CN103408577B - Based on the amino containing silane compound and preparation method thereof of aryl diamine - Google Patents
Based on the amino containing silane compound and preparation method thereof of aryl diamine Download PDFInfo
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Abstract
The invention discloses a kind of amino containing silane compound based on aryl diamine and preparation method thereof.This amino containing silane compound is such as formula shown in I, and in formula I, phenyl ring is that ortho position replaces, a position replaces or para-orientation; R
1be selected from O Yuan, – CH
2–, – C (CH
3)
2–, – C (CF
3)
2–, – SO –, – SO
2– Huo – O – Ph – SO
2– Ph – O –; R
2, R
3and R
4all be selected from H atom, C
1 – 12alkyl, C
2 – 12alkenyl, C
6 – 12aryl or trifluoro propyl.The invention provides the preparation method of above-mentioned amino containing silane compound, comprise the steps: that three organic radical chlorosilanes shown in aryl diamine and formula III shown in formula II carry out aminolysis reaction and obtain described amino containing silane compound; In formula II, R
1be selected from O Yuan, – CH
2–, – C (CH
3)
2–, – C (CF
3)
2–, – SO –, – SO
2– Huo – O – Ph – SO
2– Ph – O –; In formula III, R
2, R
3and R
4all be selected from H atom, C
1 – 12alkyl, C
2 – 12alkenyl, C
6 – 12aryl or trifluoro propyl.
formula I
Description
Technical field
The present invention relates to a kind of amino containing silane compound based on aryl diamine and preparation method thereof.
Background technology
Along with the progress of science and technology, the performance of material is had higher requirement.Organic-inorganic hybrid material is as a kind of type material, not only have advantages such as the easy machine-shaping of organic macromolecule, snappiness be good, cheap, and with high temperature resistant, the advantage such as high strength, solvent resistant of inorganic materials, show wide application prospect in fields such as aerospace, national defence, machinery, environmental protection and biologies.This wherein, siliceous organic-inorganic hybrid material is the focus that people study always, silicon is introduced in organic materials, not only can strengthen or keep the resistance toheat of material, and the excellent interface performance that can make it have and pyroceramic voltinism can wait, all there is great investigation and application in heat-stable material, optical material, coated material, electricity material and catalytic material etc. and be worth.
At present monomer containing Si – O key or polymkeric substance are mainly concentrated on for the research of siliceous organic-inorganic hybrid material, few for the report of the hybrid material containing Si – N key.The bond energy of Si – N key is higher than Si – O key, and polysilazane generally has higher thermostability, and the organic-inorganic hybrid material therefore containing Si – N key is a kind of up-and-coming high temperature material.Arylamine and chlorosilane react and generate amino containing silane small molecules, and it can be used as the monomeric compound of preparation containing Si – N key organic-inorganic hybrid material, but some amino containing silane compounds based on aryl diamine and preparation method thereof also rarely seen report.
Summary of the invention
The object of this invention is to provide a kind of amino containing silane compound based on aryl diamine and preparation method thereof.
Amino containing silane compound based on aryl diamine provided by the invention, its general structure is such as formula shown in I:
Formula I
In described formula I, the substituting group on phenyl ring is that ortho position replaces, a position replaces or para-orientation;
R
1for O Yuan, – CH
2–, – C (CH
3)
2–, – C (CF
3)
2–, – SO –, – SO
2– Huo – O – Ph – SO
2– Ph – O –;
R
2, R
3and R
4identical or different, be all selected from H atom, the alkyl of C1-C12, the alkenyl of C2-C12, the aryl of C6-C12, the aryl containing substituent C6-C12 and trifluoro propyl any one;
Described containing substituent C
6 – 12in aryl, substituting group is selected from C
1 – 6any one in alkyl.
Concrete, in described formula I, R
2, R
3and R
4in at least one substituting group be the alkenyl of C1-C12;
Described R
2, R
3and R
4in, the total number of carbon atoms of alkyl is 1-6; Described alkyl is specially methyl, ethyl or hexyl;
The total number of carbon atoms of alkenyl is 2-6; Described alkenyl is specially vinyl or allyl group;
In the described aryl containing substituent C6-C12, substituting group be selected from the alkyl of C1-C6 any one;
The described aryl containing substituent C6-C12 is specially p-methylphenyl or an aminomethyl phenyl.
