JP2002080532A - Oligostyrene (meth)acrylate polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new stereoregular oligostyrene (meth)acrylate polymer for the use of a singly dispersible oligostyrene obtained by the highly controlled thermal decomposition of polystyrene, and to produce a method for producing the same. SOLUTION: This oligostyrene (meth)acrylate polymer containing monomer units represented by formula (1) [R is H or methyl; (n) is an integer of 2 to 10] as repeating units is provided. The polymer has high stereoregularity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel oligostyrene (meth) acrylate / styrene polymer and a method for producing the same. This polymer has excellent stereoregularity and is expected to be used as an optically active substance.

Macromolecules, 22, 1546 (1989) reported that the degree of polymerization of a polymer formed by radical chain polymerization of a monodisperse polystyrene macromonomer of a terminal methacrylate type depends on the molecular weight and the charged concentration of the macromonomer. ing. In this report, a macromonomer having a repeating number of styrene monomer units of more than 10 was used, and a syndiotactic rich polymer having a comb structure was obtained.

[0003] In a radical polymerization handbook (NTS Publishing, p. 234, (1999)), in the radical polymerization of methacrylic acid ester, the stereoregularity of the obtained polymer is changed by the bulkiness of the ester group. For example, it is described that in the case of an ester group having a relatively planar spread such as a triphenylmethyl group or a 1-phenylbenzosperyl group, a polymer having extremely excellent stereoregularity is obtained.

[0004] The present inventors have disclosed the Journal of Polymer Scien.
According to ce, Polym. Chem., 36, 209 (1998), polystyrene having a high degree of monodispersity and a monodisperse vinylidene group-containing oligostyrene having a repeating number of styrene monomer units of about 2 to 10 was obtained by highly controlled pyrolysis of polystyrene. It was reported that it was obtained in yield.

[0005]

The above-mentioned oligostyrene containing a vinylidene group at one end is discarded unused for some reason, and can be produced from waste polystyrene, which poses an environmental problem as a floating product. Also, the terminal vinylidene group can be converted into a functional group such as a hydroxy group, a carboxy group, an epoxy group, and the like. However, at the present time, their effective use has not been found.

The present invention relates to the use of monodisperse oligostyrene obtained by highly controlled pyrolysis of polystyrene.
An object of the present invention is to provide a stereoregular (meth) acrylate oligostyrene ester polymer.

[0007] The present inventors have found that when radical polymerization of (meth) acrylic acid styrene dimer ester or (meth) acrylic acid styrene trimer ester is carried out by radical polymerization, the reaction behavior differs from that of the radical polymerization of the above-mentioned polystyrene methacrylate ester. The fact that the obtained polymer has a different structure was obtained, and the present invention was completed.

The present invention relates to a compound represented by the general formula (1):

Embedded image (Wherein, R represents hydrogen or a methyl group, and n represents 2 to 1)
(Representing an integer of 0) as a repeating unit.

Another aspect of the present invention provides a compound represented by the general formula (2):

Embedded image (Wherein, R and n represent the same meaning as defined above), wherein the (meth) acrylic acid oligostyrene ester is polymerized in a solvent. This is a method for producing an ester polymer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acrylic acid oligostyrene ester polymer of the present invention is represented by the above general formula (1), wherein n represents a number of repeating styrene monomer units in the formula, wherein n is 2 to 2. It is a polymer having a repeating unit of 10, preferably 2 or 3, monomer units. For example, methacrylic acid styrene dimer / ester polymer, methacrylic acid styrene trimer / ester polymer, acrylate styrene dimer / ester polymer, styrene acrylate trimer / ester polymer, etc. is there.

When these polymers are used up to a certain molecular weight, for example, in the case of styrene dimer methacrylate / ester polymer, the weight average molecular weight (Mw) is up to about 55,000, a reaction solvent such as an aromatic solvent such as benzene, toluene and xylene. Polymers that are soluble in organic solvents but have a molecular weight above that are insoluble in the reaction solvent. Further, as shown in the DSC curve of the polymer in FIG. 2, a polymer having a relatively small weight average molecular weight (Mw) does not show a heat transition peak corresponding to a glass transition point (Tg), Average molecular weight (M
As w) increases, a thermal transition peak corresponding to the glass transition temperature (Tg) appears, and a polymer insoluble in the reaction solvent shows a clear thermal transition peak corresponding to the glass transition temperature (Tg).

These characteristics of the polymer of the present invention indicate that the polymer has a very high stereoregularity. Since it is known that a (meth) acrylate polymer having a high stereoregularity has a helical structure, it is expected to be used as a carrier for separating optically active substances.

The polymer of the present invention comprises an oligostyrene (meth) acrylate represented by the general formula (2):
It can be easily produced by polymerizing in an organic solvent, preferably an aromatic solvent such as benzene, toluene and xylene.

The polymerization method is not particularly limited, and known polymerization methods such as ionic polymerization such as radical polymerization and anionic polymerization, and polymerization with an organic metal compound can be employed.
Preferably, radical polymerization or anionic polymerization is employed.

For example, in the case of radical polymerization using azobisisobutyronitrile (AIBN) as a radical initiator, a reaction solvent insoluble polymer is obtained by reacting at room temperature to 80 ° C. for 60 minutes to 25 hours. It can be obtained in high yield. Particularly, in a reaction at a temperature lower than 60 ° C., a gel-like reaction solvent-insoluble polymer can be obtained without passing through a reaction solvent-soluble polymer from the beginning of the reaction.

In the present invention, the raw material oligostyrene (meth) acrylate represented by the general formula (2) may be a monodisperse oligostyrene having a terminal hydroxy group and (meth) acrylic acid or (meth) acrylic acid. It can be easily produced by reacting with acrylic acid chloride by a conventional method.

The above monodisperse oligostyrene having a terminal hydroxy group can be produced by oxidizing the vinylidene group of the oligostyrene having a monodisperse terminal vinylidene group by a conventional method. Monodisperse terminal vinylidene group-containing oligostyrenes are described in the Journal of Polymer Sci.
, Polym. Chem., 36, 209 (1998), and can be produced in high yield by highly controlled pyrolysis of polystyrene.

[0018]

EXAMPLES Example 1 Oligostyre (meth) acrylate
A styrene dimer wherein n is 2 in the above general formula isolated and purified from a highly controlled pyrolysis product of polystyrene;
Is hydroborated, and then oxidized using an aqueous solution of sodium hydroxide and hydrogen peroxide to form a terminal hydroxy group-containing styrene dimer (SD-OH) and a terminal hydroxy group-containing styrene trimer (ST- OH) was prepared.

Next, the obtained SD-OH or ST-
OH trimethylamine / dichloromethane solution
Methacryloyl or acryloyl chloride dichlorometh
The reaction product was added dropwise at −5 ° C.
Using a silica gel column, chloroform / hexane = 2
/ 1 purified with a mixed solvent and styrene methacrylate
Mer ester (M-SD), styrene methacrylate
Rimmer ester (M-ST), styrene acrylate
Immer ester (A-SD) and acrylic acid styrene
A trimer ester (A-ST) was prepared. Obtained
M-SD, M-ST, A-SD and A-ST
R spectrum, ¹H-NMR spectrum and¹³CN
According to the MR spectrum, all of the structures of the general formula (2)
It was confirmed to have. M-SD, M-ST, A-
The yield of both SD and A-ST was about 70% by weight.
there were.

Example 2 Styrene methacrylate dimer
Polymerization of ester (M-SD) The above-prepared M-SD was charged into a polymerization tube together with azobisisobutyronitrile (AIBN) as a radical initiator and benzene as a reaction solvent, and repeated freezing, degassing, and nitrogen substitution. After that, the tube was sealed and the polymerization was started by setting the reaction temperature to two conditions of 60 ° C. and 80 ° C., and the produced polymer was recovered by reprecipitation or as a precipitate.

When the reaction temperature is 80 ° C., about 45
No polymer formation was observed for minutes (Sample Nos. 1 and 2). Thereafter, the polymerization rapidly progressed, and after 60 minutes from the start of the reaction, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the resulting polymer became 11,000 and its distribution (Mw / Mn) became almost constant at 2, indicating that the benzene-soluble polymer The polymer (Sample No. 3) was recovered. After a further 90 minutes, the weight average molecular weight (Mw) is 12,000 and its distribution (Mw
/ Mn) was almost constant at 2.3, and a benzene-soluble polymer (sample No. 4) was recovered.

As a result of continued polymerization, the weight-average molecular weight and its distribution began to rapidly increase again approximately 120 minutes after the start of the reaction (Sample No. 5), after which all of the polymer was insoluble in benzene. Precipitated (Sample No. 6
And 7). Table 1 shows the reaction conditions and the properties of the obtained polymer.

[0023]

[Table 1]

On the other hand, when the reaction temperature is 60 ° C., the polymerization proceeds rapidly after a certain start-up period after the start of the reaction as in the case of the reaction temperature of 80 ° C. Was precipitated as an insoluble material. FIG. 1 shows the relationship between the reaction time and the yield.

FIG. 2 shows the DSC curves of the solvent-soluble polymer of Sample No. 3 and the benzene-insoluble polymer (Sample No. 7) obtained above. As shown in FIG. 2, a solvent-soluble polymer having a weight average molecular weight (Mw) of 11,000 does not show a heat transition peak corresponding to a glass transition point (Tg) within the indicated temperature range, but a solvent-insoluble polymer. Shows a thermal transition peak corresponding to a glass transition point (Tg) around 65 ° C. FIG. 3 shows the ¹ H-NMR spectrum of the obtained solvent-insoluble polymer.

Example 3 Styrene methacrylate trimer
Polymerization of ester (M-ST) The styrene methacrylate trimer ester (M-ST) synthesized in Example 1 was used in place of the styrene methacrylate dimer ester (M-SD) in Example 2, and Polymerization was carried out under the same conditions as in Example 2. In this polymerization reaction, the same tendency as in the polymerization of M-SD in Example 2 was shown. FIG. 4 shows the ¹ H-NMR spectrum of the obtained solvent-insoluble polymer.

Example 4 Styrene acrylate dimer
Polymerization of Ester (A-SD) Polymerization under the same conditions as in Example 2 except that styrene dimer acrylate (A-SD) was used instead of styrene dimer methacrylate (M-SD) in Example 2. I let it. Also in this polymerization reaction, polymerization is started after a run-up period, and after a relatively monodispersed polymer dissolved in the reaction solvent is obtained, the average molecular weight increases and the polydispersity of the molecular weight distribution occurs. The reaction solution became cloudy and showed the same tendency as in Example 2. The reaction conditions and the characteristics of the polymer are shown in Table 2, and the ¹ H-NMR spectrum of a typical polymer is shown in FIG.

[0028]

[Table 2]

Example 5 Styrene acrylate trimer
Polymerization of Ester (A-ST) Acrylic acid styrene dimer ester (A-ST) was used in place of styrene methacrylate dimer ester (M-SD) in Example 2 and polymerized under the same conditions as in Example 2. I let it. In this polymerization reaction, the same tendency as in the case of polymerization of M-SD (Example 2) was shown. The characteristics of the reaction conditions and the polymer shown in Table 3, ¹ H typical polymer
FIG. 6 shows the -NMR spectrum.

[0030]

[Table 3]

[0031]

According to the present invention, as shown in the above embodiment,
New (meth) acrylate oligostyrene with high stereoregularity
An ester polymer is provided. Since this polymer has a ribbon structure, it can be used as a carrier for separating optically active substances. In addition, oligostyrene obtained by highly controlled thermal decomposition of waste polymer can be used as a raw material for the production, which is useful for solving environmental problems.

[Brief description of the drawings]

FIG. 1 shows M- in Example 2 at a reaction temperature of 60 ° C.
ST polymerization curve.

FIG. 2 is a DSC diagram of an M-SD polymer synthesized in Example 2.
curve.

FIG. 3 shows ¹ H- of the M-SD polymer synthesized in Example 2.
NMR spectrum.

FIG. 4 shows ¹ H- of the M-ST polymer synthesized in Example 3.
NMR spectrum.

FIG. 5 shows ¹ H- of the A-SD polymer synthesized in Example 4.
NMR spectrum.

FIG. 6 shows ¹ H- of the A-ST polymer synthesized in Example 5.
NMR spectrum.

Claims (10)

[Claims] 1. The following general formula (1): (Wherein, R represents hydrogen or a methyl group, and n represents 2 to 1)
(Representing an integer of 0) as a repeating unit. 2. In the general formula (1), R is a methyl group;
Is a polymer of 2 or 3. 3. In the general formula (1), R is hydrogen and n is 2
Or the polymer of claim 1. 4. The polymer according to claim 1, which is soluble in a reaction solvent. 5. The polymer according to claim 1, which is insoluble in a reaction solvent. 6. The polymer according to claim 4, wherein the DSC curve does not show a thermal transition peak corresponding to a glass transition temperature (Tg). 7. The polymer according to claim 5, which has a distinct thermal transition peak corresponding to a glass transition temperature (Tg) in a DSC curve. 8. The following general formula (2): (Wherein, R represents hydrogen or a methyl group, and n represents 2 to 1)
The method for producing a (meth) acrylic acid oligostyrene ester polymer according to claim 1, wherein the (meth) acrylic acid oligostyrene ester represented by the formula (1) is polymerized in an organic solvent. . 9. The polymerization reaction according to claim 8, wherein the polymerization reaction is radical polymerization.
The manufacturing method as described. 10. The method according to claim 8, wherein the polymerization reaction is an anionic polymerization.