CN104788486A - Synthesis method of pyrrolidyl-containing diureido silane - Google Patents
Synthesis method of pyrrolidyl-containing diureido silane Download PDFInfo
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- CN104788486A CN104788486A CN201510126457.1A CN201510126457A CN104788486A CN 104788486 A CN104788486 A CN 104788486A CN 201510126457 A CN201510126457 A CN 201510126457A CN 104788486 A CN104788486 A CN 104788486A
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- 0 *[Si](*)(N(C(N1CCCC1)=O)c1ccccc1)N(C(N1CCCC1)=O)c1ccccc1 Chemical compound *[Si](*)(N(C(N1CCCC1)=O)c1ccccc1)N(C(N1CCCC1)=O)c1ccccc1 0.000 description 1
Abstract
The invention discloses a synthesis method of pyrrolidyl-containing diureido silane. The synthesis method of the pyrrolidyl-containing diureido silane comprises the following steps: enabling dichloroalkylsilane to react with tetrahydropyrrole in a nonpolar solvent in the presence of nitrogen, then filtering and removing tetrahydropyrrole hydrochloride, carrying out reduced-pressure distillation on filtrate, collecting fractions to obtain dipyrrolidyl dialkyl silane which is an intermediate product, enabling dipyrrolidyl dialkyl silane to react with phenyl isocyanate, carrying out reduced-pressure distillation and removing the solvent to prepare pyrrolidyl-containing diureido silane. The synthesis method of the pyrrolidyl-containing diureido silane is simple and convenient; the prepared dipyrrolidyl dialkyl silane serving as the intermediate product and pyrrolidyl-containing diureido silane are high in yield and purity.
Description
Technical field
The present invention relates to a kind of synthetic method of the allophanamide base silane containing pyrrolidyl, specifically refer to the synthetic method of important monomer for the preparation of the carborane siloxane polymer, silicon arylidene-siloxane polymer etc. of high-molecular linear and the two pyrrolidyl allophanamide base silane of chainextender.
Background technology
Allophanamide base silane containing pyrrolidyl is important monomer and the chainextender of the carborane siloxane polymer, silicon arylidene-siloxane polymer etc. of synthetic linear high molecular, and its structural formula is:
Carborane siloxane polymer and silicon arylidene-siloxane polymer, by introducing carborane cage structure or phenyl ring, can significantly improve the high thermal resistance of polymkeric substance; And siloxane bond is flexible group, the snappiness of polymkeric substance can be improved.
Traditional method such as synthesis carborane siloxane polymer, silicon arylidene-siloxane polymer etc. adopts ferric trichloride catalytic method or prepares with dichlorosilane hydrolysis method, the molecular weight of the carborane siloxane polymer that the method obtains, silicon arylidene-siloxane polymer is lower, general between 1000 ~ 8000, and structure is unregulated polymer, and ferric trichloride catalytic more makes the iron trichloride in polymkeric substance be difficult to removing, and with color, affect the use of polymkeric substance.Also carborane two silanol or silicon arylidene silanol can be adopted to react with two aminosilane and to prepare carborane siloxane polymer or silicon arylidene-siloxane polymer, but the method needs to carry out more than 100 DEG C, reaction conditions is gentle not, and the by product dialkylamine generated in polymerization process can make breaking polymer chains, makes molecular weight reduce.
This patent report a kind of with dichloro organosilanes with Pyrrolidine for pair pyrrolidyl dialkyl silane intermediate product prepare by raw material, intermediate product and then react with phenylcarbimide and prepare pair pyrrolidyl allophanamide base silane synthetic method.The carborane siloxane polymer using this kind of compound to prepare and silicon arylidene-siloxane polymer, molecular weight is relatively high, several ten thousand to tens0000, is structurally alternating polymer, has good thermostability.
Summary of the invention
For overcoming deficiency of the prior art, the invention provides a kind of with dichloro alkyl silane with Pyrrolidine for pair pyrrolidyl organosilanes intermediate product prepare by raw material, intermediate product and then react with phenylcarbimide and prepare pair pyrrolidyl allophanamide base silane synthetic method.
The present invention is achieved by following technical proposals:
Containing a preparation method for the allophanamide base silane of pyrrolidyl, it is characterized in that comprising the steps:
(1) non-polar solvent through processed is joined in dry reaction vessel; under nitrogen protection; add dichloro alkyl silane; Pyrrolidine is dripped in 1h; after dropwising; at temperature is-40 ~ 40 DEG C, it is 1 ~ 10h that reaction is held time, and wherein the molar ratio of dichloro alkyl silane and Pyrrolidine is 1:3 ~ 10.
