JP4288089B2 - (Meth) acrylic acid oligoolefin ester polymer and production method thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel (meth) acrylic acid oligoolefin ester polymer and a method for producing the same. This polymer is excellent in stereoregularity and is expected to be used as an optically active substance.
[0002]
Macromolecules, 22, 1546 (1989) reports that the degree of polymerization of a polymer produced by radical chain polymerization of a terminal-dispersed monodisperse polystyrene-macromonomer depends on the molecular weight of the macromonomer and the charged concentration. In this report, a macromonomer having a repeating number of styrene monomer units larger than 10 is used, and a syndiotactic rich polymer having a comb structure is obtained (see Non-Patent Document 1).
[0003]
In the radical polymerization handbook (NTS Publishing, page 234, (1999)), the stereoregularity of the polymer obtained in radical polymerization of methacrylic acid ester varies depending on the bulk of the ester group. In the case of an ester group having a relatively planar spread such as a methyl group or 1-phenylbenzosperyl group, it is described that a polymer with extremely excellent stereoregularity can be obtained.
[0004]
The inventors of the present invention have reported in Journal of Polymer Science, Polym. Chem., 36, 209 (1998) that a monodispersed polymer having a repeating number of styrene monomer units of about 2 to 10 by highly controlled pyrolysis of polystyrene. It was reported that oligostyrene containing one-end vinylidene group was obtained in high yield (see Non-Patent Document 2).
[0005]
[Non-Patent Document 1]
Macromolecules, 22, 1546 (1989)
[Non-Patent Document 2]
Journal of Polymer Science, Polym. Chem., 36, 209 (1998)
[0006]
[Problems to be solved by the invention]
The above-mentioned one-end vinylidene group-containing oligoolefin can be produced from waste olefin that has been discarded for some reason and has caused environmental problems as an adhering material, etc. Can be converted into a functional group such as a carboxy group or an epoxy group. However, at present, their effective use has not been found.
[0007]
An object of the present invention is to provide a stereoregular (meth) acrylic oligoolefin ester polymer as a use of a monodisperse oligoolefin obtained by highly controlled pyrolysis of polyolefin.
[0008]
The present invention relates to a general formula (1)
[Chemical 3]
(Wherein R represents hydrogen, a methyl group or an ethyl group, R ′ represents hydrogen or a methyl group, and n represents an integer of 3 to 20). It is an acid oligoolefin ester polymer.
[0009]
Another aspect of the present invention is a compound of the general formula (2)
[Formula 4]
(Wherein R, R ′ and n represent the meanings as defined above), and the (meth) acrylic acid is polymerized in a solvent. This is a method for producing an oligoolefin ester polymer.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The (meth) acrylic acid oligoolefin / ester polymer of the present invention is represented by the general formula (1), wherein n represents the number of repeating olefin / monomer units in the formula, and n is a repeating unit of 3-20. A polymer as a unit. For example, (meth) acrylic oligoolefin / ester polymers such as methacrylic acid oligopropylene / ester polymer, methacrylic acid oligoethylene / ester polymer, acrylic acid oligopropylene / ester polymer, acrylic acid oligoethylene / ester polymer, etc. is there.
[0011]
These polymers are insoluble in reaction solvents such as aromatic organic solvents such as benzene, toluene and xylene in the case of, for example, methacrylic acid oligopropylene ester polymers. Moreover, in the DSC measurement of the polymer, the thermal transition peak corresponding to the glass transition point (Tg) does not appear in the polymer that is liquid at normal temperature, but the polymer that is insoluble in the reaction solvent corresponds to the glass transition temperature (Tg). Show a distinct thermal transition peak.
[0012]
These characteristics of the polymer of the present invention indicate that the polymer has a very high stereoregularity.
Since a (meth) acrylic acid ester polymer having high stereoregularity is known to have a helical structure, it is expected to be used as a separation carrier for optically active substances.
[0013]
The polymer of the present invention is obtained by polymerizing the (meth) acrylic oligoolefin ester represented by the general formula (2) in an organic solvent, preferably an aromatic solvent such as benzene, toluene, xylene, etc. It can be manufactured easily.
[0014]
There is no restriction | limiting in particular in a polymerization method, Well-known polymerization methods, such as ion polymerization, such as radical polymerization and anion polymerization, and superposition | polymerization by an organometallic compound, are employable. Preferably, radical polymerization or anionic polymerization is employed.
[0015]
For example, in the case of radical polymerization using azobisisobutyronitrile (AIBN) as a radical initiator, a reaction solvent-insoluble polymer is obtained in a high yield by reacting at room temperature to 80 ° C. for 60 minutes to 25 hours. Can be obtained at In particular, in a reaction at a temperature lower than 60 ° C., a gel-like reaction solvent-insoluble polymer can be obtained without going through the reaction solvent-soluble polymer from the beginning of the reaction.
[0016]
In the present invention, the raw material (meth) acrylic acid oligoolefin ester represented by the general formula (2) is a monodispersed terminal hydroxy group-containing oligoolefin and (meth) acrylic acid or (meth) acrylic acid salt. It can be easily produced by reacting a product with a conventional method.
[0017]
The monodispersed terminal hydroxy group-containing oligoolefin can be produced by oxidizing the vinylidene group of the monodispersed terminal vinylidene group-containing oligoolefin by a conventional method. Terminal vinylidene group containing oligoolefin of ^{monodispersity, The 2 nd International Symposium on Feedstock} Recycling of Plastics & Other Innovative Plastics Recycling Techniques, Ostend, Belgium (September 8-11, 2002) Journal of Polymer Science, Polym. Chem., 36, 209 (1998) and the like, and can be produced in high yield by highly controlled pyrolysis of polyolefin.
[0018]
【Example】
Example 1
Production of (meth) acrylic acid oligopropylene ester Average of double bonds contained per i molecule, wherein n is 3 to 20 in the above general formula and purified by reprecipitation from a highly controlled pyrolysis product of polypropylene Oligopropylene having a number (ft) of about 1.1 was hydroborated and then oxidized with an aqueous sodium hydroxide solution and hydrogen peroxide to prepare terminal hydroxy group-containing oligopropylene (PP-O-OH). Further, it can also be produced by a technique using 9-BBN described in Polymer Bulletin 29, 135-138 (1992) of Sandor Nemes et al.
[0019]
Subsequently, the obtained trimethylamine / dichloromethane solution of PP-O—OH was added dropwise to a dichloromethane solution of methacryloyl chloride or acryloyl chloride at −5 ° C., and the obtained reaction product was purified using preparative GPC. A methacrylic acid oligopropylene ester (PP-O-MC) and an acrylic acid oligopropylene ester (PP-O-AC) were prepared.
The obtained PP-O-MC and PP-O-AC were all confirmed to have the structure of the general formula (2) by IR spectrum, ¹ H-NMR spectrum and ¹³ C-NMR spectrum.
The yields of PP-O-MC and PP-O-AC were both about 70% by weight.
[0020]
Example 2
Polymerization of methacrylic acid oligopropylene ester (PP-O-MC) The above-prepared PP-O-MC together with a radical initiator azobisisobutyronitrile (AIBN) and a reaction solvent benzene is an eggplant flask. Then, after repeating freezing, degassing, and nitrogen substitution, the mixture was sealed, the reaction temperature was set to 80 ° C., and the polymerization was started. The resulting polymer was recovered by reprecipitation or as a precipitate.
[0021]
At the time of recovery, the polymerization solution was in a gel state, and all of the recovered polymer was insoluble in the reaction solvent.
[0022]
The polymer obtained without solvent had a glass transition temperature (Tg) of 41.8, but the glass transition temperature (Tg) was rapidly increased by adding the reaction solvent, and further increased with an increase in the reaction solvent. The tendency was seen.
Table 1 shows reaction conditions and characteristics of the obtained polymer.
[0023]
[Table 1]
[0024]
All the obtained polymers showed adhesiveness. In particular, the polymer of Sample No. 4 showed adhesion to plastics (PS, PP, PE, PMMA, etc.), metals, glass, bare skin, clothing and other objects.
【The invention's effect】
The present invention provides a novel (meth) acrylic acid oligoolefin ester polymer having high stereoregularity as shown in the above examples. Since this polymer has a ribbon structure, it can be used as a separation carrier for optically active substances.
Moreover, since the oligoolefin obtained by highly controlled pyrolysis of a waste polymer can be used as the manufacturing raw material, it helps to solve an environmental problem.
[Brief description of the drawings]
1 shows the ¹ H-NMR spectrum of PP-O-MC synthesized in Example 1. FIG.
2 shows a ¹ H-NMR spectrum of PP-O-AC synthesized in Example 1. FIG.
3 shows a polymerization curve of PP-O-MC in the case of Example 2. FIG.

Claims (2)

The following general formula (1)
(Wherein R represents a methyl group, R ′ represents hydrogen or a methyl group, and n represents an integer of 3 to 20) (meth) acrylic oligoolefin ester having a monomer unit as a repeating unit Polymer. The following general formula (2)
(In the formula, R represents a methyl group, R 'represents hydrogen or a methyl group, and n represents an integer of 3 to 20), and a (meth) acrylic oligoolefin ester represented by polymerization is polymerized in an organic solvent. The method for producing a (meth) acrylic oligoolefin ester polymer according to claim 1, wherein: