JPH01224380A - Silicon-containing compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The vinyl compound having silyl groups and expressed by formula I (n is integer of 1-4; R1 and R2 are H, alkyl, alkenyl or aryl which may contain functional groups such as NH2, Cl, CN, OH or COOH). EXAMPLE:The compound of formula II. USE:A monomer capable of not only polymerizing but also copolymerizing the various carbon-based monomers owing to extremely high reactivity and useful for the production of various functional polymers for water-repellent, surface- hardening agent, resist material, etc. PREPARATION:The compound of formula I can be readily produced by hydrosilylating a compound of formula III with silane, disilane, trisilane or tetrasilane.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel vinyl compound having silyl groups and a method for producing the same.

[Conventional technology]

Conventionally, several vinyl compounds having silyl groups have been developed. Silicon-containing compounds are useful as hexamers for various functional polymers because their -5i-H bonds are extremely reactive. Currently, vinylsilane, allylsilane, and the like are known as silicon-containing compounds having such unsaturated bonds.

[Problem to be solved by the invention]

However, these compounds have a low boiling point, and their polymerization requires special equipment and skilled techniques.Increasing the number of carbon atoms increases the boiling point, but the polymerizability decreases. Furthermore, it is difficult to efficiently manufacture these, and their uses are extremely limited.

The object of the present invention is to provide a new vinyl compound containing silyl groups that does not have such drawbacks.

Another object of the present invention is to provide a method for easily producing such compounds.

[Means for Solving the Problems] The object of the present invention is the general formula % (where n is an integer of 1 to 4, R1 and R2 are hydrogen, an alkyl group, an alkenyl group, or an aryl group, and -Ni+., CI, -CN, -011, -COOR
It may contain functional groups such as. Further, R1 and R2 may be the same or different. ) and a compound represented by (R+, R2 are the same as above) are hydrosilylated with silane, disilane, trisilane or tetrasilane, represented by the general formula (+) This is achieved by a method for producing silicon-containing compounds.

- In formula (1), n is an integer from 1 to 4. n is 4
Synthesis is difficult when the amount exceeds .

R1% R2 represents hydrogen, an alkyl group, an alkenyl group, or an aryl group, and these may be the same or different. R1 and R2 are -NH2, -CI, -Ko, -C
It may also contain a functional group such as OOR. Examples of R3 and R2 include =CH3 and -C2115 as alkyl groups.
, -1CJ,, -n(, +II7, etc., as an alkenyl group =CH=CIh, -CIl・ClIC1h, -C1
l□-CIl・Cl1-C1,, =C as an aryl group
Examples include b It s.

-C As the compound of formula (1), the following can be specifically exemplified.

In the method for producing a silicon-containing compound having an unsaturated bond according to the present invention, a monomer represented by the general formula NI) is subjected to a hydrosilylation reaction in the presence of a silane.

(However, R1 and R2 represent the same meanings as above, and may be the same or different.) Specific examples of compounds of general formula (I[) include CH2=CI
+-C00C1h, C11z=CH-COOCzlls
,91]3 CIlz=C1l-C00-nc*lI7, C
Ih=C-C00CHt, C11z=C-COOCtl
=CHz, CIl2 =C-C00C611s
, C112=C-COOCII□CIl□-COO1
1st prize will be given.

As the silanes, silane, disilane, trisilane, and tetrasilane can be used.

The reaction conditions are usually a temperature range of -50 to 600° C1 and a pressure of normal pressure to 100 kg/cIll. The reaction is usually 10
Completed in 0 hours.

There is no particular restriction on the reaction mode. When the reaction is carried out thermally,
It is preferable to react at 400°C to 600°C. The reaction can also be carried out under mercury lamp irradiation.

It can also perform radical reactions. For example, it may be carried out at a temperature range of 50 to 200'C in the presence of a radical initiator such as hendyl peroxide, cumene peroxide, monobutyl peroxide, abbisisobutyronitrile, etc. Furthermore, a metal catalyst can also be used. For example, Fe (Co) s, COZ (Co) a, LzNi
A (L is PΦ, PR3 (Φ is phenyl group, R
is an alkyl group), A is an olefin), LzNiC1□
, LaRhC1,L,Pd, LzPdCIz,L,
Pt, HzPtCI6・6+120, Pt/C,
, MO(Co)6, W(Co)4, Cr(Co)6,
TiCp2C1z (Cf' is a cyclopentadienyl group)
, ZrCp2C12, VCl, etc., in the presence of Group 1 to Group 2 transition metal complexes at a temperature range of -50°C to 200°C.

Among these methods, the method using a metal catalyst is the most preferred.

After the reaction is completed, the desired silicon-containing compound can be isolated from the reaction solution by conventional methods such as distillation or column chromatography.

[Effects of the Invention] The compound according to the present invention obtained in this manner is a monomer having polymerizability, particularly radical polymerizability, and is capable of not only homopolymerization but also copolymerization with various carbon-based monomers. A novel highly functional polymer can be provided. For example, it is used as a water repellent, a surface hardening agent, a resist material, etc., and has high industrial utility.

〔Example〕

Hereinafter, the present invention will be explained by examples.

Example 1 In a 100 d autoclave purged with dry nitrogen gas,
5 g of methyl methacrylate, 5 g on activated carbon as catalyst
0.2g of weight% pt supported (5XPt/C)
and then S i If a at 5 kg/c.
The pressure was reduced to +l, and the reaction was carried out at 120°C for 1 hour. The resulting reaction solution was filtered to remove PL/(:. The product was further isolated from the reaction solution by distillation.
I got g. The spectral data is shown below.

'H-NMR(100Mllz)2.0ppm
-CII3 3.6 ppm -3itl1 3.8 ppm -0CII3 4.4 ppm -CH- 5,9 ppm 1hc=I R2230cm-'v s, -.

910cnr' δ5I-H Elemental analysis theoretical value C: 45.42χ H: 9.15χ 0:24
．． 20χSi: 21.24χ Actual value C: 45.21! Old 9.30X mass spectrum M'' 132 When 1 g of product is treated with EtOH-Li, 541 d
(20°C) hydrogen was generated. This is SiH in tg
Per 22.5 mmol of binding, the theoretical amount is 22.7 mmol
Matches l.

From the above, the product of this reaction is It can be identified as

Example 2 In a 100 d autoclave purged with dry nitrogen gas,
Methyl acrylate 5g, 5χP t/C as catalyst 0
．． Prepare 2g, then prepare SiH4, 5kg/cJ
The reaction was carried out at 60°C for 4 hours. The resulting reaction solution was filtered to remove Pt/C. Furthermore, the product was isolated from the reaction solution by distillation. 2.3 g of product was obtained. The spectral data is shown below.

'H-N M R (100MHz) 3.6 ppm -5in3 3.8 ppm -0CR3 4,2 ppm -Ctl- 5,5~6.4 ppm CH,=CH-I R22
10cm-'vs=-++910cm-'
6 s+-1I Elemental analysis theoretical value C: 40.64χ H: 8.53χ O: 27
．． 07'1Si: 23.76X Actual value C: 40.30χ H: 8.62χ Mass spectrum M" 118 When 1 g of the product is treated with EtOH-Li, 605
20°C) hydrogen was evolved. This corresponds to 25.1 mmol of SiH bonds in 1 g, which agrees with the theoretical 125.4 mmol.

As a result of the above, the product of this reaction is cicu.

It can be identified as

Example 3 2.1 g of the product was obtained in the same manner as in Example 2, except that 2-hydroxyethyl acrylate was used instead of methyl acrylate. The spectral data is shown below.

' HN M R (100 MIlz )2・OppHl
-0H 3,6ppm -5iH3 3,5ppm -0CR, -4,2ppm -0Ctl-0 5,5~6.4 ppm CH2=CH-I R33
00CT11-'シG-112230cm-'
Si-H 910cm-' δ5i-H Elemental analysis theoretical value C: 40.51χ Il: 8.16χ O: 3
2.38χSi: 18.95χ Actual value C: 40.18Z) I: 8.21X mass spectrum M' 148 When 1g of product is treated with EtOII-Li, 480m
1 (20°C) of hydrogen was generated. This is Ig medium 5i
ll bond 20, per mol, theoretical amount 20.2 mm
Matches ol.

From the above, the product of this reaction is jSiH3 It can be identified as

Example 4 2.3 g of a product was obtained in the same manner as in Example 2, except that 2-chloroethyl methacrylate was used instead of methyl acrylate. The spectral data is shown below.

'H-NMR(100MIIz)2.0ppm
-CHI.

3.3 ppm -0-C1lz- 3,5 ppm -0-5iH:+ 4.0 ppm -CIIO- 5,5 ppm -CH2-Cl 3.9 ppm H2C=C- IR2230cl' vsr-n 910 cm-' δ, 11 Elemental analysis theoretical value C: 39.88! H: 1.25Z O:
17.70ICI:19.62χSi:15.54χactual value C:39.8(]! H:1.42χC1:1
9.53χ mass spectrum M' 180 When 1g of product is treated with EtOH-Li, 394m
(20°C) hydrogen was generated. This corresponds to 16.4 mmol of SiH bond in 1 g, and the theoretical amount is 16.6 mmol.
matches.

From the above, the product of this reaction is It can be identified as

Example 5 3.2 g of a product was obtained in the same manner as in Example 2, except that 2-cyanoethyl methacrylate was used instead of methyl acrylate. The spectral data is shown below.

' H-N M R (100MHz) 2.Oppm -Cl5 2.4 ppm -Cilz-CN 3-4 ppm -0CH2- 3,5ppm -05itl+ 4.0 ppm -CHo- 5,9pp+n H2C=C I R2210cwl- ' v si-H910cm
-Summer δ5. -I Elemental analysis theoretical value C: 49.09χ H near, 65! lJ:
8.18$0: 18.68χ Si: 16.40χ Actual value C: 49.82χ II near, 70χ N: 8.1
0! Mass spectrum M” 171 When 1 g of product is treated with EtOH-Li, 408
Hydrogen of In1 (20”C) was generated.This is s in 1g
iH bond 17, per 0 mmo 1, theoretical fi17
．． Matches 5 mmol. From the above, the product of this reaction is CH.

03iH3 It can be identified as

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (However, n is an integer from 1 to 4, R_1, R_2 are hydrogen, alkyl group, alkenyl group, or aryl group, and these are - NH_2, Cl, -CN, -OH, -COOH
It may contain functional groups such as. Also R_1, R_2
may be the same or different. ) A silicon-containing compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (R_1, R_2 are the same as above) A compound represented by the above is hydrosilylated with silane, disilane, trisilane or tetrasilane. A method for producing a silicon-containing compound represented by general formula (I).