(2) at 0 ~ 30 DEG C, reaction 1 ~ 20h is continued;
(3) the by product Pyrrolidine HCl, solid that reaction produces is removed through filtration under diminished pressure, collect filtrate;
(4) filtrate decompression is distilled, collect cut, obtain the two tetramethyleneimine dialkyl group base silane of required intermediate product;
(5) in two pyrrolidyl dialkyl silane, add the anhydrous diethyl ether through processed; under nitrogen protection; phenylcarbimide is dripped in 1h; after dropwising;-at temperature is 40 ~ 40 DEG C; it is 1 ~ 10h that reaction is held time, and the molar ratio of two pyrrolidyl organosilanes and phenylcarbimide is 1:1 ~ 5.
(6) at 0 ~ 30 DEG C, reaction 1 ~ 10h is continued;
(7) after reaction terminates, leave standstill, removing supernatant liquid;
(8) carry out drying under vacuum, obtain the allophanamide base silane of final product containing pyrrolidyl.
As preferably, the dichloro alkyl silane in above-mentioned preparation method in step (1) and the molar ratio of Pyrrolidine are 1:3 ~ 10, and as better selection, the dichlorosilane in above-mentioned preparation method and the molar ratio of Pyrrolidine are 1:4 ~ 6.
As preferably, the temperature of reaction in above-mentioned preparation method in step (1) is-40 ~ 40 DEG C, and as better selection, the temperature of reaction in above-mentioned preparation method is-20 ~ 10 DEG C.
As preferably, it is 1 ~ 10h that the reaction in above-mentioned preparation method in step (1) is held time, and as better selection, it is 2 ~ 5h that the reaction in above-mentioned preparation method is held time.
As preferably, the duration of the reaction in above-mentioned preparation method in step (2) is 1 ~ 20h, and as better selection, the duration of the reaction in above-mentioned preparation method is 5 ~ 15h.
As preferably, the temperature of the underpressure distillation in above-mentioned preparation method in step (4) is 50 ~ 150 DEG C, and as better selection, the temperature of the underpressure distillation in above-mentioned preparation method is 80 ~ 120 DEG C.
As preferably, the temperature of reaction in above-mentioned preparation method in step (5) is-40 ~ 40 DEG C, and as better selection, the temperature of reaction in above-mentioned preparation method is-20 ~ 10 DEG C.
As preferably, two pyrrolidyl organosilanes in above-mentioned preparation method in step (5) and the molar ratio of phenylcarbimide are 1:1 ~ 5, as better selection, the two pyrrolidyl organosilanes in above-mentioned preparation method and the molar ratio of phenylcarbimide are 1:1 ~ 3.
As preferably, it is 1 ~ 10h that the reaction in above-mentioned preparation method in step (5) is held time, and as better selection, it is 2 ~ 5h that the reaction in above-mentioned preparation method is held time.
As preferably, the duration of the reaction in above-mentioned preparation method in step (6) is 1 ~ 10h, and as better selection, the duration of the reaction in above-mentioned preparation method is 2 ~ 5h.
As preferably, the vacuum-drying temperature in above-mentioned preparation method in step (8) is 30 ~ 80 DEG C, and as better selection, the vacuum-drying temperature in above-mentioned preparation method is 50 ~ 80 DEG C.
Beneficial effect of the present invention: technological process is convenient, simple to operate, the synthesized allophanamide base silane containing pyrrolidyl is easier to store relative to two aminosilanes of liquid, be particularly useful for making carborane siloxane polymer and silicon arylidene-siloxane polymer etc., the high-molecular weight polymer of the preparing linear alternating with good heat resistance energy can be obtained.
Embodiment
Embodiment 1
Under nitrogen protection, in the reaction flask of 100ml dried and clean, 30ml normal heptane and 6.45g dichlorodimethylsilane is added, when temperature of reaction system reaches-15 DEG C; 14.30g Pyrrolidine is dripped to reaction system in 1h; after dropwising, reaction maintains 2h, continues at 25 DEG C of reaction 15h.Pyrrolidine HCl, solid by product reaction produced is crossed and is filtered under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 80 ~ 82 DEG C/0.1kPa, namely obtains the two dimethylamino pyrrolidinyl base silane of intermediate product.In reaction flask, add 30ml anhydrous diethyl ether again, when temperature of reaction reaches-15 DEG C, drip 13.20g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 2h, continues at 25 DEG C of reaction 3h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 70 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) dimethylsilane 20.14g, productive rate is 92.3%.
Embodiment 2
Under nitrogen protection, in the reaction flask of 100ml dried and clean, 25ml normal hexane and 4.80g dichlorodimethylsilane is added, when temperature of reaction system reaches-5 DEG C; 12.70g Pyrrolidine is dripped to reaction system in 1h; after dropwising, reaction maintains 5h, at 30 DEG C of reaction 12h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, the filtrate decompression obtained distillation is removed, collects the cut of 80 ~ 82 DEG C/0.1kPa, namely obtains the two dimethylamino pyrrolidinyl base silane of intermediate product.In reaction flask, add 30ml anhydrous diethyl ether again, when temperature of reaction reaches-5 DEG C, drip 10.00g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 1h, continues at 30 DEG C of reaction 3h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 65 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) dimethylsilane 14.70g, productive rate is 90.5%.
Embodiment 3
Under nitrogen protection, in the reaction flask of 100ml dried and clean, 45ml normal heptane and 8.50g dichlorodimethylsilane is added, when temperature of reaction system reaches 10 DEG C; 20.80g Pyrrolidine is dripped to reaction system in 1h; after dropwising, reaction maintains 6h, continues at 30 DEG C of reaction 10h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 80 ~ 82 DEG C/0.1kPa, namely obtains the two dimethylamino pyrrolidinyl base silane of intermediate product.In reaction flask, add 40ml anhydrous diethyl ether again, when temperature of reaction reaches 5 DEG C, drip 17.50g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 3h, continues at 30 DEG C of reaction 5h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 70 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) dimethylsilane 24.60g, productive rate is 85.6%.
To two (N-pyrrolidyl-the N '-phenyl urea groups) dimethylsilane in embodiment 1 ~ 3 carry out IR,
1h NMR analyzes, and its result is as follows:
IR：3050，2970，2874，2000～1700，1646，1595，1496，1442，1380，1297，1235，1050，1025，894，750，695。
1H NMR：0.26(6H，s，Si-CH
3)，1.90(8H，m，-CH
2-)，3.40(8H，t，-CH
2-N-CH
2-)，7.20～7.60(10H，m，-Ph)。
Embodiment 4
Under nitrogen protection; 30ml normal heptane and 9.55g dichloromethyl trifluoro propyl silane is added in the reaction flask of 100ml dried and clean; when temperature of reaction system reaches-25 DEG C; 14.20g Pyrrolidine is dripped to reaction system in 1h; after dropwising; reaction maintains 4h, continues at 20 DEG C of reaction 20h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 92 ~ 93 DEG C/0.1kPa, namely obtains the two pyrrolidinylmethyl trifluoro propyl silane of intermediate product.In reaction flask, add 30ml anhydrous diethyl ether again, when temperature of reaction reaches-25 DEG C, drip 11.70g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 5h, continues to react 8h at 20 DEG C.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 80 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) methyl trifluoro propyl silane 21.18g, productive rate is 90.3%.
Embodiment 5
Under nitrogen protection; 40ml sherwood oil and 8.60g dichloromethyl trifluoro propyl silane is added in the reaction flask of 100ml dried and clean; when temperature of reaction system reaches-10 DEG C; 12.80g Pyrrolidine is dripped to reaction system in 1h; after dropwising; reaction maintains 5h, continues to react 10h at 25 DEG C.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 92 ~ 93 DEG C/0.1kPa, obtains the two pyrrolidinylmethyl trifluoro propyl silane of intermediate product.In reaction flask, add 35ml anhydrous diethyl ether again, when temperature of reaction reaches-10 DEG C, drip 11.00g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 6h, at 25 DEG C of reaction 5h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 80 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) methyl trifluoro propyl silane 18.06g, productive rate is 85.5%.
