JPS5953515A - Novel living block copolymer and manufacture of the same - Google Patents

Abstract

PURPOSE:To readily obtain titled copolymer with narrow molecular weight distribution, by the first polymerization, in specific condition, of an intermediate prepared from a specific vinyl monomer and substituted silyl group-contg. compound, followed by copolymerization between the formed polymer and a styrene compound. CONSTITUTION:First, an intermediate of formula II [Z is of formula III (m is 0-6), etc.] prepared by bringing (A) a vinyl monomer of formula I (X is amino) (e.g., p-aminostyrene) into contact with (B) a substituted silyl group-contg. compound of formula R<1>R<2>R<3>Si-(R<1>-R<3> are each alkyl or aryl) [e.g., (CH3SiCl] is subjected to polymerization in the presence of (C) an anionic polymerization initiator (pref. n-butyl lithium) to form a living polymer having recurring unit of formula IV, which is then copolymerized with (D) a styrene compound of formula V (R is methyl; Q is vinyl, etc.) thus obtaining the objective copolymer having bond between recurring units of formulae VI and VII, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a novel living block copolymer and a method for producing the same.

From vinyl monomers with reactive groups such as hydroxyl and amino groups in the molecule, anionic living polymers of these vinyl monomers are still difficult to form due to active water Kofc in the reactive groups.
It has not been done. The present inventors have previously protected the reactive groups of the vinyl monomer with trialkylsilyl, triarylsilyl, etc. (hereinafter referred to as substituted silyl group 7.), and then allowed an anionic polymerization initiator to act thereon. It was found that the above-mentioned vinyl monomer glued polymer protected by a substituted silyl group was produced by using the method described above.However, as a result of further research, the present inventors6 found that by using the above method, a pasting polymer protected by a substituted silyl group The present invention 2 was completed by discovering that a new living block copolymer having 9 repeating units of a vinyl monomer and 9 repeating units of a styrene compound was found.

That is, the present invention [wherein 2 is (C1(2)In-OEliR1r12R
3, NR4-81RIR2R3 or N(SiR'R”R
”)2, x represents an Il number of 2 or more, m is a number from 0 to O, R1, R2 and R3 are the same or different alkyl groups or aryl groups, !(4ij: hydrogen atom or second alkyl group) [In the formula, R is a hydrogen atom or a methyl group, Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a vinyl group,
Indicates an integer greater than or equal to ]'s side i! The gist is that a new living block with a bond with the repeating unit (B) is combined with 7ff, and the nucleus is combined with 1F, [wherein, X l-1 ((R2), 0) is a group or 1-J N
R5R' T represents an amine group, m is 0
The number ˜B, Ha, and R6 represent a frozen candy atom or an alkyl group. However, B.S.

R6 is not an alkyl group at the same time. ] to the vinyl 7mer C) represented by the formula RIR2n3st- [where R1
.
, NR4-8j, R1-RZ R3 or r;i N(EI
iRIR'R3) 2, mf, fO~6 (D number, R1, R2 and n3Vt are the same or 84 alkyl or aryl group, R4 represents an aqueous atom or an alkyl group)] The vinyl monomer (1) is polymerized in the presence of an anionic polymerization initiator to form an ester compound (1) in which 2 is a mixture of 2 and 4, and x (d is an integer of 2 or more, 7] is a living polymer consisting of a repeating unit of styrene represented by [In the formula, . . . , . . . , . Thread compound 01) 2 is added and copolymerized, or styrene thread compound (11)' (anikin 1ii-copolymerization 1
51] is polymerized in the presence of an initiator, and then the polymer is polymerized [wherein R and Q have the same meanings as above, and y represents 2 or more. It can be produced by adding the above substituent to a living polymer consisting of the repeating unit (B) and copolymerizing it.

The above vinyl monomer (Ij le 1't5 in the general formula of the song)
.

The alkyl group represented by R6 preferably satisfies IL < 1t
-J, lower alkyl having 1 to 6 carbon atoms. Specific examples of these vinyl monomers (11) are t, Jl, 0H
z-○H-GOH, O%=OHOOH20H40H, 0
H2-OH2-(PaC)12) 40H, 0H2=OHC
(C!H2) 110H, CHz is ++HG N R2,
悄口an-C: いH・悄, 0H2=OL(-GNH”
0285. 0H2=OHGIJH"nC!4Hg%
are mentioned.

Reactivity p+ of vinyl monomer 010! '! The nitrous silyl group used for protection, the trial silyl group, the alkyl-aryl mixed pressure hl,
It is a compound containing a l-substituted silyl group or a triarylsilyl group, and the compound has the general formula (C) as an example.
01F(1ift"R")nL (in the formula, R1,H
4 and H3 shi1 the same or different alkyl group or aryl group, ■1 is a halogen atom nu1dNH74, υ
, n is 1 when L is a halogen atom, and #: 12 when L is an NH group. ]n- As a specific example, 1 is expressed as [(GHs)ssi]zNH, C(OzH5)s-
8i12NH, [(1,-0sH7)v811zNH,
((t-04Ho)z-0H3Si]zNH, (CH3
)3SiOt, (c2H5)3sict.

t-a4H, (cHn), 5icL, CH3(C!
2Hs)2sict, (n-(!1He)3SIO
4, [(CaHs)ssi]2NH, [((:611s
(OJ(3)2-8i]2NH, (02)15)2C6
H5SiO/1. etc. can be calculated by λh. These 7L and other compounds are not limited to -, but may be used in combination of two or more.

Contact between the vinyl monomer (till) and the substituted silyl group-containing compound at O2, usually 0.5 to 5
It will be held for 0 hours. The contact may be performed in a solvent or under an inert gas atmosphere such as nitrogen gas. Suitable solvents include DMF (dimethylformamide), T
Examples include HF (tetrahydrofuran), NMP (N-methylpyrrolidone), sulforane, and DMSO (dimethylsulfoxide) #.

The vinyl monomer (1) and the substituted silyl group-containing compound may be brought into contact in two or more stages, and if necessary (4H5
The reaction may be carried out by adding a Grignard reagent such as MgBr. The contact ratio between the two is such that the amount of the directly converted silyl group compound is at least O, S times the mole amount of the vinyl monomer, preferably equivalent to 10 times the mole amount.

By doing so, the active group in the vinyl monomer (++1) is replaced with a substituted silyl group,
[Vinyl 7] It becomes a 14-transition mountain of 1-dynamics.

The method for producing a living block copolymer with unexploded ψ1 is a method using the above-mentioned tR substituent lj! il-characterized.

As a specific example of the production method, the above-mentioned substituent is anionically polymerized in the presence of an anionic polymerization initiator, and the styrene compound (II) is added to the glueing polymer (A) of the substituent (1) obtained. In addition, the styrene compound (II) is copolymerized, or the slipping polymer (B) is prepared by copolymerizing the styrene compound (II), and then the void-containing body (1) is copolymerized.
k Z,' This is a method of copolymerizing in addition to doubling.

Examples of the anionic polymerization initiator used in the present invention include D-butyllithium, naphthalene potassium salt, naphthalene sodium salt, naphthalene potassium salt, (α-methylstyrene oligomer) sodium salt, and the like.

Animation 1 (1 batch, may be carried out at mold temperature, but preferably at -60°C or lower, !1 l←L-
The heating is carried out at a low temperature of 50 DEG C. to -100 DEG C. for 0.1 to 20 hours, preferably in the presence of a melting agent.

Examples of the 21"-4 equivalent molten) 1 include T) JF,) luene, hexane, cyclohexane, etc. Soh et al. In an inert gas atmosphere, H reduction:,'1:, especially desirable,
It is preferable to do this at a height of 9 or below.

Molecule of living polymer $44; iJ,, the if
By changing the ratio of heating element (1) or styrene compound (b)/anion a to IGi, F) fjlJ can be controlled, and by increasing the ratio, υ molecular weight can be increased. . Also, yuzu, an anionic offshore initiator? G
4 or 1 By changing the incorporation temperature, the molecule F,yr
, Ql) It""The first clause is possible.

Thus, totaling about 500 pine polymers
having a number average molecular weight of ~500,000, but then
When the living polymer is the living polymer anion compound (II) of the 1;9 polymer (1) and the styrene compound fllj glueing polymer, the [! The living block copolymer of the present invention can be obtained by copolymerizing t'L with the empty body (13).

Specific examples of the styrene compound (II) include styrene, α-methylstyrene, m-divinylbenzene, p-divinylbenzene, p-methylstyrene, m-methylstyrene, Q-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.

J to this invention? The living copolymerization method for the above-mentioned V-substituted product and the styrene compound (n) may be carried out according to the living (lf association method).

That is, the body (1) or the styrene compound (TI
After the living polymerization of ) is completed, styrenic compound (1) or the polymer is added to the polymerization system, and this is carried out by keeping it under the same conditions as the living offshore. .

The gap, temperature, and pressure ￥f may be changed from those in the case of Sakivin Kuro l (A'), or the molten sap may be replaced with a different type.

The 16-day polymer added to the living polymer (1) and the polymer after copolymerization of the styrene compound (II), 7
, +11 ELS 11 and compound (1) (II) /f>addition [i1 reaction knitting #)] can be expressed as follows.

Furthermore, the above fI! i conversion (empty body or styrenic compound (
The addition of [) and copolymerization may be repeated 11 times, and the above-mentioned
Copolymerization can also be carried out by adding itr quaternary.

By the above method, for example AB, BA.

A-B-A, B-A-B, B-A-A'-El, A-B
- Repeating unit (A) and repeating unit (B) consisting of the sequences B'-A', A-B-A-B, and A-B-A'-B
A living block copolymer of the present invention is obtained which allows the bonding of .

The conjugates of the present invention typically have about 50 [J to FJ 50Q
, Ol] 0 preferably 1 000-500.00
°1 More preferably IQ, 000 to 20 [j, 0DDO
Co-JR of )ω) in each repeating unit with a number average molecular weight
The proportion of merging is arbitrary, but usually yes)/(
B) (Molar ratio) -5 to 95/95 to 5.

The copolymer of the present invention exhibits 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, or sulfuric acid, the 16-substituted silyl group, which is the holding group, can be easily released. , a vinyl monomer (Il) that was previously impossible to synthesize.
A block co-JI combination of 1) and the styrenic compound (It) is obtained. According to this method, the molecule 1d is easily articulated, and a copolymer having an arbitrary molecular weight and repeating unit and a narrow distribution of molecules a can be easily produced.

The Living Block common body of the present invention may be useful as a synthetic intermediate for a new block common body by adding another type of vinyl 7-mer; The block copolymer treated with methanol and, if necessary, with mineral acid to remove the protective layer, has thermal properties of culm side fat and functional inverter. As a unique resin with inner properties 'i and 'j, it can be used as processed products of the gods, and its reactivity ff
'1. It is also useful as a raw material for synthesizing new polymers with both thermoplasticity and functionality, in which the substituents are replaced with other polar groups.

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples without departing from the spirit thereof.

The experiment was conducted using multiple anion polymerization initiator baths connected to a high vacuum line and an ampoule with a breaker pull seal in which the monomer solution was frozen, degassed, and sealed. The experiment was carried out in the following manner using the apparatus shown on the N side, which consisted of a flask connected to a spare branch pipe for taking out the initiator and part of the living polymer.