More specifically, compound shown in described formula I is any one in compound shown in formula IV – formula VIII:
Formula IV
Formula V
Formula VI
Formula VII
Formula VIII
Described R
2, R
3and R
4in at least one substituting group be alkenyl, the R of C1-C12
1the definition formula I identical with formula I be specially compound shown in formula V, formula VI or formula VIII.
The invention provides the preparation method of above-mentioned amino containing silane compound, comprise the steps: three organic radical chlorosilanes shown in aryl diamine and formula III shown in formula II to carry out aminolysis reaction in solvent, obtain compound shown in described formula I;
Formula II formula III
In described formula II, phenyl ring is that ortho position replaces, a position replaces or para-orientation; R
1definition identical with previously described formula I;
In described formula III, R
2, R
3and R
4definition identical with previously described formula I.
In above-mentioned preparation method, shown in described formula II, shown in aryl diamine and formula III, the molar ratio of three organic radical chlorosilanes is (1 ~ 20): (2 ~ 80), preferably (1 ~ 13): (2 ~ 55), specifically can be 1:2,2:5,4:9,5:14,7:22,9:34,13:55,2-9:5-34,4-5:9-14 or 2-7:5-22.
Described solvent is made up of component a and components b;
Described component a is acetone, tetrahydrofuran (THF) or acetonitrile;
Described components b is diisopropyl ethyl amine, pyridine or triethylamine.
The volume ratio of described component a and components b is (1 ~ 60): (1 ~ 40), preferably (1 ~ 40): (1 ~ 25), specifically can be 20:20,30:20,30:22,30:14 or 40:15.
In described aminolysis reaction step, temperature is 0 DEG C ~ 100 DEG C, preferably 20 DEG C ~ 90 DEG C, specifically can be 20 DEG C, 40 DEG C, 50 DEG C or 70 DEG C.
In described aminolysis reaction step, the time is 0.5 hour ~ 72 hours, preferably 0.5 hour ~ 48 hours, specifically can be 0.5 hour, 2 hours, 6 hours, 18 hours, 24 hours or 48 hours.
In above-mentioned preparation method, described reaction is carried out under an inert atmosphere, as argon gas or nitrogen.
In addition, shown in the formula I that the invention described above provides, compound is preparing the application in organic-inorganic thermosetting resin, also belongs to protection scope of the present invention.
The method preparing organic-inorganic thermosetting resin provided by the invention, comprises the steps: aforementioned R provided by the invention
2, R
3and R
4in at least one substituting group be C
2 – 12addition reaction of silicon with hydrogen is carried out in silane compound shown in compound, formula IX shown in the formula I of alkenyl and Ka Si Taide catalyzer (being also Karstedt catalyzer) mixing, reacts complete and obtains described organic-inorganic thermosetting resin;
Formula IX
In described formula IX, R
5be selected from H atom, the alkyl of C1-C12, the alkenyl of C2-C12, the aryl of C6-C12, the aryl containing substituent C6-C12 and trifluoro propyl any one;
Described containing in substituent C6-C12 aryl, substituting group be selected from C1 – C6 alkyl any one;
X is O Yuan, – NH –, – CH
2– or singly-bound;
N is the integer of 3 – 1000.
In formula IX described in aforesaid method, R
5be selected from H atom, C1-C6 alkyl, C2-C6 alkenyl, phenyl and C1-C3 alkyl replace phenyl in any one;
Wherein, described C1-C6 alkyl is specially methyl, ethyl or hexyl;
Described C2-C6 alkenyl is specially vinyl or allyl group;
The phenyl that described C1-C3 alkyl replaces is specially p-methylphenyl or an aminomethyl phenyl;
N is the integer of 3-100, is specially the integer of 3-50, is more specifically the integer of 3-10, is most specifically 4;
The mole dosage ratio that feeds intake of silane compound shown in compound shown in formula I, formula IX and Karstedt catalyzer is (1 ~ 200): (1 ~ 100): (1 × 10
-6~ 5000 × 10
-6), be specially 2:1:(40 × 10
-6);
In described addition reaction of silicon with hydrogen step, temperature is 0 DEG C ~ 200 DEG C, is specially 50 DEG C;
Time is 1 hour ~ 72 hours, is specially 12 hours.
Shown in through type II of the present invention, shown in aryl diamine and formula III, three organic radical chlorosilanes carry out aminolysis reaction in solvent, have synthesized amino containing silane compound shown in formula I.This simple synthetic method is easy, mild condition, and synthesized amino containing silane compound has excellent solubility property, can be used as the monomeric compound of synthesis containing Si – N key organic-inorganic hybrid material, for the preparation of high temperature resistant thermosetting resin, and ceramic forerunner etc.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.In following embodiment, No. CAS of Karstedt catalyzer used is 68478-92-2, and Chinese is platinum (0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane.
The thermal gravimetric analyzer model that the thermal weight loss (TGA) done in the following embodiment of the present invention is tested is: SII6300.
Embodiment 1,4, the synthesis of 4 ′ – two (N, N ′ – is trimethyl silicon based) amido sulfobenzide (shown in IV)
Under nitrogen atmosphere, in 100mL bis-mouthfuls of bottles, add 4 successively, 4 ' – bis-amido sulfobenzide (1.24g, 5mmol), acetone (20mL) and pyridine (20mL), stirring and dissolving, is warming up to 40 DEG C, trimethylchlorosilane (1.09g, 10mmol) is dropwise joined in above-mentioned solution, carry out aminolysis reaction after dropwising 0.5 hour, cool to room temperature, filter, after removal of solvent under reduced pressure, 50 DEG C of vacuum-dryings, obtain faint yellow solid, productive rate 91%, fusing point 168 – 170 DEG C.
The nuclear-magnetism of this product, ultimate analysis and high resolution mass spectrum characterization result are as follows:
1H–NMR(400MHz,CDCl
3):δ=7.65(d,4H),6.62(d,4H),3.81(s,2H),0.27(s,18H).
13C–NMR(400MHz,acetone-d
6):δ=153.62,131.71,129.65,116.58,–0.20.
29Si–NMR(300MHz,acetone-d
6):δ=2.80.Anal.Calcd.forC
18H
28N
2O
2SSi
2:C,55.05;H,7.20;N,7.14%.Found:C,54.75;H,6.86;N,7.08%.HRMS(EI):Calcd.:392.1410;Found:392.1414.
From above-mentioned characterization data, the structural formula of this product is such as formula shown in IV:
Formula IV
Embodiment 2,4, the synthesis of two (N, N ′ – dimethyl ethenyl is silica-based) the amido sulfobenzide (shown in V) of 4 ′ – and organic-inorganic thermosetting resin
Under nitrogen atmosphere, in 100mL bis-mouthfuls of bottles, add 4 successively, 4 ' – bis-amido sulfobenzide (1.74g, 7mmol), tetrahydrofuran (THF) (30mL) and diisopropyl ethyl amine (20mL), stirring and dissolving, at 20 DEG C, by dimethyl vinyl chlorosilane (2.11g, 17.5mmol) dropwise join in above-mentioned solution, dropwise rear aminolysis reaction 2 hours, filter, 50 DEG C of vacuum-dryings after removal of solvent under reduced pressure, obtain faint yellow solid, productive rate 92%, fusing point 127 – 128 DEG C.
The nuclear-magnetism of this product, ultimate analysis and high resolution mass spectrum characterization result are as follows:
1H–NMR(400MHz,CDCl
3):δ=7.63(d,4H),6.65(d,4H),6.18(dd,2H),6.08(dd,2H),5.86(dd,2H),3.83(s,2H),0.32(s,12H).
13C–NMR(400MHz,acetone-d
6):δ=153.36,138.09,134.28,131.92,129.52,116.82,–1.96.
29Si–NMR(300MHz,acetone-d
6):δ=–7.68.Anal.Calcd.forC
20H
28N
2O
2SSi
2:C,57.65;H,6.79;N,6.72%.Found:C,57.43;H,6.89;N,6.40%.HRMS(EI):Calcd.:416.1410;Found:416.1415.
From above-mentioned characterization data, the structural formula of this product is such as formula shown in V:
Formula V
By 1,3,5, the 7-tetramethyl-ring tetrasiloxane (D of the amino containing silane compound (2.08g, 5mmol) shown in formula V with ownership formula IX
4h, 0.60g, 2.5mmol, n=4) mix, add Karstedt catalyzer (100 × 10
-6mmol), 50 DEG C are carried out addition reaction of silicon with hydrogen 12h, can obtain organic inorganic hybridization thermosetting resin.
TGA test is carried out to resin.Test condition is as follows: high pure nitrogen or air atmosphere, and temperature rise rate is 10 DEG C/min.
Test result is: under nitrogen, the temperature of thermal weight loss 10% is 428 DEG C, at 800 DEG C residual heavy be 62.1%; Under air, the temperature of thermal weight loss 10% is 404 DEG C, at 800 DEG C residual heavy be 54.5%.
Visible, gained organic inorganic hybridization thermosetting resin has higher heat decomposition temperature and high temperature is residual heavy, shows excellent thermostability and thermo-oxidative stability.
Embodiment 3,4, the synthesis of two (N, N ′ – dimethyl ethenyl is silica-based) the amido phenyl ether (shown in VI) of 4 ′ – and organic-inorganic thermosetting resin
Under nitrogen atmosphere, in 250mL bis-mouthfuls of bottles, add 4 successively, 4 ′ – diaminodiphenyl ether (2.00g, 10mmol), acetonitrile (30mL) and triethylamine (22mL), stirring and dissolving, is warming up to 50 DEG C, by dimethyl vinyl chlorosilane (2.71g, 22.5mmol) dropwise join in above-mentioned solution, dropwise rear aminolysis reaction 18 hours, filter, 50 DEG C of vacuum-dryings after removal of solvent under reduced pressure, obtain tawny liquid, productive rate 96%.
Nuclear-magnetism and the high resolution mass spectrum characterization result of this product are as follows:
1H–NMR(400MHz,CDCl
3):δ=6.77(d,4H),6.60(d,4H),6.22(dd,2H),6.06(dd,2H),5.86(dd,2H),3.33(s,2H),0.31(s,12H).
13C–NMR(400MHz,DMSO-d
6):δ=148.85,143.18,138.55,132.93,118.91,116.63,–1.86.
29Si–NMR(300MHz,acetone-d
6):δ=–7.58.HRMS(EI):Calcd.forC
20H
28N
2OSi
2:368.1740;Found:368.1747.
From above-mentioned characterization data, the structural formula of this product is such as formula shown in VI:
Formula VI
By 1,3,5, the 7-tetramethyl-ring tetrasiloxane (D of the amino containing silane compound (1.84g, 5mmol) shown in formula VI with ownership formula IX
4h, 0.60g, 2.5mmol, n=4) mix, add Karstedt catalyzer (100 × 10
-6mmol), 50 DEG C are carried out addition reaction of silicon with hydrogen 12h, obtain organic inorganic hybridization thermosetting resin.
TGA test is carried out to resin.Test condition is as follows: high pure nitrogen or air atmosphere, and temperature rise rate is 10 DEG C/min.
Test result is: under nitrogen, the temperature of thermal weight loss 10% is 563 DEG C, at 800 DEG C residual heavy be 80.3%; Under air, the temperature of thermal weight loss 10% is 528 DEG C, at 800 DEG C residual heavy be 60.1%.
Visible, gained organic inorganic hybridization thermosetting resin has very high heat decomposition temperature and higher high temperature is residual heavy, shows excellent thermostability and thermo-oxidative stability.
Embodiment 4,4, the synthesis of two (N, N ' – dimethyl is silica-based) the amido phenyl ether (shown in VII) of 4 ' –
Under nitrogen atmosphere, in 100mL bis-mouthfuls of bottles, add 4 successively, 4 ′ – diaminodiphenyl ether (0.90g, 4.5mmol), tetrahydrofuran (THF) (30mL) and triethylamine (14mL), stirring and dissolving, at 20 DEG C, by dimethylchlorosilane (1.61g, 17mmol) dropwise join in above-mentioned solution, dropwise rear aminolysis reaction 48 hours, filter, 50 DEG C of vacuum-dryings after removal of solvent under reduced pressure, obtain weak yellow liquid, productive rate 95%.
Nuclear-magnetism and the high resolution mass spectrum characterization result of this product are as follows:
1H–NMR(400MHz,CDCl
3):δ=6.81(d,4H),6.62(d,4H),4.75–4.70(m,2H),3.30(s,2H),0.30(d,12H).
13C–NMR(400MHz,acetone-d
6):δ=150.54,143.83,119.97,117.17,–2.08.
29Si–NMR(300MHz,acetone-d
6):δ=–14.14.HRMS(EI):Calcd.forC
16H
24N
2OSi
2:316.1427;Found:316.1432.
From above-mentioned characterization data, the structural formula of this product is such as formula shown in VII:
Formula VII
Embodiment 5,4, the synthesis of two [3 – (N – dimethyl ethenyl the is silica-based) amido phenoxy group] sulfobenzide (shown in VIII) of 4 ′ – and organic-inorganic thermosetting resin
Under nitrogen atmosphere, in 250mL bis-mouthfuls of bottles, add 4 successively, two (the 3 – amido phenoxy group) sulfobenzide (5.62g of 4 ′ –, 13mmol), acetonitrile (40mL) and pyridine (15mL), stirring and dissolving, is warming up to 70 DEG C, by dimethyl vinyl chlorosilane (6.64g, 55mmol) dropwise join in above-mentioned solution, dropwise rear aminolysis reaction 24 hours, filter, 50 DEG C of vacuum-dryings after removal of solvent under reduced pressure, obtain yellow solid, productive rate 93%, fusing point 44 – 47 DEG C.
Nuclear-magnetism and the high resolution mass spectrum characterization result of this product are as follows:
1H–NMR(400MHz,CDCl
3):δ7.85(d,4H),7.10(t,2H),7.02(d,4H),6.50(d,2H),6.36(d,2H),6.32(s,2H),6.17(dd,2H),6.03(dd,2H),5.81(dd,2H),3.56(s,2H),0.29(s,12H).
13C–NMR(400MHz,acetone-d
6):δ=162.66,156.81,150.83,138.61,136.64,133.85,131.13,130.47,118.66,113.76,109.27,108.54,–1.86.
29Si–NMR(300MHz,acetone-d
6):δ=–7.64.HRMS(EI):Calcd.forC
32H
36N
2O
4SSi
2:600.1934;Found:600.1941.
From above-mentioned characterization data, the structural formula of this product is such as formula shown in VIII:
Formula VIII
By 1,3,5, the 7-tetramethyl-ring tetrasiloxane (D of the amino containing silane compound (3.00g, 5mmol) shown in formula VIII with ownership formula IX
4h, 0.60g, 2.5mmol, n=4) mix, Karstedt catalyzer (100 × 10
-6mmol), 50 DEG C are carried out addition reaction of silicon with hydrogen 12h, obtain organic inorganic hybridization thermosetting resin.
TGA test is carried out to resin.Test condition is as follows: high pure nitrogen or air atmosphere, and temperature rise rate is 10 DEG C/min.
Test result is: under nitrogen, the temperature of thermal weight loss 10% is 474 DEG C, at 800 DEG C residual heavy be 58.6%; Under air, the temperature of thermal weight loss 10% is 464 DEG C, at 800 DEG C residual heavy be 50.1%.
Visible, gained organic inorganic hybridization thermosetting resin has very high heat decomposition temperature and higher high temperature is residual heavy, shows excellent thermostability and thermo-oxidative stability.
