JPS62257919A - Graft copolymer of silylated polystyrene - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having narrow molecular weight distribution, by coupling a vinyl polymer segment to a silyl group of a polystyrene having dimethylchlorosilyl group at paraposition. CONSTITUTION:The objective graft copolymer contains (A) a unit of formula I and (B) a unit of formula II (R is H or CH3; R<1> is vinyl, isopropenyl or phenyl; n is 10-2,000; R is CH3 when R<1> is phenyl) as recurring units, wherein the amount of the component B is <40mol%. The objective copolymer can be produced by coupling a living polymer segment of formula III to a polymer having the component A as a recurring unit.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a copolymer prepared by grafting polyisoprene segments onto silylated polystyrene.

BACKGROUND OF THE INVENTION Anionic living polymers of styrenic derivatives having an active silyl group at the para position have already been developed by the present inventors. However, a graft copolymer in which a polymer segment of another vinyl compound is coupled to the silyl group of this polymer is not known.

Node points to be solved by the invention The present invention provides a whole graft copolymer obtained by coupling a segment of a vinyl polymer such as polyisobray to a silyl group of polystyrene having a dimethylchlorosilyl group at the para position. With the goal.

Means for Solving Problems Summary of the Invention The summary of the present invention is that repeating unit (+L) and repeating unit (υ) of the following general formula:
b), the repeating unit (1)) is present in a graft copolymer of silylated polystyrene of less than 40 molar units, preferably from 35 to 5 molar units.

General formula (a) [However, R is a hydrogen atom or a methyl group, R1 is vinyl, impropenyl or L< is a phenyl group, and n is 10 to 20
00, R1 is a phenyl group, n is 10 to 200
0, and when R1 is a phenyl group, R is a methyl group] Method for producing graft copolymer The graft copolymer of the present invention [hereinafter referred to as polymer (1)] has the general formula (a can be prepared by formula coupling to a polymer (117) consisting of repeating units of

Specific examples of polymers include polybutadiene, polyisoprene, poly(α-methylstyrene), and the like.

The polymer (It) is poly[4-(dimethylsilyl)] consisting of repeating units of the general formula
Styrene (hereinafter referred to as polymer) can be produced by chlorination.

Polymer Qll) is dimethylsilyl chloride (hereinafter referred to as
compound I) and the formula c H! -c H-@)-M
After reacting gOt with p-vinylphenylmagnesium chloride (hereinafter referred to as compound ■) and tFi to synthesize styrene (hereinafter referred to as compound ■),
It is obtained by polymerizing this compound.

Compound! The reaction between
The reaction is carried out for 1 minute to 25 hours, usually in the presence of a solvent. Examples of solvents that can be used include ether compounds such as tetrahydrofuran, diethyl ether, and dioxane. The contact ratio between compound I and compound Tomoe is! /■ (mole ratio) is usually (L9 to 10).

Anionic polymerization, radical polymerization, etc. can be used as the polymerization method for polymerizing compound 111 obtained in the above reaction to obtain polymer (4), but in order to obtain a polymer (In) with a narrow molecular weight distribution and close to monodisperse, Anionic polymerization is preferred.

Suitable anionic polymerization initiators used in anionic polymerization include n-butyllithium, naphthalene lithium salt, naphthalene sodium salt, naphthalene potassium salt,
(α-methylstyrene oligomer) sodium salt, (α
-methylstyrene oligomer) lithium salt, (α-methylstyrene oligomer) potassium salt, cumyl potassium salt, and the like.

The anionic polymerization may be carried out at room temperature, but preferably
Low temperature below -30℃, especially preferably -50℃~-10℃
It is carried out at a low temperature of 0° C. (LO 1 to 20 hours, preferably in the presence of a solvent. Suitable solvents include TIII
F.) Luene, hexane, cyclohexane and the like. Two or more kinds of them may be used. In addition, the polymerization reaction is
It is preferable to carry out the reaction in an inhospitable gas atmosphere under reduced pressure, particularly preferably under high vacuum.

The molecular weight of the living polymer can be controlled by changing the compound III/anionic polymerization initiator ratio,
That ratio? Is molecular weight higher than K? can be increased. Furthermore, the molecular weight can also be adjusted by changing the type of anionic polymerization initiator or the polymerization temperature.

The polymer @) obtained by living anionic polymerization as described above usually has a molecular weight of about 500 to about 50,000, preferably 2. OOO~2QQ, 000, more preferably 5,
000 to 10 (having a number average molecule t' of 1,000,
Weight average molecular weight (My)/number average molecular weight (Mn) =
It has a very narrow molecular weight distribution of 1.05 to 1.50.

The method for producing the polymer (■) by chlorinating the polymer 011) desirably uses carbon tetrachloride, methine chloride/, chloroform hydrocarbons such as chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, etc. This is achieved by contacting the polymer (ill)' with chlorine gas in the presence of a solvent such as a saturated hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, etc. Chlorination is usually carried out at -100 DEG to +100 DEG C. for 1 minute -j5o hours.

The polymer (9) thus obtained is a polymer (
The skeleton and molecular weight 2 molecular weight distribution of 110 are maintained as they are.

Polymer (1) of the present invention is obtained by coupling polymer (trans) to polymer (It).

The grafting reaction by coupling the polymer (conversion) to the polymer (1) is a reaction between the polymer (...) and the polymer (conversion).
Gluing is done by contacting polymers.

The living polymer (conversion) is a compound of the formula aH, -aRR1 (where R and R' have the same meanings as above), specifically butadiene, isoprene, and α-methylstyrene, according to a normal anionic polymerization method. It can be obtained by polymerization.

The polymer (b) obtained therein is from the following formula, M
w/Mn=t02~1.50, close to monodisperse.

Moreover, n in the following formula is 10 to 2. OOO1 is desirably 20 to 1.500 [however, R and R1 have the same meanings as above], and the coupling reaction between the polymer (If) and the coupling polymer (B) is performed according to the anionic polymerization method of the present invention. good. The grafting rate of the polymer (transfer) of the branch polymer to the polymer (It) of the trunk polymer is the polymer (■
) is up to 40 mol. This is thought to be because as the grafting rate progresses, steric hindrance becomes stronger and the reaction does not proceed any further.

The polymer (I) of the present invention obtained as described above is:
Usually about 1.000 to about 1. Q O[1, OOO1 preferably s, o o o ~ 500.000, more preferably 10.000 ~ 300.000,
The molecular weight distribution is extremely narrow, with Mw/Mn = 1.05 to 1.40.

Effects of the Invention The copolymer of the present invention is useful as an elastomer,
It can also be used as a compatibilizer when blending two or more types of polymers.

Example Hereinafter, the present invention will be explained in detail using examples.

Anionic polymerization experiments were carried out using an ampoule with a breaker pull seal in which multiple anionic polymerization initiator solutions and monomer solutions connected to a high vacuum line were frozen and degassed, and the system was cleaned with waste anionic polymerization initiator and living polymer. Part of? Using the equipment shown in FIG. 1 consisting of a flask connected to a spare branch pipe to be taken out, the following method was used.

First, flask 1 was kept at 10-' a+Hg Ic for 5 hours to degas it, and the vacuum line 8 was sealed off at point A. Then, the seal on ampoule 3 containing one anionic polymerization initiator was broken, and the system containing all of flask 1 was removed. Thoroughly clean the entire system, then lead it to the spare branch pipe 7, and remove the branch pipe 7i.
It is sealed off at point Ci, removed from the system, cooled to a predetermined temperature, the seal of ampoule 2 containing the second anionic polymerization initiator solution cooled to the predetermined temperature is broken, and the anion is added to flask 1. After introducing the polymerization initiator, the first monomer is similarly introduced into the flask 1 from the ampoule 4 and reacted for a predetermined time, and then a portion of the solution is introduced into the entire calibration tube 6 and sealed. subjected to crystallization.

The grafting reaction was carried out using the apparatus shown in FIG. 2 in the following manner. Attach the device to vacuum line J to create a vacuum, repeat baking with a Bunsen burner, deaerate for about 20 minutes, and then seal with A. Wash the inside of the device with the washing solvent E, collect in D, and seal with B. ? The polymerization initiator is O
After introducing K and cooling to a predetermined temperature, a solvent solution of G and nil monomer is added. After polymerization by standing at a predetermined temperature for a predetermined time, a part of the polymerization solution was separated into H for homopolymer analysis, and added to the solvent solution 1a of the polymer (n) cooled to a predetermined temperature. The digrafting reaction is completed by standing for a period of time. The device was then opened and subjected to polymer characterization.

Implementation ff1J 1 Add 4.89y of magnesium metal (I
12o1 mol) and tetrahydrofuran (TIF)40-
and then add 1.2 d of ethylene promide to activate the magnesium.

This Kp-chlorostyrene 14.49 t (α105
A solution consisting of mol) and THF, 60- is added dropwise while gradually heating to reflux the final KFi.

