JPS58174389A - Photodecomposable silicon compound - Google Patents

Abstract

NEW MATERIAL:A compound having a group, expressed by the formula (R is halogen, nitro, cyano, 1-5C alkyl, 1-5C alkoxyl, 1-5C acyloxyl, hydroxyl, mercapto, acetyl, allyl, etc.; n is an integer 0-4), and directly linked to the silicon atom. EXAMPLE:Trimethyl(o-nitrobenzyloxy)silane. USE:A component in insulating coating materials. PROCESS:A silicon halide compound, e.g. dimethylphenylchlorosilane, is reacted with o-nitrobenzyl alcohol in the presence of a base, e.g. triethylamine, in a solvent, e.g. tetrahydrofuran, to give the aimed compound, decomposable by light, e.g. ultraviolet light, and forming a silanol compound having the reactivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel photodegradable silicon compound, and more particularly, to a novel photodegradable silicon compound, which decomposes with light, particularly UV light, and produces a reactive silanol compound as a decomposition product. This invention relates to photodegradable silicon compounds produced.

[Contact background of the invention and its problems]

Conventionally, as photoreactive silicon compounds, compounds having groups such as vinyl groups, methacrylic esters, or acrylic esters and curing by light have been well known. However, these compounds do not have optical spectral properties.

Nata! Break et al. report that benzoylsilane is photodecomposed by UV light in the presence of a metal compound having active hydrogen, such as alcohol or water, to produce a silanol compound. However, in this case, there are drawbacks such as the need for a long time for decomposition.90 In this way, there have been no silicon compounds that rapidly release reactive silanol compounds when exposed to UV light.

However, photodegradable silicon compounds are expected to be used as photocuring catalysts for polyurethane resins, photocurable silicone resins, photocurable silicone resins, etc., and it is strongly desired to develop these compounds. 90 [Objective of the Invention] The purpose of the present invention is to provide a new and useful photodegradable silicon compound because it can quickly produce a reactive silanol compound in a short time by photolysis. It is something to do.

[Summary of the invention]

The photodegradable silicon compound of the present invention has the following formula:
Substituted or unsubstituted alkyl group, alkoxyl group having 1 to 8 carbon atoms, substituted or unsubstituted aryl group, aryloxy group, acyloyl group having 1 to 50 carbon atoms, hydrocyl group, mercapto group, acetyl group, represents an allyl group; - represents an integer of θ to 4; plural R's may be the same or different; ) is a compound in which the 0-nido-a befryloxy group is directly bonded to a silicon atom.In addition, when the above-mentioned grave is 3 or less, a hydrogen atom is bonded to the benzene ring of the -dito-tetrabefryloxy group. ing.

Among the above-mentioned nine groups, examples of substituents for alkyl groups and aryl groups having 1 to 5 carbon atoms include car-xyl groups, thiocar-xyl groups, dithiocar-xyl groups, and aryl groups having 1 to 5 carbon atoms.
The alkoxyl of 5 is an el group, a cyano group, a hol group,
Cal is a nyl group, a human gastric xyl group, a mercapto group, an artoxyl group having 1 to g+ carbon atoms, a halodane atom, 2) Ill
Examples include allyl group and trifluoromethyl group.

Examples of substituted or unsubstituted alkyl groups having 1 or more carbon atoms include methyl group, ethyl group, n-propyl group, isobutyl group, n-ethyl group, h
-pentyl group, isobutyl group, -butyl group, isopentyl group, neopentyl group, t-4entyl group, methoxymethyl group, cyanomethyl group, nitromethyl group, chloromethyl group, )9 fluoromethyl group, 2-ethoxyethyl group, Examples of alkoxyl groups having 1 to 5 carbon atoms include ethoxy group, ethoxy group, falxy group, isopentoxy group, ethoxy group, inobutoxy group, s@e-butoxy group, t-
Butoxy group, pentoxy group, isopentoxy group, neo(
and 1-indoxy group.

Examples of the substituted or unsubstituted aryl group include phenyl group, .-methylphenyl group, ugly-methylphenyl group, p-methylphenyl group, .-methoxyphenyl group, m
-Methoxy7 emyl group, p-methoxyphenyl lo-
Ethophenyl group, m-nitrophenyl group, p-nitrophenyl group, 0-cyanophenyl group, m-cyanophenyl group, p-cyanophenyl group, -chlorophenyl group,
Examples include m-chlorophenyl group, p-chlorophenyl group, 0-amino 7-ethyl group, m-amino 7-ethyl group, and p-7 minophenyl group.

Examples of the aryloxy group include phenoxy group, 0
-methylphenoxy group, m-methylphenoxy group, p-
Methylphenoxy group, 0-methoxyphenoxy group, m-
Methoxyphenoxy group, p-methoxyphenoxy group, 0
-nitrophenoxylJsm-nidophenoxy group, p
- engineering) Elphenol group, 0-cyanophenoxy group, m
-cyanophenoxy group, p-cyanophenoxy group, 0-
Examples include chlorophenoxy group, m-chlorophenoxy group, p-chlorophenoxy group, Q-aminophenoxy group, m-aminophenoxy group, and p-aminophenoxy group.

Examples of the alkoxy group having 1 to 5 carbon atoms include a holyloxy group, an acetoxy group, a fa pionyloxy group, a butyryloxy group, a valeryloxy group, an isovaleryloxy group, and a piparoyloxy group.

In addition to the 0-etroindyloxy group, examples of the group directly bonded to the silicon atom include a hydrogen atom, a halodane atom, a substituted 4-carbon unsubstituted alkyl group having 1 to 1 G carbon atoms, and a C 1 to 1 G alkyl group. 10 alkoxyl groups, substituted or unsubstituted aryl groups, aryloxy groups, vinyl groups, and allyl groups.

Among the nine groups mentioned above, examples of substituents for the alkyl group and aryl group having 1 to 100 carbon atoms include xyl group,
Thiocar is xyl group, dithiocar-xyl group, carbon number 1
~5C) Cical d-er group, cyano group, formyl group, car-1 group, hydroxyl group, Mercag F group, alkoxyl group having 1 to s carbon atoms, halo r:/nico, etho-
group, allyl group, and trifluoromethyl group.

Examples of substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, th-, I: globyl group, isodetetravir group...n-butyl group, ■c
-butyl group, t-butyl group, n-(l tyl group, neopentyl group, iso(l tyl group, t-pentyl group, hexyl group, inhexyl group, hel tyl group, octyl group, nonyl group, decyl group) , methoxymethyl group, cyanomethyl group, nitromethyl group, chloromethyl group, 2-trifluoromethylethyl group, 2-ethyl group, 2-eth-4thyl group, 3-coulohexyl group, and 5-cyanoheptyl group. It will be done.

Examples of the alkoxyl group having 1 to 10 carbon atoms include methoxy group, ethoxy group, gummy/oxy group, isopropoxy group, butoxy group, isobutoxy group, 16 (1-butoxy group, t-butoxy group, pentyloxy group, Examples include isopentyloxy group, neopentyloxy group, t-pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, and decyloxy group.

The substituted or unsubstituted aryl group and aryloxy group are exemplified by the same groups as in the above-mentioned 90-nido-n-befryloxy group.

Two or more silicon atoms to which the t+,0-nitrobenzyloxy group is directly bonded may be bonded via an oxygen atom; an alkyl group such as methylene or ethylene; or an aryl group such as phenylene. The photodegradable silicon compounds of the present invention in which the V group in 〇〇-nitropenfurio is directly bonded to the silicon atom are exemplified below. ) 1
1゜Silane 2, ゛Dimethyl (0-ditropendyloxy) fluoride 1
2-enylcine 2-3, diphenylmethyl (0-nido-tetra-pencilyl 13)
゛xy)silane 4, )9 phenyl(0-etroindyloxy)
14. Silane 5, triethyl (0-nitrobenzyloxy) 15. Silane 6, tri(2-chlorotetraethyl) 0-eth-yne 16
・Zyloxysilanedi(0-etroindyloxy)methylphenylsilanediethyldi(0-nitrobenzyloxy)silanedimethyldi(0-nitro(furyloxy)silane)IF(o-nidotetrapefuryloxy+silane) 9(·-nitrobenzyloxy)methyl7randi(p-methoxyphenyl) sP (o-nitropenzyloxy)silanedi(p-chlorophenyl)di(0-etroinzyloxy)silanedi(p-cyanophenyl) )zo(0-nitrobenzyloxy)silane)U(p-trifluoromethylphenyl)0-=)lopenzyloxysilane 18, )IJ phenyl(2,6-nonitofourpentyloxy)silane 19, dimethyl( 4-methoxy-2-2)114
Dimethyl(4,5-dimethoxy-2-nitro(furyloxy)phenyloxy)phenylsilane 20, Trimethyl(4,5-dimethoxy-2-nitropenzyloxy)silane 21, Dimethyl(4,5-dimethoxy-2-nitro(furyloxy)phenylsilane 22, Diphenylmethyl(4,5) ,6-)rimexyxy-2-nitropennoroxy)silane 23,
Diphenylmethyl (3,4,ms -) Rimetoshi 2
-nitropenzyloxy)silane 24, / (p
-10--etho-indyloxy)methylphenylsilane 25, triphenyl(p-phenoxy-ethroindyloxy)silane 26, triethyl(3,4-dimethyl-2-nitrobenzyloxy)silane 27, C4,6-siloro-nitropenzyloxy)dimethylsilane 2B, di(3,4,-benzyloxy-2-nido-benzyloxy)dimethylsilane 29, 2(4,5-dimethoxy-2- ditropendyloxy)dimethylsilane 3a t(4-cyano-2-nitrobenzyloxy)dimethylsilane 31 /(4-ethoxy-2-nitroinzyloxy)dimethylsilane 32, di(4-fluoro-2-eth Q4 (benzyloxy)dimethylsilane 33, p-bis(〇-〇)0benzyloxydimethylsilyl)benzene 34, 1.1,3,3,5.5-hexamethyl-1
,5-di(2-nitroindyloxy)siloxane 35
, 1,1.3.3-tetrapher-1,3-di(
2-nitropenzyloxy)siloxane 36, 1.1,3,3,5.5-hexaphenyl-
1#! S-zo(2-nitroinzyloxy)siloxane 37 1.3.5-)dimethyl-1,3,5-triphenyl-1,5-f(2-nitroinzoloxy)siloxane 38, (o- Nitropenzyloxy)vinyldiphenylsilane 39, (o-nitrobenzyloxy)vinylphenylmethylsilane 40, Butylsilane 42, J) (3-Methyl-2-nitrobenzyloxy7) diphenylsilane 43, (5-methyl-2-nido-benzyloxy)triphenylsilane 44 (3-methoxy-2-ethyl) Tan 4/Zyloxy)diphenylsilane 45, Di(2-chloro-6-nitropenzyloxy)diphenylsilane 46, (5-chloro-2-nitropenzoloxy)triphenylsilane 47, Zo(2,4 -dinitobenzyloxy)diphenylsilane 48, (6-nitroindyloxy)triphenylsilane 49, diphenyl(3-methyl-4-methoxy-
2-Nitrobenzyloxy,) Silane 50, (3
, 4-dimethoxy-2-nitrobenzyloxy)) 9-phenylsilane In addition to these, there may be mentioned, for example, a resin obtained by reacting silicon-containing silico 711 with aliphatic o-nide benzyl alcohol.

The compound of the present invention is synthesized, for example, by the following reaction.

(In the formula, R is 0- directly bonded to the silicon atom described above.
Has the same meaning as groups other than benzyloxy;
represents a h vsf h atom. ) This reaction involves the reaction between silicon halide compound (I) and 0-nitropenzylalfur@),! :t) ethyl aza 2,N,N-dimethylaniline, bi(lysine♂1jdine, 1,5-diazobicyclo(4,3,0)nonene-bi(DBN), 1,8-diazobicyclo(1, 4,0) ?Ndesen-7 (DBU)
, tri-a-butylamine, sodium hydride,
The metal compound of the present invention is synthesized by reacting it in the presence of a base appropriately selected from the group consisting of turtle-butyllithium. The reaction is carried out in a solvent, and examples of the solvent include ethers such as tetrahedral, diethyl ether, dimethoxyethane, and dioxane; -Hekina y1 Petroleum ether, °Petroleum benzine, toluene, and benzene are vignetted.

The amount of raw materials etc. to be blended is 1.0 to 3.04 mol, preferably 1.0 to 1.2 mol, of compound (1) to the amount of compound α) O atoms lII. The reagent used for the 0-driethyl-a-den y cape is 1.gl to 3.0 mol of supercharge for compound (I) and (1 and OVS Homa ItK, and the solvent is also usually 2.0 mol.
~2000 weight - used. The reaction temperature is □, usually 2i~
The temperature is 110°C, preferably 4°C to 4°C, and the reaction time is usually 0. ! s~48 hours, preferably 1~20 hours
It's time.

The decentralization of the target product is not constant (depending on the base, solvent, etc. used), but it can usually be done more easily than by filtering the salt from the reaction mixture and then carefully removing the base and solvent from the filter. . If necessary, the usual post-processing operations of one column Chroma F, extraction, and reconsolidation may be performed for dispersion.

By light irradiation, the compound of the present invention can be produced, for example, by the following reaction formula:
It has the same meaning as groups other than nitrofuryl group.

) The silanol compound is liberated by rapidly causing a more radical decomposition reaction.

As the light source used in this reaction, for example, high-pressure mercury can be used. The irradiated light rapidly photodecomposes the compound of the present invention, and UV light is preferably used. The photolysis reaction is carried out without a solvent or in a solvent. Examples of solvents include ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, zokiosa, acetonitrile, benzene, toluene, U-
Hechusan is given. The reaction temperature for this and IIO is usually 0 to 109°C, preferably! It is IO'C. The reaction time is usually 30 seconds to 2 hours, preferably 1
~30 minutes.

The silanol compound, which is a photodecomposition product of the compound of the present invention, has, for example, the following types of reactivity and reaction mode.

Self-condensation; ■) Addition to a 4-hydroxy group; (f) Polymerization of a polymerization compound - The compound of the present invention which liberates a silanol compound having reactivity as described above by light irradiation is, for example, It is used for applications such as fat filler, which frequently occurs when forming motor insulation layers, and insulating paints containing silicone resin, axy silicone resin, epoxy resin, etc.

[Embodiments of the invention]

Example 1 Zomethylphenylchlorosilane 1711 (t14),
0-benzyl alcohol 1681 (1 mol) and triethylamine 1011 (1 mol) were stirred in 500 d of tetrahydrofuran (THF) at 60°C for 5 hours. After stirring, the precipitated salt was filtered off, and THF was distilled off from the resulting filtrate under reduced pressure at 10 rmHIO to obtain the desired product 272I (0,946 mol). Yield is 94.6
- 9. The 'I(-NM:R) spectrum of the compound was measured at room temperature in heavy-weight form-: 0.46
゜5.10, 7.34-8. A signal corresponding to IO was observed (FIG. 1), confirming that this compound was dimethyl(0-nitropenzyloxy)7.

Next, add this compound to 11tTHF10aJKS and place it in a quartz tube. At 40°C and 10 cm + O [from a distance, UV light (
The sample was irradiated with a 400W quartz high-pressure mercury lamp). about 10
Over 90 minutes of irradiation decomposed this compound. shiw2pr#(HllG-10eHOG-15, HO
G-20) Identification by GPC using a column confirmed that a considerable amount of triphenylsilanol was produced.

Incidentally, even if the compound was left at temperature for 30 minutes without being irradiated with UV light, it did not decompose at all.

Example 2.

Triphenylchlorosilane 295I (14k), -Nitrobenzyl alcohol 153g (1 Minekari and N,N-
Dimethylaniline 1211 (14 l) to ether 800
11j at room temperature for 18 hours. After stirring, the precipitated round ring was removed by filtration, and the resulting filtrate was heated to 50°C to distill off the diether.
0,9314 le). The yield was 93.191G. 'H-NMR of this compound, measured at room temperature in deuterated chloroform at 9? : 5.32, 7
．． A rumbling signal was observed between 3 seconds and 8.14 seconds (Figure 2), confirming that this compound was triphenyl(0-nitrobenzyl)silane. The solution was dissolved in 0.5-tonisylyl dihydrogenate in 40° C. and irradiated with UV light (40 GW high-pressure water chain made of quartz) from a distance of 10 cm. After about 30 minutes of irradiation, more than 90% of this compound was decomposed and triphenylsilanol was produced.

Example 3 Using cyclodiphenylsilane and H@-E)114)/dyl alcohol, the same procedure as in Example 2 was carried out to obtain the desired product. The yield was 98-day).

NMRX of this compound (J: 5.27.7.40-1.99 in weighted W-form at room temperature (Figure 3
).

Next, this compound was placed in an NMR check and irradiated with UV light in the same manner as in Example 2 in heavy THF.

