JP2002293833A - Copolymer of oligostyrene (meth)acrylate and methyl (meth)acrylate and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel copolymer of an oligostyrene (meth)acrylate and a methyl (meth)acrylate. SOLUTION: The copolymerization of the oligostyrene (meth)acrylate and the methyl (meth)acrylate produces the novel copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel copolymer of oligostyrene (meth) acrylate and methyl (meth) acrylate and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, copolymers of methyl (meth) acrylate and styrene (meth) acrylate have been known. Not known at all.

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel copolymer of oligostyrene (meth) acrylate and methyl (meth) acrylate and a method for producing the same.

[0004]

SUMMARY OF THE INVENTION The present invention provides a novel monomer, a novel monomer developed by the present inventor, by radical polymerization of (meth) acrylic acid oligostyrene ester with methyl (meth) acrylate. It has been found that a (meth) acrylic acid oligostyrene ester and a methyl (meth) acrylate copolymer can be obtained, and the present invention has been completed.

That is, the copolymer according to the present invention is a copolymer having a number average molecular weight of 1,000 to 500,000 and comprising a repeating structural unit represented by the following general formulas (1) and (2).

Embedded image In the formula, R represents hydrogen or a methyl group, and n represents 2 to 10
Represents an integer.

Embedded image In the formula, R ¹ represents hydrogen or a methyl group.

Further, the copolymer according to the present invention wherein R ¹ is a methyl group R, and (2) of the general formula (1),
It is characterized in that n is 2 or 3.

Further, a method of producing a copolymer of oligostyrene (meth) acrylate and methyl (meth) acrylate according to the present invention is represented by the following general formula (3):

Embedded image (Wherein, R represents hydrogen or a methyl group, and n represents 2 to 1)
(Representing an integer of 0) (meth) acrylic acid oligostyrene ester represented by

Embedded image (Wherein R ¹ represents hydrogen or a methyl group), and is characterized by being polymerized in an organic solvent with methyl (meth) acrylate.

Further, the present invention is characterized in that the polymerization reaction is radical polymerization.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. (Meth) acrylic acid oligostyrene ester
(T) Copolymer with methyl acrylate The copolymer according to the present invention has a repeating structural unit
It is characterized by being represented by the general formulas (1) and (2). The molecular weight is not particularly limited, and can be obtained in a wide range by controlling the polymerization reaction described below. Molecular weight (Mn, Mw) and molecular weight distribution (Mw
/ Mn) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard. The preferred molecular weight in the present invention is 10,000 to 10
0000.

[0010] The abundance ratio (molar ratio) of each repeating structure in the copolymer is not particularly limited, and can be obtained in a wide range by the production method described below. In the present invention, the ratio of the repeating structure represented by the general formula (1) to the repeating structure represented by the general formula (2) is 0.1: 0.9.
It is preferably in the range of 9 to 0.99 to 0.1, and more preferably in the range of 1:99 to 99: 1.

Tables 1 and 2 show typical copolymers of the invention for the mole fraction of charged methyl methacrylic acid (MMA), Mw, Mw / Mn, yield and MMA units of the resulting copolymer. Are summarized. In addition, Table 3 summarizes the molar fraction of charged MMA and the molar fraction of MMA units in the obtained copolymer when A-SD is used.

[0012]

[Table 1]

Here, ^{a) The} molecular weight was measured by GPC using polystyrene as a standard. ^b) The molar fraction of MMA units in the copolymer was determined by ¹ HNMR in deuterated chloroform. [Polymer concentration] = 0.18 mol / L, [AIB]
N] = 0.0036 mol / L, at 60 ° C. for 3 hours.

[0014]

[Table 2]

Here, ^{a) the} molecular weight was measured by GPC using polystyrene as a standard. ^b) The molar fraction of MMA units was determined by ¹ H NMR in chloroform- ^d . In the polymerization reaction, [monomer concentration] = 1.87 mol / L, [AIBN] = 0.02 in toluene using a glass ampoule substituted with nitrogen.
The reaction was performed under the conditions of mol / L, 60 ° C. and 3 hours.

