JPS62201910A - Living polymer - Google Patents

Abstract

PURPOSE:To obtain a living polymer which can undergo a chemical reaction with the surface of an inorganic substance and crosslinking with another poly mer, by anion-polymerizing a reaction product obtained by reacting a tetraalkoxysilane with p-vinylphenylmagnasium chloride. CONSTITUTION:1mol of a tetraalkoxysilane of formula I (wherein R is a lower alkyl) is reacted with 0.9-10mol of p-vinylphenylmagnesium chloride of formula II at -70-100 deg.C for 1min-25hr in the presence of a solvent such as tetrahydrofuran to obtain a p-tolylalkoxysilystyrene of formula III as a product. This product is anion-polymerized at room temperature or below, preferably, a temperature <=-30 deg.C for 0.1-20hr in the presence of an anionic polymeriza tion initiator [e.g., alpha-methylstyrene oligomer (di)potassium salt] in, optionally, a solvent such as tetrahydrofuran to obtain a living polymer having a repeating unit which is a styrene derivative with an alkoxysilyl group in the para position and having a number-average MW of 500-500,000 and a MW distribution of 1.05-1.50.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to bright pink polymers of aromatic vinyl compounds.

Prior Art An anionic lipin polymer of a styrene derivative having an active silyl group at the para position has already been developed by the present inventors [Polymer, Proceedings.

54, No. 2, p. 189 (1985)).

An object of the present invention is to provide a styrene derivative slipping polymer having a trialkoxysilyl group at the para position.

SUMMARY OF THE INVENTION Means for Solving the Problems The present invention relates to a compound of the general formula [wherein R represents a lower alkyl group]. 1. Manufacturing method of living polymer The pasting polymer of the present invention is a living polymer having a repeating unit of 5 Si(OR)4 (hereinafter referred to as compound 2). silylstyrene (hereinafter referred to as the compound I
That's what it means. ) can be synthesized by reacting with an anionic polymerization initiator.

R in the above formula of compound ① represents a lower alkyl group,
Specific examples include methyl, ethyl, n-propyl, 1-propyl, n-butyl, 1-butyl, t-butyl, n-pentyl, n-hexyl and the like.

The reaction between compound 1 and compound I is -70C to +1o a
c 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 1 is! /summer (molar ratio) is usually 0.9 to 10.

Compound 117f that cannot be obtained by the above reaction! :, anion 1
The pasting polymer of the present invention can be obtained by anionic polymerization in the presence of a polymerization initiator.

Suitable anionic polymerization initiators include lobethyllithium, naphthalene lithium salt, naphthalene sodium salt,
Naphthalene potassium salt, (α-methylstyrene oligomer) sodium salt, (α-methylstyrene oligomer)
Lithium [, (a-methylstyrene oligomer) potassium salt, cumyl potassium salt, etc. can be mentioned.

The anionic polymerization may be carried out at room temperature, but preferably
-s oC or lower, particularly preferably from -50C to -1
000 for 0.1 to 20 hours 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. The polymerization reaction is preferably carried out in an inert gas atmosphere under temperature and pressure, particularly preferably under high vacuum.

The molecular weight of the living polymer can be controlled by changing the compound m1/anion 1 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 temperature of the polymerization.

The phosphor polymer thus obtained usually has a molecular weight of about 500 to
Approximately s o o, o o o, preferably 2,000 to 2
00,000, more preferably 5,000 to 1o o,
It has a number average molecular weight of o o o, and has a very narrow molecular weight distribution of polymerization average molecular weight/number average molecular weight = 1.05 to 1.50. It also has stable properties at relatively low temperatures.

Effects of the Invention The glue pink polymer of the present invention can be expected to undergo a chemical reaction with the surface of an inorganic substance such as glass or gold oxide by acid treatment or heating, and crosslinking between polymers is also possible. or,
It is also useful as a raw material for synthesizing other 7-mers such as styrene and pink floc copolymers.

Examples Hereinafter, the present invention will be explained in detail with reference to Examples.
"Unexploded ψ" is not limited to these examples unless it goes against the spirit thereof.

The experiment was conducted using an ampoule with a breaker pull seal, in which several anionic polymerization initiator solutions and a seven-mer solution were frozen, degassed, and sealed, connected to a high-vacuum line, and the inner ring was cleaned.
c Waste anionic polymerization initiator and part of living polymer f
Using the apparatus shown in FIG. 1, which consists of a running flask connected to a spare branch pipe for ejecting c, the following method was used.

