CN104910201A - Disiloxane-based aromatic diamine and preparation method thereof - Google Patents
Disiloxane-based aromatic diamine and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a disiloxane-based aromatic diamine and a preparation method thereof, 1,3-divinyl-1,1,3,3-tetra-substituted disiloxane and nitro-styrene are used as raw materials for catalytic olefin metathesis reaction to produce intermediate 1,3-bis (nitrostyryl)-1,1,3,3-tetra-substituted disiloxane, and the corresponding disiloxane-based aromatic diamine can be obtained by catalytic hydrogenation. Two amino group-containing benzene rings of the compound are connected respectively by two carbon atoms with a silicon atom, two silicon atoms are connected by an oxygen atom, and the disiloxane-based aromatic diamine has good flexibility, flame retardancy and heat resistance. The synthesis process of the disiloxane-based aromatic diamine has the characteristics of simple operation, mild conditions, high yield, low cost, greenness and environmental friendliness, solves the problems of high cost, serious three wastes and the like of the prior art, and has high industrial value.
Description
Technical field
The present invention relates to a kind of aromatic diamine based on sily oxide and preparation method thereof.
Background technology
Aromatic diamine is the important monomer of macromolecular material polymeric amide, polyimide etc., also be the important solidifying agent of epoxy resin, siliceous aromatic diamine is a wherein important class, the introducing of silicon can improve the key property such as thermotolerance, snappiness, flame retardant resistance of material, is thus paid attention to widely.
Siliceous aromatic diamine conventional at present is mainly divided into following a few class: the first kind is directly connected with silicon containing amino phenyl ring, if dimethyl two (3-aminophenyl) silane (7) is (as Pratt etc., Journal of Organic Chemistry, 1975,40,1090-1094) He 1,3-bis-(4-aminophenyl)-1,1,3,3-tetramethyl disiloxane (8) (as Dougherty etc., US Patent No. 5286890); Equations of The Second Kind is connected with silicon through Sauerstoffatom containing amino phenyl ring, if dimethyl two (4-amino-benzene oxygen) silane (9) is (as Patterson, US Patent No. 3660434) and 1,3-bis-(4-amino-benzene oxygen)-1,1,3,3-tetramethyl disiloxane (10) (as Rossi etc., US Patent No. 4581461); 3rd class contains Sauerstoffatom and carbon atom containing the connection between amino phenyl ring and silicon simultaneously, as 1,3-bis-[(4-p-aminophenyl oxygen base) butyl]-1,1,3,3-tetramethyl disiloxane (11) is (as Shoji etc., Chemistry Letters, 2009,38 (7), 716-717).Wherein the compound of first kind structure needs to use the synthesis of organolithium, organic sodium or organomagnesium reagent, and condition is comparatively harsh, and amino needs the raw material protecting or use nitro in advance, increases the additional step of Deprotection or reduction; The compound of Equations of The Second Kind structure reacts with p-aminophenol and dichloro (or dialkoxy) silane or dichloro (or dialkoxy) sily oxide to be prepared, but oxygen siloxane bond connects the defects such as existence and stability is not enough; The compound of the 3rd class formation uses hydrosilation reaction preparation, and platinum catalyst is expensive, and the flexible chain between two phenyl ring is long.
Therefore, existing siliceous aromatic diamine poor performance, and/or synthetic method complex operation, condition is harsh, yield is on the low side, serious three wastes etc., is difficult to realize large-scale industrial production.
Summary of the invention
An object of the present invention is to provide a kind of aromatic diamine based on sily oxide with new molecular architecture, two are connected with a Siliciumatom through two carbon atoms respectively containing amino phenyl ring, connect with a Sauerstoffatom between two Siliciumatoms, resulting structures has good snappiness, flame retardant resistance and thermotolerance concurrently again.
The aromatic diamine based on sily oxide that the present invention proposes, its molecular structure is such as formula (1)
shown in, wherein, amino at phenyl ring 3 or 4, R
1during for methyl, R
2for methyl, phenyl or 3,3,3-trifluoro propyl, R
1during for phenyl, R
2for phenyl or 3,3,3-trifluoro propyl.
Consider the snappiness of aromatic diamine, the connection of aryl and silicon, the difficulty or ease of synthesis, and the factor such as economy, the present invention especially proposes such as formula (2)
with formula (3)
the shown aromatic diamine based on sily oxide, wherein R
1during for methyl, R
2for methyl or phenyl, R
1during for phenyl, R
2for phenyl.
Above-claimed cpd is applied in the materials such as aromatic polyamide, polyimide, epoxy resin, compared with existing siliceous aromatic diamine, shows better comprehensive physicochemical property.
Another object of the present invention is to provide the preparation method that one has the aromatic diamine based on sily oxide of above-mentioned general formula (1) constitutional features, can overcome the shortcomings such as severe reaction conditions in existing synthesis technique, complex operation, yield are low, serious three wastes.
Above-mentioned purpose of the present invention is achieved by following scheme:
First, 1, the 3-divinyl-1,1,3,3-tetra-such as formula structure (5) Suo Shi replaces sily oxide,
Wherein, R
1during for methyl, R
2for methyl, phenyl or 3,3,3-trifluoro propyl, R
1during for phenyl, R
2for phenyl or 3,3,3-trifluoro propyl, with the nitrostyrolene such as formula structure (4) Suo Shi,
Wherein nitro is at 3 or 4 of phenyl ring, and under the catalysis of ruthenium catalyst, the replacement(metathesis)reaction through alkene obtains replacing sily oxide such as formula the intermediate 1,3-bis-(nitrostyrolene base)-1,1,3,3-tetra-of structure (6) Suo Shi,
Wherein, nitro at 3 or 4 of phenyl ring, R
1during for methyl, R
2for methyl, phenyl or 3,3,3-trifluoro propyl, R
1during for phenyl, R
2for phenyl or 3,3,3-trifluoro propyl.
Then, upper step gained is such as formula intermediate 1,3-bis-(the nitrostyrolene base)-1,1 of structure (6) Suo Shi, 3,3-tetra-replaces sily oxide under the catalysis of nickel or palladium or platinum catalyst, obtains product 1,3-bis-(aminophenethyl)-1 such as formula structure (1) Suo Shi through hydrogenating reduction, 1,3,3-tetra-replaces sily oxide
The i.e. aromatic diamine based on sily oxide of the present invention, wherein, amino at phenyl ring 3 or 4, R
1during for methyl, R
2for methyl, phenyl or 3,3,3-trifluoro propyl, R
1during for phenyl, R
2for phenyl or 3,3,3-trifluoro propyl.
The reaction formula of preparation method of the present invention is as follows, and wherein nitro or amino are at 3 or 4 of phenyl ring, R
1during for methyl, R
2for methyl, phenyl or 3,3,3-trifluoro propyl, R
1during for phenyl, R
2for phenyl or 3,3,3-trifluoro propyl.
The preparation method of the aromatic diamine based on sily oxide provided by the invention, the ruthenium catalyst preferred ruthenium catalyst I or ruthenium catalyst II or ruthenium catalyst III that olefin metathesis reaction is used.The structure of these catalyzer is as follows, and wherein Cy is cyclohexyl, and Mes is 2,4,6-trimethylphenyl.
Aforesaid method provided by the invention has the features such as simple to operate, mild condition, product yield are high, quality good, cost is low, the three wastes are few, has higher industrial value.
Embodiment
Following examples are raw materials used, solvent etc. is technical grade product, without being further purified.Assay uses high performance liquid chromatography (HPLC) normalization method.Ultimate analysis and mass spectrum (MS) structural characterization use elemental analyser and mass spectrograph respectively.
the replacement(metathesis)reaction of alkene:
the synthesis of embodiment 11,3-bis-(4-nitrostyrolene base)-1,1,3,3-tetramethyl disiloxane
Under nitrogen protection; by 1; 3-divinyl-1; 1; the 90mL dichloromethane solution of 3,3-tetramethyl disiloxane 18.6g (0.10 mol), 4-nitrostyrolene 35.8g (0.24mol) is heated to the 15min that refluxes, and adds 3.2g ruthenium catalyst I; stirring and refluxing reaction 12h; boil off solvent, residue, with isopropyl acetate recrystallization, obtains off-white color solid product 1; 3-bis-(4-nitrostyrolene base)-1; 1,3,3-tetramethyl disiloxane 39.9g; yield 93.2%, content 97.8%.Ultimate analysis measured value (calculated value)/%:C 56.24(56.07), H 5.80(5.61).MS（m/z）：429 [M+H]
+。
the synthesis of embodiment 21,3-bis-(3-nitrostyrolene base)-1,3-dimethyl-1,3-phenylbenzene sily oxide
Under nitrogen protection; by 1; 3-divinyl-1; 3-dimethyl-1; the 100mL cyclohexane solution of 3-phenylbenzene sily oxide 31.0g (0.10 mol), 3-nitrostyrolene 34.3g (0.23mol) is heated to 60 DEG C; add 2.4g ruthenium catalyst III; stir insulation reaction 12h, boil off solvent, residue is with recrystallisation from isopropanol; obtain off-white color solid product 1; 3-bis-(3-nitrostyrolene base)-1,3-dimethyl-1,3-phenylbenzene sily oxide 52.6g; yield 95.3%, content 98.4%.Ultimate analysis measured value (calculated value)/%:C 65.41(65.22), H 5.22(5.07).MS（m/z）：553 [M+H]
+。
the synthesis of embodiment 31,3-bis-(4-nitrostyrolene base)-1,1,3,3-tetraphenyl sily oxide
Under nitrogen protection; by 1; 3-divinyl-1; 1; the 100mL benzole soln of 3,3-tetraphenyl sily oxide 43.4g (0.10 mol), 4-nitrostyrolene 34.3g (0.23mol) is heated to backflow, adds 3.0g ruthenium catalyst II; stirring and refluxing reaction 10h; boil off solvent, residue, with isopropyl acetate recrystallization, obtains off-white color solid product 1; 3-bis-(4-nitrostyrolene base)-1; 1,3,3-tetraphenyl sily oxide 65.1g; yield 96.3%, content 98.4%.Ultimate analysis measured value (calculated value)/%:C 71.23(71.01), H 4.87(4.73).MS（m/z）：677 [M+H]
+。
the synthesis of embodiment 41,3-bis-(3-nitrostyrolene base)-1,3-dimethyl-1,3-bis-(3,3,3-trifluoro propyl) sily oxide
Under nitrogen protection; by 1; 3-divinyl-1,3-dimethyl-1,3-bis-(3; 3; 3-trifluoro propyl) sily oxide 35.0g (0.10 mol), 3-nitrostyrolene 37.3g (0.25mol) 100mL toluene solution be heated to 80 DEG C, add 2.5g ruthenium catalyst II, stir insulation reaction 10h; boil off solvent; residue, with isopropyl acetate recrystallization, obtains off-white color solid product 1,3-bis-(3-nitrostyrolene base)-1; 3-dimethyl-1; 3-bis-(3,3,3-trifluoro propyl) sily oxide 55.4g; yield 93.6%, content 98.3%.Ultimate analysis measured value (calculated value)/%:C 48.78(48.65), H 4.56(4.39).MS（m/z）：593 [M+H]
+。
the synthesis of embodiment 51,3-bis-(4-nitrostyrolene base)-1,3-phenylbenzene-1,3-bis-(3,3,3-trifluoro propyl) sily oxide
Under nitrogen protection; by 1; 3-divinyl-1,3-phenylbenzene-1,3-bis-(3; 3; 3-trifluoro propyl) sily oxide 47.4g (0.10 mol), 4-nitrostyrolene 35.8g (0.24mol) 110mL dichloromethane solution be heated to backflow, add 2.6g ruthenium catalyst III, stirring and refluxing reaction 15h; boil off solvent; residue, with butylacetate recrystallization, obtains off-white color solid product 1,3-bis-(4-nitrostyrolene base)-1; 3-phenylbenzene-1; 3-bis-(3,3,3-trifluoro propyl) sily oxide 68.4g; yield 95.5%, content 98.5%.Ultimate analysis measured value (calculated value)/%:C 57.16(56.98), H 4.33(4.19).MS（m/z）：717 [M+H]
+。
the catalytic hydrogenation of ethylene linkage:
the synthesis of embodiment 61,3-bis-(4-aminophenethyl)-1,1,3,3-tetramethyl disiloxane
Add Raney's nickel catalyst 1.5g in the solution of embodiment 1 products therefrom 25.0g and 100mL ethanol, with nitrogen replacement air, then be charged to 15 kilograms of pressure with hydrogen exchange nitrogen, stirring and refluxing reaction no longer declines to hydrogen pressure, cooling, elimination catalyzer, remove solvent under reduced pressure, residue, with butylacetate recrystallization, obtains off-white color solid product 1,3-bis-(4-aminophenethyl)-1,1,3,3-tetramethyl disiloxane 20.5g, yield 94.3%, content 98.6%.Ultimate analysis measured value (calculated value)/%:C 64.67(64.52), H 8.78(8.60).MS（m/z）：373 [M+H]
+。
the synthesis of embodiment 71,3-bis-(3-aminophenethyl)-1,3-dimethyl-1,3-phenylbenzene sily oxide
Add 10% Pd/carbon catalyst 0.8g in the solution of embodiment 2 products therefrom 28.0g and 100mL Virahol, with nitrogen replacement air, then be charged to 12 kilograms of pressure with hydrogen exchange nitrogen, stirring and refluxing reaction no longer declines to hydrogen pressure, cooling, elimination catalyzer, remove solvent under reduced pressure, residue, with re-crystallizing in ethyl acetate, obtains off-white color solid product 1,3-bis-(3-aminophenethyl)-1,3-dimethyl-1,3-phenylbenzene sily oxide 24.1g, yield 95.8%, content 98.3%.Ultimate analysis measured value (calculated value)/%:C 72.77(72.58), H 7.39(7.26).MS（m/z）：497 [M+H]
+。
the synthesis of embodiment 81,3-bis-(4-aminophenethyl)-1,1,3,3-tetraphenyl sily oxide
Add 5% Pd/carbon catalyst 1.2g in the solution of embodiment 3 products therefrom 30.0g and 90mL methyl alcohol, with nitrogen replacement air, then be charged to 12 kilograms of pressure with hydrogen exchange nitrogen, stirring and refluxing reaction no longer declines to hydrogen pressure, cooling, elimination catalyzer, remove solvent under reduced pressure, residue, with ethyl acetate/recrystallisation from isopropanol, obtains off-white color solid product 1,3-bis-(4-aminophenethyl)-1,1,3,3-tetraphenyl sily oxide 26.0g, yield 94.5%, content 98.4%.Ultimate analysis measured value (calculated value)/%:C 77.67(77.42), H 6.56(6.45).MS（m/z）：621 [M+H]
+。
the synthesis of embodiment 91,3-bis-(3-aminophenethyl)-1,3-dimethyl-1,3-bis-(3,3,3-trifluoro propyl) sily oxide
Raney's nickel catalyst 1.8g is added in the solution of embodiment 4 products therefrom 30.0g and 110mL Virahol, with nitrogen replacement air, 20 kilograms of pressure are charged to again with hydrogen exchange nitrogen, stirring and refluxing reaction no longer declines to hydrogen pressure, cooling, elimination catalyzer, removes solvent under reduced pressure, and residue is with butylacetate recrystallization, obtain off-white color solid product 1,3-bis-(3-aminophenethyl)-1,3-dimethyl-1,3-bis-(3,3,3-trifluoro propyl) sily oxide 25.4g, yield 93.5%, content 98.3%.Ultimate analysis measured value (calculated value)/%:C 53.96(53.73), H 6.60(6.34).MS（m/z）：537 [M+H]
+。
the synthesis of embodiment 10 1,3-bis-(4-aminophenethyl)-1,3-phenylbenzene-1,3-bis-(3,3,3-trifluoro propyl) sily oxide
Platinum catalyst 1.0g is added in the solution of embodiment 5 products therefrom 26.0g and 100mL methyl alcohol, with nitrogen replacement air, 8 kilograms of pressure are charged to again with hydrogen exchange nitrogen, stirring and refluxing reaction no longer declines to hydrogen pressure, cooling, elimination catalyzer, removes solvent under reduced pressure, and residue is with isopropyl acetate recrystallization, obtain off-white color solid product 1,3-bis-(4-aminophenethyl)-1,3-phenylbenzene-1,3-bis-(3,3,3-trifluoro propyl) sily oxide 22.5g, yield 93.9%, content 98.5%.Ultimate analysis measured value (calculated value)/%:C 62.03(61.82), H 5.91(5.76).MS（m/z）：661 [M+H]
+。
the present invention is based on the aromatic diamine and 4 of sily oxide, the Performance comparision of 4 '-diaminodiphenylmethane, structural formula (7) and structural formula (8) siliceous diamine solidification bisphenol A type epoxy resin moulding material
respectively with the aromatic diamine based on sily oxide synthesized by the present invention, 4,4 '-diaminodiphenylmethane (being called for short DDM), structural formula (7) and structural formula (8) siliceous diamine are as solidifying agent, according to currently known methods solidification bisphenol A type epoxy resin, epoxide resin material is obtained again through molding, then determine the shock strength of these materials, flexural strength, limiting oxygen index(LOI) and initial pyrolyzation temperature according to national standard method respectively, data are as shown in table 1.