After about 15 minutes of irradiation, more than 9 o- of this compound was decomposed and diphenylsilanediol was produced. Operate to obtain the target object. The yield was 95-.

NMR of this compound
J at room temperature: 0,56, 5,22, ? , 31~
It was 1.10 (Figure 4).

Next, add this compound 0.1F to acetoink tolyl lO@jK
Interpret II and put it in a quartz tube. UV light (400 W quartz-like high pressure mercury run f) was irradiated at 40° C. from a distance of 10°. After about 10 minutes of irradiation, 90ws of this compound
The above decomposed 0zo JIyA Tsuknu OD8 column (4,
Identification was made by liquid chromatography using a 6-x S scratch (2 pieces), and it was confirmed that methylphenylsilanediol was produced in a phase-like amount.

Furthermore, even if the compound was left at 40° C. for 30 minutes without being irradiated with UV light, it did not decompose at all.

Example 5 / W III d Using phenylvinylsilane and .-nitro-4y-dyl alcohol, the same procedure as in Example 1 was carried out to obtain the desired product. The yield is ・4. It was S-.

The NMRjC4 tuttle of this compound is in weight four parts form,
J at room temperature: 5.2 S,! $, γ8~6.74
．． It was 7.30 to 8.11 (Figure S).

Next, this compound was placed in an NMR chaser and irradiated with UV light in the same manner as in Example 2 in deuterated acetonitrile. Approximately 1
Upon irradiation for 5 minutes), more than 90-g of this metal compound was decomposed and diphenyl C-ersilanol was produced.

Example 6 The desired product was obtained by carrying out the same procedure as in Example 1 using chlorovinyl 7, ethylmethylthione, and peflyl arsur. The yield is 93.4-〇This compound ONM
The RJ petator is placed in a heavy-duty room at room temperature: 0.
53,! 1.15, 1.7 @ ~al17.3
4 to 8.11 seconds (ms) Next, this compound was placed in a quartz tube, and as in Example 4, it was irradiated with UV light. Approximately 1
``When sacrificed for 0 minutes, more than 90% of this compound is decomposed, and V-elphenylmethylsilanol can be produced.

The photoreaction product was separated using Silica Dull 60 (manufactured by Melta), and from the distillate part (1G11 ether-toluene), 9 pierphenylmethylsitunol was extracted.
It can be obtained with a yield of 0.

41CK without irradiating the chemical metal with UV light.
Even after leaving it for an hour, it did not decompose at all.

Example 7 The desired product was obtained in the same manner as in Example 2. Yield is 93.
391 and nine.

The NMB spectrum of this compound was measured in deuterated chloroform at room temperature f(: 5.27, 6.06-6.40, 7.3
1 to 8.10 (Figure 7).

This compound was then dissolved in heavy dioquinane in an NMR tube and irradiated with UV light as in Example 2. After about 30 minutes of irradiation), this compound was partially decomposed by more than 90% to form vinylphenylsilanediol.

In addition, the above compound was heated at 60°C without irradiating with UV light.
When I left it for 30 minutes, it did not decompose.

Based on these facts, the compound of the present invention can be easily synthesized with high yield by using UV light,
It has become clear that it decomposes rapidly to produce silanol compounds.

〔Effect of the invention〕

The compound according to the invention comprises a hydrogenated silicon compound and an 0-
By reacting with Nido-C14-dyl alcohol, a compound can be synthesized with extremely high yield and high yield. nine,
When exposed to light, it decomposes into crystalline crystals to produce useful silanol compounds. Utilizing this property, the compounds of the present invention can be used in a variety of applications such as insulating paints, trout sealing materials, coating materials, etc. It has great potential and its industrial value.

[Brief explanation of drawings]

1 to 7 show compound numbers 2, 4, 7, and 8 in Examples 1 to 7, respectively. NMR spectra of $8, 3, and 40 substances in deuterated chloroform.

Claims (1)

[Scope of Claims] The following formula: (wherein, R is a hydrogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a carbon number 1
-5 alkoxyl group, substituted or unsubstituted aryl group, aryloxy group, acyloxy group having 1 to 5 carbon atoms, P4xyl group, mercapto group, acetyl group, oryl group; n is O-4 represents an integer; multiple ORs may be the same or different. ) A photodegradable silicon compound 0 in which the 0-nitrobenzyloxy group shown in the formula is directly bonded to a silicon atom.