JPS5953509A - Novel living polymer and manufacture of the same - Google Patents

Abstract

PURPOSE:To obtain titled polymer easy to introduce functional group, useful for functional polymer, by first allowing a specific styrene derivative to react with a substituted silyl group-contg. compound followed by polymerization in the presence of an amionic polymerization initiator. CONSTITUTION:A vinyl monomer of formula I [X is (CH2)mOH(m is 0-6), or NR<5>R<6> (R5 and R6 are each H, or alkyl)] is allowed to react with a substituted silyl group-contg. compound of formula R<1>R<2>R<3>Si-(R<1>, R<2>, and R<3> are each alkyl or aryl) to prepare a substituted silyl group-contg. vinyl monomer which is then encapsulated in tube 4 with breakable seal. This tube is connected to the flask 1 along with another tube 2 of the same type encapsulated with an amion polymerization initiator, followed by making both tubes vacuumed by the vacuum line 8, then by breaker rupture by the magnet 10 to mix the monomer with the initiator, thus obtaining the objective living polymer having recurring unit of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new paper-based polymer and a method for producing the same.

From vinyl monomers having reactive groups such as hydroxyl groups and amine groups in their molecules, anionic living polymers of these vinyl monomers have not yet been obtained due to the active hydrogen in the reactive groups. After the reactive group of a vinyl monomer having a reactive group is protected in advance with a trialkylsilyl group, triarylsilyl group, etc. (hereinafter referred to as a substituted silyl group), the substituted silyl group is fully reacted with an anionic polymerization initiator. The present invention was completed by discovering that a living polymer of the above-mentioned vinyl monomer protected with a group is formed.
R2113, NR', 8i, R' R2R3 or 4.
i N(S jL'Ti211')z l), m
Number of IJO~6, Hl.

R2 and II'6; A novel living polymer (1) and -C formula C, or (C1, tag, OH group i, j: NR'
The amino group represented by R' is shown, m is IJ of θ ~ 6,
R5゜R6 represents a hydrogen atom or an alkyl group 0 However, R
5, R6 is not an alkyl group at the same time] A vinyl monomer represented by the formula R1R2R'Si- (however, -RIR
2 and R3 are di- or different alkyl groups or R-
The substituted silyl group of the vinyl monomer is brought into contact with a modified silyl group-containing compound represented by 1, Hs in the general formula of the vinyl monomer (11).

The alkyl group represented by R6 preferably has 1 to 1 carbon atoms.
A specific example of a vinyl monomer (lI) that is 6 lower alkyls is OH2= CH-@
)−? tH-02H5, cl(2=OH-(como=
==≦〕)←N'H-n-04J1, etc. are used to protect the reactive groups of vinyl monomers (tjIt, substituted silyl group-containing compounds, trialkylsilyl groups, alkyl groups, It is a compound containing an aryl mixed trisubstituted silyl group or a triarylsilyl group, and the compound has the general formula (SiRIR2
R3) nL C In the formula, R1, RZ and R3 are the same or different alkyl groups or aryl groups, L is a norogen atom or an NH group, and when n[L is) an hrogen atom, F
i1, and is represented by NT (0, which is 2 in the case of a group), and a specific example thereof is [' (OH3hSi]2NE
I, ((C2HshSi)+NH.

((C1C!3)17)! ”1)2NT(,((t-0
4'(9hCT(*Si)2NH.

(CHs)3s1ct, (0,115)3'iC4t-
C4■■9(OB3hSiC4CH3(02H51,8
1C/, (n-C4Hc+)ssiol, ((
Oa HslxSi,]zNH.

(06H5(OH3)2[31], NH, (02H5)
Examples include 206T(, 5iCt, etc.) These compounds are not limited to one type, and two or more types may be used simultaneously.

The vinyl monomer (11) and the substituted silyl group-containing compound are brought into contact at room temperature or under heating, usually for 0.5 to 50 hours. The contact may be performed in a solvent or under an atmosphere of an inert gas such as nitrogen gas. Suitable solvents include DMF (dimethyl heptamide), THF
(tetrahydrofuran), NMP (N-methylpyrolidone).

Sulforane, T)MOO (dimethyl sulfoxide)
etc. is Nogemo no 1. The contact between the vinyl comonomer (11) and the Wt JI'4 silyl group-containing compound may be carried out in two or more stages, and if necessary, a Grignard standard such as 02H5Mf Br may be added. 0 The contact ratio between the two is vinyl monomer
The amount of the substituted silyl group-containing compound is 0.5 times mole or more, preferably 1 to 1 to 10 times mole, relative to (II).

As a result, the active hydrogen in the reactive group of the vinyl monomer (II) is substituted with a substituted silyl group, resulting in a substituted product of the vinyl monomer (II), which is then replaced by the presence of an anionic polymerization initiator. The substituent pasting polymer (1) is obtained by anionic polymerization as shown below. Suitable anionic polymerization initiators include n-butyllithium, naphthalene lithium salt, naphthalene sodium salt,
Naphthalene potassium salt.

(α-methylstyrene oligomer) sodium salt, etc. The anionic polymerization may be carried out at room temperature, but preferably,
Low temperature below -50℃, especially preferably between -50℃ and -10℃
The process is carried out at a low temperature of 0° C. for 0.1 to 20 hours, preferably in the presence of a solvent.
II', toluene, hexane, cyclohexane, etc. O. Two or more types of them may be used. The polymerization reaction is preferably carried out in an atmosphere of inert gas W under reduced pressure, particularly preferably under high vacuum. The molecular weight can be controlled by changing the ratio, and the molecular weight can be increased by increasing the ratio.Also, the molecular weight can be controlled by changing the type of anionic polymerization initiator or the polymerization temperature.

The phosphor polymer (1) obtained by smelting usually has a molecular weight of about 5
00 to about so o, o mouth 0, preferably 2,000 to
200,000, more preferably s, ooo to 100.
The glueing polymer (1) of the present invention, which has a number average molecular weight of 0.000 and is stable at relatively low temperatures, is useful as a synthetic raw material for (living) block covalent (coalescence) with other monomers, such as styrene. Moreover, by contacting with a proton donor such as methanol, ethanol, phenol, mH, '#L acid, etc., the substituted silyl group, which is a protective group, is easily removed, and the method for producing the polymer of vinyl monomer (11) is completed. According to this method, the vinyl monomer (II) is produced by radical polymerization of the known vinyl monomer (II) (compared to the old polymer production method, the molecular weight can be easily adjusted, and any molecular chain has a narrow molecular i distribution. Polymer?It has the characteristics of being easy to manufacture.

The UV-protected polymer thus removed can be used as a functional polymer, with all its reactive substituents
: substituted with a group f (Synthesis of new functional polymers 19 and () is also useful.

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 central experiment consists of multiple anion polymerization initiator bath liquids and 7-mer solutions that are connected to a high vacuum line, frozen, degassed, and sealed with a breaker pull seal. The process was carried out in the following manner using the apparatus l/k shown in the drawings consisting of 2 tubes, in which a portion of the living polymer was taken out and a spare branch pipe was ligated.

1. First, the flask I 'z l O-' vtanHf was kept for 5 hours to degas it, and the vacuum line 8 was sealed off at point A. Next, the ampoule 5 containing one anionic polymerization initiator was
Break the seal, introduce it into the system including flask 1, thoroughly wash the entire system, guide it to a spare branch pipe 7, seal off the branch pipe 7 at the zero point, remove it from the system, and then After cooling to a predetermined temperature, break the seal of the angle 2 containing the second anionic polymerization initiator solution, introduce the anionic polymerization initiator into the flask 1, and then cool the first anionic polymerization initiator solution.
monomer? After introducing the solution into flask 1 from ampoule 4 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 and sealed off, and was subjected to characterization of the living polymer.

The monomer remaining in the flask 1 was introduced into the polymer bath solution from the second monomer ampoule 5, subjected to block copolymerization, post-treated, and subjected to measurements of physical properties, etc.

When block copolymerization was not performed, the whole living polymer was used for 7-dimensional characterization.

