroxyl groups | |
| CN109293648B (en) | Benzoxazine monomer containing ethynyl and norbornene, preparation method and application thereof | |
| CN110003443A (en) | A kind of recoverable version epoxy resin and its preparation and recovery method | |
| CN108059701A (en) | Biomass phenolphthalein-chaff amine type benzoxazine colophony and preparation method thereof | |
| CN115260489B (en) | Bio-based difunctional benzoxazine resin and preparation method thereof | |
| CN106967002A (en) | A kind of ternary benzoxazine intermediate, preparation method and its polymer | |
| CN109535655B (en) | Epoxidized soybean oil maleimide, and preparation method and application thereof | |
| CN101824137B (en) | Modified bisphenol A epoxy acrylate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |