CN101560192B - 2-oxazoline derivant and preparation method thereof - Google Patents
2-oxazoline derivant and preparation method thereof Download PDFInfo
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- CN101560192B CN101560192B CN200910143889.8A CN200910143889A CN101560192B CN 101560192 B CN101560192 B CN 101560192B CN 200910143889 A CN200910143889 A CN 200910143889A CN 101560192 B CN101560192 B CN 101560192B
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- oxazoline
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Abstract
The invention discloses a 2-oxazoline derivative and a preparation method thereof. With a propargyl functional group, the related 2-oxazoline derivative can be heated for self crosslinking and solidifying and can also be co-polymerized and crosslinked with other thermosetting resins. Furthermore, the derivative can be used as thermosetting resin or for modifying other thermosetting resin.
Description
Technical field
The present invention relates to 2-oxazoline derivant and preparation method thereof.Specifically, the present invention relates to 2-oxazoline derivant of Han You oxazoline five-ring heterocycles and propargyl groups and preparation method thereof.
Background technology
2-oxazoline is a kind of five member ring heterocyclic compound containing nitrogen oxygen atom, containing a carbon-to-nitrogen double bon in molecular structure.The people such as C.Stefano (C.Sstefano, S.Dominique, J.Comb Chem.2005,7,668) research finds, all contains 2-oxazoline structure, be day by day subject to the attention of researcher due to the chemism of its uniqueness in many bioactive compound structures.Patent about 2-oxazoline and derivative thereof is also a lot, mainly have studied 2-oxazoline compounds at acrylic coating (U.S.Patent 2,831,858 (1958), 2,897,182 (1959)), hard-gloss paint (U.S.Patent 3,348,958 (1967)), textile fabric conditioning agent (German Patent 1,048,862 (1959)), pharmaceuticals (British Patent 957,297 (1964)) and adhesive auxiliary agent (German Patent 1,287,039 (1969)) application of aspect such as.The chemical constitution of its uniqueness makes it can react with the compound with functional groups such as carboxylic acid, acid anhydrides, amido, halogen, sulfydryl, aldehyde, epoxy, hydroxyl, isocyanates.2-oxazoline compounds is used as the chain extender such as PET, nylon-6 and achieves good effect by the people such as George (P.K.George, A.P.Eleni, J.Appl.Polym.Sci.2000,77,2206).The people such as Kimura (H.Kimura, A.Matsumoto, K.Hasegawa, A.Fukuda, J.Appl.Polym.Sci.1999,72,1551) research finds that bisoxazoline joins in bisphenol A benzoxazine system by, can reduce the melt viscosity of system, the phenolic hydroxyl group Yin Fa oxazoline ring cation ring-opening reaction in system.You Yu oxazoline compound has unique chemical constitution and chemical reactivity, and it will to become increasingly abundant and perfect in the research of chemical field and polymeric material field, and its application also will be expanded day by day.
The present inventor is in " 2-oxazoline-benzo oxazinyl compound and its composition and method of making the same " (Chinese Patent Application No.: disclose 200610114118.2) and use 4-hydroxy phenyl-2-oxazoline and primary amine, formaldehyde to prepare 2-oxazoline-benzo oxazinyl compound through being dehydrated into ring.This compounds contains two kinds of polymerizable groups, and the cross-linked network of formation has good heat resistance.
But not yet find the report about the 2-oxazoline derivant containing alkynyl, the present inventor then proposes to utilize propargyl bromide and hydroxy phenyl 2-oxazoline through etherification reaction, preparation propynyloxy base phenyl 2-oxazoline compound.
Summary of the invention
The object of this invention is to provide 2-oxazoline derivant of a kind of Han You oxazoline five-ring heterocycles and propargyl groups and preparation method thereof.
2-oxazoline derivant provided by the present invention, its structure is such as formula shown in I:
(formula I)
Wherein propargyl ether be between position or contraposition.
The preparation method of 2-oxazoline derivant provided by the present invention, comprises the steps: under basic conditions, and obtained hydroxy phenyl 2-oxazoline and propargyl bromide are carried out substitution reaction, obtains propynyloxy base phenyl 2-oxazoline.
The preparation method of 2-oxazoline derivant provided by the present invention, described hydroxy phenyl 2-oxazoline: propargyl bromide: the mol ratio of highly basic is 1: 1-4: 1-7.
The preparation method of 2-oxazoline derivant provided by the present invention, described highly basic is NaOH well known to those skilled in the art, potassium hydroxide, lithium hydroxide etc.
The preparation method of 2-oxazoline derivant provided by the present invention, reaction dissolvent is water well known to those skilled in the art, methyl alcohol, cyclohexane, toluene, dimethyl formamide, dimethyl sulfoxide (DMSO) etc.
2-oxazoline derivant of the present invention has the propargyl functionalities that can react, and by the solidification of heating self-crosslinking, without the need to additional other auxiliary agent blended, and cured resin keeps higher heat resistance; Be solid under this 2-oxazoline derivant room temperature, stable performance, is easy to preserve; It prepares raw materials used wide material sources, with low cost, and combined coefficient is high.
Detailed description of the invention
Embodiment 1
The preparation of 4-propynyloxy base phenyl-2-oxazoline: in the 150ml there-necked flask being equipped with reflux condensing tube and magneton, add 1.5g (0.009mol) 4-hydroxy phenyl 2-oxazoline, 2.4g (0.06mol) NaOH, 20ml toluene, oil bath is warming up to 70 DEG C of reactions 1 hour, then the propargyl bromide 2g (0.016mol) of excessive new distillation is added, reaction is continued 4 hours at 70 DEG C, be cooled to room temperature and obtain pale yellow precipitate, filtration drying obtains 4-propynyloxy base phenyl-2-oxazoline, and productive rate is about 80%.
Compound passes through
1h-NMR and GC/MS carries out structural characterization: the chemical shift (CDCl of each functional group of gained compound
3, ppm) as follows: 7.96 (2H, D, phenyl), 7.00 (2H, D, phenyl), 4.73 (2H, S, methylene), 4.47 (2H, T, methylene), 4.06 (2H, T, methylene), 2.54 (1H, S, ≡ CH); The mass-to-charge ratio of gained compound is: m/z=201; Show that gained compound structure is correct.
Characterize with the curing action of differential calorimetric scan instrument (DSC) to gained 4-propynyloxy base phenyl-2-oxazoline, measurement atmosphere is N
2, heating rate is 10 DEG C/min.Result shows, 4-propynyloxy base phenyl-2-oxazoline is melted into liquid at 120-121 DEG C, and curing reaction occurs between 200-235 DEG C.
Evaluate with the heat endurance of thermogravimetic analysis (TGA) (TGA) to 4-propynyloxy base phenyl-2-oxazoline solidfied material: adopt the temperature of TGA thermal weight loss 5% and its hot property of residual heavy sign of 900 DEG C.Condition of cure is: N
2under condition, 160 DEG C 2 hours, 200 DEG C 2 hours, 270 DEG C 4 hours, obtain black compact solid, TGA analyze show, 5% thermal weight loss temperature of solidfied material is 321 DEG C, and the carbon left 900 DEG C time is 28%.
Embodiment 2
The preparation of 3-propynyloxy base phenyl-2-oxazoline: in the 150ml there-necked flask being equipped with reflux condensing tube and magneton, add 1.5g (0.009mol) 3-hydroxy phenyl 2-oxazoline, 2.4g (0.06mol) NaOH, 20ml toluene, oil bath is warming up to 70 DEG C of reactions 1 hour, then the propargyl bromide 2g (0.016mol) of excessive new distillation is added, reaction is continued 4 hours at 70 DEG C, be cooled to room temperature and obtain pale yellow precipitate, filtration drying obtains 3-propynyloxy base phenyl-2-oxazoline, and productive rate is about 87%.
Compound passes through
1h-NMR and GC/MS carries out structural characterization: the chemical shift (CDCl of each functional group of gained compound
3, ppm) as follows: 7.63 (2H, T, phenyl), 7.58 (1H, S, phenyl), 7.00 (1H, D, phenyl), 4.74 (2H, S, methylene), 4.47 (2H, T, methylene), 4.06 (2H, T, methylene), 2.53 (1H, S, ≡ CH); The mass-to-charge ratio of gained compound is: m/z=201; Show that gained compound structure is correct.
Characterize with the curing action of differential calorimetric scan instrument (DSC) to gained 3-propynyloxy base phenyl-2-oxazoline, measurement atmosphere is N
2, heating rate is 10 DEG C/min.Result shows, 3-propynyloxy base phenyl-2-oxazoline is melted into liquid at 117-118 DEG C, and curing reaction occurs between 200-235 DEG C.
Evaluate with the heat endurance of thermogravimetic analysis (TGA) (TGA) to 4-propynyloxy base phenyl-2-oxazoline solidfied material: adopt the temperature of TGA thermal weight loss 5% and its hot property of residual heavy sign of 900 DEG C.Condition of cure is: N
2under condition, 160 DEG C 2 hours, 200 DEG C 2 hours, 270 DEG C 4 hours, obtain black compact solid, TGA analyzes and shows, 5% thermal weight loss temperature of solidfied material is 329 DEG C, and residual heavy 900 DEG C time is 32%.
Embodiment 3
According to embodiment 1, just sodium hydroxide concentration is 2.52g (0.063mol), and other raw material dosage, reaction condition are identical with embodiment 1, productive rate 89%.
Embodiment 4
According to embodiment 1, just sodium hydroxide concentration is 0.36g (0.009mol), and other raw material dosage, reaction condition are identical with embodiment 1, productive rate 46.2%.
Embodiment 5
According to embodiment 1, just sodium hydroxide concentration is 2.52g (0.063mol), propargyl bromide 4.5g (0.036mol), and other raw material dosage, reaction condition are identical with embodiment 1, productive rate 85%.
Embodiment 6
According to embodiment 1, just sodium hydroxide concentration is 2.52g (0.063mol), propargyl bromide 1.125g (0.009mol), and other raw material dosage, reaction condition are identical with embodiment 1, productive rate 26%.
Claims (3)
1. a class 2-oxazoline derivant, is characterized in that having structure as follows:
Wherein propargyl ether be between position or contraposition.
2. the preparation method of 2-oxazoline derivant according to claim 1, it is characterized in that: under basic conditions, 4-hydroxy phenyl 2-oxazoline or 3-hydroxy phenyl 2-oxazoline and propargyl bromide are carried out substitution reaction, obtains 4-propynyloxy base phenyl 2-oxazoline or 3-propynyloxy base phenyl 2-oxazoline.
3. the preparation method of 2-oxazoline derivant according to claim 2, is characterized in that: hydroxy phenyl 2-oxazoline: propargyl bromide: the mol ratio of highly basic is 1: 1-4: 1-7.
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2009
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| US4886868A (en) * | 1985-07-01 | 1989-12-12 | Rhone-Poulenc Specialites Chimiques | Thermosetting composition from bis-maleimide and n-allyl oxy-phenyl maleimide |
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| CN1944429A (en) * | 2006-10-30 | 2007-04-11 | 北京化工大学 | 2-oxazolinyl-benzo oxazinyl compound and its composition and preparing method |
| CN101323602A (en) * | 2007-06-14 | 2008-12-17 | 上海商学院 | 2-oxazoline derivates and method for preparing the same |
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