[0016]

[Table 3]

Here, the molar fraction of MMA units was determined by ¹ H NMR in chloroform-d. In the polymerization reaction, [monomer concentration] = 0.18 mol / L, [AIBN] = 0.003 m in toluene using a glass ampoule substituted with nitrogen.
ol / L, 60 ° C., 3 hours.

Further, there is no particular limitation on the bonding mode of the repeating structural units of the copolymer of the present invention, and it includes from a completely random copolymer to a completely block copolymer, but preferably has a partially blockable property. It is a random copolymer. Blocking properties are, for example, ¹ H NMR, ¹³ C NM
From the microstructure of R, it can be estimated whether the copolymer is a random copolymer or a block copolymer. FIGS. 1 and 2 show the copolymer of the present invention (MMA 70% molar composition, n =
2) and polystyrene distyrene methacrylate (P
¹ H NMR of a blend of M-SD) and polymethyl methacrylate (PMMA) is shown. It is apparent that the copolymer of the present invention is blockable.

In order to estimate the blocking property, Fineman-
R value measurement by the Ross method is possible. Specifically, FIG.
As an example, the r value is larger than 1 as shown by the mole fraction of MMA in the charged amount and the mole fraction of MMA in the copolymer, and it can be seen that the blockability is greater than random.

One of the thermal properties of the copolymer of the present invention is a glass transition temperature (Tg) measured by DSC. As an example is shown in FIG. 4, as the molar ratio of two repeating structural units in the copolymer approaches 1: 1, Tg decreases, and at 1: 1 it can reach about 40 ° C. Understand. This decrease in Tg is due to the Tg of PMMA.
Is about 130 ° C. and the Tg of polystyrene dimethacrylate (PM-SD) is about 70 ° C., which is characteristic of the copolymer of the present invention.

Production Method The copolymer according to the present invention is a methyl (meth) acrylate represented by the general formula (4) using a monomer of the oligostyrene (meth) acrylate represented by the general formula (3) as a monomer. And polymerized together. Here, the synthesis of the (meth) acrylic acid oligostyrene ester is not particularly limited, but can be easily obtained by the method described below.

The pyrolysis method developed by the present inventors (Journal
of Polymer Science, Polym. Chem., 36, 209 (1998))
As a result, a monodisperse oligostyrene containing one terminal vinylidene group having a repeating number of styrene monomer units of about 2 to 10 is obtained. Monodisperse oligostyrene having a terminal hydroxy group can be obtained by oxidizing the vinylidene group of the monodisperse oligostyrene having a terminal vinylidene group by a conventional method.

Further, the monodisperse oligostyrene having a terminal hydroxy group obtained here is reacted with (meth) acrylic acid or (meth) acrylic acid chloride by a conventional method to obtain a compound represented by the general formula (3). (Meth) acrylic acid oligostyrene ester can be easily produced. Commercially available methyl (meth) acrylate can be preferably used.

The copolymer of the present invention can be easily produced by polymerizing the monomer in an organic solvent, preferably an aromatic solvent such as benzene, toluene and xylene. The polymerization method is not particularly limited, and a known polymerization method such as ionic polymerization such as radical polymerization or anionic polymerization, or polymerization using an organometallic 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, the reaction solvent insoluble polymer is reacted at a temperature of room temperature to 80 ° C. for 60 minutes to 25 hours. It can be obtained in high yield.

[0026]

Embodiment 1Oligostyrene (meth) acrylate
Production of ester Isolated and purified from highly controlled pyrolysis products of polystyrene
A styrene dimer wherein n in the general formula is 2;
Each of the styrene trimers having
Sodium hydroxide solution and hydrogen peroxide
Styrene dimer containing terminal hydroxy group
(SD-OH) and Styrene Containing Terminal Hydroxy Group
A rimer (ST-OH) was prepared. Then, the obtained S
D-OH or ST-OH trimethylamine / dichloro
Methane solution or acryloyl chloride
To a solution of Royl in dichloromethane was added dropwise at -5 ° C.
Chloroform the reaction product obtained using a silica gel column.
Purified with a mixed solvent of form / hexane = 2/1 and meta
Styrene dimer ester (M-SD),
Styrene trimer ester (M-ST),
Acrylic acid styrene dimer ester (A-SD)
And styrene acrylate trimer ester (AS
T) was prepared. Obtained M-SD, M-ST, AS
D and A-ST are IR spectra, ¹H-NMR
Vector and¹³According to the C-NMR spectrum,
Was also confirmed to have the structure of the general formula (2). M
The yields of -SD, M-ST, A-SD and A-ST are:
All were about 70% by weight.

Example 2 Styrene methacrylate dimer
・ Ester (M-SD) and methyl methacrylate (MM
A) M-SD and MM prepared as shown in Tables 1 and 2
A was charged into a polymerization tube at various charging ratios together with azobisisobutyronitrile (AIBN) as a radical initiator and benzene as a reaction solvent, followed by repeated freezing, degassing, and nitrogen substitution, and then sealing the tube. Was set to 60 ° C. to initiate polymerization, and the produced polymer was recovered by reprecipitation or as a precipitate. The reaction conditions and the characteristics of the obtained polymer are shown in Tables 1 and 2.

Example 3 Styrene acrylate dimer
Ester (A-SD) and methyl methacrylate (MMA)
Copolymerization of M-SD and MMA prepared above at various charging ratios,
Radical initiator azobisisobutyronitrile (AIB)
N) and benzene as a reaction solvent were charged into a polymerization tube,
After repeated freezing, degassing, and nitrogen substitution, the tube was sealed, the reaction temperature was set to 60 ° C., and polymerization was started, and the produced polymer was recovered as a reprecipitate. The reaction conditions and the properties of the obtained polymer are shown together with other polymers in Tables 3 and 4 (DS
(Tg determined by C and number average molecular weight determined by GPC). FIG. 5 shows PMMA, PA-SD and a copolymer of MMA and A-SD (preparation composition ratio MMA:
The ¹ HNMR spectrum of A-SD = 8: 2) is shown. Similarly, FIG. 6 is a plot of the mole fraction of MMA during the preparation of the copolymer in the radical copolymerization of A-SD and MMA, and the mole fraction of MMA units in the copolymer (copolymer composition curve). ).

[0029]

[Table 4]

[0030]

The present invention provides a novel oligostyrene (meth) acrylate and a methyl (meth) acrylate by using a copolymer of an oligostyrene (meth) acrylate and a methyl (meth) acrylate. Can be obtained.

[Brief description of the drawings]

FIG. 1 is a ¹ HNMR spectrum of a copolymer of the present invention having a charged composition ratio of MMA: M-SD = 7: 3.

FIG. 2: ¹ HNM of a blend of PMMA and PM-SD
R spectrum.

FIG. 3 is a plot of the molar fraction of MMA during the preparation of the copolymer in the radical copolymerization of M-SD and MMA, and the molar fraction of MMA units in the copolymer (copolymer composition curve).
Where (a) was measured in benzene and (b) was measured in toluene.

FIG. 4 is DSC data of a copolymer of MMA and M-SD.

FIG. 5: PMMA, PA-SD and a copolymer of MMA and A-SD (prepared composition ratio MMA: A-SD = 8: 2)
¹ HNMR spectrum of

FIG. 6 is a plot (copolymer composition curve) of the mole fraction of MMA during the preparation of the copolymer in the radical copolymerization of A-SD and MMA, and the mole fraction of MMA units in the copolymer.

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Claims (4)

[Claims] 1. A number average molecular weight of 1,000 to 50,000 comprising a repeating structural unit represented by the following general formulas (1) and (2):
0 copolymer. Embedded image In the formula, R represents hydrogen or a methyl group, and n represents 2 to 10
Represents an integer. Embedded image In the formula, R ¹ represents hydrogen or a methyl group. 2. R in the general formula (1) and R in (2)
The polymer according to claim 1, wherein ¹ is a methyl group and n is 2 or 3. 3. The following general formula (3): (Wherein, R represents hydrogen or a methyl group, and n represents 2 to 1)
(Meth) acrylic acid oligostyrene ester represented by the formula: (Meth) according to claim 1, wherein methyl (meth) acrylate represented by the formula (wherein R ¹ represents hydrogen or a methyl group) is polymerized in an organic solvent.
A method for producing an oligostyrene acrylate / ester polymer. 4. The method according to claim 3, wherein the polymerization reaction is a radical polymerization.
The manufacturing method as described.