First, flask 1 was kept at 10-6+n+Hg for 5 hours to degas it, and the vacuum line 8 was sealed at point A. Then, the seal on ampoule 3 containing one anionic polymerization initiator was broken, and the system containing flask 1 was After thoroughly cleaning the metal inside the system, it was introduced into a spare branch pipe 7, and the branch pipe was sealed off at the 7fC point, removed from the system, and then cooled to a predetermined temperature. Break the seal of ampule 2 containing the cooled second anionic offshore initiator solution, pour the anionic polymerization initiator into flask 1, and then add the first monomer from ampoule 4 in the same way. After reacting for a predetermined period of time, a portion of the solution was introduced into the branch pipe 6 and sealed off, allowing the living polymer to be characterized.

Example 1 Magnesium metal 4.89 in a 20 ant flask,
F (0,201 mol) and tetrahydro7rane (T)i
F) Add 40- and then add ethylene promide 1,2- to activate the magnesium. This Kp-chlorostyrene 14.49 J (0,105 mol) and THF60
- While dropping the solution, it is gradually heated until it finally refluxes. Finish the dripping for 1 hour, then add another 1 hour.
After continuing the reaction for 5 minutes, it was cooled and a solution of p-vinylphenylmacnesium chloride was prepared.

3001 flask, 4 f of tetraethoxysilane,
96, f (0,20f mol) and THF8Qyd are added, and the solution of p-vinylphenylmagnesium chloride obtained above is added dropwise thereto over 1 hour at room temperature.

The reaction mixture was further stirred at room temperature for 5 hours to complete the reaction, and then left to stand for 12 hours. After filtering the generated salt and removing THF by distillation, tetraethoxysilane was distilled out at 40 to 50 C under a reduced pressure of 10 g Hg, and further heated under reduced pressure, p-)
Ethoxysilylstyrene 10.45 / (0,039
2 mol) was obtained. Is the purity of this thing all rectified? 9.
1 $ p-triethoxysilylstyrene (boiling point; 90
C/1 Hg) was obtained.

'H-N of the obtained fcP-)ethoxysilylstyrene
The chemical shift values of MH were as follows.

'H-NMR (OC!/4): a = 1.24 p
pm (t, 9 H.

51ocH2a! 3), 3.85 pl) Ill (q
, 6H,5iOcH2CH5 containing 5.24, 5.
74 ppm (2d, 2H, CH2= , J
= 11.18EX), 6.72 ppm (2d,
IH.

=■-), 7.20-7.80 ppm (m, 4H
, Q) In the apparatus of the first prisoner, in the presence of THF solvent, 3.87 mmol of p-1 ethoxysilyl styrene obtained above, 0 α-methylstyrene oligomer dipotassium salt
．． - using 137 mmol (as K+ ion)
After polymerization was carried out for 4 minutes at 78t:'', the polymerization reaction was stopped with an aqueous ether solution, and the polymer was extracted into the ether layer. Ether Nk was dried with MgSO4 for one day, and the ether was removed under reduced pressure. -1 Then, the operation of pouring water and performing reprecipitation was repeated twice.The obtained polymer was finally freeze-dried from a benzene solution, and was used to conduct polymer characterization and solubility experiments. I went.The result.

As shown in the table, the calculated molecular weight and the measured value are in good agreement, and as shown in the GPO chart for the second factor, there is a single peak and the molecular weight distribution is very narrow (Mw/Mn=1.
09) It turns out that it is a polymer.

Furthermore, as a result of H-NMR analysis of this polymer, the p-
Since the same peak appears in the main part of the H-NMR chart of 9-ethoxysilylstyrene, this polymer is polyCp-triethoxysilylstyrene]
It turned out to be nine. Therefore, it is certain that the polymer obtained by the above anionic polymerization is living poly(p-triethoxysilylstyrene). The resulting polymer was soluble in almost all organic solvents and remained insoluble when washed with water.

In the anionic polymerization of Example 1, use of fcp-triethoxysilylstyrene was used, and α-methylstyrene oligomer dilithium salt was used as an anionic polymerization initiator (Example 2), or α-methylstyrene oligomer dipotassium salt was used as an anionic polymerization initiator. The anion 1 reaction of p-triethoxysilylstyrene was carried out in the same manner as in Example 1 except that the use was changed (Sister Example 5.4), and the results are shown in the table. Further, the GPC chart of the polymer obtained in Example 2 is shown in FIG.

[Brief explanation of drawings]

FIG. 1 is a conceptual diagram of an example of an apparatus for carrying out all anionic polymerization in the present invention, and FIGS. 2 and 3 are GPC charts of one combination in the present invention. 1... Flask, 2, 3... Anionic polymerization initiator-filled ampoule, 4.5... Monomer-filled ampoule, 6.
7... Branches! , 8... Vacuum line, 9... Cock,
10...Magnet

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a lower alkyl group. ] A living polymer with repeating units.