Male, keep flask 1 at 10-' THg for 5 hours to degas it, seal it off from vacuum line 8 at point A, and proceed to the next stage! 7) Spread the cool of the ampoule 6 containing the anionic polymerization initiator into the MIV and the flask 1, thoroughly wash the inside of the system, and lead it to the spare branch pipe 7.
Cut it into pieces at point C, remove it from the system, and then cool it to the specified temperature of FM.
Break the seal of ampoule 2 containing the anionic polymerization initiator All solution, add 7 anionic polymerization initiators to flask 1, and then add the first 7-mer to flask 1 in the same manner from ampoule 4. After reacting for a certain amount of time, a portion of the solution was introduced into a branch pipe 6, sealed off 9, and subjected to characterization of the living polymer.

The second monomer is introduced from ampoule 5 into the living polymer solution remaining in flask 1, block copolymerized, subjected to various treatments, and then subjected to measurements of physical properties, etc.

Some of the above methods &j, must be presented according to the changes, additions,
Omitted 1, Example 1 (Synthesis and identification of VPA-st) In a reactor, p-vinylphenethyl alcohol (OH2=OHG(jH2O
f-120H) (VPA) and the current molar [(CR3)3st]2hn (nraDs
) and stirred for 1 hour at 50°C under a nitrogen gas atmosphere.

The product was then distilled under reduced pressure to obtain p-vinylphene 08i (
C1(3)3] (VFA-Bi) was obtained, and VPA-8 was purified with a yield of 82 cm by adding Klinia sample (OzH5MgBr) and vacuum distillation.
i & got it.

This VPA-8i (li73℃/2 vmHg,
of? 1. We had regular meetings.

This VPA-8i'HNME (60MIIz:
TM8 standard) Ifi, 0.24 ppm (n,
9 ■1. 0-8l-(3H3), 7! , 4!
l T) Tll:It (t, 2H,, T= 7
Hz, PhCH2CR2), 5.68 ppm (
t, 2H,J-7H2,0H2-0-8i),
[5,32,5,86ppm (2cl, 2H, J=10
゜'18 H2,O)]2=OH)], 6.87 p
pm (2(1, In, CH-CH2j, [
7, 21, 7, 52 ppm (2d.

4 I(, J-s9.9 Hz, Plia, b
) ] on He = #R;' = "i" ntc.

[Gluing polymerization and identification of VPA-81] The obtained VPA-8i was incubated at -78°C for 1 hour in Tll using the anionic polymerization initiation method 11 of each column shown in the first column. I got 10 go. In the case of Izu 7L, it also had a slightly blackish or tinged red color that is characteristic of polymeric anions.

The results are shown in 1 table for 1 item, and the Q of 14 was constant L1. , i! ) Is the living polymer stable? ? Since r and t are unstable, you performed the following processing and characterization.

By treating this living polymer with methanol in a THF-H20 bath at LkW temperature, the trimethylsilyl protecting group was deionized and poly(p-vinylphenethyl alcohol) (pvpA) was obtained. PVPA i has a glass transition temperature of 108°C, and ethanol, ttr
M, pyridine, dioxane K Tll bath, THF,
It was insoluble in benzene, water, chloroform, and acetone.

In the engineering R spectrum of PVPA, 3300-3350z
-5(-OH) showed IFI absorption of 1610 and 1510 tM-1 (endocyclic skeleton) and 820 cm-' (Miyabi 0-H), and no absorption based on trimethylsilyl group was observed.

Also, 1) I NMI' (but similarly, no characteristic absorption of the trimethylsilyl group was observed. 1) Therefore, PVPAO
H20H20H Akira was lent.

In addition, the obtained PVPA was acetylated in pyridine 11'4 medium, sedimentation and dissolution were repeated, the sheath was dried, and the acetylated PVPA was dried.
+, using V P O (Vapor Free>
The number average molecular weight was measured using an ure Osmometer), and assuming that all the phenethyl groups in PVPA were acetylated, it was determined that il'j? -The truncated average molecular weight is shown in the first @. It can be seen that the two are in good agreement.

