JPS6339001B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer of styrene derivatives having reactive groups. Polymers of styrene derivatives having reactive hydroxyl groups, amino groups, etc. in their molecules have not yet been obtained by anionic polymerization because they have active hydrogen in their reactive groups. The present inventors have prepared a reactive group of a styrene derivative having a reactive group, such as a trialkylsilyl group, a triarylsilyl group (hereinafter referred to as a substituted silyl group), in advance.
By acting with an anionic polymerization initiator, a living polymer of the styrene derivative protected with a substituted silyl group is obtained, and then by acting with an active hydrogen-containing compound, the protecting group is removed and the styrene The present invention was completed by discovering that a polymer of the derivative can be obtained. That is, an object of the present invention is to provide a method for producing a polymer of a styrene derivative having a reactive group by anionic polymerization. ^[ _{wherein ,} ^{_ _ _}
represents a hydrogen atom or an alkyl group. However, R ₁ ,
R ² is not at the same time an alkyl group. ] The styrene derivative represented by the general formula (SiR ³ R ⁴ R ⁵ ) _o L [however,
R ³ , R ⁴ and R ⁵ are the same or different alkyl groups or aryl groups, L is a halogen atom or NH group, n is 1 when L is a halogen atom,
In the case of NH group, it is 2. ], and the resulting substituted silyl group of the styrene derivative is polymerized in the presence of an anionic initiator to form a living polymer of the substituted product, and then brought into contact with a proton donor. The gist of this invention is a method for producing a styrene derivative polymer. R ¹ and R ² in the general formula of the above styrene derivative
The alkyl group represented by is preferably a lower alkyl group having 1 to 6 carbon atoms. Specific examples of these styrene derivatives include:
【formula】 Examples include [Formula]. The substituted silyl group-containing compound used to protect the reactive group of the styrene derivative is a compound containing a trialkylsilyl group, an alkyl/aryl mixed trisubstituted silyl group, or a triarylsilyl group. General formula (SiR ³ R ⁴ R ⁵ )
_o L [wherein R ³ , R ⁴ and R ⁵ are the same or different alkyl groups or aryl groups, L is a halogen atom or NH group, and n is 1 when L is a halogen atom
and 2 in the case of NH group],
Specific examples include [(CH ₃ ) ₃ Si] ₂ NH,
[(C ₂ H ₅ ) ₃ Si] ₂ NH, [(i-C ₃ H ₇ ) ₃ Si] ₂ NH, [(t
−C ₄ H ₉ ) ₂ CH ₃ Si〕 ₂ NH, (CH ₃ ) ₃ SiCl,
(C ₂ H ₅ ) ₃ SiCl, t-C ₄ H ₉ (CH ₃ ) ₂ SiCl, CH ₃
( _C2H5 ) _2SiCl , (n _{- C4H9} ) _{3SiCl ,}
[(C ₆ H ₅ ) ₂ Si] ₂ NH, [C ₆ H ₅ (CH ₃ ) ₂ Si] ₂ NH,
Examples include (C ₂ H ₅ ) ₂ C ₆ H ₅ SiCl. These compounds are not limited to one type, and two or more types may be used simultaneously. The styrene derivative and the substituted silyl group-containing compound are brought into contact at room temperature or under heating, usually for 0.5 to 50 hours. Contacting may be carried out in a solvent,
Alternatively, it may be carried out under an inert gas atmosphere such as nitrogen gas. Suitable solvents include DMF (dimethylformamide), THF (tetrahydrofuran), NMP (N
-methylpyrrolidone), sulforane, DMSO
(dimethyl sulfoxide) and the like. The styrene derivative and the substituted silyl group-containing compound may be brought into contact in two or more stages, and if necessary,
The reaction may be carried out by adding a Grignard reagent such as C ₂ H ₅ MgBr. The contact ratio between the two is 0.5 times mole or more of the substituted silyl group-containing compound to the styrene derivative,
Desirably, the amount is equimolar to 10 times the molar amount. By doing so, the active hydrogen in the reactive group of the styrene derivative is substituted with the substituted silyl group, resulting in a substituted product of the styrene derivative, which is then anionically polymerized in the presence of an anionic polymerization initiator. A living polymer of the substituted product is obtained. Suitable anionic polymerization initiators include n-butyllithium, naphthalene lithium salt, naphthalene sodium salt, naphthalene potassium salt, (α-methylstyrene oligomer) sodium salt, and the like. The anionic polymerization may be carried out at room temperature, but preferably at a low temperature of -30°C or lower, particularly preferably at -50°C.
The reaction is carried out at a low temperature of 0.degree. C. to -100.degree. C. for 0.1 to 20 hours, preferably in the presence of a solvent. Suitable solvents include THF, toluene, hexane, cyclohexane, and the like. Two or more kinds of them may be used. Further, the polymerization reaction is desirably carried out in an inert gas atmosphere under reduced pressure, particularly desirably under high vacuum. The molecular weight of the living polymer can be controlled by changing the substituent/anionic polymerization initiator ratio, and the molecular weight can be increased by increasing the ratio. The molecular weight can also be controlled by changing the type of anionic polymerization initiator or the polymerization temperature. The living polymer thus obtained usually has a
It has a number average molecular weight of 500 to about 500,000 and is stable at relatively low temperatures. In the present invention, the living polymer obtained above is brought into contact with a proton donor such as methanol, ethanol, phenol, hydrochloric acid, sulfuric acid, etc. to remove the substituted silyl group that is a protecting group, thereby forming the desired reactive group. It is a polymer of styrene derivative. The method of the present invention allows for easier control of molecular weight than known methods for producing polymers of styrene derivatives such as radical polymerization and cationic polymerization, and allows for the production of polymers with any desired molecular weight and narrow molecular weight distribution. It is easy to produce, and the anionic polymerization of the substituted product is carried out almost quantitatively, so that the polymer can be obtained in high yield. The polymer obtained by the method of the present invention is usually about
having a number average molecular weight of 500 to about 500,000, preferably 2,000 to 200,000, more preferably 5,000 to 100,000,
Since it has a reactive group, it can be easily reacted with other functional groups and is useful as a reactive polymer. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples unless it goes against the gist thereof. The experiment consisted of an ampoule with a breakable seal in which multiple anionic polymerization initiator solutions and monomer solutions were frozen and degassed, which were connected to a high vacuum line, and a sample of the waste anionic polymerization initiator and living polymer that had been cleaned inside the system. Using the apparatus shown in the drawing, which consists of a flask connected to a spare branch pipe for taking out the sample, the following method was used. First, the flask 1 was kept at 10 ^-5 mmHg for 5 hours to degas it, the vacuum line 8 was sealed off at point A, and then the ampoule 3 containing one anionic polymerization initiator was
break the seal, introduce it into the system containing the flask 1, thoroughly wash the inside of the system, guide it to a spare branch pipe 7, seal off the branch pipe 7 at point C, remove it from the system, and then, Cool to a predetermined temperature, break the seal of the ampoule 2 containing the second anionic polymerization initiator solution cooled to the predetermined temperature, introduce the anionic polymerization initiator into the flask 1, and then introduce the first monomer into the ampoule 4. After introducing the solution into flask 1 in the same manner and allowing it to react for a predetermined period of time, a portion of the solution was introduced into branch pipe 6.
The polymer was introduced into a container, sealed, and subjected to the characterization of a living polymer. Example 1 p-vinylphenethyl alcohol in the reactor and equimolar [(CH ₃ ) ₃ Si] ₂ NH with respect to VPA
(HMDS) was added and stirred for 1 hour at 30°C under a nitrogen gas atmosphere. The product is then distilled under reduced pressure to p
-Vinylphenethyrotrimethylsilane By further adding a Grignard reagent (C ₂ H ₅ MgBr) and vacuum distilling, purified VPA-Si was obtained with a yield of 82%. This VPA-Si is 73℃/2mm
It had a boiling point of Hg. The results of NMR analysis of this VPA-Si are shown below. ^1H NMR (60MHz: TMS standard): 0.24ppm (S, 9H, O-Si- CH ₃ ), 2.93ppm (t, 2H, J = 7Hz, Ph CH _2
CH2 ), 3.68ppm (t: 2H, J=7Hz, _CH2 -O-
Si), [5.32, 5.86ppm (2d, 2H, J=10,
18Hz, CH ₂ = CH)], 6.87ppm (2d, 1H, CH ₂ = CH ), [7.21,
7.52ppm (2d, 4H, J=9, 9Hz, Pha,
b)] This data confirmed the above structure. The obtained VPA-Si was polymerized in THF at -78°C for 1 hour using various anionic polymerization initiators shown in Table 1. In both cases, the polymerized system exhibited a slightly blackish red color characteristic of living anions. The results are shown in Table 1, and the yield was almost quantitative. By treating this living polymer with methanol in a THF-H ₂ O solvent at room temperature, the trimethylsilyl protecting group was removed and poly(p-vinylphenethyl alcohol) (PVPA) was obtained.
PVPA has a glass transition temperature of 108℃ and is soluble in ethanol, acetic acid, pyridine, and dioxane.
It was insoluble in THF, benzene, water, chloroform, and acetone. The results of IR and NMR analysis of PVPA are shown below. IR: 3300~3350cm ^-1 (-OH), 1610 and 1510cm
^-1 (endocyclic skeleton), 820cm ^-1 (ring C-H)
No characteristic absorption of the (CH ₃ ) ₃ Si group was observed. Similarly, no characteristic absorption of trimethylsilyl group was observed in ¹ H NMR. Therefore, it was confirmed that the obtained polymer was composed of repeating units of the following formula. Since this PVPA is insoluble in benzene, it cannot be used as is by VPO (Vapor Pressuse Osmometer).
Since it is difficult to measure the molecular weight using pyridine, we acetylated it in pyridine, purified it by repeating precipitation and dissolution, and then dried it to obtain acetylated PVPA, which we used to measure its molecular weight using VPO. Since it is quantitative, Table 1 shows the molecular weight calculated assuming that all phenethyl groups in PVPA are acetylated. It can be seen that the two agree quite well. The molecular weight of the PVPA itself obtained in this example can be easily calculated from the measured values in Table 1. About acetylated PVPA with THF as solvent
GPC (Gelpermeation Chromatography) measurements were performed and it was confirmed that the polymer had an extremely narrow molecular weight distribution. [Table] Example 2 5 times the mole of HMDS and 0.5 times the mole of Si(CH ₃ ) ₃ Cl were added to p-aminostyrene [Formula], and a reaction was carried out at reflux temperature for 2.5 hours. By distilling the product under reduced pressure, the trimethylsilyl group 1 of AS
Substituted products were obtained almost quantitatively. This substitute is 90
It had a boiling point of °C/5 mmHg. _{Furthermore , 84 _} p-(bistrimethylsilylamino)styrene with a yield of % I got it. This BTMSAS had a boiling point of 60-80°C/2mmHg. ^1H NMR of BTMSAS is 0.0ppm (S, 18H, Si-
_CH3 ), [5.08, 5.57ppm (2d, 2H, J=10,
17Hz, CH ₂ = CH)], 6.55ppm (2d, 1H, CH =
_CH2 ), [6.75, 7.18ppm (2d, 4H, J=9.0Hz,
Pha, b)], and the above structure was confirmed. The obtained BTMSAS was incubated at -78 in THF using lithium naphthalene as an anionic polymerization initiator.
Polymerization was carried out at ℃ for 1 hour. The results are shown in Table 2. The polymerization system had a brownish orange color and was stable even at room temperature (when treated with a large excess of methanol, the polymer separated as a white precipitate), and the polymer was obtained almost quantitatively. This polymer can be handled with the protective group attached if handled carefully, and the polymer after methanol treatment was soluble in THF, benzene, and chloroform, insoluble in methanol, and had the molecular weight shown in Table 2. The results of NMR analysis and IR analysis of the polymer after this methanol treatment are shown below. ^1H NMR: 0.0ppm (reference) (Si− _CH3 ), 0.7~
2.5( _-CH2 - CH- )6.5ppm
[Formula] Number of H (TMS group + -CH ₂ -CH-): Number of H [Formula] Calculated value 21:4: Actual value 24:4 IR: 1605cm ^-1 (endocyclic skeleton), 1250cm ^-1 [Si
(CH ₃ ) ₃ ], 1175 cm ^-1 (Si-N-Si), 933
cm ^-1 (Si-N-Si), 844 cm ^-1 [Si(CH ₃ ) ₃ ],
752cm ^-1 [Si(CH ₃ ) ₃ ] From the results of these analyses, it is clear that the above living polymer has the structural formula of [Formula]. By treating this polymer having a trimethylsilyl protecting group with a 2N-HCl aqueous solution, the protecting group was easily removed and an aqueous solution of polyaminostyrene was obtained under acidic conditions. This water-soluble polyaminostyrene (PAS)
The results of NMR analysis and IR analysis are shown below. ¹ H NMR (D ₂ O solution): 1 to 2 ppm [broad;
3H, [Formula]], 6.3-7.3ppm [broad2peaks; 4H, [Formula]] IR: Characteristic absorption of -NH ₃ Cl is observed at 1580 cm ^-1 , but characteristic absorption of (CH ₃ ) ₃ Si group is not observed. Nakatsuta. A water-insoluble formula was obtained by neutralizing the acidity. The structure of PAS is based on the above various analysis data.
