CN110078682A - A kind of preparation method of biology base low viscosity benzoxazine intermediate - Google Patents
A kind of preparation method of biology base low viscosity benzoxazine intermediate Download PDFInfo
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- CN110078682A CN110078682A CN201910275545.6A CN201910275545A CN110078682A CN 110078682 A CN110078682 A CN 110078682A CN 201910275545 A CN201910275545 A CN 201910275545A CN 110078682 A CN110078682 A CN 110078682A
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- Prior art keywords
- benzoxazine
- low viscosity
- aliphatic
- preparation
- anacardol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A kind of preparation method of biology base low viscosity benzoxazine intermediate, it is related to a kind of preparation method of macromolecule thermosetting material, after polyformaldehyde and aliphatic diamine are directly stirred at room temperature this method, then by anacardol addition reactor, back flow reaction is reacted 4-8 hours at low temperature.Product is washed 3-5 times with alkaline solution after reaction, is then washed with deionized water to neutrality to get low-viscosity (mobile) liquid product is arrived；The preparation method is the poly- aliphatic amine type benzoxazine intermediate of main Material synthesis with formaldehyde, anacardol and binary aliphatic primary amine, such benzoxazine intermediate has good mobility, the benzoxazine resin of function admirable is obtained after solidification with formaldehyde, intermediate good fluidity at normal temperature.Carbon yield is up to 40% or more under the conditions of 800 degree after intermediate solidification crosslinking, and glass transition temperature is more than 230 DEG C, and impact strength is in 100MPa or more, and water absorption rate is less than 0.2%, and 1 grade of flame retardant rating.
Description
Technical field
The present invention relates to a kind of preparation methods of macromolecule thermosetting material, more particularly to a kind of biology base low viscosity benzene
And the preparation method of oxazines intermediate.
Background technique
Currently, RTM moulding process matrix variety is more, including unsaturated polyester (UP), vinyl ester resin, polyurethane tree
Rouge, phenolic resin, epoxy resin, bimaleimide resin, polyimide resin etc..It is special that high-performance resin matrix has
Chemical structure and shaping characteristic, usually at high temperature have high dimensional stability, excellent thermo-oxidative stability, agent of low hygroscopicity,
Wearability, radiation hardness and excellent comprehensive mechanical property etc..For dimensional stability, when preparing thermoplastic resin,
Nearly all olefin monomer can all generate volume contraction when polymerizeing, one reason for this is that monomer passes through polymerization reaction, molecule
Between active force be transformed into the chemical bond (covalent bond) of intramolecular by intermolecular Van der Waals force.Since covalent bond distance is less than Van der Waals
Distance, atom is just much closer than arranging in monomer in the polymer, and polymer volume is caused to be shunk.
Benzoxazine is the hexa-member heterocycle system by O atom and N atomic building, it is by phenolic compound, formaldehyde
With aminated compounds through condensation reaction be made, such compound can under the action of heating or catalyst ring-opening polymerisation formed it is similar
The polymer of phenolic resin structure.Polybenzoxazine is in addition to having the advantages of traditional phenolic resin, because not having in its solidification process
The advantages such as small molecule is released, and cure shrinkage is almost nil, and modulus is high, and intensity is big, heat-resisting good, and water absorption rate is low, therefore have extensively
Purposes.
But tert-butyl aniline, dimethylaniline, diethylaniline, ethyl methyl benzene are often used in order to improve heat resistance
Amine, diisopropyl aniline and the such aromatic amine of di-tert-butyl aniline and (bisphenol-A), 4,4 '-dihydroxydiphenyl methane
(Bisphenol F), 4,4 '-dihydroxydiphenylsulisomers (bisphenol S), 2,2 '-dimethyl -2,2- are bis- (p-hydroxybenzene)
Propane (bisphenol-c) and 2, bis- (p-hydroxybenzene) propane (allyl bisphenol-A) of 2 '-diallyls -2,2-
These dihydric phenols, leading to the glass transition temperature of benzoxazine intermediate is solid at least under 150 DEG C or more, room temperature, often
The liquid for meeting processing request could be made in the monocycle benzoxazine dilution for needing to add all kinds of solvents or low viscosity low crosslinking degree
Body resin.
The study found that with single phenol synthesis single functionality benzoxazine, at room temperature or be heated to 100 DEG C or so at
It is low viscous
The liquid of degree, then ring-opening polymerisation obtain polymer.It is found in use process, despite the benzoxazine of simple function, but it
Polymerizable obtain higher molecular weight or cross-linked network, it may be possible to other side reactions are accompanied by during open loop,
Such as, there are chain transfer reactions in ring-opening polymerisation for the benzoxazine of single functionality, and the molecular weight of resulting polymers is low, limits it
Application range, this kind of material only can be used as adhesive, coating, sealing material for electric appliance, molded composite material etc..
In order to improve the degree of cross linking of low viscosity monocycle benzoxazine, the Shandong of Shandong University is equal by disliking in monocycle benzo in monarch
Introduced on piperazine it is multiple can the method for reactive group be successfully prepared low viscosity product, 250 DEG C of glass transition temperature or more after solidification,
800 DEG C of carbon yields have a extensive future 50% or more in ablation resistant material and field of charcoal material.Bifunctionality (such as bisphenol-A
Type) benzoxazine though useful as high performance material, but the characteristics of due to molecular structure itself, cause benzoxazine polymer
The disadvantages of crosslinking density is low, property is crisp, toughness is poor, having researcher that low viscosity monocycle benzoxazine is blended therewith thus can be with
Improve above-mentioned deficiency.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of biology base low viscosity benzoxazine intermediate, the present invention will
After polyformaldehyde and aliphatic diamine are directly stirred at room temperature, then by anacardol addition reactor, obtain low-viscosity (mobile) liquid production
Object.The present invention prepares novel low viscosity benzoxazine intermediate safe and simplely, changes the processing technology of traditional benzoxazine
Property, and maintain the excellent performance of benzoxazine resin.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of biology base low viscosity benzoxazine intermediate, the method includes following preparation process:
After polyformaldehyde and aliphatic diamine are directly stirred at room temperature, then by anacardol addition reactor, back flow reaction exists
It is reacted 4-8 hours under low temperature.Product is washed 3-5 times with alkaline solution after reaction, is then washed with deionized water to neutrality,
Obtain low-viscosity (mobile) liquid product；
The preparation method is disliked with the poly- aliphatic amine type benzo that formaldehyde, anacardol and binary aliphatic primary amine are main Material synthesis
Piperazine intermediate, such benzoxazine intermediate have good mobility, the benzoxazine resin of function admirable are obtained after solidification；
Wherein the chemical structural formula of the poly- aliphatic amine type benzoxazine intermediate is shown below.
Wherein, H2N-R1-NH2For aliphatic diamine；
A kind of preparation method of biology base low viscosity benzoxazine intermediate, aliphatic diamine are pentanediamines, hexamethylene diamine,
Decamethylene diamine, the alkyl diamines such as dodecamethylene diamine；
A kind of biology base low viscosity benzoxazine intermediate, synthesize poly- aliphatic amine type benzoxazine intermediate be
In 30-80 DEG C, anacardol and aliphatic diamine are first added into formalin back flow reaction at this temperature after mixing
4-10 hours, anacardol: aliphatic diamine: formaldehyde=1:2-3:0.5-2(mass ratio).
A kind of biology base low viscosity benzoxazine intermediate, the poly- aliphatic diamine type benzoxazine of synthesis glue
Degree is no more than 10Pa.s at a temperature of 40 DEG C.
A kind of biology base low viscosity benzoxazine intermediate, gained benzoxazine intermediate solidify after 800 degree
Under the conditions of carbon yield up to 40% or more, glass transition temperature is more than 240 DEG C, and impact strength is in 100MPa or more, water suction
Rate is less than 0.2%, and 1 grade of flame retardant rating.
The advantages and effects of the present invention are:
The synthesis of low viscosity benzoxazine monomer according to the present invention be by aliphatic diamine, formaldehyde and anacardol in a solvent
It carries out Mannich reaction and obtains, resulting viscosity product meets resin forming processing request, and function admirable is obtained after solidification
Polybenzoxazine resin.The reaction dissolvent that can break even has at least one of chloroform, methylene chloride or dioxane, can also be with
Not solubilizer.Aliphatic diamine, formaldehyde and anacardol can be added using various ways.The present invention can be safe, simply
Novel low viscosity benzoxazine intermediate is prepared, the processing technology of traditional benzoxazine is changed, and maintains benzoxazine
The excellent performance of resin.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The synthesis of low viscosity benzoxazine monomer of the present invention is to carry out aliphatic diamine, formaldehyde and anacardol in a solvent
Mannich is reacted and is obtained, and resulting viscosity product meets resin forming processing request, and the polyphenyl of function admirable is obtained after solidification
And oxazines resin.This reaction dissolvent has at least one of chloroform, methylene chloride or dioxane, can not also solubilization
Agent.Aliphatic diamine, formaldehyde and anacardol can using various ways be added, for example, three simultaneously be added in solvent into
Row reaction, or be that solvent is first first added in two kinds in aliphatic diamine, formaldehyde and anacardol, then add another kind.
The present invention is after polyformaldehyde and aliphatic diamine are directly stirred at room temperature, then anacardol is added in reactor, and reflux is anti-
It should react at low temperature 4-8 hours.Product is washed 3-5 times with alkaline solution after reaction, be then washed with deionized water to
Neutrality to get arrive low-viscosity (mobile) liquid product.
Example 1
Equipped with the aliphatic amine that 47 parts are added in the reactor of thermometer, agitating paddle, condenser and charge pipe, 91 parts of formaldehyde
Aqueous solution stirs 30 minutes to the middle anacardol for being added 37 parts after stirring evenly.Increase temperature to 65 degree, at a reflux temperature
Reaction 7 hours, obtains the oily crude product of buff.Crude product is anti-with 30% sodium hydrate aqueous solution solution and deionized water
After backwashing is washed at least three times, then is dried under 60 degree of vacuum condition to constant weight, and filemot liquid biological base low viscosity benzene is obtained
And oxazines intermediate.