The dropwise addition was completed over 1 hour, and the reaction was continued for an additional 15 minutes, and then cooled to prepare a solution of p-vinylphenylmagnesium chloride.

Synthesis of 4-(dimethylsilyl)styrene Into a 300-ml flask, add 19.0 Of dimethylsilyl chloride ((
1201 mol) and THF80- are added, and the solution of p-vinylphenylmagnesium chloride obtained above is added dropwise thereto over 1 hour at room temperature. The mixture was further stirred at room temperature for 5 hours to complete the reaction, and left to stand for 12 hours.

After separating the generated salt tP and removing it by THF') distillation, dimethylsilyl chloride was distilled off at 20 to 30°C under a reduced pressure of 100 mHg, and further heated under reduced pressure to obtain 4-(
dimethylsilyl) styrene 2! L9F (116 mol) was obtained. This product was purified by rectification to obtain 4-(
dimethylsilyl) styrene (boiling point: 58℃/2gIsH
g) was obtained.

The IH-IJMH chemical shift values of this product were as shown below.

IH-NMR (Tys/cat,) δ: α33ppm (
a16H.

SiC Dan 3), 4.40 ppm (m: IH, Si Dan),
a19ppm (d: ”
H, :r= 11MZ), 5.69ppm (d: IH
,trans,Cdan-CH,,T=17H2),6.6
7ppm (2d; 111.-CHI-(H), 7.1
7-7.5J) I) m(m; 4H, C11H4-) Anionic polymerization of 4-(dimethylsilyl)styrene In the apparatus shown in the figure, 4-(dimethylsilyl) obtained above in the presence of THF solvent. Styrene & 47 ml J moles,
α-methylstyrene oligomer dipotassium salt (1194
4 at -78C using mmol (as K ions)
After polymerization was carried out for a minute, the reaction was stopped with an aqueous methanol solution, and reprecipitation was repeated with methanol to obtain a polymer. As a result of characterizing the polymer, the number average molecule [IC600, weight average molecule i (MW)
It was found that this was a nearly monodisperse polymer with /number average molecule i1 (Mn)=1.13.

As a result of IH-NMR analysis, the chemical shift value coincided with that of 4-(dimethylsilyl)styrene, and therefore, this polymer was found to be poly[4-(dimethylsilyl)styrene].

The above obtained poly[4-
(dimethylsilyl)styrene] a29562 (monomer equivalent: 1.82 mmol), dehydrated carbon tetrachloride 5 as a solvent
- and 2 mg of 2.3N chlorine in carbon tetrachloride solution (
1.26 equivalents) were added. After stirring at -20°C for 30 minutes, carbon tetrachloride was removed under reduced pressure, and the IH-NMR of the polymer was
Analysis was carried out. Finally, everything was freeze-dried from the benzene solution, and engineering R analysis and elemental analysis 2 were performed. The isolated yield of polymer was 8Q, 6%.

As a result of engineering R analysis, 2100 cm-” and 8800F+
-" SiH absorption, and the results of H-NMR analysis show that the S1 peak at 4.3 ppm has completely disappeared, and its integral value also agrees well with the calculated value. It is considered that the reaction proceeded quantitatively.

In addition, as a result of IH-NMR analysis, a, s 3ppm
The peaks of Vch and 5iOH8 have all shifted to α63 ppm, and this is thought to be due to the shift to the lower magnetic field as a result of chlorine bonding to silicon atoms.

The results of elemental analysis were as follows.

OHC1 analysis value (%) 61.78 &66 t
a96 calculated value part) 62.81 &85
From the results of 1 & 94, it was found that the obtained polymer had the following structure, and its Mn=12,800.

CHI-8i-OHs ■ t Grafting reaction Imprene 3α 97 mmol of THF solution was added to cumyl potassium [L980 mmol of THIF as a polymerization initiator]
The solution was left in contact for 4 hours at -78°C. The Mn of the obtained polyisoprene (GPC ratio = 2,580 (polystyrene equivalent)) was confirmed to be 4-bonded by IH-NMRK.

Next, the above-obtained BoIJC4-(dimethylchlorosilyl)styrene](-s1ct group, "'(Q, 4
A THF' solution of 95 mmol) was mixed with the above-obtained polyisoprene [poly(4-(dimethylchlorosilyl)styrene) 1.67 times equivalent to -51ct group] solution at -78°C for 24 hours. brought into contact. Immediately thereafter, in order to prevent gelation due to unreacted -81(!) groups, an appropriate amount of an ether solution of methyllithium was added to methylate the unreacted -81(!) groups, and methanol was further added to form living polyimprene. Made it react.