Claims (6)
1. prepare a method for organic-inorganic thermosetting resin, comprise the steps: R
2, R
3and R
4in at least one substituting group for compound, 1,3,5,7-tetramethyl-ring tetrasiloxane and Ka Si Taide catalyzer shown in the formula I of C2 – C12 alkenyl mixing carry out addition reaction of silicon with hydrogen, react complete and obtain described organic-inorganic thermosetting resin;
In described formula I, the substituting group on phenyl ring is that ortho position replaces, a position replaces or para-orientation;
R
1for O Yuan, – CH
2–, – C (CH
3)
2–, – C (CF
3)
2–, – SO –, – SO
2– Huo – O – Ph – SO
2– Ph – O –;
R
2, R
3and R
4identical or different, be all selected from H atom, the alkyl of C1-C12, the alkenyl of C2-C12, the aryl of C6-C12, trifluoro propyl and containing any one in the aryl of substituent C6-C12;
In the described aryl containing substituent C6 – C12, substituting group be selected from the alkyl of C1 – C6 any one.
2. method according to claim 1, is characterized in that: in described formula I, and the total number of carbon atoms of the alkyl of C1-C12 is 1-6;
The total number of carbon atoms of the alkenyl of C2-C12 is 2-6.
3. method according to claim 2, is characterized in that: in described formula I, and the alkyl of C1-C6 is methyl, ethyl or hexyl;
The alkenyl of described C2-C12 is vinyl or allyl group;
The described aryl containing substituent C6-C12 is p-methylphenyl or an aminomethyl phenyl.
4. method according to claim 1, is characterized in that: compound shown in described formula I is formula V, any one in compound shown in formula VI and formula VIII:
5. according to described method arbitrary in claim 1-4, it is characterized in that: compound, 1 shown in described formula I, the mole dosage ratio that feeds intake of 3,5,7-tetramethyl-ring tetrasiloxane and Ka Si Taide catalyzer is (1 ~ 200): (1 ~ 100): (1 × 10
-6~ 5000 × 10
-6);
In described addition reaction of silicon with hydrogen step, temperature is 0 DEG C ~ 200 DEG C;
Time is 1 hour ~ 72 hours.
6. method according to claim 5, is characterized in that: the mole dosage ratio that feeds intake of compound shown in described formula I, 1,3,5,7-tetramethyl-ring tetrasiloxane and Ka Si Taide catalyzer is 2:1:(40 × 10
-6);
In described addition reaction of silicon with hydrogen step, temperature is 50 DEG C;
Time is 12 hours.
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| CN107955157B (en) * | 2016-10-14 | 2020-11-20 | 徐州工程学院 | Crosslinkable silicon-containing main chain arylethernitrile copolymer and preparation method thereof |
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|---|---|---|---|---|
| US4393180A (en) * | 1981-06-30 | 1983-07-12 | Ciba-Geigy Corporation | Curing agents for epoxide resins and compositions containing them |
| US5889128A (en) * | 1997-04-11 | 1999-03-30 | Massachusetts Institute Of Technology | Living olefin polymerization processes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6431150A (en) * | 1987-07-27 | 1989-02-01 | Toa Nenryo Kogyo Kk | Heat resistant photosensitive material |
-
2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4393180A (en) * | 1981-06-30 | 1983-07-12 | Ciba-Geigy Corporation | Curing agents for epoxide resins and compositions containing them |
| US5889128A (en) * | 1997-04-11 | 1999-03-30 | Massachusetts Institute Of Technology | Living olefin polymerization processes |
Non-Patent Citations (3)
| Title |
|---|
| Monomer reactivity and steric factors affecting the synthesis of aromatic polyamides;Munoz, Dulce M.等,;《High Performance Polymers》;20071031;第592-602页, 尤其是第594页方案1 * |
| N-Dimethylsilyl derivatives of certain industrial diamines and their phosgenation;Vostokov, I. A.等,;《Zhurnal Obshchei Khimii》;19751231;第2025-2029页 * |
| N-Organosilyl derivatives of some diamines and their phosgenation;Vostokov, I. A.等,;《Trudy po Khimii i Khimicheskoi Tekhnologii》;19751231;第31-35页 * |
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