Example 2
Equipped with the aliphatic amine that 55 parts are added in the reactor of thermometer, agitating paddle, condenser and charge pipe, 123 parts of first
Aldehyde aqueous solution stirs 30 minutes to the middle anacardol for being added 30 parts after stirring evenly.Temperature is increased to 50 degree, in reflux temperature
Lower reaction 10 hours, obtains the oily crude product of buff.Crude product with 30% sodium hydrate aqueous solution solution and deionized water
It washs at least three times, then dries under 60 degree of vacuum condition to constant weight repeatedly, obtain filemot liquid biological base low viscosity
Benzoxazine intermediate.
Example 3
Equipped with the aliphatic amine that 28 parts are added in the reactor of thermometer, agitating paddle, condenser and charge pipe, 89 parts of formaldehyde
Aqueous solution stirs 30 minutes to the middle anacardol for being added 22 parts after stirring evenly.Increase temperature to 75 degree, at a reflux temperature
Reaction 6 hours, obtains the oily crude product of buff.Crude product is anti-with 30% sodium hydrate aqueous solution solution and deionized water
After backwashing is washed at least three times, then is dried under 60 degree of vacuum condition to constant weight, and filemot liquid biological base low viscosity benzene is obtained
And oxazines intermediate.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explain the certain principles and practical application of invention,
So that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes and various of invention
Different selections and change, the scope of the present invention are intended to be limited by claims and its equivalent form.
Claims (5)
1. a kind of preparation method of biology base low viscosity benzoxazine intermediate, which is characterized in that the method includes following systems
Standby process:
After polyformaldehyde and aliphatic diamine are directly stirred at room temperature, then by anacardol addition reactor, back flow reaction exists
It is reacted 4-8 hours under low temperature；
Product is washed 3-5 times with alkaline solution after reaction, is then washed with deionized water to neutrality to get low viscosity liquid is arrived
Body product；
The preparation method is disliked with the poly- aliphatic amine type benzo that formaldehyde, anacardol and binary aliphatic primary amine are main Material synthesis
Piperazine intermediate, such benzoxazine intermediate have good mobility, the benzoxazine resin of function admirable are obtained after solidification；
Wherein the chemical structural formula of the poly- aliphatic amine type benzoxazine intermediate is shown below:
Wherein, H2N-R1-NH2For aliphatic diamine.
2. a kind of preparation method of biology base low viscosity benzoxazine intermediate, feature exist according to claim 1
In aliphatic diamine is pentanediamine, hexamethylene diamine, decamethylene diamine, the alkyl diamines such as dodecamethylene diamine.
3. a kind of biology base low viscosity benzoxazine intermediate according to claim 1, which is characterized in that synthesize poly-
Aliphatic amine type benzoxazine intermediate is first to add anacardol after mixing with aliphatic diamine in 30-80 DEG C
Formalin back flow reaction 4-10 hours at this temperature, anacardol: aliphatic diamine: formaldehyde=1:2-3:0.5-2(mass
Than).
4. a kind of biology base low viscosity benzoxazine intermediate according to claim 1, which is characterized in that synthesis gathers
The viscosity of aliphatic diamine type benzoxazine is no more than 10Pa.s at a temperature of 40 DEG C.
5. a kind of biology base low viscosity benzoxazine intermediate according to claim 1, which is characterized in that gained benzo
Oxazines intermediate solidify after 800 degree under the conditions of carbon yield up to 40% or more, glass transition temperature is more than 240 DEG C, impact
Intensity is in 100MPa or more, and water absorption rate is less than 0.2%, and 1 grade of flame retardant rating.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550235A (en) * | 2009-06-02 | 2009-10-07 | 北京化工大学 | Benzoxazine colophony based on renewable resources, its composition and preparing method thereof |
| KR20160117046A (en) * | 2015-03-31 | 2016-10-10 | 코오롱인더스트리 주식회사 | Benzoxazine and Preparing Method thereof |
| CN107973888A (en) * | 2017-12-05 | 2018-05-01 | 武汉理工大学 | A kind of functional graphene oxide/full bio-based benzoxazine colophony composite material and preparation method thereof |
-
2019
- 2019-04-08 CN CN201910275545.6A patent/CN110078682A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550235A (en) * | 2009-06-02 | 2009-10-07 | 北京化工大学 | Benzoxazine colophony based on renewable resources, its composition and preparing method thereof |
| KR20160117046A (en) * | 2015-03-31 | 2016-10-10 | 코오롱인더스트리 주식회사 | Benzoxazine and Preparing Method thereof |
| CN107973888A (en) * | 2017-12-05 | 2018-05-01 | 武汉理工大学 | A kind of functional graphene oxide/full bio-based benzoxazine colophony composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘红果等: ""二胺型腰果酚基苯并噁嗪的合成工艺"", 《化工进展》 * |
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