JPS6367485B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel living block copolymer and a method for producing the same. Anion living polymers of vinyl monomers having reactive groups such as hydroxyl groups and amino groups in their molecules have not yet been obtained due to the active hydrogen in the reactive groups. The inventors
The reactive groups of the above vinyl monomers are added in advance to trialkylsilyl groups, triarylsilyl groups, etc. (hereinafter referred to as
It is called a substituted silyl group. ) and then treated with an anionic polymerization initiator to form a living polymer of the above vinyl monomer protected with a substituted silyl group.As a result of further research, the present inventors found that The inventors have completed the present invention by discovering that, by using this method, a novel living block copolymer having repeating units of the above vinyl monomer protected with a substituted silyl group and repeating units of a styrene compound can be obtained. That is, the present invention has the general formula [In the formula, Z is (CH ₂ ) _n・OSiR ¹ R ² R ³ or N
(SiR ¹ R ² R ³ ) ₂ , m is a number from 0 to 6, R ¹ , R ²
and R ³ represent the same or different alkyl groups having 1 to 6 carbon atoms. ] Repeating unit (A) and general formula [In the formula, R represents a hydrogen atom or a methyl group. ] has a bond with the repeating unit (B), and its sequence is
A novel living block copolymer which is AB, BA, ABA or BAB and has a number average molecular weight of 500 to 500,000 [provided that (A)/(B) (molar ratio) = 5 to 95/95 to 5. ], and the copolymer has the general formula [In the formula, X represents a (CH ₂ ) _n OH group or an amino group, and m represents a number from 0 to 6. ] The vinyl monomer () represented by the formula (SiR ¹ R ² R ³ ) _o L [however,
R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 6 carbon atoms, L is a halogen atom or an NH group, n is 1 when L is a halogen atom,
In the case of NH group, it is 2. ] The general formula obtained by contacting with a substituted silyl group-containing compound represented by [In the formula, Z is (CH ₂ ) _n O・SiR ¹ R ² R ³ or N
(SiR ¹ R ² R ³ ) ₂ , m is a number from 0 to 6, R ¹ , R ² and R ³
has the same meaning as above. ] The substituted silyl group substituted product of the vinyl monomer () is polymerized in the presence of an anionic polymerization initiator to obtain the general formula [In the formula, Z has the same meaning as above. ] is a living polymer consisting of repeating units of the general formula [In the formula, R represents a hydrogen atom or a methyl group. The general formula obtained by adding and copolymerizing a styrenic compound ( ) represented by ], or by polymerizing a styrene compound ( ) in the presence of an anionic polymerization initiator [In the formula, R has the same meaning as above. It can be produced by adding the above substituent () to a living polymer consisting of the repeating unit (B) and copolymerizing it. Specific examples of the above vinyl monomer () include:
[Formula] [Formula] [Formula] [Formula] [Formula] etc. The substituted silyl group-containing compound used to protect the reactive group of the vinyl monomer () is a compound containing a trialkylsilyl group, and for example, the compound has the general formula (SiR ¹ R ² R ³ ) _o L
(In the formula, R ¹ , R ² and R ³ have the same meanings as above, L is a halogen atom or an NH group, and n is 1 when L is a halogen atom and 2 when L is an NH group. ]
As a specific example,
[(CH ₃ ) ₃ Si] ₂ NH, [(C ₂ H ₅ ) ₃ −Si] ₂ NH, [(i−
_C3H7 ) _{3Si 〕 2NH ,} [(t- _C4H9 ) ₂ - _CH3Si 〕 ₂ ,
_{( CH3} ) _3SiCl , _{( C2H5} ) _3SiCl , t- _C4H9
(CH ₃ ) ₂ SiCl, CH ₃ (C ₂ H ₅ ) ₂ SiCl, (n-
Examples include C ₄ H ₉ ) ₃ SiCl. These compounds are not limited to one type, and two or more types may be used simultaneously. The vinyl monomer () and the substituted silyl group-containing compound are brought into contact at room temperature or under heating, usually with a 0.5%
It will last ~50 hours. The contact may be performed in a solvent or under an inert gas atmosphere such as nitrogen gas. Suitable solvents include DMF (dimethylformamide), THF (tetrahydrofuran),
NMR (N-methylpyrrolidone), sulforane,
Examples include DMSO (dimethyl sulfoxide). The contact between the vinyl monomer () and the substituted silyl group-containing compound may be carried out in two or more stages, and if necessary, a Grignard reagent such as C ₂ H ₅ MgBr may be added. The contact ratio between the two is determined by the ratio of the substituted silyl group-containing compound to the vinyl monomer ().
The amount is 0.5 times the mole or more, preferably equimolar to 10 times the mole. As a result, the active hydrogen in the reactive group of the vinyl monomer () is substituted with the substituted silyl group, resulting in a substituted product () of the vinyl monomer (). The method for producing a living block copolymer of the present invention is characterized by using the above-mentioned substituent (). As a specific example of the production method, the above substituted product ()
is subjected to anionic polymerization in the presence of an anionic polymerization initiator to obtain a living polymer of the substituted product ().
The styrene compound () is added to (A) and copolymerized, or the order is reversed to first produce a living polymer (B) of the styrene compound (), and then the above substituted product ( ) is added to the polymerization system for copolymerization. Suitable anionic polymerization initiators used in the present invention 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 preferably under high vacuum. The molecular weight of the living polymer is the substituent ()
Alternatively, it can be controlled by changing the styrene compound ()/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 typically has a
500 to about 500,000, but then
When the living polymer is a living polymer of the substituent (), the styrenic compound ()
In the case of a living polymer of a styrene compound (), the living block copolymer of the present invention can be obtained by copolymerizing with the substituent (). Specific examples of the styrene compound () include styrene, α-methylstyrene, m-divinylbenzene, p-divinylbenzene, p-methylstyrene, m-methylstyrene, o-methylstyrene, and the like. Two or more of these compounds can be used, and in that case, the repeating unit (B) consists of a random copolymer. The living copolymerization method in the present invention may be carried out in accordance with the living polymerization method of the above-mentioned substituent () and styrene compound (). That is, after the living polymerization of the substituted product () or the styrenic compound () is completed, the styrenic compound () or the substituted product () is added to the polymerization system.
is added and maintained under the same conditions as in the previous living polymerization. At that time, the temperature, pressure, etc. may be changed from those in the above living polymerization, and the solvent may be replaced with a different type. The polymer chain length after copolymerization of the substituent () or styrenic compound () added to the living polymer is determined by the amount of these compounds () () added,
It can be controlled by the reaction temperature. Furthermore, addition and copolymerization of the above-mentioned substituents () or styrene-based compounds () may be repeated in sequence, or different above-mentioned substituents () or styrene-based compounds () may be sequentially added and copolymerized. By the above method, for example, A-B, B-A, A
-B-A, B-A-B, B-A-A'-B, A-
B-B'-A, A-B-A-B, A-B-A'-B
A repeating unit (A) consisting of an array of
A living block copolymer of the present invention having the bond (B) is obtained. The copolymer of the present invention has a molecular weight of about 500 to about 500,000, preferably 3,000 to 300,000, more preferably 10,000 to
Each repeating unit (A) has a number average molecular weight of 200000
The proportion of (B) in the copolymer is (A)/(B) (molar ratio) = 5-95/95-5. The copolymer of the present invention has stable properties at relatively low temperatures. When the copolymer of the present invention is brought into contact with a proton donor such as methanol, ethanol, phenol, hydrochloric acid, or sulfuric acid, the substituted silyl group, which is a protective group, is easily removed, and vinyl Monomer () and styrenic compound ()
A block copolymer is obtained. This method is characterized in that the molecular weight can be easily controlled, and a copolymer having an arbitrary molecular weight and repeating unit and a narrow molecular weight distribution can be easily produced. The living block copolymer of the present invention is useful as a synthetic intermediate for a new block copolymer by adding another type of vinyl monomer, and
The living block copolymer of the present invention is treated with methanol or the like and further treated with mineral acid to remove the protective groups.The block copolymer itself is both a thermoplastic resin and a functional resin. As a unique resin with the properties of is also useful. 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. A second monomer was introduced from ampoule 5 into the living polymer solution remaining in flask 1, block copolymerization was performed, and after post-treatment, the living polymer solution was subjected to measurements of physical properties and the like. Parts of the above method were changed, added, or omitted as necessary. Example 1 [Synthesis and identification of VPA-Si] In a reactor, p-vinylphenethyl alcohol [formula] (VPA) and equimolar amount of [(CH ₃ ) ₃ Si] ₂ NH to VPA were added.
(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
-Vinylphenethyloxytrimethylsilane (VPA-Si) was obtained, and by further adding a Grignard reagent (C ₂ H ₅ MgBr) and vacuum distilling, VPA-Si purified with a yield of 82% was obtained. This VPA-Si had a boiling point of 73°C/2mmHg. ^1H NMR (60MHz: TMS standard) of this VPA-Si is 0.24ppm (s, 9H, O-Si- CH ₃ ),
2.93ppm (t, 2H, J=7Hz, Ph CH ₂ CH ₂ ),
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 = CH ₂ ), [7.21,
7.52 ppm (2d, 4H, J=9, 9Hz, Pha, b)], the above structure was confirmed. [Synthesis and Identification of Living Polymer of VPA-Si] The obtained VPA-Si was polymerized using various anionic polymerization initiators shown in Table 1 in THF at -78°C for 1 hour. 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. The living polymer [formula] obtained was stable at -78°C but unstable at room temperature, so it was subjected to the following treatment and then subjected to character clarification. 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. In the IR spectrum of PVPA, 3300-3350 cm ^-1
(-OH) 1610 and 1510 cm ^-1 (endocyclic skeleton), 820 cm ^-1
(ring C-H), and no absorption based on the trimethylsilyl group was observed. Similarly, no characteristic absorption of trimethylsilyl group was observed in ¹ H NMR. Therefore, it was confirmed that PVPA has the structure of [Formula]. In addition, the obtained PVPA was acetylated in a pyridine solvent, purified by repeated precipitation and dissolution, and then dried to obtain acetylated PVPA. Using this, the number average molecular weight was measured using a VPO (Vapor Pressure Osmometer). Table 1 shows the number average molecular weight calculated assuming that all phenethyl groups in PVPA are acetylated. It can be seen that the two agree quite well. 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] [Table] [Synthesis of living block copolymer] Naphthalene sodium salt (0.26 mmol)
A THF solution containing 48 mmol of styrene was added to the THF solution, and polymerization was carried out at -78°C for 1 hour. The polymer solution had a dark red color characteristic of living polymers. 35% of this polymer solution (confirmed by sodium titration) was taken out and treated with methanol according to the above method to obtain a polymer with a yield of 99%.
The number average molecular weight of the obtained polystyrene was 39,000. GPC was measured under the conditions of 40° C., elution rate of 1.4 ml/min, and THF solvent, and the elution curve a shown in FIG. 2 was obtained. Next, VPA-Si (8.7 mmol) was added to the remaining styrene living polymer (65%) and polymerized at -78°C for 1 hour. Even after the reaction, the solution remained dark red, a color characteristic of living polymers. By treating this living polymer with methanol, a copolymer was obtained with a yield of 98%, and the copolymer was soluble in benzene and THF, but insoluble in methanol. IR analysis of the copolymer purified by repeated dissolution and precipitation revealed that the absorption peak of trimethylsilyl groups was no longer observed. ¹ H NMR analysis was performed, and the area ratio of the ring-bonded hydrogen to the methylene substituent and the total methylene and methine hydrogen in the main chain was 1.29, which was 1.24, which was calculated from the styrene/VPA monomer ratio charged in the polymerization system. Good agreement was shown. The block composition ratio was calculated from the above measured values and found to be a block copolymer consisting of polystyrene blocks (81.0 mol%) and PVPA blocks (19.0 mol%). The number average molecular weight of the block copolymer determined by VPO measurement was 57,000. When the GPC of the above copolymer was measured, the second
It is clear that it is a block copolymer because it shows a single elution curve b in the figure and clearly shifts to the high molecular side and no peak is observed in the elution curve region of the original styrene homopolymer. Therefore, in the above copolymerization, (polyVPA-Si) -
(Polystyrene)-(PolyVPA-Si) form, i.e. (A)-
It can be seen that a living block copolymer of type (B)-(A) was obtained. Example 2 Naphthalene sodium salt (0.19 mmol) in THF
VPA-Si obtained in Example 1 (6.5 mmol) in the solution
was added and polymerized at -78°C for 1 hour. The polymer solution was dark red and it was clear that living polymer had formed. A THF solution of styrene (56.9 mmol) was added to this living polymer solution, and polymerization was further carried out at -78°C for 1 hour. The solution after the reaction had the same dark red color characteristic of living polymers as in Example 1. By treating this living polymer with methanol, a copolymer was obtained with a yield of 99%. This copolymer is benzene,
It was soluble in THF and insoluble in methanol.
IR analysis of the copolymer purified in the same manner as in Example 1 confirmed that no trimethylsilyl protecting group remained. The polymer thus obtained
When GPC was measured under the same conditions as Example 1, the third
The elution curve shown in the figure was obtained. This elution curve is similar to the original
The elution line is located far on the higher molecular weight side than the elution line expected from PVPA obtained by living polymerization of VPA-Si, and it is a single peak with no peak observed on the low molecular weight side, making it a block copolymer. It is clear that it is generated. Furthermore, based on the ¹ H NMR measurement values of this copolymer, polystyrene block (88.6 mol%) and PVPA block (11.4 mol%) were calculated using the same calculation method as in Example 1.
It was found that it was composed of (mol%). or,
The number average molecular weight of the block copolymer was 76,000. The above results indicate that in this copolymerization example, a living block copolymer of the (polystyrene)-(polyVPA-Si)-(polystyrene) type, that is, the (B)-(A)-(B) type, was obtained. confirmed. Example 3 VPA-Si (9.8 mmol) obtained in Example 1 was added to a THF solution of butyllithium (0.18 mmol).
The solution was added and polymerized at -78°C for 1 hour, then α-methylstyrene (50.3 mmol) was added.
Polymerization was further carried out at -78°C for 1 hour to obtain living block copolymers of types (A) and (B). This living block copolymer was precipitated in methanol, filtered, and dried to obtain a block copolymer consisting of a PVPA block and a polyα-methylstyrene block. The yield was 98%. Furthermore, this copolymer had a number average molecular weight of 53,000, and was found to be composed of polyα-methylstyrene blocks (84.9 mol%) and PVPA blocks (15.1 mol%) using the same calculation procedure as in Measurement Example 1. Ta. Example 4 5 times the mole of HMDS and 0.5 times the mole of Si(CH ₃ ) ₃ Cl were added to p-aminostyrene [Formula] (AS), 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 are obtained almost quantitatively. This substitute is 90
It had a boiling point of °C/5 mmHg. Furthermore, 2 times the mole of Clinard reagent (C ₂ H ₅ MgBr) was added to this substituted product, and the mixture was reacted in THF at room temperature for 2 hours, and then 4 times the mole of Si(CH ₃ ) ₃ Cl was added to give 12
By standing for a period of time and distilling under reduced pressure, p-(bistrimethylsilylamino)styrene (BTMSAS) was obtained with a yield of 84%. This BTMSAS is 60-80
It had a boiling point of °C/2 mmHg. ^1H NMR of BTMSAS is 0.0ppm (S, 18H, Si-
CH ₃ ) [5.08, 5.57ppm (2d, 2H, J=10, 17Hz,
_CH2 =OH)], 6.55ppm (2d, 1H, CH2 = _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 is
If handled carefully, the polymer can be handled with the protective groups still attached, and the polymer after methanol treatment can be treated with THF,
It was soluble in 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 H number (TMS group + -CH ₂ -CH-): H number [Formula] Calculated value 21:4, measured value 24:4) IR: 1605 cm ^-1 (endocyclic skeleton), 1250 cm ^-1 [Si (CH ₃ ) ₃ ],
1175cm ^-1 (Si-N-Si), 933cm ^-1 (Si-N-Si),
844cm ^-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 a polyaminostyrene which was water-soluble under acidic conditions was obtained. 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 to 7.3ppm [Broad2 peaks; 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. Ta. A water-insoluble formula was obtained by neutralizing the acidity. [Table] [Synthesis of living block copolymer] A THF solution of lithium naphthalene (0.17 mmol) and a THF solution of BTMSAS (4.3 mmol) were mixed and polymerized at -78°C for 1 hour. A THF solution of styrene monomer (45.1 mmol) was added thereto, and polymerization was further carried out at -78°C for 1 hour. The final polymerization solution was also red in color and was treated with methanol to obtain the polymer in 99% yield. The trimethylsilyl protecting group was retained from the IR of the polymer, and GPC measurement revealed that
A single elution curve was observed for the BTMSAS/lithium naphthalene ratio shown in Table 2, which was clearly on the higher molecular weight side than the BTMSAS homopolymer obtained in the same experiment. Therefore, it can be seen that the polymer obtained by the above copolymerization is a living block copolymer of the (B)-(A)-(B) type. of the copolymer with the above trimethyl protecting group
From NMR, the ratio of ring-bonded hydrogen to trimethylsilyl group hydrogen was 3.14, and the styrene/trimethylsilyl group hydrogen ratio used for polymerization was 3.14.
Since it was in good agreement with 3.05 calculated from the BTMSAS ratio, it is a block copolymer composed of polystyrene block (91.1 mol%) and polyBTMSAS block (8.9 mol%). Further, the number average molecular weight of this block copolymer was 75,000. Example 5 In a reactor, p-vinylphenol [formula] (VP) and equimolar t-C ₄ H ₉ (CH ₃ ) ₂ SiCl (BDMS) to VP were added.
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. (VP-BDMS) was obtained with a yield of 76%. This VP
-BDMS had a boiling point of 80°C/0.1mmHg. The results of NMR analysis of VP-BDMS are shown below. ^1H NMR: 0.0ppm standard (S, 3H, O-Si-
_CH3 ), 0.80ppm (S, 9H, Si-C- _CH3 ),
[4.87, 5.44ppm (2d, 2H, J=10, 17Hz, CH ₂
= CH)], 6.56 ppm (2d, 1H, CH = _CH2 ),
[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 treated with THF using the anionic polymerization initiator shown in Table 3.
After polymerization is carried out at -78°C 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 VPO 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-
_CH3 ), 0.83ppm (S, 9H, Si-C- _CH3 ), 1
~2ppm (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), 1170 cm ^-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]. [Table] [Synthesis of living block copolymer] [α-methylstyrene] ² ₄ ^-・2Na ⁺ (0.20 mmol)
A THF solution of VP-BDMS (8.7 mmol) was added to the THF solution of and polymerized at -78°C for 1 hour. Styrene (57.6 mmol) was added to this dark red living polymer solution, and polymerization was further carried out at -78°C for 1 hour. This polymerization solution still had a red color, and by treating the same solution with methanol, 97%
The polymer was obtained in a yield of . IR of the polymer showed that the BDMS protecting group was retained, and GPC measurements showed a single elution curve in a higher molecular weight range than expected from the original VP-BDMS homopolymer. The number average molecular weight of the obtained copolymer was 89,000. Also, it was determined from the results of NMR measurement using the same calculation method as in Example 4, and polystyrene block (87.9
It was found to be a block copolymer consisting of polyVP-BDMS block (12.1 mol%) and polyVP-BDMS block (12.1 mol%). From the above results, the polymer obtained by the above copolymerization is of the (B)-(A)-(B) form [strictly speaking, since there is an α-methylstyrene oligomer as an anionic initiator, the polymer is of the (B)-(A)-(B)-
It can be seen that it is a living block copolymer of the form (A)-(B)-(A)-(B).

[Brief explanation of drawings]

FIG. 1 schematically shows 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. FIGS. 2 and 3 are GPC charts of the (co)polymer of the present invention.

Claims (1)

[Claims] 1. General formula [In the formula, Z is (CH ₂ ) _n・OSiR ¹ R ² R ³ or N
(SiR ¹ R ² R ³ ) ₂ , m is a number from 0 to 6, R ¹ , R ²
and R ³ represent the same or different alkyl groups having 1 to 6 carbon atoms. ] Repeating unit (A) and general formula [In the formula, R represents a hydrogen atom or a methyl group. ] has a bond with the repeating unit (B), and its sequence is
A novel living block copolymer which is AB, BA, ABA or BAB and has a number average molecular weight of 500 to 500,000 [provided that (A)/(B) (molar ratio) = 5 to 95/95 to 5]. 2 General formula [In the formula, X represents a (CH ₂ ) _n OH group or an amino group, and m represents a number from 0 to 6. ] The vinyl monomer () represented by the formula (SiR ¹ R ² R ³ ) _o L [however,
R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 6 carbon atoms, 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. ] The general formula obtained by contacting with a substituted silyl group-containing compound represented by [In the formula, Z is (CH ₂ ) _n O・SiR ¹ R ² R ³ or N
(SiR ¹ R ² R ³ ) ₂ , m=number of 0 to 6, R ¹ , R ² and R ³
has the same meaning as above. ] The substituted silyl group substituted product of the vinyl monomer ( ) represented by the following formula is polymerized in the presence of an anionic polymerization initiator to obtain the general formula [In the formula, Z has the same meaning as above. ] is a living polymer consisting of repeating units of the general formula [In the formula, R represents a hydrogen atom or a methyl group. ] or by copolymerizing the styrene compound () represented by the following formula in the presence of an anionic polymerization initiator: [In the formula, R has the same meaning as above. General formula characterized by adding the above substituent () to a living polymer consisting of the repeating unit (B) of ] and copolymerizing it. [In the formula, Z has the same meaning as above. ] Repeating unit (A)
and the general formula [In the formula, R has the same meaning as above. ] Repeating unit (B)
and the array is AB, BA,
ABA or BAB number average molecular weight 500~
500,000 new living block copolymer [However,
(A)/(B) (molar ratio) = 5-95/95-5].