THF'5-G as solvent for acetylated PVPA
PO(GelperIII)ation Ohr
(oroatography) measurement, and it was confirmed that the polymer had an extremely narrow molecular weight distribution.

Note 1) VPO (Vapor Pressure O)
smometer) f (use pen!)
5i (hereinafter the same as Table 6).

2) As an acetylated product? ', i2'9(
Same goes for outrageous).

5) At 30℃ in methanol? l1lI constant (non-acetylated one is constant at '61) [Synthesis of living block copolymer] Nantalene sodium salt ([1,26rn mol
) of T Stereph 48 mmol of T in the HF bath solution
) IF solution was added and the mixture was heated at -78°C for 1 hour) (
Polymerized.

The polymer solution had a dark red color characteristic of peeling polymer.

35% of this polymer solution (confirmed by i-sufficiency of sodium) 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 Nl polystyrene was 59,000. 40
℃, elution rate of 1.4 me/min, THF solvent condition. When δl is determined, Fig. 2 O
The fr-out curve (a) shows VPA-8i (PL7
Polymerization was carried out at -78°C for 1 hour.

Even after the reaction, the dark door color characteristic of Ping polymer was faster than the color of Numami.

By treating this living polymer with methanol, a copolymer was obtained with a yield of 98%, and the copolymer was 743 soluble in benzene and THF, but insoluble in methanol. Upon dissolving and precipitating Sat<returning, R analysis of the privately produced co-M1 composite revealed that the absorption peak of the trimethylsilyl group was no longer observed.

'HNMR analysis was performed, and the area ratio of the abduction scale to the methylene of the substituent, the methylene of the main chain, and the chorus of methine hydrogen was t.
1.29 Styrene charged in υ, ノ, Ji dowel /
This showed good agreement with the calculated value of 1.24 from the VPA monomer ratio. Above Minoki 1 (+6 to block m#lt ratio &
It was obtained by calculating i41゛, and polystyrene block (81,
It was found to be a block copolymer consisting of a PVPA block (19.0 molar mass) and a PVPA block (19.0 molar mass).

Further, the number average molecular weight of the V' P O (the above-mentioned blocks determined by the +l11 constant) 1 combination was S 7. Ov O.

TI! GPC of the above copolymer! 11, the second
1'n1's elution song I71. ．． ! (b) is shown;
Obviously, the island molecule 1i+il K +8 rows of the original styrene homopolymer? Since no peak is observed in the Taniyama curve θ region, it is a block copolymer.
It is clear.

Therefore, in the above joint combination, (BoIJVI)A-Gi)-
It can be seen that the living block 5Q combination of the (polystyrene)-(polyVPA-8i) type, that is, the (he)-(B)-(A) type, is 11t.

Kyojiki 12 Naphthalene Sodium Soil'q (019rn mol,
) was added to the THF bath solution of VPA-8j obtained in Example 1 (
15 rotnol) was added thereto, and polymerization was carried out at -78°C for 1 hour. The polymer bath solution had a dark η color, and it was clear that living polymer was being produced. Add styrene (56.9m mol) to this living polymer solution.
) was added, and the mixture was further incubated at -78°C for 1 hour. The bath solution after the reaction had a dark color similar to that of Example 1. By treating the paste-polymer with methanol, the polymer was co-merged with a yield of 99%. was obtained.This copolymer was composed of benzene,
It took 9 baths in THF and was insoluble in methanol. IR analysis of the copolymer purified in the same manner as in Example 1 confirmed that no trimethylsilyl protecting group remained. When the GPO of the polymer thus obtained was measured under the same conditions as in Example 1, the elution curve shown in FIG. 6 was obtained. This bathing curve shows the PV obtained by living polymerization of the original VPA-81.
As predicted from PA, the value of p6 is far on the high molecular weight side, and there is a single peak on the low molecular weight side; there is no twist, so it is locked. It is clear that a copolymer is produced.

Based on the measured value of lHNMH of the copolymer with Sarashi [,
It was found that it was composed of a PVPA block (11.4 mol%) and a PVPA block (11.4 mol%). Moreover, the number average molecular weight of the block copolymer is 76. I had to go to Ou U.

From the above results, in the case of υ this case, (holisnarene)-(polyvpA-si)-(hollisguren) form, R11
(D) -(A) -(BJ-shaped living flocs', i'l'+,'It is ηiA that the coalescence is
F<2.

Real h(lj 1f'J 3 Butyllithium ([118 mmol) of T HF
? %; VPA-8i (9
, 8rnmol) of THF% was added, and the mixture was heated to -78°C.
, for 1 hour, and then α-methylstyrene (
50.5 m mob) and further incubated at -78°C for 1 hour.
Time man 1 is combined and living flocks of shapes (A) and (B) are combined.

The living block copolymer was precipitated with methanol, filtered, and dried to obtain a PV PA block heptapolyα-
A block copolymer consisting of methylstyrene flocs was made.

The yield is 9ε easy and fr.

Also, this copolymer has a number average molecular h) of s3. o u
Using the calculation method of the same strain as in Example 1, 'tN h? , it was found that

Example 4 p-zuminostyrene (an2-an()hn2) (AS
) with 5 times molar HMDEI and α5 times molar 08i (C!H
)30t'fc was added and the reaction was carried out at reflux temperature for 2.5 hours. By distilling the product under reduced pressure, AE3
A 114-substituted trimethylsilyl group was obtained quantitatively. This substituted product had a boiling point of 90° C./5 anH,fl. Furthermore, add 2 times the molar amount of Clinillard's reagent (02H5MgBr) to this substituted product,
T) After reacting for 2 hours at room temperature in IF, 4 times the molar amount of S
i(CH3)301 was added, left for 12 hours, and distilled under reduced pressure to obtain p-(bistrimenalsilylamino)styrene(OH2CbeI)-Bs with a yield of 84%.
i(aI(s)a〕+ ) (nTm5Aa) as i(
I was. This INTMSA8 had a boiling point of 60-60 b.

BTMBAB 1) (NMR) Bivalent, converted trimenalcyl group L: 0.0 ppm based on DH ()13.
1811゜5i-ORB) (io 8. 5.5
7p(JIll(2d, 2H.

, r-10,1'7) (Z, 0H2-OH)],
6.5 5 ppm (2(1,IH,0H-OH2
), [475,7:18ppm (2d, 4H
, J-9, OH2, Pha, b)], and the above structure was confirmed.

The obtained B T M S A S was treated with -7 in THF using lithium naphthalene as an anionic polymerization initiator.
The results are shown in Table 2. The system was brown and six orange in color and stable at room temperature. The polymer can be quantitatively obtained by handling the polymer with protective groups (dT) (F, benzene, chloroform) after treatment with methanol. Soluble in methanol, insoluble in methanol υ, molecular weight shown in Table 2: h
'L/I was there.

This metal place, Ill! 11 The results of NMR and IR analysis of the polymer are shown below.

”HNMR: Q, Oppm (Standard) (B1-C1
(3), 17-2.5 (-0H2-CAI-),
6.5 ppmH? kV ('rMtJ 蘂+ -Ok
+2-CI-1-) :■Book l :1'4 1+white 21:4. Real value 24:4)I
R: 1605rrn-' (jQi endoskeleton),
1250m-'(rll(CI+3)1], 1
175 cm-' (Si-N-Bi).

935rm-' (5i-N-8i), 844c
m-'[), 41(OH3)3], 752ty
n-' [: R1(OH3)3] From the results of these analyses, it is clear that A).

This trimethylsilyl group I? c41 polymer-i
21J -HCt water&'G (f(j)
Under liF conditions, polyaminostyrene in a water bath of 1゛+ is a)+
Rasai 1. Ta.

N)A of this water-soluble polyaminostyrene (FAG)
The results of R analysis and IR analysis are shown below.

'HNMR (D20 #*) = 1~2pPnl Cbr
oad: 31, R,: 1580tyn'-N
U3■C1(:)(1:rSpecial absorption:Xgmera0ru,(OH3)s Si 7A (7) Characteristics
The income was not evaluated.

1. Water fu-1,Q i′p is used to neutralize the tonality.
fJ)+2 ;, (Tables 1 and 2 [Synthesis of living block co-M [combination]) T11FW+ x+ of lithium naphthalene (0.17 mmol) and THE' fry of 13TMSA day (4.3 mmol)
Styrene monomer (45.1 mmo
l) THF iIr? %'l was added and combined for an additional 1 hour at ~78°C.

The final) 11 [combined solution was pale red in color, and the same bath solution was treated with methanol to obtain a polymer with a yield of 99%.

It is assumed that the trimethylsilyl group is retained from the polymer structure R, and the G P Ot i++++ is determined.However, the BTMSAS/lithium naphthalene ratio in Table 2 was obtained in the same experiment. A single elution curve was clearly observed on the higher molecular weight side than the BTM8AS homopolymer! It was.

Therefore, the polymer obtained by the above copolymerization is (
It can be seen that it is a living block copolymer of B)-(A)-(B) type.

The above-mentioned trimethyl group, co-i with lφ group
According to NMR, the ratio of silane bonded hydrogen to trimethylsilyl group hydrogen is 5.14, and the ratio of styrene/BTM8 used for polymerization is 5.14.
), which was in good agreement with 505 calculated from the B ratio,
Polystyrene block (91.1 mol%) and polyBTM
Correlated with SAS block (+19%)
) It is a h5-combined block copolymer. Moreover, the average molecular weight of this block copolymer is 75.0 [J [J
Met.

Example 0H) (VP) and equimolar t-c4H with respect to vp,
(OH,)2Sioz (BDMS) was added and reacted in the presence of imidazole in a DMF solvent at room temperature for 4 hours. The product was distilled under reduced pressure to give 1p-vinylphenoxyt-butyldimethylsilane (cHt=aHGo-si(c+a
3), t-a, H,) (VP-BDMEI) to 76
%+7) yield. KonoVP-BDMS is 80℃
/ [had a boiling point of 11 m'Hg.

The results of NMR analysis of VP-I3DMS are shown below.

"HNMR: 11 (] pprn standard (61,3I
(,0-8i-OH3), 0.8 (l ppm
(8,9H,5i-0-CH3).

[4, '87, 5.44 ppm (2d, 2H, J = 10
゜17Hz, 0111-011)], 6.56
ppm (2(1,IH,C)T-OH,), [6,
54,7,06 ppm (2d.

4H, J -10Hz, Ph a, b)].

'From this result, it was confirmed that the structure was VP-BDMS. Using the thus obtained VP-BPMSIt anionic polymerization initiator shown in Table 3, T) (-78 in F)
After polymerization is carried out at ℃ 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 quality of the polymer was constant.1 The living polymerization system had a slightly blackish red color and was stable without fading even at room temperature.

In the polymer obtained by water treatment of the above polymerization system, the BDM sun-protecting group remained without being eliminated, and it was soluble in benzene, methanol, and chloroform, and insoluble in hexane and acetone. Therefore, the average molecular weight of this polymer was measured by the VPO method. The results are shown in Table 5.

The results of NMR analysis and engineering R analysis of the polymer after treatment are shown below.

'HNMR: 0. Oppm standard (S, 5H,
0-8i-OH3), 0.83 ppm (S,
9H,5i-0-OH3).

1-2 ppm (broad, 2H,C)I2
) 1-2 ppm (broad, IH, OH)
, 6.53 ppm (broad.

4H, 0sHs) Engineering R: 1610cm-' (endocyclic skeletal vibration), 139
5 and 13651M-” [0-(OH5)s],]
1265 cm-' (5i-0), 1170 cm-"
(Si-0-C), 920 cm' (5i-0-
Ar), 846OOH out-of-plane angle) It is clear from the results of these analyzes that the properties obtained in this example are the same.

By treating a polymer having a BDMS-protecting group with a 2 N -HO1 aqueous solution, the protecting group is removed and THF,
Polyp-vinylphenol (J-soluble in methanol and acetone, insoluble in benzene, n-hexane, and chloroform)
pvp) was obtained.

As a result of NMR analysis and engineering R analysis of pvp, the characteristic absorption based on the DDM3 protecting group was not suppressed, and it was confirmed that it was OH.

Table 3 Note 2) Polymerization temperature: room temperature [Synthesis of living block copolymer] [α-methylstyrene]-・2Na+ ([120 m m
VP-BDMS (a 7m
mol) of THF was added, and polymerization was carried out at -78°C for 1 hour. Styrene (57.6 mmol) was added to this dark red pasting 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 .

The BDMS protecting group was retained from the polymer structure, and GPO measurements showed a single elution curve in a higher molecular weight range than expected from the original V'P-BDMS homopolymer. Ta.

The number average molecular weight of the obtained copolymer was 89. It was OOO.

In addition, from the results of NMR measurement, it was found to be a block copolymer consisting of a polystyrene block (87-9 mol%) and a polyVP-BDMS block (12.1 mol%), using the same calculation method as in Example 4. .

According to the above results, υ is the polymer i obtained by the above copolymerization.
, i (13) -(A) -(E) form [strictly speaking, CB since there is an anionic initiator α-methylstyrene oligomer) -(A) -(function-(A)-(B) form)] It can be seen that it is a living block copolymer.

[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 H
p1 ampoule, 4... first monomer-filled ampoule, 5... second seven-monomer-filled ampoule, 6, 7...
Branch pipe, 8... Vacuum line, 9... Cock, 10...
- Magnet Figures 2 and 3 show the APA lumi chart of the (co)polymer in the present invention. Agent Uchiguchi 1 Akira Agent g−1Φ Arm・,−

Claims (1)

[Claims] [In the formula, 2 is (CH2), n*0BiRIR2R'',
NFt4・Eli-RI Bll R3 or N(BiR
IR2R3), X represents an integer of 2 or more, m is 0 to
The number 6, R1, R and R3 are the same or different alkyl groups or aryl groups, and R4 is a hydrogen atom or an alkyl group. ] repeating unit φ), [wherein R is a water atom or t is a methyl group, Q is a hydrogen atom,
1 to 6 alkyl groups or nyl groups; y represents an integer of 2 or more. ] A novel living block copolymer having a bond with the repeating unit (B). [In the formula, x #i (Out) mOH group or 1'1NR6R
' represents an amino group, where m is a number from 0 to 6, and R' and R6 represent a hydrogen atom or an alkyl group. However, 1. R6,116 is not an alkyl group at the same time. ]
The vinyl monomer (+1) represented by the formula RIR”R
3EIi- [wherein 2 is OHrim0-8iR'R2R3, NIR
'-81RIR2R3 or N (SiRIR"R3),
, m Id O~6 (7) number, F, I , R2 and R3 are the same or different alkyl groups or aryl groups,
R4 represents a hydrogen atom or an alkyl group. [In the formula, 2 has the same meaning as above, and show. To a living polymer consisting of repeating units of or styrenic compound Q'a IJI)
The product is obtained by polymerization in the presence of a k anion polymerization initiator [wherein R and Q have the same meanings as above, and y represents an integer of 2 or more. ) by adding the above-mentioned substituent (1) to a living polymer consisting of repeating units (homogeneous) and copolymerizing fr
:I:P? [In the formula, 2 and X have the same meanings as above.] ]) and the general formula [wherein RlQ and y have the same meanings as above. ] A method for producing a novel living block copolymer having a bond with the repeating unit (13).