To two (N-pyrrolidyl-the N '-phenyl urea groups) methyl trifluoro propyl silanes in embodiment 4 ~ 5 carry out IR,
1h NMR analyzes, and its result is as follows:
IR：3050，2972，2874，2000～1700，1646，1595，1496，1442，1380，1368，1315，1297，1235，1210，1068，1025，902，750，695。
1H NMR：0.30(6H，s，Si-CH
3)，0.90(2H，m，Si-CH
2-)，2.20(2H，m，-CH
2-CF
3)，1.90(8H，m，-CH
2-)，3.40(8H，t，-CH
2-N-CH
2-)，7.20～7.60(10H，m，-Ph)。
Embodiment 6
Under nitrogen protection, in the reaction flask of 100ml dried and clean, 30ml normal hexane and 6.05g dichloromethyl vinyl silanes is added, when temperature of reaction system reaches-5 DEG C; 13.50g Pyrrolidine is dripped to reaction system in 1h; after dropwising, reaction maintains 4h, continues at 25 DEG C of reaction 10h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 95 ~ 96 DEG C/0.1kPa, namely obtains the two pyrrolidinylmethyl vinyl silanes of intermediate product.In reaction flask, add 35ml anhydrous diethyl ether again, when temperature of reaction reaches-5 DEG C, drip 11.40g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 2h, continues at 25 DEG C of reaction 8h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 80 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) ethylene methacrylic base silane 15.70g, productive rate is 81.6%.
Embodiment 7
Under nitrogen protection; 20ml Skellysolve A, 20ml normal hexane and 6.70g dichloromethyl vinyl silanes is added in the reaction flask of 100ml dried and clean; when temperature of reaction system reaches-20 DEG C; 14.90g Pyrrolidine is dripped to reaction system in 1h; after dropwising; reaction maintains 4h, continues at 25 DEG C of reaction 10h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 95 ~ 96 DEG C/0.1kPa, namely obtains the two pyrrolidinylmethyl vinyl silanes of intermediate product.In reaction flask, add 35ml anhydrous diethyl ether again, when temperature of reaction reaches-20 DEG C, drip 14.50g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 3h, continues at 25 DEG C of reaction 8h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 80 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) ethylene methacrylic base silane 18.35g, productive rate is 86.1%.
Embodiment 8
Under nitrogen protection, in the reaction flask of 100ml dried and clean, 35ml normal hexane and 7.20g dichloromethyl phenyl silane is added, when temperature of reaction system reaches-5 DEG C; 11.85g Pyrrolidine is dripped to reaction system in 1h; after dropwising, reaction maintains 3h, continues at 25 DEG C of reaction 12h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 108 ~ 110 DEG C/0.1kPa, namely obtains the two pyrrolidinylmethyl phenyl silane of intermediate product.In reaction flask, add 35ml anhydrous diethyl ether again, when temperature of reaction reaches-5 DEG C, drip 9.90g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 5h, continues at 20 DEG C of reaction 10h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 75 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) aminomethyl phenyl silane 14.25g, productive rate is 75.8%.
Embodiment 9
Under nitrogen protection, in the reaction flask of 100ml dried and clean, 40ml normal heptane and 7.20g dichloro base silane is added, when temperature of reaction system reaches-10 DEG C; 8.85g Pyrrolidine is dripped to reaction system in 1h; after dropwising, reaction maintains 3h, continues at 20 DEG C of reaction 8h.Pyrrolidine HCl, solid by product reaction produced is filtration under diminished pressure removing under 0.1kPa, by the filtrate decompression distillation obtained, collects the cut of 113 ~ 115 DEG C/0.1kPa, obtains the two pyrrolidyl diphenyl silane of intermediate product.In reaction flask, add 35ml anhydrous diethyl ether again, when temperature of reaction reaches-10 DEG C, drip 7.55g phenylcarbimide in 1h in reaction system, after dropwising, reaction maintains 3h, continues at 20 DEG C of reaction 10h.After reaction terminates, stratification, removing supernatant liquid, by the vacuum-drying at 75 DEG C of lower floor's solid, obtain two (N-pyrrolidyl-N '-phenyl urea groups) diphenyl silane 11.25g, productive rate is 70.6%.
Embodiment 10
Under nitrogen protection; 15ml chlorobenzene and two (hydroxyl dimethyl the is silica-based)-m-carborane of 0.80g is added in the reaction flask of 100ml dried and clean; when temperature of reaction system reaches-5 DEG C; two (N-pyrrolidyl-N '-phenyl urea groups) dimethylsilane 1.20g of synthesis in embodiment 1 are added to reaction system; reaction continues 3h; continue to react 12h at 25 DEG C; after reaction terminates; adding 80ml methyl alcohol makes product be precipitated out; vacuum-drying at 70 DEG C; obtain m-carborane siloxane polymer 0.75g, productive rate is 76.0%.Through gel permeation chromatography test, the weight-average molecular weight of polymkeric substance is 30000.Through thermogravimetic analysis (TGA), the temperature of weightless 5% is 374 DEG C, and carbon yield is up to 72%.