Appropriate amount of TH? After removing the polymer under reduced pressure, pour it into a large amount of methanol, separate and dry the polymer, and measure the total yield.
PO measurement was performed.

The Mn of the copolymer was determined by LS-GPO and found to be 72.600. Molecular weight of the backbone polymer (Mn =
12,800), -Number of 81H groups in the molecule (60)
The total grafting rate was calculated from the polyisoprene molecule i (Mn=2,580) to be 30. Therefore, the graft copolymer obtained here was found to be a copolymer in which the following (a) segment) (1:+) segment was bonded.

(a) (b) lcH! Examples 2 and 3 Isoprene in the grafting reaction in Example 1,
A grafting reaction was carried out in the same manner as in Example 1, except that the amount of poly[4-(dimethylchloro)styrene] used and the type of polymerization initiator were changed as shown in Table 2. The results are shown in the table.

Implementation Project In the grafting reaction of Example 1, butadiene (Example 4) or α-methylstyrene (Example 5) was used instead of isoprene? , living polymerization of butadiene and α-methylstyrene was carried out, except that n-butyllithium was used in place of cumylpotassium in the amounts shown in the table, and polybutadiene and polyα- Methylstyrene was obtained.

Next, the poly[4-(dimethylchlorosilyl)styrene] obtained in Example 1 and the polybutadiene or polyα-methylstyrene obtained above were subjected to pressure in the same manner as in Example 1 to perform a graft reaction. A graft copolymer having a molecular weight distribution of 1 and a total grafting rate as shown was obtained.

From the above results, (a) segments are respectively Example 1
The (b) segment was as follows.

Example 4 Example 5 (b) (b) 1 Homo Isoprene 5CL97
Cumil Potassium [1980 Graft
-51ct α495
(L67jiku2 homo imprene S54B n-butyl lithium
l1619 graft-BICl
1.01 (α
40 and 3 homo inprene 4α57
n-butyllithium 1764 graph)
-8in! [1961 (α63 Todoroki 4 Ho Mo Butadien 6Q, 10
n-butyllithium LL990 graft
-81C1[LaB5
(7-06 To 5 homo α-methylstyrene 2 (145n-butyllithium l1871 graft -a1ct α487
(1,79 happy 2 a) i
n: ape (polystyrene equivalent) b) Mn
: 1st - G C) Calculated from Mn of poly[monomer] "n 88 2.150 2.5aOa) L45
- Creation -165,0OOC) 72,600b
) 1.28 13077 4.400
5,220 li 1.07 -31) 85 1
62. tlook) 94,300b) t19
CL2787 4.200 5.410a
) 1.08 -jl) 8B 245,
000c) 92,800b) t17 CL
2787 to 340 to 800°”)
1.10 -Wound -23a000°> 79.6
00b) i, 20 t13 [1932, ,50
02,700a) 1.09 -, i) -1
72,000c) 59.800b) t25
l130

[Brief explanation of drawings]

Figure 1 is a conceptual diagram of a line of equipment for anionic polymerization in the present invention, and Figure 2 is a diagram showing the grafting reaction in the present invention. It is a conceptual diagram of -144 of the apparatus which performs. Figure 3 shows the polyisoprene in Example 2, Figure 4 shows the graft copolymer in Example 2, Figure 5 shows the polyimprene in Example 3, and Figure 6 shows the graft copolymer in Example 3. The combined GPC charts are shown respectively. In FIG. 1, 1... flask, 2, 3... ampoule containing an anionic polymerization initiator, 4.5... ampoule containing seven polymers, 6.
7... Branch pipe, 8... Vacuum line, 9... Cock,
10... Magnet In Figure 2, C... Flask, D... Receiver for cleaning liquid, E... Ampoule for cleaning liquid, ? ...- Ampoule for polymerization initiator, G
... Ampoule for vinyl monomer, ■... Receiver for sample, Engineering... Ampoule for poly[4-(dimethylchlorosilyl)styrene], J... Vacuum line connection cock

Claims (1)

[Claims] Repeating unit (a) and repeating unit (b) of the following general formula
), and the repeating unit (b) is less than 40 mol%. General formula (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R is a hydrogen atom or a methyl group, and R^1 is a vinyl, isopropenyl, or phenyl group , n is 10-2
000, and when R^1 is a phenyl group, R is a methyl group. ]