CN110387043A - Dendritic organosilicon compound with multi-terminal functional groups and preparation method thereof - Google Patents

Abstract

The present invention provides a method for preparing a class of dendritic organosilicon compounds with multi-terminal functional groups through a two-step cycle method, comprising the following steps: S1, mixing polymethoxysilane and tetramethyldihydrodisiloxane, using The pH value is adjusted to 1 with an acid, and a catalyst is added to react to obtain a silicon-hydrogen bond-terminated organosilicon product; S2, in a nitrogen atmosphere, the silicon-hydrogen bond-terminated organosilicon product obtained in step S1 is mixed with vinyltrimethoxysilane , a hydrosilylation reaction occurs under the action of a platinum catalyst to obtain an organosilicon product with multiple methoxyl groups at the end; S3, the organosilicon product with multiple methoxyl groups at the end obtained in step S2 is used as a reactant, The reactions of steps S1 and S2 are repeated in sequence to obtain dendritic organosilicon compounds with multi-terminal functional groups (-Si(OCH ₃ ) ₃ or -SiH) of different structures.

Description

Dendritic organosilicon compound with multi-terminal functional groups and preparation method thereof

technical field

The invention relates to the field of preparation of organic functional materials, in particular to a class of dendritic organosilicon compounds with multi-terminal functional groups and a preparation method thereof.

Background technique

Dendrimers have the advantages of good solubility, low viscosity, no crystallization, and no entanglement between molecular chains, and they have been widely used in fluorescent materials, optoelectronic materials, modified materials and other fields. The preparation of dendrimers is mainly a cyclic two-step process. Patent CN102863623A publicly reported a two-step cyclic method to prepare dendritic organosilicon products through hydrosilylation reaction and then through reduction reaction. Patent CN104817702A publicly reported another kind of first through hydrosilylation reaction and then through nucleophilic substitution reaction. The branched organosilicon product is prepared by a two-step cycle method, but the above synthesis process is uncertain and the reproducibility of the reaction is poor.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a class of dendritic organosilicon compounds with multi-terminal functional groups and a preparation method thereof through a two-step cycle method of controllable hydrolysis condensation-hydrosilylation reaction. The dendritic organosilicon compound prepared by the present invention With specific structural end functional groups, it can be used to prepare functional polymers.

The present invention provides a method for preparing a class of dendritic organosilicon compounds with multi-terminal functional groups through a two-step recycling method, comprising the following steps:

S1, polymethoxysilane (R _(4-n) Si(OCH ₃ ) _n ; R is either an alkyl group or a phenyl group, n=2, 3) and tetramethyldihydrodisiloxane (HSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ H) mixing, adjusting the pH value to 1 with acid, adding a catalyst to carry out the reaction, controlling the reaction conditions, and distilling under reduced pressure after the reaction to obtain an organosilicon product with a terminal silicon-hydrogen bond (R _(4-n) Si(OSi( _{CH3 )} 2H) _n );

S2, in a nitrogen atmosphere, combine the silicon-hydrogen bond-terminated organosilicon product (R _(4-n) Si(OSi(CH ₃ ) ₂ H) _n ) obtained in step S1 with vinyltrimethoxysilane (CH ₂ = CHSi(OCH ₃ ) ₃ ) is mixed, and hydrosilylation reaction occurs under the action of platinum catalyst to obtain an organosilicon product (R _(4-n) Si(OSi(CH ₃ ) ₂ CH) with multiple methoxy groups at the end. ₂ CH ₂ Si(OCH ₃ ) ₃ ) _n );

S3, the organosilicon product (R _(4-n) Si(OSi(CH ₃ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ) _n ) obtained in step S2 with multiple methoxy groups at the end is used as a reactant , and the reactions of steps S1 and S2 are repeated in sequence to obtain dendritic organosilicon compounds with multi-terminal functional groups (-Si(OCH ₃ ) ₃ or -SiH) with different structures.

Further, in step S1, the pH value is adjusted to 1 by using an acid, and the acid is selected from any one of hydrochloric acid, sulfuric acid or glacial acetic acid.

