JP2016204455A - Method for producing (meth)acrylic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a (meth)acrylic polymer which, in an atom transfer radical polymerization method using a transition metal compound as a catalyst, provides a polymerization rate of 90% or more, shortens the reaction time, and provides a polymer having a narrow molecular weight distribution, even when polymerizing (meth)acrylic monomers, the ester portion of which has a carbon number of 8 to 24.SOLUTION: Provided is a method for producing a (meth)acrylic polymer which, in an atom transfer radical polymerization method using a transition metal compound as a catalyst, adds a quaternary ammonium salt in an amount of 100 mol% or less relative to the transition metal catalyst in a process of polymerizing (meth)acrylic monomers, the ester portion of which has a carbon number of 8 to 24.EFFECT: According to the polymerization method, the polymerization rate becomes 85 to 100% and the molecular weight distribution becomes 1.25 or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a (meth) acrylic polymer and a polymer. More specifically, the present invention relates to a method for producing a (meth) acrylic polymer containing a (meth) acrylic monomer having an ester moiety having 8 to 24 carbon atoms, and a polymer.

  As a method for producing a (meth) acrylic polymer, a living radical polymerization method (LRP) capable of controlling a polymer structure is a technique that has been known for a long time. Among them, atom transfer radical polymerization (ATRP) using a transition metal complex consisting of a transition metal or a transition metal compound and a polydentate amine ligand as a polymerization catalyst is a surface modification of a polymer or a modification of nanoparticles. Various application developments are made possible and have attracted a great deal of attention (Patent Documents 1 and 2). Many production methods utilizing the ATRP method have been reported, and it can be said that the polymerization method is excellent in practicality (Patent Documents 3 and 4).

  Have reported that the activity of the catalyst is enhanced by adding a quaternary ammonium salt having a bulky organic counter ion to a transition metal complex such as iron (Fe) or chromium (Cr). . However, the polymerization time was as long as about 8 hours to 24 hours, and the polymerization rate was about 5 to 70% (Patent Document 5).

  In addition, it has been reported that, in the polymerization of a methacrylic polymer and a block copolymer of an acrylic polymer, a quaternary ammonium salt can be used as a catalyst in order to increase the activity of the copper (Cu) complex. However, it was a (meth) acrylic monomer having 1 to 4 carbon atoms in the ester moiety such as methyl methacrylate (MMA), butyl acrylate (BA), and t-butyl acrylate (Patent Document 6). ). On the other hand, an example of polymerization of dodecyl methacrylate (LMA) in which the ester part has 12 carbon atoms using a quaternary ammonium salt in a polymerization method not using ATRP but a transition metal has been reported (Patent Document 7). ).

WO96 / 30421 WO97 / 18247 JP 2005-307220 A JP 2010-126680 A Special table 2002-540234 JP2007-161877 JP2011-74325A

  In the primary transfer radical polymerization method using a transition metal compound as a catalyst, when a (meth) acrylic monomer having 8 to 24 carbon atoms in the ester moiety is polymerized, the reaction stops at a polymerization rate of 70 to 85%. There was a problem. Further, since the polymerization rate is very slow, the polymerization time is long and the molecular weight distribution is widened. In such a case, it is conceivable to add an additional transition metal catalyst. However, if the amount of the transition metal is increased, the efficiency in the purification process is lowered, and it is easily estimated that the production efficiency deteriorates.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

  That is, the present invention adds a quaternary ammonium salt in the process of polymerizing a (meth) acrylic monomer having 8 to 24 carbon atoms in the ester transfer radical polymerization method using a transition metal compound as a catalyst. The present invention relates to a method for producing a (meth) acrylic polymer.

  As a preferred embodiment, the present invention relates to a method for producing a (meth) acrylic polymer comprising 1 to 100% by weight of a (meth) acrylic monomer having an ester part having 8 to 24 carbon atoms.

  A preferred embodiment relates to a method for producing a (meth) acrylic polymer, wherein the quaternary ammonium salt is tetrabutylammonium bromide.