In table 1, the data of shock strength and flexural strength show, the bisphenol A type epoxy resin of the present invention's siliceous aromatic diamine solidification is better than the bisphenol A type epoxy resin of not siliceous aromatic diamine DDM solidification greatly, obviously be better than the bisphenol A type epoxy resin of siliceous aromatic diamine solidification shown in structural formula (7) or structural formula (8), the siliceous aromatic diamine of the present invention has good toughness.The data of limiting oxygen index(LOI) show, the bisphenol A type epoxy resin of the siliceous aromatic diamine solidification of the present invention is nonflammable material, its flame retardant resistance is obviously better than the bisphenol A type epoxy resin of DDM solidification, and the bisphenol A type epoxy resin solidified with siliceous aromatic diamine shown in structural formula (7) or structural formula (8) is in peer-level.Initial pyrolyzation temperature data show, the bisphenol A type epoxy resin that the thermostability of the bisphenol A type epoxy resin of the present invention's siliceous aromatic diamine solidification solidify apparently higher than DDM, bisphenol A type epoxy resin solidify with siliceous aromatic diamine shown in structural formula (7) or structural formula (8) is in equal or omits high-level.Therefore, siliceous aromatic diamine of the present invention has good toughness, flame retardant resistance and thermotolerance concurrently.
The technician of the industry should be appreciated that, the present invention is not restricted to the described embodiments, describe in above-described embodiment and specification sheets just in order to principle of the present invention is described.Without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these all fall in the scope of protection of present invention.
Claims (5)
1. such as formula the aromatic diamine based on sily oxide of structure (1) Suo Shi,
Wherein, amino at phenyl ring 3 or 4, R
1during for methyl, R
2for methyl, phenyl or 3,3,3-trifluoro propyl, R
1during for phenyl, R
2for phenyl or 3,3,3-trifluoro propyl.
2. as claimed in claim 1 based on the aromatic diamine of sily oxide, it is characterized by: based on the structure of the aromatic diamine of sily oxide such as formula (2)
shown in, wherein R
1during for methyl, R
2for methyl or phenyl, R
1during for phenyl, R
2for phenyl.
3. as claimed in claim 1 based on the aromatic diamine of sily oxide, it is characterized by: based on the structure of the aromatic diamine of sily oxide such as formula (3)
shown in, wherein R
1during for methyl, R
2for methyl or phenyl, R
1during for phenyl, R
2for phenyl.
4. prepare as claimed in claim 1 based on a method for the aromatic diamine of sily oxide, it is characterized by: such as formula the nitrostyrolene of structure (4) Suo Shi,
Under the effect of ruthenium catalyst, replace sily oxide with 1, the 3-divinyl-1,1,3,3-tetra-such as formula structure (5) Suo Shi,
The obtained intermediate 1,3-bis-(nitrostyrolene base)-1,1,3,3-tetra-such as formula structure (6) Suo Shi of replacement(metathesis)reaction through alkene replaces sily oxide,
Gained obtains replacing sily oxide such as formula the product 1,3-bis-(aminophenethyl)-1,1,3,3-tetra-of structure (1) Suo Shi accordingly such as formula intermediate hydrogenation under nickel or palladium or platinum catalyst existence of structure (6) Suo Shi,
The i.e. aromatic diamine based on sily oxide of the present invention, the R in above-mentioned formula (4), (5), (6) and (1)
1and R
2indication is identical with the indication in claim 1, and nitro or amino are at 3 or 4 of phenyl ring.
5. as claimed in claim 4 based on the preparation method of the aromatic diamine of sily oxide, it is characterized by: olefin metathesis reaction ruthenium catalyst used is ruthenium catalyst I or ruthenium catalyst II or ruthenium catalyst III, and its structure is shown below respectively,
Wherein Cy is cyclohexyl, and Mes is 2,4,6-trimethylphenyl.
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| US4535099A (en) * | 1984-04-03 | 1985-08-13 | Imi-Tech Corporation | Polyimide foam from mixture of silicon containing diamine and different aromatic diamine |
| CN102675596A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Organic silicon epoxy resin curing agent and epoxy curing system containing same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4535099A (en) * | 1984-04-03 | 1985-08-13 | Imi-Tech Corporation | Polyimide foam from mixture of silicon containing diamine and different aromatic diamine |
| CN102675596A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Organic silicon epoxy resin curing agent and epoxy curing system containing same |
Non-Patent Citations (3)
| Title |
|---|
| UNDINA CERNENCO等: "Synthesis and characterization of α,ω-bis(maleimide-ester) and α,ω-bis(maleimide-amide) substituted polysiloxanes", 《REVUE ROUMAINE DE CHIMIE》 * |
| YU SHOJI等: "Synthesis of Thermotropic Liquid Crystalline Polyimides with Siloxane Linkages", 《CHEMISTRY LETTERS》 * |
| 陈蓓等: "含硅芳香二胺的合成及其聚酰亚胺硅氧烷的热性能", 《高分子学报》 * |
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