It is clear that it is a polymer having the following structural formula. Although the molecular weight of PAS has not been directly measured, it can be easily calculated from the values in Table 2. [Table] Example 3 In the reactor, equimolar amount of t-C ₄ H ₉ (CH ₃ ) ₂ SiCl (BDMS) was added to p-vinylphenol [formula] and VP.
in DMF solvent in the presence of imidazole,
The reaction was allowed to proceed at room temperature for 4 hours. The product was distilled under reduced pressure to obtain p-vinylphenoxyt-butyldimethylsilane. was obtained in 76% yield. This VP-BDMS is 80℃/
It had a boiling point of 0.1 mmHg. The results of NMR analysis of VP-BDMS are shown below. ^1H NMR: 0.0ppm standard (S, 3H, O-Si-
CH ₃ ), 0.80ppm (S, 9H, Si-C-
CH ₃ ), [4.87, 5.44ppm (2d, 2H, J
= 10, 17Hz, CH ₂ = CH)], 6.56ppm
(2d, 1H, CH = CH ₂ ), [6.54,
7.06ppm (2d, 4H, J=10Hz, Ph
a, b)]. This result confirmed that the structure was VP-BDMS. The thus obtained VP-BDMS was incubated at -78°C in THF using the anionic polymerization initiator shown in Table 3.
After polymerization is carried out for 1 hour, the living polymer is treated with a large amount of methanol to form a white precipitate and the polymer is separated. The yield of polymer was almost quantitative. The living polymerization system had a slightly blackish red color and was stable without fading even at room temperature. The polymer obtained by water treatment of the above polymerization system is
The BDMS protecting group remained without being removed, and it was soluble in benzene, methanol, and chloroform, and insoluble in hexane and acetone. Therefore, the number average molecular weight of this polymer was measured by the VPC method. The results are shown in Table 3. The results of NMR analysis and IR analysis of the polymer after treatment are shown below. ^1H NMR: 0.0ppm standard (S, 3H, O-Si-
CH ₃ ), 0.83ppm (S, 9H, Si-C
-CH ₃ ), 1 to 2 ppm (broad, 2H,
_CH2 ), 1~2ppm (broad, 1H,
CH), 6.33ppm (broad, 4H,
C ₆ H ₅ ) IR: 1610 cm ^-1 (endocyclic skeletal vibration), 1395 and 1365
cm ^-1 [C(-CH ₃ ) ₃ ], 1265 cm ^-1 (Si-C),
1170cm ^-1 (Si-O-C), 920cm ^-1 (Si-O
-Ar), 846cm ^-1 (Si-C), 776cm ^-1
(CH out-of-plane bending angle of [Formula]) From the results of these analyses, it is clear that the polymer obtained in this example has the structural formula of [Formula]. By treating a polymer with a BDMS protecting group with a 2N-HCl aqueous solution, the protecting group is removed.
Soluble in THF, methanol, acetone, benzene,
Polyp-vinylphenol (PVP) insoluble in n-hexane and chloroform was obtained. Results of NMR analysis and IR analysis of PVP, BDMS
No characteristic absorption based on protecting groups was observed, and it was confirmed that this polymer had the structural formula of [Formula]. Although the molecular weight of PAS was not directly measured, it can be easily calculated from Table 3. 【table】

[Brief explanation of drawings]

The drawings schematically show an apparatus for carrying out anionic polymerization and anionic block copolymerization in the present invention. 1... Flask, 2, 3... Anionic polymerization initiator-filled ampoule, 4... First monomer-filled ampoule, 5... Second monomer-filled ampoule, 6,
7...Branch pipe, 8...Vacuum line, 9...Kotuku,
10...Magnet.

Claims (1)

[Claims] 1. General formula ^[ _{wherein ,} ^{_ _ _}
represents a hydrogen atom or an alkyl group. However, R ¹ ,
R ² is not at the same time an alkyl group. ] The styrene derivative represented by the general formula (SiR ³ R ⁴ R ⁵ ) _o L [wherein,
R ³ , R ⁴ and R ⁵ are the same or different alkyl groups or aryl groups, L is a halogen atom or NH group, n is 1 when L is a halogen atom,
In the case of NH group, it is 2. ], and the resulting substituted silyl group of the styrene derivative is polymerized in the presence of an anionic polymerization initiator to form a living polymer of the substituted product, and then contacted with a proton donor. A method for producing a styrene derivative polymer, which comprises: