JPS6263595A - Vinylphenylketene methyltrimethylsilyl acetal - Google Patents

Abstract

NEW MATERIAL:m- or p-Vinylphenylketene methyltrimethylsilyl acetal expressed by formula I or II. USE:A polymerization initiator in ioinic polymerization or raw material intermediate for coating materials, adhesives, etc., capable of facilitating the curing reaction after copolymerization and scarcely causing problems, e.g. coloring or deteriorating. PREPARATION:For example, m-vinylbenzyl chloride expressed by formula III is reacted with NaCN in a mixed solvent of methanol and water while refluxing to give m-vinylbenzyl cyanide, which is then reacted with an equimolar amount of hydrogen chloride in methanol to afford a compound expressed by formula IV. The resultant compound expressed by formula IV is then hydrolyzed with water in an amount of 6 times based on the above-mentioned compound expressed by formula IV to give a compound expressed by formula V, which is then reacted with lithium isopropylamide in THF at 0 deg.C. An excess amount of trimethylchlorosilane is then added thereto and reacted therewith at room temperature.

Description

Detailed Description of the Invention (a) Purpose of the Invention (Field of Industrial Application) The present invention is useful as a polymerization initiator in ionic polymerization methods, and as a raw material intermediate for paints, adhesives, rubber, engineering plastics, etc. Certain new m-vinyl or P
- Vinylphenylketene methyltrimethylsilyl acetal.

(Prior art) Conventionally, m- or P-chloromethylstyrene, m- or P-cyanomethylstyrene, α-methylstyrene, m- or P-methylstyrene, P-hydroxystyrene, etc. are known as styrene derivatives. These styrene derivatives can be used for various purposes by copolymerizing with styrene, acrylic esters, methacrylic esters, etc., but due to the poor reactivity of functional groups such as chloromethyl groups, cyanmethyl groups, and hydroxyl groups, As a curing means after copolymerization, it was necessary to use a strongly basic material such as amine to heat-cure.

However, this leads to disadvantages in that the cured product becomes colored and easily deteriorates, so that it has not been used much in practice. For this reason, these styrene derivatives are rarely copolymerized as they are, but rather are used as intermediates for producing new functional monomers. However, due to the poor reactivity of the functional groups, it was necessary to tighten the conditions for producing functional monomers.

(Problems to be Solved by the Invention) The present invention facilitates the curing reaction after copolymerization, and also eases the conditions for producing functional monomers or expands the range of condition selection. The present invention aims to provide a styrene derivative having a functional group.

(B) Structure of the Invention (Means for Solving the Problems) In order to solve the above problems, the inventor of the present invention has conducted extensive research on styrene derivatives having functional groups, and as a result, has developed highly reactive functional groups. The present invention was achieved by discovering a styrene derivative with the following characteristics.

That is, the compound according to the present invention is a vinyl phenylketene methyltrimethylsilyl acetal having a vinyl group at the m- or P-position, and is represented by the following structural formula.

m-Vinylphenylketene methyltrimethylsilylacetal: P-vinylphenylketenemethyltrimethylsilylacetal; An example of the method for producing vinylphenylketenemethyltrimethylsilylacetal having a vinyl group at the m- or P-position of the present invention is as follows.

That is, using m- or p-vinylbenzyl chloride as a starting material, this and NaCN were reacted under reflux in an alcohol-water mixed solvent, and the mixture was heated to 87°C/87°C by filtration and distillation.
2 Synthesize m- or p-vinylbenzylic cyanide as a fraction of wsHll, then blow equimolar hydrogen chloride into methanol and leave it for a day and night to obtain m- or p-vinylbenzylimide ester hydrochloride as a precipitate. After purification, it is hydrolyzed with 6 times the amount of water, extracted with a large excess of petroleum ether, and distilled to obtain m- or P-vinylphenyl acetic acid methyl ester as a fraction at 97°C/3sm H, lit.

Next, m- or P-vinylphenyl acetic acid methyl ester obtained above was added to a tetrahydrofuran solution of lithium diisopropylamide in an amount equimolar to that of lithium diisopropylamide, and the mixture was kept at about 0°C for 60 minutes with stirring, and then an excess amount was added. Add trimethylchlorosilane and return to room temperature, then stir at room temperature for 30 minutes, filter the reaction mixture,
Concentrate the solution. This was washed with anhydrous ether to remove the anhydrous ether, and the oily liquid was distilled under reduced pressure at 110°C/3.
m- or P-vinylphenylketene methyltrimethylsilyl acetal is obtained as a fraction of mH&.

This is expressed by the following formula. Note that the position of the vinyl group is either m- or P-.

H2C1 The aforementioned raw material m- or P-vinylphenyl acetic acid methyl ester is already known, and the method for producing it is described, for example, in USP No. 3,073,862, in which P-vinylbenzyl cyanide is hydrolyzed and then methyl A method for synthesizing esters is described.

The m- or P-vinylphenylketene methyltrimethylsilyl acetal thus obtained was identified by NMR spectrum, IR spectrum, and elemental analysis, as shown in each example below.

[Reference examples, working examples and application examples]

The present invention will be explained in more detail with reference to Reference Examples and Examples below.

Reference Example 1 (Synthesis of p-vinylbenzylcyanito) Commercially available P
-vinylbenzyl chloride at 122.9r, reagent-grade N
aCN 501r, methanol 122&r as solvent
and 5011 r of water were added at once and refluxed for 12 hours. The temperature at that time was 64°C. After cooling, the by-produced NaCl was removed using paper, and the mixture was concentrated using a rotary evaporator. After being separated again, vacuum distillation was performed. The main distillate was 2ysHI with a distillation temperature of 87°C at 80.1. ! I got ilr. The yield was 70%.

IR Saki, Spectrum 2) The yield of IJ group is 2250cIL'
Nearby, the absorption of vinyl groups appeared around 1650 cIt-1, and the formation of P-vinylbenzyl cyanide was confirmed.

Reference Example 2 (Synthesis of P-vinylphenyl acetic acid methyl ester) P-vinylbenzyl cyanide 64.411r obtained in Reference Example 1 and methanol were placed in a glass flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a gas blowing tube. 17.6&
I put r. Dry hydrogen chloride 19IIr was blown into the solution and absorbed while keeping the liquid temperature at 0° C. without stirring. After finishing, I left it in the refrigerator overnight. After that, take out the formed precipitate,
By washing with anhydrous ether and vacuum drying without pulverization, imidoester hydrochloride was obtained at a yield of 66.71/r.

The yield was 70 cm.

Further, this hydrochloric acid foundation fit 66.7 jW r was stirred with 6 times the equivalent of water 54.0.9 r at room temperature for 15 minutes, and then 20 times the amount of petroleum ether was added and stirred for 2 days. After separation, the upper layer was concentrated using a rotary evaporator, and then distilled under reduced pressure. 3mH as main fraction
1, a 97°C fraction of 46.6&r was obtained.

The yield based on P-vinylbenzyl cyanide was 58.8%.

In the IR spectrum, the absorption of the nitrile group is 2250 cm-'
It was found that the nitrile group had completely reacted because it was not in the vicinity, and on the other hand, an absorption peak of the ester bond was observed near 1740α-1, and absorption of the vinyl group remained near 1635cM7', indicating that methyl P-vinylphenyl acetate It was confirmed that ester was produced.

Reference Example 6 (Synthesis of m-vinylbenzyl cyanide) Using raw materials, m-
m-vinylbenzyl cyanide was synthesized in the same manner as in Reference Example 1 except that vinylbenzyl chloride was used. The yield was 70%. The IR spectrum of this m-vinylbenzyl cyanide was similar to that of p-vinylbenzyl cyanide.

Reference Example 4 (Synthesis of m-vinylphenyl acetic acid methyl ester) m-vinylphenyl acetic acid methyl ester was synthesized in the same manner as in Reference Example 2 except that m-vinylbenzyl cyanide obtained in Reference Example 6 was used. The yield based on m-benzyl cyanide was 595 cm. The boiling point and IR spectrum of this m-vinylphenyl 6-acid methyl ester were similar to that of P-vinylphenyl acetic acid methyl ester.

Example 1 (Synthesis of p-vinylphenylketene methyltrimethylsilyl acetal) After a glass flask equipped with a stirrer, a thermometer, a dropping funnel, and a Dimroth condenser was sufficiently purged with nitrogen, 8-thilithium diimpropylamide was added in a nitrogen atmosphere. Put the tetrahydrofuran solution 2681r into a flask, and cool the P- obtained in Reference Example 2 while cooling from the outside with an ice-water bath.
Vinyl phenylacetic acid methyl ester 65.2jlr 5
After dripping for a minute, continue to maintain O'C for 30 minutes.
The reaction was stirred for a minute. Thereafter, excess trimethylchlorosilane 54.3#r was added dropwise over 5 minutes at the same temperature.

The temperature of the solution was gradually returned to room temperature while stirring, and after 30 minutes at room temperature, the reaction solution was passed through dI, and the P solution was concentrated using a rotary evaporator. The residue was washed with anhydrous ethyl ether and filtered to extract the desired product into ether. After removing the ether using a rotary evaporator, the remaining oily liquid was distilled under reduced pressure.

The main fraction is the fraction 22. I got lr. The yield was 45 cm.

As a polymerization inhibitor, 15% of 4-t-butylcatechol was added.
ppm and stored in a cool dark place.
=Absorption peak derived from C bond is 1630-1670α
-1, while the absorption peak due to 5i-C is 85
Since it appears strongly near 0cIL', it is fully confirmed that it has a ketene trimester silyl acetata structure.

On the other hand, the NMR spectrum shows 5i(C
A peak based on H5)3 is seen around 0.3δ, a peak based on OCH3 is seen around 6.65δ, and a peak based on the phenyl group is seen around 72δ.

Elemental analysis values are C67,75 (calculated value 6770%), H
It was 8.06 inches (calculated value 8.11 inches).

Example 2 (Synthesis of m-vinylphenylketene methyltrimethylsilyl acetal) m-vinylphenylketene methyltrimethylsilyl acetal was produced in the same manner as in Example 1 except that the m-vinylphenyl acetic acid methyl ester obtained in Reference Example 4 was used. Synthesized. The yield was 48.3%.

As a result of measuring the IR spectrum of the obtained m-vinylphenylketene methyltrimethylsilylacetal, it was found that the peak was 1630-1670c based on the C=C bond.
m, a peak based on 5i-C bond is 850c+
I confirmed that it appeared near a'.

In addition, the NMR spectrum is as shown in Figure 2,
5i(CH,), the peak based on OC
It was confirmed that the peak based on H3 was around 3.65[delta]K, and the peak based on phenyl group was around 7.2J.

Elemental analysis value is C67.75% (calculated value 67.70%)
, 88.06 inches (calculated value 8.11 inches).

Application example 1 100 grams of anhydrous tetrahydrofuran (TH) under dry nitrogen
F) 1c, m, P-vinylphenylketene methyltrimethylsilyl acetal (hereinafter referred to as VPKTSA)
(Mixture of 60% meta and 40% bulk) 1.585
(5.65 mmol) and tris(dimethylamino)sulfonium difluorotrimethylsilicate (hereinafter referred to as TA
S F2S iMe3) 0.0 part (0,11
16.9 parts (0.17 mol) of methyl methacrylate (hereinafter abbreviated as MMA) purified on calcium hydride (CaH2) were added and polymerized at room temperature for 3 hours. In addition to the hexane solution containing 5 timemethanol,
Mn=5500. Mw/Mn = tO9(7)
A polyMMA macromonomer having a styryl group at one end was obtained in a yield of 90.3 times.

A peak due to the enyl proton was observed, and as a result of comparing the integral value of the peak due to this phenyl proton and the integral value of the peak due to the methyl proton of the methoxy group (3.6 ppm), it was found that there is one steryl group at the end of PoIJ MMA. I found out that it has been installed.

Further, when the toughness of this polymer was examined by NMR, it was found to be 58.6% syndiotactic, 56.0% isotactic, and 54% heterotactic.

Application examples 2 to 4 MMA monomer and initiator V P K 'l' S A
The molar ratio of VPKTSA and the catalyst 'I'ASF2SiMe3 was kept constant at 100:5, and polymerization was carried out in the same manner as in Example 1 at room temperature for a predetermined period of time. The results obtained are shown in Table-1. In all of the examples, the molecular weight distribution of the macro-natsummer was 1.1 or less, which was close to monodisperse.

Application Examples 5 to 10 MMA was polymerized in the same manner as in Example 1, except that the charging ratio of MMA and initiator was varied between 60 and 1000, and the polymerization temperature was 0°C and room temperature.The results are shown in the table below. I got it.

A GPC chart of the polyMMA macromonomer obtained in Example 6 is shown in FIG. From FIG. 4, it can be seen that even when the molecular weight is 1 ooooo or more, the GPC chart has excellent symmetry and is a macromonomer with good monodispersity.

Application example 11 20 under dry nitrogen! Initiator VPKTSA 1.23 parts (5 mmol) and TA in anhydrous tetrahydrofuran in R1
S F25j Mes 0.03 part (0.1 mmol) and ethyl acrylate purified with CaH (hereinafter referred to as E
10 parts (abbreviated as A) (100 mmol) were mixed and polymerized at room temperature for 24 hours. This was washed four times with a hexane solution containing 5-timeethanol to obtain a macromonomer of poIJEA (yield: 4B, 2%). The molecular weight of this substance is GP
When I checked with C, Mn=1800, Mw/Mn=12
It was 8.

Application example 12 62 parts of initiator VPKTSAα (2.5 mmol) and TAS in 20 ml of anhydrous tetrahydrofuran under dry nitrogen
0.05 parts (o, 1 mmol) of F2SiMe+ and 3.36 parts (20 mmol) of cyclohexyl methacrylate purified over CaH were polymerized for 24 hours while being maintained at 0-35°C. After the polymerization was completed, this solution was added to methanol to precipitate the polymer, and when dried under reduced pressure, Mn
Poly(cyclohexyl methacrylate) macromonomer with =1280 and Mw/Mn =115 was obtained in a yield of 92.0%.

Application example 13 Initiator VPKTS in anhydrous THF for 50 d under dry nitrogen
1.23 parts (5 mmol) of A and TASF SiMes
Q. Mix 03 parts (0.1 mmol)? solution KCaH, butyl methacrylate 2 purified above
8.4 parts (0.2 mol) was added dropwise little by little so that the temperature did not rise above 30° C., and the mixture was polymerized for 12 hours. The resulting solution was evaporated in vacuo, Mn=4700, Mw/Mn=
111 poly(butyl methacrylate) macromonomers were obtained in a yield of 893 cm.

Application example 14 V in 50 ml of anhydrous THF at 0°C under dry nitrogen
23 parts (5 mmol) of PKTSAt and TASF2S
A mixture of 5 parts of MMA purified on CaH2 (O, OS mol) and 11 parts of glycidyl methacrylate purified on alumina (O, OS mol) was added dropwise to a mixed solution of iMes O, 3 parts (0,1 mmol). Humidity 0-60℃
It was dripped while maintaining the temperature.

After the addition was completed, the mixture was further stirred for 3 hours, and then the polymer was precipitated with hexane and dried under reduced pressure to obtain a 12.05I poly(MMA/glycidyl methacrylate copolymer) macromonomer. Mn=2500, Mw/M of this
n was 1.15.

Application example 15 IJMMA macromono-r-(Mn = 3500, Mw/Mn =
1.09) 28 parts (8 mmol) and initiator AIBN0
．． 25 parts (1.5 mmol) were dissolved in benzene 1001 and subjected to radical polymerization at 60° C. under vacuum. Figure 5 shows the change in polymerization rate over time. As a result, the polyMMA macromonomer has high radical polymerizability and at the same time has a purity of 9.
It was found that it was 5% or more.

(c) Effects of the invention The m- or P-vinylphenylketene methyltrimethylsilyl acetal of the present invention can be used as a polymerization initiator in an ionic polymerization method by utilizing its methyltrimethylsilylketene acetal group, such as methacrylic acid. In the ionic polymerization of methyl, m- or P-vinylphenylketene methyl trimethylsilyl acetal is used as a polymerization initiator, and tris(
By polymerizing methyl methacrylate using dimethylamino)sulfonium difluorotrimethylsilicate at room temperature, polymethyl methacrylate having a radically polymerizable steryl group at one end can be produced, and this can be further combined with other monomers to form a radically polymerizable steryl group. A graft polymer can be easily produced by polymerization.

In addition, since the m- or P-vinylphenylketene methyltrimethylsilyl acetal of the present invention has a highly reactive trimethylsilyl group, it can be easily used as a crosslinking agent, such as ethylene glycol, butanediol, or polyester polyol, after radical polymerization. It can be hardened to Since this curing method does not use amines or the like, problems such as coloring and deterioration are less likely to occur. Further, functional monomers can be easily synthesized by reacting with alcohols having special functions, and various resins can be produced based on this.

The various polymers obtained as described above are industrially useful as paints, rubbers, adhesives, and the like.

[Brief explanation of drawings]

FIG. 1 shows the NMR spectrum of P-vinylphenylketenemethyltrimethylsilylacetal obtained in Example 1, and FIG. 2 shows the m-
1 shows an NMR spectrum of vinyl phenylketene methyltrimethylsilyl acetal. Figure 3 is an NMR chart of the macromonomer of polyMMA having a steryl group at one end obtained in Application Example 1, and Figure 4 is an NMR chart of the macromonomer of polyMMA having a styryl group at one end obtained in Application Example 6. GPC chart of monomer) (UV is 245 nm, R
I represents the refractive index), and FIG. 5 is a graph showing the relationship between the polymerization rate and time in Application Example 15.

Claims (1)

[Claims] 1. Vinyl phenylketene methyltrimethylsilyl acetal having a vinyl group at the m- or P-position represented by the following formula (1) or (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2)