CN108059701A - Biomass phenolphthalein-chaff amine type benzoxazine colophony and preparation method thereof - Google Patents
Biomass phenolphthalein-chaff amine type benzoxazine colophony and preparation method thereof Download PDFInfo
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- CN108059701A CN108059701A CN201810014012.8A CN201810014012A CN108059701A CN 108059701 A CN108059701 A CN 108059701A CN 201810014012 A CN201810014012 A CN 201810014012A CN 108059701 A CN108059701 A CN 108059701A
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- 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
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Abstract
The present invention provides a kind of biomass phenolphthalein chaff amine type benzoxazine colophony and preparation method thereof, and preparation process includes：Solvent, phenolphthalein and formaldehyde are added in into reaction vessel, chaff amine is then added dropwise into reaction vessel, reflux state is stirred and heated to after being added dropwise to complete, reacts 20~25h；Solvent is removed after the completion of reaction, is washed out, dries to obtain biomass phenolphthalein chaff amine type benzoxazine monomer；Benzoxazine monomer is placed in mold and carries out staged curing, obtains thermosetting property biomass phenolphthalein chaff amine type benzoxazine colophony.Biomass phenolphthalein chaff amine type benzoxazine colophony has relatively low solidification temperature, higher heat resistance and carbon residue retention rate, is suitable for manufacturing high-performance heat-resisting material.The structure of biomass phenolphthalein chaff amine type benzoxazine colophony is：
Description
Technical field
The present invention relates to a kind of novel biomass thermosetting resin and its preparing technical fields, are specifically related to a kind of biology
Matter phenolphthalein-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, suitable for preparing low porosity, high-performance, low cost
Fiber reinforced polymer matrix composite, by MOLECULE DESIGN and with phenolic resin, epoxy resin or bismaleimide tree
Fat is compound to prepare many new composite materials with special physical property.And catalyst is made without acid or alkali in solidification process,
It is environmentally safe, cure when without small molecule release, cubical contraction zero, its comprehensive performance better than phenolic resin, epoxy
Resin and maleimide resin are widely used in the fields such as aviation and wide, medical material and electronic material.
In recent years, various industry rapid developments, the value to social creativity is also more and more abundanter, but petrochemical industry is produced
Product are still undue to be relied on, and people increasingly pay attention to environmental protection in addition, and bio-based compounds increasingly attract people's attention,
Progressively substitute the chemical products to have become a kind of inevitable trend with bio-based compounds, and how a kind of biomass is provided and is prepared
Benzoxazine colophony be known as research hotspot.
The content of the invention
The technical problems to be solved by the invention are for the above-mentioned deficiency of existing technology, provide a kind of novel biomass
Phenolphthalein-chaff amine type benzoxazine colophony and preparation method thereof.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：A kind of biomass phenolphthalein-chaff amine type benzene
Bing oxazines resin (Bio-PolyBoz-PF), structural formula is as follows：
The above-mentioned biomass phenolphthalein-chaff amine type benzoxazine colophony of the present invention, by the monomer of the benzoxazine of such as lower structure
(Bio-Boz-PF) it is prepared：
Above-mentioned phenolphthalein-chaff amine type the benzoxazine colophony of the present invention, therefore, can under conditions of heating and/or adding catalyst
The net structure of the nitrogenous and similar phenolic resin of polymerisation generation occurs.
The preparation method of the above-mentioned phenolphthalein-chaff amine type benzoxazine colophony of the present invention, preparation process include：
(1) solvent, phenolphthalein and formaldehyde are added in into reaction vessel, chaff amine is then added dropwise into reaction vessel, is added dropwise to complete
After be stirred and heated to reflux state, react 20~25h；Solvent is removed after the completion of reaction, is washed out, dries to obtain biomass phenol
Phthalein-chaff amine type benzoxazine monomer；
(2) the biomass phenolphthalein obtained by step (1)-chaff amine type benzoxazine monomer is placed in progress ladder in mold to consolidate
Change, obtain thermosetting property biomass phenolphthalein-chaff amine type benzoxazine colophony.
