CN108997574A - A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization - Google Patents
A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization Download PDFInfo
- Publication number
- CN108997574A CN108997574A CN201810961895.3A CN201810961895A CN108997574A CN 108997574 A CN108997574 A CN 108997574A CN 201810961895 A CN201810961895 A CN 201810961895A CN 108997574 A CN108997574 A CN 108997574A
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- isonitrile
- polyamide
- prepared
- reaction
- 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.)
- Pending
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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/38—Polyamides prepared from aldehydes and polynitriles
Abstract
The present invention relates to nylon material fields, the method for preparing polyamide-based derivative is copolymerized by benzoxazine and isonitrile more particularly to a kind of, using benzoxazine compounds, different nitrile compounds and water under conditions of catalyst, by the room temperature of short time, synthesis under normal pressure, polyamide-based derivative can be obtained.The method of the present invention is easy to operate, is not necessarily to metal catalytic, and water energy directly participates in reaction and the reaction time is short, and resulting polymers structure is clear, is the mass production of such material and lays a solid foundation with follow-up study.
Description
Technical field
The present invention relates to nylon material fields, and in particular to one kind is prepared by benzoxazine with isonitrile copolymerization polyamide-based
The method of derivative.
Background technique
Polyamide (PA), is commonly called as nylon, and in last century the '30s, DuPont Corporation just has been realized in the industry of PA
Change.PA has wear-resisting, oil resistant, weak acid and alkali resistance, self-lubricating, self-extinguishment, insulation, mechanics as a kind of high performance engineering plastics
The features such as function admirable, makes it be widely used in automobile, mechanical, electronic apparatus, aerospace etc..Polyamide is usually by two
Kind of method is prepared, first is that the ring-opening polymerisation of lactams, second is that by diacid/diester and diamine/amino fatty acid polycondensation and
At not having Atom economy such as, and pair can be generated during the reaction however, both methods all has certain defect
Product etc..So the synthetic method and modified research to polyamide have great significance.Benzoxazine is that one kind contains N, O's
Open loop can occur under high temperature or acid condition for 6-membered heterocyclic compound, after open loop can self-polymerization formed polybenzoxazine,
It can also be reacted with some nucleopilic reagents.Currently, it is many for the research of benzoxazine self-polymerization, and for itself and parent
The correlative study of the reaction of core reagent is relatively fewer, as can the synthesis of polymer is carried out using such reaction, for benzoxazine
The development of chemistry has great significance.
Summary of the invention
In view of the above technical problems, the present invention is using benzoxazine, isonitrile and water as raw material, provide it is a kind of prepare it is poly-
The method of amide derivatives can quickly prepare polyamide-based derivative under no metal catalytic and room temperature condition of normal pressure.
Specific technical solution are as follows:
A method of polyamide-based derivative, including following procedure are prepared by benzoxazine and isonitrile copolymerization:
(1) synthesis of benzoxazine compounds.
In reaction vessel, phenolic substances, primary amine substance and aldehyde material is added, adds low polar solvent, reflux is anti-
After answering 6-12h, reaction to stop, organic phase is washed with lye and deionized water respectively, is then isolated and purified using column chromatography,
Benzoxazine is obtained after drying.Wherein the ratio between amount of phenolic hydroxyl group, amino, aldehyde radical substance is 1:1-1.2:2-2.4, aldehyde material
For formalin or paraformaldehyde, low polar solvent is at least one of chloroform, dioxane, toluene, dimethylbenzene.
Its reaction equation is one such as follows:
Wherein R1For following one kind: the hetero atoms such as N, Si, O, S, P, sulfonyl, the alkyl chain of C1 to C10, C1 to C10's
Containing heteroatomic aliphatic chain, the aromatic ring of C6-C20；
R2For following one kind: the alkyl chain of C1 to C10, in the aromatic ring of C6-C20；
R3For following one kind: the alkyl chain of C1 to C10, in the aromatic ring of C6-C20；
R4For following one kind: the alkyl chain of C1 to C10, in the aromatic ring of C6-C20.
(2) synthesis of different nitrile compounds.
In reaction vessel, amine substance is added, adds methylene chloride as solvent, then sequentially adds chloroform and surface
Activating agent back flow reaction 1-5 hours under alkaline condition, is washed with deionized three times after reaction, then passes through column color
Separating-purifying is composed, obtains product after dry.Wherein the ratio between amount of substance of amino, chloroform is 1:0.8-1.2, and surfactant is
One of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium fluoride, tetrabutylammonium hydroxide, alkaline environment is by hydrogen-oxygen
Change sodium solution or potassium hydroxide solution provides.
Its reaction equation is as follows:
R5For the alkyl chain of C1 to C10, C1 to C10's contains heteroatomic aliphatic chain, one of aromatic ring of C6-C20.
(3) synthesis of polyamide derivative
In reaction vessel, benzoxazine compounds, different nitrile compounds and water is added, adds low polar solvent and urges
Agent is reacted 3-12 hours under room temperature, is carried out reprecipitation operation after crude product is concentrated, is obtained product after filtering.Wherein low pole
Property solvent be one of methylene chloride, chloroform, toluene, catalyst be p-methyl benzenesulfonic acid, acetic acid, picric acid, silica gel, iodate
One of lithium, aluminium chloride, iron chloride, phosphorus pentachloride, phenyl hypophosphorous acid, octylphosphonic acid, the solvent that reprecipitation uses be methanol,
One of ether, petroleum ether.
Its reaction equation is one such as follows:
A kind of method that polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization provided by the invention, operation letter
It is single, it is not necessarily to metal catalytic, water energy directly participates in reaction and the reaction time is short, and resulting polymers structure is clear, is such material
It mass production and lays a solid foundation with follow-up study.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of substance M1, M2 and P1 in embodiment；
Fig. 2 is the infrared spectrogram of substance M3, M4 and P2 in embodiment；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of substance M1 in embodiment；
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of substance M2 in embodiment；
Fig. 5 is the nucleus magnetic hydrogen spectrum figure of substance M3 in embodiment；
Fig. 6 is the nucleus magnetic hydrogen spectrum figure of substance M4 in embodiment；
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of Substance P 1 in embodiment；
Fig. 8 is the nucleus magnetic hydrogen spectrum figure of Substance P 2 in embodiment.
Specific embodiment
It is described in conjunction with the embodiments the specific technical solution of the present invention.
Embodiment 1
(1) difunctional benzoxazine (M1): 1,4- bis- (2- (4- (6- nonyl -2H- benzo [e] [1,3] e oxazines -3
(4H)-yl) phenyl) propyl- 2- yl) and benzene synthesis, reaction equation is as follows:
By 4,4 '-(1,3- phenylene diisopropylidene) diphenylamines (1.378g, 4mmol), nonyl phenol (1.76g,
8mmol), paraformaldehyde (480mg, 16mmol) is added in two-mouth bottle, adds 16mL toluene as reaction dissolvent, back flow reaction
10h, crude product are washed three times with the sodium hydroxide solution of 0.1M and deionized water respectively, utilize silica gel column chromatography after boiling off solvent