Claims (7)
1., containing a synthetic method for the allophanamide base silane of pyrrolidyl, it is characterized in that comprising the steps:
(1) non-polar solvent through processed is joined in dry reaction vessel, under nitrogen protection, add dichloro alkyl silane, Pyrrolidine is dripped in 1h, after dropwising, at temperature is-40 ~ 40 DEG C, it is 1 ~ 10h that reaction is held time, and wherein the molar ratio of dichloro alkyl silane and Pyrrolidine is 1:3 ~ 10;
(2) at 0 ~ 30 DEG C, reaction 1 ~ 20h is continued;
(3) the by product Pyrrolidine HCl, solid that reaction produces is removed through filtration under diminished pressure, collect filtrate;
(4) filtrate decompression is distilled, collect cut, obtain the two tetramethyleneimine dialkyl group base silane of required intermediate product;
(5) in two pyrrolidyl dialkyl silane, add the anhydrous diethyl ether through processed, under nitrogen protection, phenylcarbimide is dripped in 1h, after dropwising, at temperature is-40 ~ 40 DEG C, it is 1 ~ 10h that reaction is held time, and the molar ratio of two pyrrolidyl organosilanes and phenylcarbimide is 1:1 ~ 5;
(6) at 0 ~ 30 DEG C, reaction 1 ~ 10h is continued;
(7) after reaction terminates, leave standstill, removing supernatant liquid;
(8) carry out drying under vacuum, obtain the allophanamide base silane of final product containing pyrrolidyl.
2. according to the preparation method in claim 1, it is characterized in that, the non-polar solvent described in step (1) is the mixed solvent of one or more in Skellysolve A, normal hexane, normal heptane, sherwood oil.
3. according to the preparation method in claim 1, it is characterized in that, the pressure described in step (3) is 0.1kPa, and the by product Pyrrolidine hydrochloride obtained is white solid.
4. according to the preparation method in claim 1, it is characterized in that, the pressure described in step (4) is 0.1kPa, and vacuum distillation temperature is 50 ~ 150 DEG C.
5. according to the preparation method in claim 1, it is characterized in that, the structural formula of the two pyrrolidyl dialkyl silane of the intermediate product described in step (4) is:
In formula, R
1, R
2representative-CH
3,-CH
2cH
3,-CH
2cH
2cF
3,-CH=CH
2, one in phenyl.
6. according to the preparation method in claim 1, it is characterized in that, the vacuum-drying temperature described in step (8) is 30 ~ 80 DEG C.
7. according to the preparation method in claim 1, it is characterized in that, the structural formula of the allophanamide base silane containing pyrrolidyl described in step (8) is:
In formula, R
1, R
2representative-CH
3,-CH
2cH
3,-CH
2cH
2cF
3,-CH=CH
2, one in phenyl.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801864A (en) * | 2016-03-26 | 2016-07-27 | 北京化工大学 | Synthesis method for preparing alternating organic silicon polymers at low temperature |
| CN113372378A (en) * | 2021-05-21 | 2021-09-10 | 安徽沸点新材料有限公司 | Preparation process of phenylureido silane coupling agent |
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| US4132842A (en) * | 1978-02-23 | 1979-01-02 | The United States Of America As Represented By The Secretary Of The Navy | Silicon-phthalocyanine-siloxane polymers |
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2015
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| US4132842A (en) * | 1978-02-23 | 1979-01-02 | The United States Of America As Represented By The Secretary Of The Navy | Silicon-phthalocyanine-siloxane polymers |
| US5208310A (en) * | 1991-12-16 | 1993-05-04 | Hughes Aircraft Company | Method for preparation of very high molecular weight polycarborane siloxanes |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801864A (en) * | 2016-03-26 | 2016-07-27 | 北京化工大学 | Synthesis method for preparing alternating organic silicon polymers at low temperature |
| CN105801864B (en) * | 2016-03-26 | 2019-02-01 | 北京化工大学 | A kind of synthetic method of low temperature preparation alternating organosilicon polymer |
| CN113372378A (en) * | 2021-05-21 | 2021-09-10 | 安徽沸点新材料有限公司 | Preparation process of phenylureido silane coupling agent |
| CN113372378B (en) * | 2021-05-21 | 2023-11-21 | 安徽沸点新材料有限公司 | Preparation process of phenylureido silane coupling agent |
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Application publication date: 20150722 |