Solvent in above-mentioned steps (1) of the present invention mixes three kinds of composition with toluene, dioxane, dimethylbenzene respectively for ethyl alcohol
At least one of mixed solvent, and the volume ratio that ethyl alcohol is mixed with above-mentioned other components is 1：(3~5).
Formaldehyde in above-mentioned steps (1) of the present invention is paraformaldehyde, one kind of formalin.
Chaff amine time for adding in above-mentioned steps (1) of the present invention is 0.5~1h.
The proportioning of phenolphthalein, chaff amine, formaldehyde and solvent in above-mentioned steps (1) of the present invention is followed successively by 0.02~0.10mol：
0.04~0.20mol：0.088~0.44mol：30~80ml.Said ratio is not limited be subject to concrete unit, in above-mentioned number
Scaled down or increase are thought to fall into the range of aforementioned proportion on the basis of ratio.
In above-mentioned steps (2) of the present invention stage curing (staged curing)：170-180 DEG C, 0.5-1.5h, 185-495 DEG C,
1.5-2.5h, 200-220 DEG C, 1.5-2.5h, 230-240 DEG C, 0.5-1.5h, 24,5-255 DEG C, 0.5-1.5h.Preferably,
In above-mentioned steps (2) of the present invention stage curing (staged curing)：175 DEG C, 1h, 190 DEG C, 2h, 210 DEG C, 2h, 235 DEG C, 1h, 250
℃、1h。
Compared with prior art, the present invention has following remarkable advantage and advantageous effect：
(1) synthesis technology of biology base phenolphthalein of the present invention-chaff amine type benzoxazine colophony (Bio-PolyBoz-PF) is simple
Rationally, cost is relatively low, purity is high, yield is high；
(2) the amine source that uses of the present invention is chaff amine, is derived from the plants such as corncob, cotton seed hulls and bagasse in nature
The common fine chemical material of raw material production, has broken away from the undue dependence to oil product.
(3) the method for the present invention prepare biomass phenolphthalein-chaff amine type benzoxazine colophony have relatively low solidification temperature, compared with
High heat resistance and carbon residue retention rate are suitable for manufacturing high-performance heat-resisting material.
(4) temperature is decomposed in the starting of biomass phenolphthalein-chaff amine type benzoxazine colophony (Bio-PolyBoz-PF) of the invention
Spend (T5%) 372 DEG C are up to, at 800 DEG C, carbon residue retention rate is up to 65%.And traditional bisphenol-A-aniline type benzoxazine colophony
(PolyBoz-BA) initial decomposition temperature (T5%) for 343 DEG C, at 800 DEG C, carbon residue retention rate only has 34%.It can be seen that
Initial decomposition temperature (Ts of the Bio-PolyBoz-PF than PolyBoz-BA5%) and carbon residue retention rate has been respectively increased 29 at 800 DEG C
DEG C and 31%.It can illustrate that this novel biomass benzoxazine colophony has good heat resistance by TG results.
Description of the drawings
Shown in FIG. 1 is the FTIR spectrograms of biomass phenolphthalein of the present invention-chaff amine type benzoxazine monomer.
Shown in Fig. 2 is biomass phenolphthalein of the present invention-chaff amine type benzoxazine monomer1H NMR spectras.
Shown in Fig. 3 is biomass phenolphthalein-chaff amine type benzoxazine monomer and comparative example tradition bisphenol-A-aniline of the present invention
The DSC spectrograms of type benzoxazine monomer.
Shown in Fig. 4 is biomass phenolphthalein-chaff amine type benzoxazine colophony and comparative example tradition bisphenol-A-aniline of the present invention
The TG spectrograms of 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：175 DEG C maintain 1h, then heat to 190 DEG C and maintain 2h, then heat to 210 DEG C and maintain 2h, then
235 DEG C are warming up to maintain 1h, then heat to 250 DEG C of maintenance 1h.Obtain thermosetting property tradition bisphenol-A-aniline type benzoxazine tree
Fat.
Embodiment 1：
The preparation method of the present embodiment biomass phenolphthalein-chaff amine type benzoxazine colophony, comprises the following steps：
(1) equipped with magnetic stirring apparatus, spherical condensation tube, thermometer, constant pressure funnel four round flask in, according to
The secondary mixed solution for adding in phenolphthalein 0.02mol, polyformaldehyde 0.088mol, 5ml ethyl alcohol and 25ml toluene, is heated with stirring to reflux shape
Then the chaff amine of 0.04mol is added dropwise in state with constant pressure funnel to the inside, 5min is dripped off, when then isothermal reaction 23 is small.Revolving
Extra solvent is removed, yellow-white powder is obtained, is then washed with absolute ethyl alcohol, removes the complete raw material of a small amount of unreacted.Vacuum is done
It is dry 24 it is small when (65 DEG C), obtain biomass phenolphthalein-chaff amine type benzoxazine monomer, yield 86.5%.
(2) phenolphthalein obtained by step (1)-chaff amine type benzoxazine monomer is placed in the mold prepared in advance, be put in
(the staged curing same comparative example of temperature) stage curing in air dry oven obtains thermosetting property biomass phenolphthalein-chaff amine type Ben Bing Evil
Piperazine resin.
Embodiment 2：
The preparation method of the present embodiment biomass phenolphthalein-chaff amine type benzoxazine colophony, comprises the following steps：
(1) equipped with magnetic stirring apparatus, spherical condensation tube, thermometer, constant pressure funnel four round flask in, according to
The secondary mixed solution for adding in phenolphthalein 0.05mol, polyformaldehyde 0.22mol, 10ml ethyl alcohol and 40ml dioxane, is heated with stirring to back
Then the chaff amine of 0.10mol is added dropwise in stream mode with constant pressure funnel to the inside, 10min is dripped off, and then isothermal reaction 20 is small
When.Revolving removes extra solvent, obtains yellow-white powder, is then washed with absolute ethyl alcohol, removes the complete raw material of a small amount of unreacted.
Be dried in vacuo 24 it is small when (65 DEG C), obtain biomass phenolphthalein-chaff amine type benzoxazine monomer, yield 80.5%.
(2) phenolphthalein obtained by step (1)-chaff amine type benzoxazine monomer is placed in the mold prepared in advance, be put in
(the staged curing same comparative example of temperature) stage curing in air dry oven obtains thermosetting property biomass phenolphthalein-chaff amine type Ben Bing Evil
Piperazine resin.
Embodiment 3：
The preparation method of the present embodiment biomass phenolphthalein-chaff amine type benzoxazine colophony, comprises the following steps：
(1) equipped with magnetic stirring apparatus, spherical condensation tube, thermometer, constant pressure funnel four round flask in, according to
The secondary mixed solution for adding in phenolphthalein 0.075mol, polyformaldehyde 0.33mol, 20ml ethyl alcohol and 60ml dimethylbenzene, is heated with stirring to back
Then the chaff amine of 0.15mol is added dropwise in stream mode with constant pressure funnel to the inside, 15min is dripped off, when isothermal reaction 25 is small.Rotation
Extra solvent is evaporated off, obtains yellow-white powder, is then washed with absolute ethyl alcohol, removes the complete raw material of a small amount of unreacted.Vacuum
When drying 24 is small (65 DEG C), biomass phenolphthalein-chaff amine type benzoxazine monomer, yield 89.5% are obtained.
(2) phenolphthalein obtained by step (1)-chaff amine type benzoxazine monomer is placed in the mold prepared in advance, be put in
(the staged curing same comparative example of temperature) stage curing in air dry oven obtains thermosetting property biomass phenolphthalein-chaff amine type Ben Bing Evil
Piperazine resin.
Embodiment 4：
Biomass phenolphthalein-chaff amine type the benzoxazine colophony and intermediate product benzoxazine monomers that obtained to embodiment 1 and
Traditional bisphenol-A that comparative example obtains-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 phenolphthalein-chaff amine type benzoxazine monomer.It can be seen from the figure that benzoxazine
The characteristic absorption peak of structure appears in：1761cm-1(peak of carbonyl in five-membered ring lactone in phenolphthalein structure), 1235cm-1(oxazines
The stretching vibration peak of Ar-O-C on ring), 1154cm-1The peak of C-N-C in (oxazine rings), 932cm-1CH in (oxazine rings2Face outside
Bending vibration).
Fig. 2 is biomass phenolphthalein-chaff amine type benzoxazine monomer1H NMR spectras.As can be seen from the figure：Oxazine ring
In Hydrogen Proton chemical shift appear in 3.90ppm and 4.80ppm, be respectively belonging to-Ar-CH2- N- and-O-CH2- N-, N and furan
The methylene Hydrogen Proton chemical shift of ring of muttering connection appears in 3.80ppm, and area ratio is 0.93：1.00：0.97, close to 1：1：
1 is consistent with the number ratio of Hydrogen Proton in target product.
Therefore, from FTIR and1Seen in H NMR spectras, the structure of prepared product and target product be it is consistent, i.e.,
The structure of biomass phenolphthalein-chaff amine type benzoxazine monomer.
Fig. 3 is biomass phenolphthalein-chaff amine type benzoxazine monomer and comparative example tradition bisphenol-A-aniline type benzoxazine list
The DSC spectrograms of body.As can be seen from the figure：The starting of biomass phenolphthalein-chaff amine type benzoxazine monomer (Bio-Boz-PF) is consolidated
It is 174.1 DEG C to change temperature, and cure peak temperature is 203.9 DEG C, far below traditional bisphenol-A-aniline type benzoxazine monomer (Boz-
BA (the initial cure temperature and cure peak temperature of bisphenol-A-aniline type benzoxazine colophony are respectively 212.0 to solidification temperature)
DEG C and 252.4 DEG C).
Fig. 4 is the biomass phenolphthalein-chaff amine type benzoxazine colophony and comparative example tradition bisphenol-A-aniline type benzene after curing
The TG spectrograms of Bing oxazine resins.As can be seen from the figure：Biomass phenolphthalein-chaff amine type benzoxazine colophony (Bio-PolyBoz-
PF initial decomposition temperature (T)5%) 372 DEG C are up to, at 800 DEG C, carbon residue retention rate is up to 65%.And traditional bisphenol-A-aniline
Initial decomposition temperature (the T of type benzoxazine colophony (PolyBoz-BA)5%) for 343 DEG C, at 800 DEG C, carbon residue retention rate only has
34%.It can be seen that initial decomposition temperature (Ts of the Bio-PolyBoz-PF than PolyBoz-BA5%) and carbon residue retains at 800 DEG C
29 DEG C and 31% has been respectively increased in rate.It is resistance to well can to illustrate that this novel biomass benzoxazine colophony has by TG results
Hot property.
Embodiment 5：
The biomass benzoxazine colophony and intermediate product benzoxazine monomer obtained to embodiment 2 carries out index of correlation inspection
It surveys, it is as a result similar to Example 4, therefore be just not repeated to enumerate here.
Embodiment 6：
The biomass benzoxazine colophony and intermediate product benzoxazine monomer obtained to embodiment 3 carries out index of correlation inspection
It surveys, 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, on the premise of the core technology of the present invention is not departed from, 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 phenolphthalein-chaff amine type benzoxazine colophony, it is characterised in that：Its structural formula is as follows：
2. biomass phenolphthalein according to claim 1-chaff amine type benzoxazine colophony, it is characterised in that：The biology
Matter phenolphthalein-chaff amine type benzoxazine colophony is prepared by the monomer of such as lower structure：
3. the preparation method of biomass phenolphthalein according to claim 1 or 2-chaff amine type benzoxazine colophony, feature exist
In：Preparation process includes：
(1) solvent, phenolphthalein and formaldehyde are added in into reaction vessel, chaff amine is then added dropwise into reaction vessel, is stirred after being added dropwise to complete
It mixes and is heated to reflux state, react 20~25h；Solvent is removed after the completion of reaction, is washed out, dries to obtain biomass phenolphthalein-chaff
Amine type benzoxazine monomer；
(2) the biomass phenolphthalein obtained by step (1)-chaff amine type benzoxazine monomer is placed in mold and carries out staged curing, obtained
To thermosetting property biomass phenolphthalein-chaff amine type benzoxazine colophony.