  As a preferred embodiment, the present invention relates to a method for producing a (meth) acrylic polymer, wherein tetrabutylammonium bromide is contained in an amount of 100 mol% or less based on the transition metal catalyst.

  As a preferred embodiment, the present invention relates to a method for producing a (meth) acrylic polymer, wherein the polymerization rate of the (meth) acrylic polymer is 85 to 100%.

  As a preferred embodiment, the present invention relates to a method for producing a (meth) acrylic polymer, wherein the molecular weight distribution is 1.25 or less.

  Furthermore, this invention relates to the (meth) acrylic-type polymer obtained by the manufacturing method in any one of said.

  According to the present invention, by adding a quaternary ammonium salt, the polymerization rate is improved to 90% or more, the polymerization time is shortened, and a polymer having a narrow molecular weight distribution is obtained.

  Specific examples of the present invention are shown below, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “ppm” represent “parts by weight” and “weight percentage”, respectively.

  In the primitive transfer radical polymerization method using a transition metal compound as a catalyst, the present invention adds a quaternary ammonium salt in the process of polymerizing a (meth) acrylic monomer having an ester moiety having 8 to 24 carbon atoms. This is a method for producing a (meth) acrylic polymer.

<Primary transfer radical polymerization>
The present invention relates to a method for primitive transfer radical polymerization of a (meth) acrylic monomer using a transition metal complex comprising a transition metal or a transition metal compound and a polydentate amine ligand as a catalyst.

  Atom transfer radical polymerization using a transition metal complex as a catalyst is called Atom Transfer Radical Polymerization: ATRP (J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules. 1995, 28, 1721) and has a narrow molecular weight. Since a polymer having a distribution and a high chain end functional group ratio can be obtained, various application developments such as polymer surface modification and nanoparticle surface modification are possible. Various transition metals such as iron (Fe), copper (Cu), ruthenium (Ru), nickel (Ni), chromium (Cr) can be used as the transition metal used in ATRP. For example, when copper is used, the reaction mechanism is that a monovalent copper complex reacts with an initiator (organic halide) to form a divalent copper complex with a radical. The radical reacts with the monomer, the divalent copper complex returns to the monovalent copper complex by returning the halogen to the polymerization terminal radical of the monomer, and the polymerization proceeds by such an equilibrium reaction.

<(Meth) acrylic monomer (monomer)>
In the (meth) acrylic polymer of the present invention, the (meth) acrylic monomer having an ester part having 8 to 24 carbon atoms is contained in an amount of 1 to 100% by weight from the viewpoint of obtaining a low-polarity polymer. It is preferable.

  The (meth) acrylic monomer having 8 to 24 carbon atoms in the ester portion is preferably a (meth) acrylic acid ester monomer. Specifically, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, toluyl (meth) acrylate, (Meth) acrylic acid real allyl, (meth) acrylic acid-2-decyltetradecanyl, (meth) acrylic acid ethylene glycol, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid-2-perfluorohexylethyl, (Meth) acrylic acid-2-perfluorodecylethyl acrylate, (meth) acrylic acid 2-perfluorohexadecylethyl and the like. Two or more of these may be used in combination.

<Initiator>
The organic halide is a polymerization initiator and is an organic halide having a highly reactive carbon-halogen bond. For example, a carbonyl compound having a halogen at the α-position, a compound having a halogen at the benzyl-position, or a sulfonyl halide compound is exemplified. Specifically, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C ( _{H) (X) CH 3,} C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4,
(Wherein R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine). X is preferably highly reactive bromine or iodine.

  An organic halide having two or more starting points or a sulfonyl halide compound may be used as an initiator.

  It is a feature of living radical polymerization that the desired polymer molecular weight can be set by adjusting the ratio of the monomer and the initiator amount.