Example 1 (Synthesis and Identification of VPA-6i 9 and 1SKp-vinylphenethyl alcohol (0H2=
A lot of trouble to OH←CH2C! H20H) (VPA) Equal % to VPA and H20H (7) ((CH3) 3s
i) zNH(HMDs)''; z Input i1, g7g Stirring was performed at 50°C for 1 hour in a gas atmosphere.Then, the product was distilled under reduced pressure to obtain p-vinylphenethyyl chloride.
71f Lucin7 (OH,=O/H8H2OH2O5
i(OHs)s)(VPA-8i)'robtain,
Furthermore, by adding 2 Grignard test mulberry (OzHsMlBr) and vacuum distilling, VPA-8i having a sheath layer was obtained with a yield of 82%.

This VPA-8i had a boiling point of 75° C./2 Ga Hf.

KonoVPA-IEi (7) 'HNMR (60MHz
: TMS standard is 0.24 ppm (S, 9
H,0-5l-OH3), 2.95ppm (t,
2 H,,7= 7 Hz, Ph, CTT, 0H2
), 168M+m (Ot, 2 H, J = y
H2, OH; -0-81).

(5,52,5,86ppm (2d, 2H, J
= + o.

+ 8 Hz, 0H2=CH)), 6.8 7
ppm (2d, +H.

cn=aH2), (7,21,7,52ppm(2
d, 4H.

J = = 9.9Hz, Pha, b)') above He? 4
It was confirmed that it was a construction.

(VPA-81 pasting polymer synthesis and identification)
1l) f'-treated VPA-8i was treated with various anionic polymerization initiators shown in Table 1 at -78°C.

Polymerized under conditions of 1 hour. In either case, is it a slightly blackish red characteristic of polymerized beam anions? It was showing.

The results are shown in Table 1. The convergence was almost quantitative. The resulting polymer was stable at -78°C but unstable at room temperature, so the following treatment was necessary. After that, I went to characterization.

Tl1F-11□0 at this rehing volume market 1S temperature
By treatment with methanol in a solvent, the trimethylsilyl group of the retention group was removed and poly(p-vinylphenethyl alcohol) (PVPA) was removed. PV PA is glass rolling JηL'+ at 108℃
X, l holder, ethanol, i'j'l moromi,
Possible for pyridine, dioxane iJ I THF, pen-
It was inactive in pin, water, chloroform, and architon.

T'VPA (1) IR, X 5500 for vector
~5550 on-1(-0I() 1610 and 1
510 cm-' (i, 5j endoskeleton 1.820 cm"
(J:￥J CI■)! It showed a 1% i,;'λ convergence, and no absorption 11 due to the trimethylsilyl group was observed.

Also, IHNMR did not show any 4'Y absorption of the trimethylsilyl group as in 1FiJ. Therefore, PVPA
The obtained PVPA was acetylated in a pyridine solvent, purified by repeated precipitation and dissolution, and then dried and acetylated. PVPA' (f7 obtained, using this, VPO (Vapor Pressure Osmom
Table gg1 shows the number-average molecular ik measurement using PVPA and the number-average molecular ik calculated assuming that all 7 enethyl groups in PVPA are acetylated. It can be seen that the two agree quite well and -C0.0 For acetylated pvpa, GPO (Gelpermotion Chromatography) was used as THF i solvent.
It was confirmed that there is a polymer with an extremely narrow molecular distribution. When THF H*'x of styrene is added under high vacuum at -78°C, it reacts with Sumiya 1 to obtain a block copolymer consisting of VPA-81 polymer segments and polystyrene segments, and this block copolymer The combined trimethylsilyl blocking group is methanolyzed to remove -C and the block copolymer 1i is soluble in THF, and using Tl as a common medium, G
By performing PC foot measurements, the molecular fraction I [1 is the original PV
PA I am being sidelined by my own child Z)! , l also shows a single flake in the molecule j (l flail, and the small molecule I
No peak was observed in the P region and Part 11 (
From the analysis results of 1, it was proved that the polymer obtained by anionic polymerization of VPA-8i, which was first synthesized, was a living polymer having 10e repeating units.

/″ / 7,・′ / Example 2 p-zuminostyrene (CH2==CI(-QXNH2)
(As) with 5 times the molar amount of HMDS and 0.5 times the molar amount of Si (O)I,)3C/.

In addition, the reaction was carried out for 2.5 hours at reflux temperature.

By distilling the entire product under reduced pressure, the trimethylsilyl group 11ζC of AS was obtained in a nearly identical manner. This substituted product had a boiling point of 15 H2 at 90°C. Furthermore,
This substituent was added with 2 times the molar amount of Grignard reagent (02HsM
9'Br)'j5 was added and reacted for 2 hours at room temperature in TI(F), and then 4 times the mole of Si (C113), Cl
By adding k, leaving it for 12 hours, and distilling it under reduced pressure,
p-(bistrimethylsilylaminostyrene (C1(z=OH@-N[Si, (CHsn3]2
(BTMI9AS) was obtained. This BTMSAS
had a boiling point of 60-80C/2 trm+Hf.

BTMSAS Lv'HNMR is 0.0 ppm (S, 1
8H, 5i-OH, -).

(s, os, 5.57 ppm (2a, 2H, J=1o.

17 Hz, CH,=CH)), 6.55 pp
m (2d.

1H, (EH=CH, l, [6,75,7,+8
ppm (2(1゜4H,J=9.01]z, Ph
a, b)') It was confirmed that the above structure was present.

Ikurahata+l'rMRAEI Using a care anion polymerization initiator (7) and lithium naphthalene, in THF, -
Polymerization was carried out at 78°C for 1 hour. The results are shown in No. 28. The polymerization system was brownish orange and stable even at room temperature (when treated with a large excess of methanol, the polymer separated as a white precipitate), and poly-r (, almost quantitatively obtained. The polymer after methanol treatment is soluble in THF, benzene, and chloroform, insoluble in methanol, and has the molecular weight shown in Table 2. The results of NMR analysis and IR analysis of the polymer after this metal treatment are shown below.

”HNMR: O, Oppm (standard) (B1-CH
3).

0.7-2.5 (-CH2-OH-) Calculated value 2+: 4
: Actual value 24:4 Engineering R: + 6056n-' (1m endoskeleton).

1250α-' (5i(OH3)s).

1175α-+ (5l-N-8i).

9 5 5 am-' (5i-N-Eli)
.

844 cm-' (5i (OHsh).

752 cm-' [Si(OH3)g] From the results of these analyses, the above living, l? It is clear that halogen has the structural formula N-(81-OH3)2CH3.

Does this have a trimethylsilyl protecting group? 1 Tsuma-'
By treating with a 2N-HCI aqueous solution, the securing group is easily removed, and a water-bathable monoaminosugrain is obtained under acidic conditions.

Results of NMR analysis and IR analysis of this water-soluble polyaminostyrene (FAS) - 0114 NMR shown below
(T″2Oi liquid): 1~2ppm ('br Oe, d
; 5 H, (-CH2-CH→-].

Engineering, R: + 58 [-NH3°c t at 16n-1
The characteristic of e (11') is reduced by B1, but (OH3
At 1 o'clock of the 3si group ('l exposure V, B9 was not recognized.

In addition, by adding 1 of this living polymer styrene and combining it, a B-A-B type living block copolymer with polystyrene can be obtained. Rano 1. When the GPOi of the given polymer was determined, a transition to the polymer 111 was clearly observed in a single peak, indicating that a block copolymer was being formed.

Table 2 Example 5 (vp) and equimolar t-O4 for vp
Enter Hg (OHs) 28101 (BDMS) f,
In the presence of imidazole, the mixture was reacted in a DMF solvent at room temperature for 4 hours. The product was subjected to wave distillation to obtain p-vinylphenoxyt-pugludimethylsilane (CH,=cH-(yo))O8i (CH3), t
-0411J (VP-111D), 4S l f
With a yield of 76%? 3 fc. This VP-BDMFI had a boiling point of 41°C at 80'C10.
NMR: O, Oppm group qx (S, 5 T(,
0-8i-0) Hani.

0.80 ppm (S, 9Tl, Si
OpHa,).

(4, F37. 5.44 ppm (2d, 2H
.

, Ding ---+ D, 1 7
Hz, CH2==OH)).

6,56 ppm (2c+, IT-1,9H=
CHa), (6,54,7,06ppm (2a.

t+ )], J= j o H+y,
Ph a,b) ).

As a result, it was confirmed that it was the 11th structure of the 3DMS. The thus obtained VP-BP) was dissolved in THF using the anionic polymerization initiator shown in Table 5.
After polymerization at 78°C for 1 hour, the living polymer is treated with large-chain methanol to separate the polymer using a white method.
The O living polymerization system, which was stationary, had a slightly dull red color and did not fade even at room temperature and had a value of >7.

The above polymerization system was treated with water. In the fc polymer, the nnMc protecting group remains without being removed, and it is insoluble in benzene, methanol, and chloroform, and insoluble in hexane and acetone. All 0 results are shown in No. 5.

Place 8! The results of the subsequent NMR analysis and Ill analysis of the polymer are shown below.

IHNMR: 0. Oppm standard (S, 5H
, 0-8i-OH3).

αB”r ppm (B, 9H, F31-C
-CH,,).

1-2 ppm (broad, 2H, 0H2).

j ~ 2 ppm (broad, IH, OH
).

6,55 ppm (broad, 4H,06)
(5) IR: 16 + Orm-' (9 endoskeletal vibration i!+).

1595 and +565 eM-'(C(-0'h)
s).

+265 cm-” (81-Cl.

1170 cm-' (Si-0-0).

920 I:tn-' (Eli-0-Ar), 8
46nn-' (Si-C).

As a result of these analyses, it is clear that the first structural formula obtained in this example is different from that of the OBDM8 polymer having a protective group when treated with a 2N-HOt aqueous solution.
l! -j, the t!! group is eliminated and THF
', methano-A., soluble in acetone, benzene.

Polyp-vinylphenol (PVP) insoluble in n-hexane' and chloroform. 5Raha, 101'VP NMi (As a result of analysis and IR analysis, characteristic absorption based on the BDMS retention group was confirmed. (For the living polymer of VP-BDMS prepared by
By adding α-methyl styrene gel to λ- and polymerizing it, poly α-methyl styrene segment V))
-FtT)MS A block copolymer having 11 tons of polymer segments was prepared.

The obtained polymer was then converted to the original VP-BDM by GPO.
From the distribution of molecules 11 of the S polymer, it was confirmed that the polymer bone 1]11]7 was present, and that it was a block copolymer by NMR, solution M tests, etc.

As a result, the polymer obtained by anionic polymerization of VP-BT)+48 in this example has the above t, ¥4
It has been proven that it is a living polymer with a turning unit.
Table 6 2) Combination temperature: room temperature

[Brief explanation of the drawing]

Drawings tj, ;11-, schematically show a device for performing anionic polymerization and anionic blocking mold f) in the invention; 1. Flask, 2, 5. Anionic polymerization initiator" 11
Human ampoule, 4. First monomer-filled ampoule, 5.
・Second monomer-filled ampoule, 6.7... Branch pipe, 8.
・Vacuum line? ...Cook, 10...Magnet agents 1) Akira agent Ryo Hagiwara -

Claims (1)

[Claims] (1) General formula [in the formula, Z l-4(O)]2) m-O8iRIR2R
3, NR4-8iRIR2R3 or N (S ], R'
R2R3) 22,1-indicated, m IrJ, 0-6
, R1, B2 and R3 are the same or different alkyl groups or aryl groups, and 4 represents a hydrogen atom or an alkyl group. ] A novel living polymer with repeating units. [In the formula, is not a group.] Vinyl monomer formula RI R2R381- (However, RI R2 and R
3 is the same or different alkyl group or aryl group], and the obtained vinyl monomer is polymerized in the presence of a wholly anionic polymerization initiator with a substituted silyl group. Formula [wherein 2 is (OH2zui, 08iR, lR2R3, NR
C8iRIR2R3 or N (sIR1R2R3), 5
m is a number from o to 6, R1, B2 and R3 are the same or different argyl groups or aryl groups, and R4 is a hydrogen atom or an alkyl group. ] A method for producing a new living polymer having repeating units.