Separation, eluent is petroleum ether: ethyl acetate=30:1, and faint yellow solid (1.5g) is obtained after drying.FT-IR(KBr,cm-
1): 3035,2959,2868,1613,1504,1454,1237 (C-O-C), 1017,945 (oxazines rings), 829.1H NMR
(400MHz,CDCl3) δ (ppm): 7.10 (dd, J=10.8,4.2Hz, 9H), 7.02-6.80 (m, 7H), 6.72 (dd, J=
8.4,3.9Hz,2H),5.30(s,4H),4.57(s,4H),1.70–1.51(m,16H),1.33–1.07(m,16H),0.90–
0.49(m,18H)。
(2) synthesis of difunctional isonitrile (M2): 4,4'- bis- isonitrile yl diphenyl ethers, reaction equation are as follows:
4,4'- diaminodiphenyl ether (1g, 5mmol) is added in two-mouth bottle, adds 10mL methylene chloride as solvent,
Then chloroform (407 μ L, 5mmol), the hydroxide of tetrabutylammonium hydroxide (26mg, 0.1mmol) and 10mL 50% are sequentially added
Sodium solution, back flow reaction 3 hours, deionized water was washed three times, was separated after boiling off solvent by aluminum oxide column chromatography, eluent is
Petroleum ether: ethyl acetate=10:1 obtains yellow solid (750mg) after drying.FT-IR(KBr,cm-1):3070,2125(C≡
N),1589,1486,1245,837.1H NMR(400MHz,CDCl3)δ(ppm):7.43–7.35(m,4H),7.04–6.98(m,
4H)。
(3) synthesis of polyamide-based derivative P1, reaction equation are as follows:
By benzoxazine M1 (208mg, 0.25mmol), isonitrile M2 (55mg, 0.25mmol), OPA (19.4mg,
It 0.1mmol) is added in two-mouth bottle with water (9 μ L, 0.5mmol), adds chloroform 5mL as reaction dissolvent, react 3h under room temperature,
After concentrating part solvent, instills in 200mL ether and carry out reprecipitation, yellow powder (204mg) is obtained after filtration drying.FT-IR
(KBr, cm-1): 3301,3035,2963,2922,2868,1672,1611,1501,1302,1214,822.1H NMR
(400MHz,CDCl3)δ(ppm):9.15,7.21–6.13,4.43,3.85,2.03–0.24.The test map of each substance is as schemed
1, shown in Fig. 3, Fig. 4, Fig. 7.
Embodiment 2
(1) difunctional benzoxazine (M3): 3,3'- dihexyl -3,3', 4,4'- tetrahydro -2H, 2'H-6,6'- dibenzo
The synthesis of [e] [1,3] oxazines, reaction equation are as follows:
By xenol (744mg, 4mmol), hexylamine (696g, 8mmol), paraformaldehyde (480mg, 16mmol) is added two mouthfuls
In bottle, add 16mL toluene as reaction dissolvent, back flow reaction 10h, crude product use respectively the sodium hydroxide solution of 0.1M with
Deionized water is washed three times, is separated after boiling off solvent using silica gel column chromatography, and eluent is petroleum ether: ethyl acetate=30:1,
White solid (760mg) is obtained after drying.FT-IR(KBr,cm-1):3002,2922,2857,1607,1578,1484,1222
(C-O-C), 927 (oxazines ring), 811.1H NMR(400MHz,CDCl3) δ (ppm): 7.27 (dd, J=8.3,2.1Hz, 2H),
7.11 (d, J=2.1Hz, 2H), 6.81 (d, J=8.4Hz, 2H), 4.89 (s, 4H), 4.03 (s, 4H), 2.80-2.71 (m,
4H), 1.62-1.51 (m, 4H), 1.36-1.26 (m, 12H), 0.88 (t, J=6.8Hz, 6H).
(2) synthesis of difunctional isonitrile (M4): 4,4'- bis- different cyanobiphenyls, reaction equation are as follows:
Benzidine (920mg, 5mmol) is added in two-mouth bottle, adds 10mL methylene chloride as solvent, then according to
Secondary addition chloroform (407 μ L, 5mmol), the sodium hydroxide of tetrabutylammonium hydroxide (26mg, 0.1mmol) and 10mL 50% are molten
Liquid, back flow reaction 3 hours, deionized water was washed three times, was separated after boiling off solvent by aluminum oxide column chromatography, eluent is petroleum
Ether: ethyl acetate=10:1 obtains yellow solid (650mg) .FT-IR (KBr, cm after drying-1):3030,2124(C≡N),
1640,1486,816.1H NMR(400MHz,CDCl3)δ(ppm):7.63–7.55(m,4H),7.52–7.44(m,4H).
(3) synthesis of polyamide-based derivative P2, reaction equation are as follows:
By benzoxazine M3 (109mg, 0.25mmol), isonitrile M4 (51mg, 0.25mmol), OPA (19.4mg,
It 0.1mmol) is added in two-mouth bottle with water (9 μ L, 0.5mmol), adds chloroform 5mL as reaction dissolvent, react 3h under room temperature,
After concentrating part solvent, instills in 200mL ether and carry out reprecipitation, white powder (60mg) is obtained after filtration drying.Each substance
Test map as shown in Fig. 2, Fig. 5, Fig. 6, Fig. 8.
Claims (6)
1. a kind of be copolymerized the method for preparing polyamide-based derivative by benzoxazine and isonitrile, which is characterized in that including following
Step: benzoxazine compounds, different nitrile compounds and water are added in reaction vessel, adds low polar solvent and catalysis
Agent is reacted 3-12 hours under room temperature, is carried out reprecipitation operation after crude product is concentrated, is obtained product after filtering.
2. a kind of method that polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization according to claim 1,
It is characterized in that, the low polar solvent is one of methylene chloride, chloroform, toluene, the catalyst is to toluene
Sulfonic acid, acetic acid, picric acid, silica gel, lithium iodide, aluminium chloride, iron chloride, phosphorus pentachloride, phenyl hypophosphorous acid, in octylphosphonic acid
One kind, the solvent that the reprecipitation uses are one of methanol, ether, petroleum ether.
3. a kind of method that polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization according to claim 1,
It is characterized in that, the benzoxazine compounds, are difunctional benzoxazine；Gained is prepared by following methods: reaction
Phenolic substances, primary amine substance and aldehyde material are added in container, adds low polar solvent, back flow reaction 6-12h, reaction stops
After only, organic phase is washed with lye and deionized water respectively, is then isolated and purified using column chromatography, obtains benzene after dry
And oxazines.
4. a kind of method that polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization according to claim 3,
It is characterized in that, the ratio between the phenolic hydroxyl group, amount of amino, aldehyde radical substance are 1:1-1.2:2-2.4, the aldehyde material is
Formalin or paraformaldehyde, the low polar solvent are at least one of chloroform, dioxane, toluene, dimethylbenzene.
5. a kind of method that polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization according to claim 1,
It is characterized in that, the different nitrile compounds, are difunctional isonitrile；Gained is prepared by following methods: being added in reaction vessel
Enter amine substance, adds methylene chloride as solvent, then sequentially add chloroform and surfactant, return under alkaline condition
Stream reaction 1-5 hours, is washed with deionized three times after reaction, is then purified by pillar layer separation, obtains after dry
Product.
6. a kind of method that polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization according to claim 5,
It is characterized in that, the ratio between amount of substance of the amino, chloroform be 1:1, the surfactant be tetrabutylammonium chloride,
One of tetrabutylammonium bromide, tetrabutyl ammonium fluoride, tetrabutylammonium hydroxide, the alkaline environment is by sodium hydroxide solution
Or potassium hydroxide solution provides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810961895.3A CN108997574A (en) | 2018-08-22 | 2018-08-22 | A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810961895.3A CN108997574A (en) | 2018-08-22 | 2018-08-22 | A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108997574A true CN108997574A (en) | 2018-12-14 |
Family
ID=64593024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810961895.3A Pending CN108997574A (en) | 2018-08-22 | 2018-08-22 | A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108997574A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041345A (en) * | 2019-05-10 | 2019-07-23 | 福建泓光半导体材料有限公司 | A kind of resist lower membrane monomer and composition and pattern forming method |
| CN113278164A (en) * | 2021-05-13 | 2021-08-20 | 电子科技大学 | Preparation method of high-strength thermosetting resin hydrogel material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103748084A (en) * | 2011-08-11 | 2014-04-23 | 亨斯迈先进材料美国有限责任公司 | Method for producing benzoxazine compounds |
| US20140206864A1 (en) * | 2011-10-18 | 2014-07-24 | Shengyi Technology Co., Ltd. | Benzoxazine intermediate and preparation method thereof |
| CN106366309A (en) * | 2016-08-25 | 2017-02-01 | 浙江大学 | Polyamide compound and preparation method of same |
-
2018
- 2018-08-22 CN CN201810961895.3A patent/CN108997574A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103748084A (en) * | 2011-08-11 | 2014-04-23 | 亨斯迈先进材料美国有限责任公司 | Method for producing benzoxazine compounds |
| US20140206864A1 (en) * | 2011-10-18 | 2014-07-24 | Shengyi Technology Co., Ltd. | Benzoxazine intermediate and preparation method thereof |
| CN106366309A (en) * | 2016-08-25 | 2017-02-01 | 浙江大学 | Polyamide compound and preparation method of same |
Non-Patent Citations (2)
| Title |
|---|
| 张艺鹏: ""苯并噁嗪和异腈化合物的制备及性质分析"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 恽魁宏主编: "《有机化学（第二版）》", 31 May 1990, 高等教育出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041345A (en) * | 2019-05-10 | 2019-07-23 | 福建泓光半导体材料有限公司 | A kind of resist lower membrane monomer and composition and pattern forming method |
| CN113278164A (en) * | 2021-05-13 | 2021-08-20 | 电子科技大学 | Preparation method of high-strength thermosetting resin hydrogel material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2955169B1 (en) | Novel allyl compound and method for producing the same | |
| CN108383733A (en) | Diamine monomer containing tertiary butyl and cycloaliphatic ring and its preparation and application | |
| US20140213789A1 (en) | Stannyl derivatives of naphthalene diimides and related compositions and methods | |
| CN108997574A (en) | A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization | |
| CN103172523B (en) | The method of the selective N-primary amine that methylates | |
| CN106938976B (en) | A method of imine compound is prepared by catalytic material oxidation of alkohol and amine | |
| CN103274908B (en) | Bisphenol monomer containing bi-tert-butyl and fluorenyl structure, and preparation method and application thereof | |
| CN104193999B (en) | A kind of preparation method of fluorine silicon benzoxazine multipolymer | |
| CN102424645A (en) | Method for synthesizing aromatic amide and aromatic methanol | |
| CN102206178A (en) | Method for preparing imrecoxib | |
| CN102234256A (en) | Novel diepoxide | |
| CN104860833A (en) | Purification method of dobutamine hydrochloride | |
| CN109942436B (en) | Method for preparing N, N-dialkyl aniline compound by alkylation of alkyl p-toluenesulfonate | |
| CN106946682B (en) | A kind of preparation method of propine acid compounds | |
| CN103724237B (en) | A kind of containing fluorene structured sulfonated aromatic diamine monomer of tetramethyl-and preparation method thereof | |
| CN105384652A (en) | Method for preparing 2,5-di(substituted) arylamino terephthalic acid | |
| CN101367762B (en) | Preparation method of midbody 7-chloroquinaldine | |
| CN109422656B (en) | Method for synthesizing nonane diamine | |
| CN106187943B (en) | A kind of preparation method of 1,4- benzothiazines | |
| CN111153854B (en) | Preparation method of 2-methylquinoline | |
| CN105152903A (en) | Preparation method for aliphatic dicarboxylic acids | |
| CN104525253B (en) | Application of triethylene diamine as catalyst in catalyzing reaction of aromatic aldehyde and nitro-hydrocarbon to generate nitryl aromatic alcohol | |
| CN109796372B (en) | Method for preparing polysubstituted alkenyl amidine | |
| CN113717207B (en) | Method for synthesizing indene compounds | |
| CN109336741B (en) | Preparation method of substituted styrene |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181214 |
|
| RJ01 | Rejection of invention patent application after publication |