<Polymerization catalyst>
As the polymerization catalyst, a copper complex composed of metallic copper or a copper compound and a ligand is used. Examples of copper compounds include chlorides, bromides, iodides, cyanides, oxides, hydroxides, acetates, sulfates and nitrates, but are not limited thereto.

  The copper atom can have a valence of 0, 1, or 2 depending on the electronic state, but the valence is not limited.

  The weight of the copper atom is preferably 500 to 10,000 ppm with respect to the total charged weight of the (meth) acrylic monomer, and the purification step is facilitated if the amount of copper can be reduced. 2000 ppm is particularly preferred.

<Quaternary ammonium salt>
The quaternary ammonium salt to be added is tetrabutylammonium halide such as tetrabutylammonium chloride, tetrabutylammonium bromide or tetrabutylammonium iodide. Tetrabutylphosphonium halides such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide. And tetraphenylphosphonium halides such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide. By adding a quaternary ammonium salt, the catalytic activity is increased and the catalyst cycle is fast, so the reaction rate of the main reaction is increased and the polymerization efficiency is improved. The quaternary ammonium salt to be used is preferably tetrabutylammonium chloride of tetrabutylammonium halide, tetrabutylammonium bromide, tetrabutylammonium iodide, and particularly preferably activates the catalytic activity of the transition metal to efficiently It is tetrabutylammonium bromide from the viewpoint of being able to rotate the catalytic cycle of ATRP. Further, the halogen portion is preferably unified with the halogen of the catalyst to be used, but is not limited, and a different type of halogen is also possible.

  Further, the larger the amount used, the more the refining cost is applied, so it is necessary to keep it to the minimum necessary. The amount is preferably 100 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less with respect to the catalyst.

<Multidental amine>
Although the polydentate amine used as a ligand is illustrated below, it is not restricted to these.

Bidentate polydentate amines: 2,2-bipyridine, 4,4′-di- (5-nonyl) -2,2′-bipyridine, N- (n-propyl) pyridylmethanimine, N- (n -Octyl) pyridylmethanimine Tridentate polydentate amines: N, N, N ', N ", N" -pentamethyldiethylenetriamine, N-propyl-N, N-di (2-pyridylmethyl) amine Tetradentate polydentate amine: hexamethyltris (2-aminoethyl) amine, N, N-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine, 2,5,9,12-tetramethyl -2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4,11-dimethyl-1,4,8,11- Tetraazabicyclohexadecane, N ', N ″ -dimethyl-N ′, N ″ -bis ((pyridin-2-yl) methyl) ethane-1,2-diamine, tris [(2-pyridyl) methyl] amine, 2,5,8 , 12-tetramethyl-2,5,8,12-tetraazatetradecane pentadentate polydentate amine: N, N, N ′, N ″, N ′ ″, N ″ ″, N ′ '''-Heptamethyltetraethylenetetramine Hexadentate polydentate amine: N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine Polyamine: Polyethyleneimine

  In addition, the polydentate amine is involved in the polymerization termination reaction due to chain transfer, and it imposes a load on the purification cost. Therefore, it is necessary to keep it to the minimum necessary, preferably 120 mol% or less, more preferably 110 mol% or less with respect to the copper atom. Preferably, 100 mol% or less is particularly preferable.

<Solvent>
The solvent is not particularly limited, but a combination of a polar solvent capable of dissolving the copper complex and a nonpolar solvent capable of dissolving the polymer is preferable, and the ratio is preferably 2: 1. 5 to 100 parts are preferable with respect to the total charge of (meth) acrylate monomer, 5 to 80 parts are more preferable, 5 to 60 parts are more preferable, and the smaller the solvent, the shorter the evaporation step. 5 to 30 parts are particularly preferred.

<Polymerization temperature>
The polymerization temperature is not limited, but is preferably in the range of 20 to 100 ° C., more preferably 30 to 90 ° C., further preferably 40 to 80 ° C., and the higher the temperature, the easier the chain transfer occurs. Is particularly preferred.

<Reaction time>
The polymerization time of the (meth) acrylic polymer obtained by the production method of the present invention is not particularly limited, but is preferably 300 minutes or less, preferably 250 minutes or less, more preferably 210 minutes or less.

<Molecular weight>
The number average molecular weight of the (meth) acrylic polymer obtained by the production method of the present invention is not particularly limited, but is preferably in the range of 500 to 1000000, more preferably in the range of 1000 to 500000, and further in the range of 3000 to 300000. 5,000 to 300,000 is preferable.

<Molecular weight distribution>
The molecular weight distribution of the (meth) acrylic polymer obtained by the production method of the present invention, that is, the ratio of the weight average molecular weight (Mn) and the number average molecular weight (Mw) measured by gel permeation chromatography is 1.55. Preferably, 1.45 is more preferable. In particular, 1.25 or less is preferable. In the GPC measurement of the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

<Conversion rate>
Conversion rate of (meth) acrylic monomer that is a monomer of (meth) acrylic polymer obtained by the production method of the present invention, that is, the number of moles of (meth) acrylic monomer remaining in the reaction system The ratio of the total charged moles of the (meth) acrylic monomer is not particularly limited, but is preferably 75 to 100%, more preferably 80 to 100%, and particularly the physical properties to the remaining monomer. From the viewpoint of influence, 85 to 100% is preferable.

(Measurement method)
The “polymerization rate” was calculated using gas chromatography (GC). However, a polyethylene glycol column (Supelcoux 10; manufactured by Sigma Aldrich) was used as the GC column, and toluene was used as the GC measurement solvent.
“Polymerization rate” was plotted with the reaction time on the horizontal axis and the polymerization rate on the vertical axis, and the slope was taken as the polymerization rate. Hereinafter referred to as Ln.
“Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by standard polystyrene conversion using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used as the GPC measurement solvent with chloroform.

  In the following examples, “functionalization rate (number of (meth) acryloyl groups introduced per molecule of polymer)” was calculated from 1H-NMR analysis and number average molecular weight determined by GPC. Measurement was performed at 23 ° C. using ASX-400 manufactured by Bruker and using deuterated chloroform as a solvent.

Example 1
0.97 parts by weight of CuCl (I) (Cu amount = 6200 ppm) and 0.91 parts by weight (9100 ppm, 94 mol%) of tetrabutylammonium chloride (hereinafter referred to as TBACl) were charged into a separable flask, and nitrogen substitution was performed. Separately nitrogen bubbling dodecyl methacrylate (hereinafter referred to as LMA) 100 parts by weight, acetonitrile 20 parts by weight, toluene 10 parts by weight, initiator p-toluenesulfonyl chloride (hereinafter TS-Cl) 0.94 parts by weight Was placed in a separable flask and stirred at 80 ^° C. under a nitrogen stream. N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (hereinafter, PMDETA) was added to the mixed solution to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 90.3% in 210 minutes from the start of polymerization. Ln was 21.1, the number average molecular weight of the polymer [1] was 24100, and the molecular weight distribution was 1.30.

(Example 2)
CuBr (I) 0.18 parts by weight (Cu content = 1160 ppm) and tetrabutylammonium bromide (hereinafter, TBABr) 0.13 parts by weight (1300 ppm, 94 mol%) were charged into a separable flask, and nitrogen substitution was performed. Separately, 100 parts by weight of dodecyl methacrylate (LMA) subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 1.92 parts by weight of ethyl 2-bromoisobutyrate (hereinafter referred to as EtBriB) as an initiator are separable flasks. And stirred at 80 ^° C. under a nitrogen stream. PMDETA was added to the mixture to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 98.5% within 180 minutes from the start of polymerization. Ln was 29.1, the number average molecular weight of the polymer [2] was 10100, and the molecular weight distribution was 1.19.

Example 3
CuSe (I) 0.18 parts by weight (Cu content = 1160 ppm) and tetrabutylammonium bromide (TBABr) 0.07 parts by weight (700 ppm, 44 mol%) were charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of dodecyl methacrylate (LMA), 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 0.65 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator were charged into a separable flask. The ^mixture was stirred at 80 ^° C. under a nitrogen stream. PMDETA was added to the mixture to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 98.2% in 170 minutes from the start of polymerization. Ln was 33.8, the number average molecular weight of the polymer [3] was 34000, and the molecular weight distribution was 1.24.

Example 4
CuSe (I) 0.18 parts by weight (Cu content = 1160 ppm) and tetrabutylammonium bromide (TBABr) 0.04 parts by weight (400 ppm, 22 mol%) were charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of dodecyl methacrylate (LMA), 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 1.92 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator were charged into a separable flask. The ^mixture was stirred at 80 ^° C. under a nitrogen stream. PMDETA was added to the mixture to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 99.1% in 180 minutes from the start of polymerization. Ln was 31.1, the number average molecular weight of the polymer [4] was 11000, and the molecular weight distribution was 1.23.

(Example 5)
CuSe (I) 0.18 parts by weight (Cu content = 1160 ppm) and tetrabutylammonium bromide (TBABr) 0.04 parts by weight (400 ppm, 22 mol%) were charged into a separable flask and purged with nitrogen. A separable flask was charged with 100 parts by weight of dodecyl methacrylate (LMA) separately subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 0.96 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator. The ^mixture was stirred at 80 ^° C. under a nitrogen stream. PMDETA was added to the mixture to initiate polymerization. PMDETA was added by shot so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 98.7% within 180 minutes from the start of polymerization. Ln was 31.8, the number average molecular weight of the polymer [5] was 12100, and the molecular weight distribution was 1.22.

(Example 6)
CuSe (I) 0.18 parts by weight (Cu content = 1160 ppm) and tetrabutylammonium bromide (TBABr) 0.04 parts by weight (400 ppm, 22 mol%) were charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of 2-ethylhexyl methacrylate (hereinafter referred to as 2-EHM) subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 0.96 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator The mixture was placed in a separable flask and stirred at 80 ^° C. under a nitrogen stream. PMDETA was added to the mixture to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 99.1% in 180 minutes from the start of polymerization. Ln was 28.5, the number average molecular weight of the polymer [6] was 16000, and the molecular weight distribution was 1.25.

(Comparative Example 1)
0.97 parts by weight of CuCl (I) (Cu amount = 6200 ppm) was charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of nitrogen bubbling dodecyl methacrylate (LMA), 20 parts by weight of acetonitrile, 10 parts by weight of toluene and 0.94 parts by weight of p-toluenesulfonyl chloride (TS-Cl) as an initiator were added to a separable flask. The mixture was stirred and stirred at 80 ^° C. under a nitrogen stream. To the mixture, pentamethyldiethylenetriamine (PMDETA) was added to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 74.0% in 300 minutes from the start of polymerization. The reaction was further continued for 90 minutes, but the polymerization was stopped at a polymerization rate of 74.0%. Ln was 11.7, the number average molecular weight of the polymer [7] was 29400, and the molecular weight distribution was 1.30.

(Comparative Example 2)
0.97 parts by weight of CuCl (I) (Cu amount = 6200 ppm) was charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of dodecyl methacrylate (LMA) subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 0.60 part by weight of methyl 2-chloropropionate (hereinafter, MCLP) as an initiator are separable flasks. And stirred at 80 ^° C. under a nitrogen stream. To the mixture, pentamethyldiethylenetriamine (PMDETA) was added to initiate polymerization. PMDETA was shot added so that the internal temperature would be 80 ^° C. to 90 ^° C., and the polymerization rate reached 87.2% in 210 minutes from the start of polymerization, and the polymerization was stopped. Ln was 18.2, the number average molecular weight of the polymer [8] was 31400, and the molecular weight distribution was 2.42.

(Comparative Example 3)
0.36 parts by weight of CuBr (I) (Cu content = 2320 ppm) was charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of dodecyl methacrylate (LMA) subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 0.96 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator were charged into a separable flask. The mixture was stirred at 80 ^° C. under a nitrogen stream. 4,4′-Dinonyl-2,2′-dipyridyl (hereinafter, dNbpy) dissolved in a mixed solvent (acetonitrile: toluene = 2: 1) subjected to nitrogen substitution was added to the mixed solution to initiate polymerization. . DNbpy was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 84.2% in 720 minutes from the start of polymerization. Ln was very slow as 4.5. The number average molecular weight of the polymer [9] was 12800, and the molecular weight distribution was 1.26.

(Comparative Example 4)
0.36 parts by weight of CuBr (I) (Cu content = 2320 ppm) was charged into a separable flask and purged with nitrogen. Separately nitrogen bubbling dodecyl methacrylate (LMA) 100 parts by weight, acetonitrile 20 parts by weight, toluene 10 parts by weight, initiator ethyl 2-bromoisobutyrate (EtBriB) 0.96 parts by weight, The mixture was stirred at 80 ^° C. under a nitrogen stream. Pentamethyldiethylenetriamine (hereinafter, PMDETA) was added to the mixed solution to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 83.0% in 720 minutes from the start of polymerization. Ln was 18.9, the number average molecular weight of the polymer [10] was 19000, and the molecular weight distribution was 1.30.

(Comparative Example 5)
0.36 parts by weight of CuBr (I) (Cu content = 2320 ppm) was charged into a separable flask and purged with nitrogen. Separately nitrogen bubbling dodecyl methacrylate (LMA) 100 parts by weight, acetonitrile 20 parts by weight, toluene 10 parts by weight, initiator ethyl 2-bromoisobutyrate (EtBriB) 0.96 parts by weight, The mixture was stirred at 80 ^° C. under a nitrogen stream. Tris [2- (dimethylamino) ethyl] amine (hereinafter, Me ₆ TREN) was added to the mixed solution to initiate polymerization. Me ₆ TREN was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 86.1% in 205 minutes from the start of polymerization. Ln was 18.9, the number average molecular weight of the polymer [11] was 22700, and the molecular weight distribution was 1.48.

(Comparative Example 6)
0.18 parts by weight of CuBr (I) (Cu content = 1160 ppm) was charged into a separable flask and purged with nitrogen. Separately nitrogen bubbling dodecyl methacrylate (LMA) 100 parts by weight, acetonitrile 20 parts by weight, toluene 10 parts by weight, initiator ethyl 2-bromoisobutyrate (EtBriB) 0.96 parts by weight, The mixture was stirred at 80 ^° C. under a nitrogen stream. To the mixture, pentamethyldiethylenetriamine (PMDETA) was added to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 83.0% in 240 minutes from the start of polymerization. Ln was 18.9, the number average molecular weight of the polymer [12] was 19000, and the molecular weight distribution was 1.30.

(Comparative Example 7)
0.18 parts by weight of CuBr (I) (Cu content = 1160 ppm) was charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of 2-ethylhexyl methacrylate (2-EHM) separately subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 0.96 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator are separable. The flask was charged and stirred at 80 ^° C. under a nitrogen stream. To the mixture, pentamethyldiethylenetriamine (PMDETA) was added to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 78.8% in 290 minutes from the start of polymerization. Ln was 16.5, the number average molecular weight of the polymer [13] was 22700, and the molecular weight distribution was 1.48.

(Comparative Example 8)
0.18 parts by weight of CuBr (I) (Cu content = 1160 ppm) was charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of methyl methacrylate (MMA) subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 2.4 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator were charged into a separable flask. The mixture was stirred at 80 ^° C. under a nitrogen stream. To the mixture, pentamethyldiethylenetriamine (PMDETA) was added to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 97.7% in 240 minutes from the start of polymerization. Ln was 18.5, the number average molecular weight of the polymer [14] was 8090, and the molecular weight distribution was 1.24.

(Comparative Example 9)
CuSe (I) 0.18 parts by weight (Cu content = 1160 ppm) and tetrabutylammonium bromide (TBABr) 0.04 parts by weight (400 ppm, 22 mol%) were charged into a separable flask and purged with nitrogen. Separately, 100 parts by weight of methyl methacrylate (MMA) subjected to nitrogen bubbling, 20 parts by weight of acetonitrile, 10 parts by weight of toluene, and 2.4 parts by weight of ethyl 2-bromoisobutyrate (EtBriB) as an initiator were charged into a separable flask. The mixture was stirred at 80 ^° C. under a nitrogen stream. To the mixture, pentamethyldiethylenetriamine (PMDETA) was added to initiate polymerization. PMDETA was shot added so that the internal temperature was 80 ^° C. to 90 ^° C., and the polymerization rate reached 98.1% in 190 minutes from the start of polymerization. Ln was 28.1, the number average molecular weight of the polymer [15] was 7980, and the molecular weight distribution was 1.26.

  In Comparative Examples 1 and 2 in which a quaternary ammonium salt was not added in a system using a chlorine-based initiator and copper (I) chloride, the polymerization rate was 90% or less, and the molecular weight distribution was very wide. . Also, the polymerization time was long and the polymerization efficiency was very poor. When tetrabutylammonium chloride (TBACl) was added thereto, the polymerization rate was increased to 90.3% and the polymerization time could be further shortened. Therefore, the addition of TBACl effectively activated the catalyst. It was suggested that However, since the polymerization rate was still insufficient, a brominated initiator and copper (I) bromide were used as catalysts.

  In Comparative Examples 3 to 7 in which a quaternary ammonium salt was not added in a system using a bromine-based initiator and copper (I) bromide, the polymerization rate and molecular weight distribution were slightly improved, but the polymerization rate was Previously it was below 90%. When tetrabutylammonium chloride (TBABr) was added there, the polymerization rate was improved to 98% or more, and the polymerization time could be shortened. Therefore, the addition of TBABr effectively activated the catalyst. It was suggested that

  In Comparative Examples 8 and 9, the effect of adding tetrabutylammonium bromide (TBABr) was examined using methyl methacrylate having an ester moiety with 1 carbon atom. Regardless of the presence or absence of TBABr, the polymerization rate was about 98% and the molecular weight distribution was about 1.25.

From the above results, in the process of polymerizing the (meth) acrylic monomer having 8 to 24 carbon atoms in the ester portion, by adding a quaternary ammonium salt, the polymerization rate is improved, the polymerization time is shortened, The molecular weight distribution can be controlled and the polymerization efficiency has been greatly improved.

Claims (7)

In the primitive transfer radical polymerization method using a transition metal compound as a catalyst, a quaternary ammonium salt is added in the process of polymerizing a (meth) acrylic monomer having an ester moiety having 8 to 24 carbon atoms. A method for producing a (meth) acrylic polymer. 2. The method for producing a (meth) acrylic polymer according to claim 1, comprising 1 to 100% by weight of a (meth) acrylic monomer having 8 to 24 carbon atoms in the ester part. The method for producing a (meth) acrylic polymer according to claim 1 or 2, wherein the quaternary ammonium salt is tetrabutylammonium bromide. Tetrabutylammonium bromide contains 100 mol% or less with respect to a catalyst with respect to a transition metal catalyst, The manufacturing method of the (meth) acrylic-type polymer in any one of Claims 1-3 characterized by the above-mentioned. The method for producing a (meth) acrylic polymer according to any one of claims 1 to 4, wherein the polymerization rate of the (meth) acrylic polymer is 85 to 100%. Molecular weight distribution is 1.25 or less, The manufacturing method of the (meth) acrylic-type polymer in any one of Claims 1-5 characterized by the above-mentioned. The (meth) acrylic-type polymer obtained by the manufacturing method in any one of Claims 1-6.