4. the preparation method of biomass phenolphthalein according to claim 3-chaff amine type benzoxazine colophony, it is characterised in that：
Solvent in step (1) mixes for ethyl alcohol with toluene, dioxane, dimethylbenzene respectively forms at least the one of three kinds of in the mixed solvents
Kind, and the volume ratio that ethyl alcohol is mixed with above-mentioned other components is 1：(3~5).
5. the preparation method of biomass phenolphthalein according to claim 3-chaff amine type benzoxazine colophony, it is characterised in that：
Formaldehyde in step (1) is paraformaldehyde, one kind of formalin.
6. the preparation method of biomass phenolphthalein according to claim 3-chaff amine type benzoxazine colophony, it is characterised in that：
Chaff amine time for adding in step (1) is 0.5~1h.
7. the preparation method of biomass phenolphthalein according to claim 3-chaff amine type benzoxazine colophony, it is characterised in that：
The proportioning of phenolphthalein, chaff amine, formaldehyde and solvent in step (1) is followed successively by 0.02~0.10mol：0.04~0.20mol：0.088
~0.44mol：30~80ml.
8. the preparation method of biomass phenolphthalein according to claim 3-chaff amine type benzoxazine colophony, it is characterised in that：
It is stage curing in step (2)：170-180 DEG C, 0.5-1.5h, 185-495 DEG C, 1.5-2.5h, 200-220 DEG C, 1.5-2.5h,
230-240 DEG C, 0.5-1.5h, 24,5-255 DEG C, 0.5-1.5h.
9. the preparation method of biomass phenolphthalein according to claim 9-chaff amine type benzoxazine colophony, it is characterised in that：
It is stage curing in step (2)：175 DEG C, 1h, 190 DEG C, 2h, 210 DEG C, 2h, 235 DEG C, 1h, 250 DEG C, 1h.
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| CN201810014012.8A CN108059701B (en) | 2018-01-08 | 2018-01-08 | Biomass phenolphthalein-furfuryl amine type benzoxazine resin and preparation method thereof |
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| CN201810014012.8A CN108059701B (en) | 2018-01-08 | 2018-01-08 | Biomass phenolphthalein-furfuryl amine type benzoxazine resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| CN1733760A (en) * | 2005-08-08 | 2006-02-15 | 北京化工大学 | Phenolphthalein type benzoxazine intermediate and composition and method of making the same |
| CN101899155A (en) * | 2010-05-21 | 2010-12-01 | 北京化工大学 | Benzoxazine resin based on furfuryl amine, composition and preparation method thereof |
| US20110152453A1 (en) * | 2004-09-28 | 2011-06-23 | Huntsman Advanced Materials Americas Inc. | Benzoxazine Compounds Derivated From Phenolphtalein Having Flame-Retardant Properties And A Process For Their Preparation |
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| US20110152453A1 (en) * | 2004-09-28 | 2011-06-23 | Huntsman Advanced Materials Americas Inc. | Benzoxazine Compounds Derivated From Phenolphtalein Having Flame-Retardant Properties And A Process For Their Preparation |
| CN1733760A (en) * | 2005-08-08 | 2006-02-15 | 北京化工大学 | Phenolphthalein type benzoxazine intermediate and composition and method of making the same |
| CN101899155A (en) * | 2010-05-21 | 2010-12-01 | 北京化工大学 | Benzoxazine resin based on furfuryl amine, composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
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