Further, in step S1, the catalyst is selected from any one of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, acetic anhydride or trifluoromethanesulfonic acid.

Further, in step S1, the reaction temperature is 50±2° C., and the reaction time is 1 h to 1.5 h.

Further, in step S1, the process of vacuum distillation is as follows: the pressure is reduced to 6 kPa and distilled at 120° C. for 2 hours.

Further, in step S2, the reaction conditions for the hydrosilylation reaction are 80°C to 100°C for 5 hours.

Further, in step S2, the process of vacuum distillation is as follows: the pressure is reduced to 6 kPa and distilled at 120° C. for 2 hours.

The present invention also provides a kind of dendritic organosilicon compounds with multi-terminal functional groups prepared by the above preparation method.

The beneficial effects brought by the technical solution provided by the present invention are: the dendritic organosilicon compound prepared by the present invention has a clear structure, and different preparation strategies can be selected to adjust the terminal functional group of the dendritic organosilicon compound, so the structure has controllable characteristics The dendritic organosilicon compound prepared by the present invention has the characteristics of low viscosity, good solubility, no entanglement between molecular chains, and has better modifiability; the polyfunctional dendritic organosilicon compound prepared by the present invention It can be widely used in the fields of optoelectronic materials, nanomaterials, biomedicine, composite materials and surface engineering materials.

Description of drawings

FIG. 1 is a schematic diagram of the synthesis principle of the present invention for preparing dendritic organosilicon compounds with multi-terminal functional groups.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the embodiments of the present invention will be further described below with reference to the accompanying drawings.

Embodiments of the present invention provide a method for preparing a dendritic organosilicon compound with multi-terminal functional groups, comprising the following steps:

Step S1, combine polymethoxysilane (R _(4-n) Si(OCH ₃ ) _n ; R is any one of alkyl group or phenyl group; n=2, 3) and tetramethyldihydrodisiloxane Alkane (HSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ H) was mixed in a certain proportion, the pH value was adjusted to 1 with acid, a catalyst with a total mass of 2000 ppm was added, and the reaction was carried out at 50±2 °C for 1 h to 1.5 h. After the reaction was completed The pressure was reduced to 6kPa and distilled at 120°C for 2h to obtain the organosilicon product (R _(4-n) Si(OSi(CH ₃ ) ₂ H) _n ) with terminal silicon-hydrogen bonds; the acid used for pH adjustment was selected from hydrochloric acid, sulfuric acid, ice Any of acetic acid and the like; the catalyst is selected from any of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, acetic anhydride or trifluoromethanesulfonic acid.

Step S2, in a nitrogen atmosphere, mix the silicon-hydrogen bond-terminated organosilicon product obtained in step S1 with vinyltrimethoxysilane (CH ₂ =CHSi(OCH ₃ ) ₃ ) in a certain proportion, and then add 5ppm of total mass. The platinum catalyst undergoes a hydrosilylation reaction, and the reaction is carried out at 80 °C-100 °C for 5 hours. After the reaction is completed, the pressure is reduced to 6 kPa and distilled at 120 °C for 2 hours to obtain an organosilicon product (R _(4-n ) with multiple methoxy groups at the end. ₎ Si(OSi(CH ₃ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ) _n );

In step S3, the organosilicon product (R _(4-n) Si(OSi(CH ₃ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ) _n ) obtained in step S2 with multiple methoxy groups at the end is used as a reaction The reaction of steps S1 and S2 is repeated in sequence, that is, dendritic organosilicon compounds with multi-terminal functional groups (-Si(OCH ₃ ) ₃ or -SiH) with different structures are obtained.

The schematic diagram of the reaction principle of the above preparation steps is shown in Figure 1a and Figure 1b. In Figure 1, R is any one of alkyl and phenyl; in this embodiment, a two-step cycle method is used to synthesize a multi-terminal functional group (-Si (OCH ₃ ) ₃ or -SiH) dendritic organosilicon compound, its two-step cycle method includes controlled hydrolysis condensation reaction and hydrosilylation reaction. The controllable hydrolysis-condensation reaction is to introduce the polymethoxyl monomer into the active site of the terminal silicon-hydrogen bond that can undergo the hydrosilylation reaction. The purpose of the hydrosilylation reaction is to introduce more active reaction sites (a oxy). Through the two-step cycle method, dendritic organosilicon compounds can be synthesized.

The dendritic organosilicon compounds with multi-terminal functional groups provided by the present invention and the preparation method thereof will be described in detail below with reference to the examples.

Example 1:

(1) Mix 41.27 g of benzenetrimethoxysilane with 44.80 g of tetramethyldihydrodisiloxane, adjust the pH to 1 with hydrochloric acid, then add 1.56 g of trifluoromethanesulfonic acid and react at 50 ° C for 1 h, after the reaction is completed The pressure was reduced to 6kPa and distilled at 120°C for 2h to obtain 59.49g of organosilicon product A with silicon-hydrogen bonds at the end;

(2) in a nitrogen atmosphere, take 33.06g of the silicon-hydrogen bond-terminated organosilicon product A obtained in step (1) and mix it with 88.94g of vinyltrimethoxysilane, and then add 0.1220g of platinum catalyst to generate a hydrosilylation reaction, The reaction was carried out at 80 °C for 5 h, and after the reaction was completed, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 71.45 g of organosilicon product A with multiple methoxy groups (-Si(OCH ₃ ) ₃ ) at the end;

(3) Mix 31.00g of the organosilicon product A with multiple methoxy groups at the end obtained in step (2) with 31.44g of tetramethyldihydrodisiloxane, adjust the pH to 1 with hydrochloric acid, and then add 0.20 g trifluoromethanesulfonic acid was reacted at 50 °C for 1 h, and after the reaction was completed, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 46.27 g of the organosilicon product B with terminal silicon-hydrogen bonds;

(4) in a nitrogen atmosphere, take 32.80g of the silicon-hydrogen bond-terminated organosilicon product B obtained in step (3) and mix it with 56.04g of vinyltrimethoxysilane, and then add 0.0888g of platinum catalyst to generate a hydrosilylation reaction, The reaction was carried out at 90 °C for 5 h, and after the reaction was completed, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 56.58 g of an organosilicon product B with multiple methoxy groups (-Si(OCH ₃ ) ₃ ) at the end;

(5) Mix 39.81 g of the organosilicon product B with multiple methoxy groups at the end obtained in step (4) with 43.53 g of tetramethyldihydrodisiloxane, adjust the pH to 1 with hydrochloric acid, and then add 0.25 g g trifluoromethanesulfonic acid was reacted at 50 °C for 1 h, after the reaction was completed, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 40.25 g of the dendritic organosilicon compound with multi-terminal functional groups of formula I;

The structural formula of the dendritic organosilicon compound with multi-terminal functional groups of formula I is;

The product obtained in Example 1 was analyzed by infrared and hydrogen nuclear magnetic spectrum. The dendritic organosilicon compound with multi-terminal functional groups of formula I was found in the infrared spectrum at a wavenumber of 2100cm ^-1 with a peak of silicon-hydrogen bonds, and For the peak without methoxy group, the peak with silicon-hydrogen bond near the chemical shift of 4.7 ppm was found in the hydrogen NMR spectrum, and the peak without methoxy group was found.

Example 2:

(1) Mix 27.20g methyltrimethoxysilane with 52.49g tetramethyldihydrodisiloxane, adjust the pH to 1 with hydrochloric acid, then add 0.24g trifluoromethanesulfonic acid and react at 50°C for 1h, the reaction After the end, the pressure was reduced to 6kPa and distilled at 120°C for 2h to obtain 40.58g of organosilicon product C with silicon-hydrogen bonds at the end;

(2) in a nitrogen environment, take 24.15g of the silicon-hydrogen bond-terminated organosilicon product C obtained in step (1) and mix it with 60.06g of vinyltrimethoxysilane, and then add 0.0675g of platinum catalyst to generate a hydrosilylation reaction, The reaction was carried out at 90 °C for 5 h, and after the reaction was completed, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 55.86 g of an organosilicon product C with multiple methoxy groups (-Si(OCH ₃ ) ₃ ) at the end;

(3) Mix 14.26 g of the organosilicon product C with multiple methoxy groups (-Si(OCH ₃ ) ₃ ) at the end obtained in step (2) with 15.72 g of tetramethyldihydrodisiloxane, and use The pH value was adjusted to 1 with hydrochloric acid, and then 0.10 g of trifluoromethanesulfonic acid was added to react at 50 °C for 1 h. After the reaction, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 24.43 g of organosilicon product D with a silicon-hydrogen bond at the end;

(4) In a nitrogen atmosphere, take 7.77g of the silicon-hydrogen bond-terminated organosilicon product D obtained in step (3) and mix it with 20.77g of vinyltrimethoxysilane, and then add 14.01g of platinum catalyst to generate a hydrosilylation reaction, The reaction was carried out at 100 °C for 5 h, and after the reaction was completed, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 14.12 g of an organosilicon product D with multiple methoxy groups (-Si(OCH ₃ ) ₃ ) at the end;

(5) Mix 9.77 g of the organosilicon product D with multiple methoxy groups (—Si(OCH ₃ ) ₃ ) at the end obtained in step (4) with 9.43 g of tetramethyldihydrodisiloxane, and use The pH value was adjusted to 1 with hydrochloric acid, and then 0.07 g of trifluoromethanesulfonic acid was added to react at 50 °C for 1 h. After the reaction, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 13.20 g of a dendrimer with a multi-terminal functional group of formula II. organosilicon compounds;

The structural formula of the dendritic organosilicon compound with multi-terminal functional groups of formula II is:

The product obtained in Example 2 was analyzed by infrared and hydrogen NMR. The dendritic organosilicon compound with multi-terminal functional groups of formula II was found in the infrared spectrum at a wavenumber of 2100cm ^-1 with a peak of silicon-hydrogen bonds, and For the peak without methoxy group, the peak with silicon-hydrogen bond near the chemical shift of 4.7 ppm was found in the hydrogen NMR spectrum, and the peak without methoxy group was found.

Example 3:

(1) Mix 47.95g of dimethyldimethoxysilane with 60.73g of tetramethyldihydrodisiloxane, adjust the pH to 1 with hydrochloric acid, then add 1.70g of trifluoromethanesulfonic acid and react at 50°C for 1h , after the reaction, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 53.07 g of an organosilicon product E with a silicon-hydrogen bond at the end;

(2) In a nitrogen atmosphere, take 10.41g of the silicon-hydrogen bond-terminated organosilicon product E obtained in step (1) and mix it with 16.80g of vinyltrimethoxysilane, and then add 0.0500g of platinum catalyst to generate a hydrosilylation reaction, The reaction was carried out at 80 °C for 5 h, and after the reaction, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 23.62 g of an organosilicon product E with multiple methoxy groups (-Si(OCH ₃ ) ₃ ) at the end;

(3) Mix 10.08 g of the organosilicon product E with multiple methoxy groups (—Si(OCH ₃ ) ₃ ) at the end obtained in step (2) with 11.21 g of tetramethyldihydrodisiloxane, and use hydrochloric acid. Adjust the pH value to 1, then add 0.37g of trifluoromethanesulfonic acid to react at 50°C for 1h, after the reaction, reduce the pressure to 6kPa and distill at 120°C for 2h to obtain 13.03g of organosilicon product F with terminal silicon-hydrogen bonds;

(4) In a nitrogen atmosphere, take 11.55g of the silicon-hydrogen bond-terminated organosilicon product F obtained in step (3) and mix it with 13.94g of vinyltrimethoxysilane, and then add 0.0400g of platinum catalyst to generate a hydrosilylation reaction, The reaction was carried out at 90 °C for 5 h, and after the reaction, the pressure was reduced to 6 kPa and distilled at 120 °C for 2 h to obtain 13.66 g of an organosilicon product F with multiple methoxy groups at the end;

(5) Mix 6.62g of the organosilicon product F with multiple methoxy groups at the end obtained in step (4) with 6.32g of tetramethyldihydrodisiloxane, adjust the pH to 1 with hydrochloric acid, and then add 0.07g of trifluoromethanesulfonic acid was reacted at 50°C for 1h, after the reaction was completed, the pressure was reduced to 6kPa and distilled at 120°C for 2h to obtain 8.12g of a dendritic organosilicon compound with a multi-terminal functional group of formula III;

The structural formula of the dendritic organosilicon compound with multi-terminal functional groups of formula III is:

The product obtained in Example 3 was analyzed by infrared and hydrogen nuclear magnetic spectrum. The dendritic organosilicon compound with multi-terminal functional groups of formula III was found to have a peak of silicon-hydrogen bonds at a wavenumber of 2100cm ^-1 in the infrared spectrum, and For the peak without methoxy group, the peak with silicon-hydrogen bond near the chemical shift of 4.7 ppm was found in the hydrogen NMR spectrum, and the peak without methoxy group was found.

In the above embodiment, the organosilicon products A to F with silicon-hydrogen bonds at the end and the organosilicon products A to F with multiple methoxy groups at the end are organosilicon products prepared by different steps, and the letters themselves have no meaning.

The above-described embodiments and features of the embodiments herein may be combined with each other without conflict.

The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (8)

1. the preparation method of the dendroid organo-silicon compound with multiterminal functional group, which comprises the following steps:

Polymethoxylated silane is mixed with tetramethyldihydrogendisiloxane, is adjusted with acid pH value by S1, and catalyst is then added and carries out Reaction, is evaporated under reduced pressure after reaction, obtains the silicone product of end si-h bond；Wherein, the molecular formula of Polymethoxylated silane are as follows: R_(4-n)Si(OCH₃)_n, R be alkyl, phenyl any, n=2,3；The molecular formula of tetramethyldihydrogendisiloxane are as follows: HSi (CH₃)₂OSi(CH₃)₂H；Hold the molecular formula of the silicone product of si-h bond are as follows: R_(4-n)Si(OSi(CH₃)₂H)_n；

S2 mixes the silicone product for the end si-h bond that step S1 is obtained with vinyltrimethoxysilane in nitrogen atmosphere It closes, hydrosilylation occurs under platinum catalyst effect, is evaporated under reduced pressure after reaction, obtain end with multiple methoxyl groups Silicone product；Wherein, the molecular formula of silicone product of the end with multiple methoxyl groups are as follows: R_(4-n)Si(OSi(CH₃)₂CH₂CH₂Si(OCH₃)₃)_n；

S3, silicone product of the end obtained using step S2 with multiple methoxyl groups are repeated in order as reactant The reaction of step S1 and S2 are to get the dendroid organo-silicon compound with multiterminal functional group for arriving different structure.

2. the preparation method of the dendroid organo-silicon compound according to claim 1 with multiterminal functional group, special Sign is, in step S1, using acid for adjusting pH value to 1, acid selects any of hydrochloric acid, sulfuric acid or glacial acetic acid.

3. the preparation method of the dendroid organo-silicon compound according to claim 1 with multiterminal functional group, special Sign is, in step S1, catalyst selects any of p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, acetic anhydride or trifluoromethanesulfonic acid Kind.

4. the preparation method of the dendroid organo-silicon compound according to claim 1 with multiterminal functional group, special Sign is, in step S1, reaction temperature is 50 ± 2 DEG C, and the reaction time is 1h~1.5h.

5. the preparation method of the dendroid organo-silicon compound according to claim 1 with multiterminal functional group, special Sign is, in step S1, the process of vacuum distillation are as follows: be depressurized to 6kPa in 120 DEG C of distillation 2h.

6. the preparation method of the dendroid organo-silicon compound according to claim 1 with multiterminal functional group, special Sign is, in step S2, the reaction condition of hydrosilylation is 80 DEG C~100 DEG C reaction 5h.

7. the preparation method of the dendroid organo-silicon compound according to claim 1 with multiterminal functional group, special Sign is, in step S2, the process of vacuum distillation are as follows: be depressurized to 6kPa in 120 DEG C of distillation 2h.

8. the dendroid organo-silicon compound that one kind has multiterminal functional group, which is characterized in that by any one of claim 1-7 The preparation method is prepared.