KR100496901B1 - Manufacturing Method for Block Copolymer of Vinylalcohol-styrene and Copolymer thereof - Google Patents

Abstract

The present invention relates to a method for preparing a vinyl alcohol-styrene block copolymer and to a copolymer produced therein, (a) adding a molecular weight modifier to telomerization of the vinyl alcohol monomer, and (b) producing a telomer. Block copolymerization with styrene followed by atomic transfer radical polymerization, and (c) hydrolyzing the block copolymer produced by step (b). It includes a method.

According to the present invention, the production method is simpler and more advantageous in terms of economics than the conventional production method, and the vinyl alcohol-styrene block copolymer having the molecular weight and syndiotacticity of the vinyl alcohol block can be prepared.

Description

Manufacturing Method for Block Copolymer of Vinyl Alcohol-Styrene Block Copolymer and Copolymer Made Thereby

The present invention relates to a method for preparing a vinyl alcohol-styrene block copolymer and to a copolymer produced therein, and more particularly, to a vinyl alcohol-styrene block having excellent self-assembly performance with a unique phase structure and form. It relates to a method for producing a copolymer and a copolymer produced thereby.

Styrene is block copolymerized with other monomers to suit various applications. Among these styrene block copolymers, vinyl alcohol-styrene block copolymers containing hydroxyl groups have an amphiphilic structure and are coated. It can be used in the areas of adhesion, adhesion, dispersion stability of polymerization reaction, pharmaceutical, photographic technology, oil recovery.

In general, a method of preparing a block copolymer of vinyl alcohol-styrene is performed by hydrolyzing a vinyl acetate-styrene block copolymer, and a method of preparing a vinyl acetate-styrene block copolymer includes, for example, benzophenone and benzophenone. A method of preparing a block copolymer by polymerizing styrene under UV irradiation using an ethanolamine photochemical initiator to obtain polystyrene containing imine groups and then polymerizing with vinyl acetate under UV irradiation using a benzophenone photochemical initiator, Oxidation-reduction reaction of vinyl acetate with carbon tetrachloride under catalytic (transition metal compound) / ligand reaction yields a telomer with controlled polymer ends, followed by atom transfer radical polymerization with styrene to form a block copolymer. Method of manufacturing, radiate vinyl acetate with carbon trichloride as molecular weight regulator The general radical polymerization initiator under the disclosed method are known, such as by atom transfer radical polymerization of styrene and after obtaining the telomerization of a polymer control terminal for producing a block copolymer.

Among the various methods of preparing the vinyl acetate-styrene block copolymer, the first method is a vinyl alcohol-styrene block by hydrolyzing the vinyl acetate-styrene block copolymer at 70 ° C. using a benzene solution of 5% sodium ethoxide. Although copolymers have been synthesized, this process requires complicated equipment and is disadvantageous in terms of process and economics. The second and third methods are economically advantageous over the first method, but the method of hydrolyzing to obtain a vinyl alcohol-styrene block copolymer has not been reported until now.

The present invention is simpler and more advantageous in terms of economics than conventional methods for synthesizing vinyl alcohol-styrene block copolymers, and the vinyl alcohol-styrene block in which the molecular weight of the two blocks and the syndiotacticity of the vinyl alcohol blocks are controlled. It is an object to provide a method for producing a copolymer.

To this end, the present invention comprises the steps of (a) adding a molecular weight modifier to the telomerization reaction of the vinyl alcohol monomer, (b) generating a telomer and then subjecting the block copolymerization to styrene and atomic transfer radical polymerization, and (c) It is to provide a method for producing a vinyl alcohol-styrene block copolymer comprising the step of hydrolyzing the block copolymer produced by step (b).

That is, the present invention controls the syndiotacticity of the vinyl alcohol block by using a vinyl alcohol monomer, and adjusts the molecular weight of the vinyl alcohol block by applying a molecular weight modifier, and adjusts the molecular weight of the styrene block using atomic transfer radical polymerization of styrene. I would like to.

In the present invention, the vinyl alcohol-styrene block copolymer is preferably a degree of polymerization of the vinyl alcohol block in the total composition of the copolymer is 5 to 100, the degree of polymerization of the polystyrene block can be arbitrarily adjusted according to the intended use of the vinyl alcohol block Syndiotacticity (diad) includes block copolymers that are 40-63%.

In the present invention, as the monomers capable of synthesizing the vinyl alcohol block, vinyl acetate substituents are generally mainly used as vinyl acetate, vinyl acetate substituents and vinyl ethers. Examples of the vinyl acetate substituent include vinyl propionate (Vryl), vinyl trifluoroacetate (VTFAc), vinyl fivalate (VPi), vinyl benzoate (Vinyl Benzoate, VBz) ), Vinyl isobutyrate (Vinu), vinyl butyrate (VBu), vinyl 2,2'-dimethylbutyrate (VDMB), vinyl 2,2'-dimethylbarrate (Vinyl 2,2'-dimethylvalerate, VDMV), vinyl hexafluoropivarate (VF6Pi), and the like, and may be used alone or in combination of two or more of the above monomers.

In the present invention, the telomer may use a bulk polymerization (Solution Polymerization), a solution polymerization (Solution Polymerization), etc., which is a general polymerization reaction, wherein the solvent can be used methanol, acetone, benzene, ethyl acetate, tert-butyl alcohol (TBA), DMSO, terfluoro as tert-butyl alcohol ((CF ₃ ) ₃ COH), 1,1,1,3,3,3-hexaprouro-2-propanol ((CF ₃ ) ₂ CHOH) 2, 2,2'-tripururoethanol (CF ₃ CH ₂ OH) and the like. Among the solvents exemplified above, methanol and acetone and ethyl acetate are preferred for use in terms of price and process, and the amount of the solvent is determined by polymerization rate, conversion rate, and the like under the premise that it does not affect the polymer terminal control.

In the present invention, the molecular weight modifier used for the radical polymerization is preferably polyhaloalkane CX _n R _4-n (n = 2, 3 and 4; X = Cl, Br). Carbon bromide, carbon tribromide, carbon trichloride, 1,1,1-trichloroalkane (RCCl ₃ , R = -CH ₂ OCOC (CH ₃ ) ₃ , -CH ₂ CH ₂ OCOCH ₃ , -CH ₂ CH ₂ CH ₂ OCOCH ₃ , -CO ₂ CH ₃ , -CF ₃ , -CH ₂ OH, alkyl group, and the like), 1,1-dichloroalkane (RCHCl _2, R = CO ₂ CH _3, etc.), brominated alkanes, and the like. Among the polyhaloalkanes used as the molecular weight modifiers exemplified above, carbon tetrachloride, carbon tetrabromide, carbon trichloride, 1,1,1-trichloride alkanes are used in determining the molecular weight of the telomer and are generally monomers. The molar ratio with is in the range of 10 ⁻³ to 10 ² .

In the present invention, the initiator used for the radical polymerization may be used as an azo compound, a peroxide compound, a percarbonate, and the like, and examples of AIBN (2,2'-azobisisobutyronitrile), ADMVN (2,2'-azobis (2) , 4-dimethylvaleronitrile)), BPO, and DTCP (di- (4-tert-butylcyclohexyl) percabonate). Preferred among the exemplified initiators are AIBN, ADMVN, the amount of use of which affects the polymerization rate and molecular weight. Generally, the molar ratio with the monomer is in the range of 10 ⁻⁵ to 10 ⁻¹ .

The catalyst of atomic transfer radical polymerization (ATRP) used in the present invention may be used as a transition metal compound. Examples include CuX (X = Cl, Br), RuCl ₂ (PPh ₃ ) ₃ , RuH ₂ (PPh ₃ ) ₃ , FeCl ₂ (PPh ₃ ) ₃ , NiBr ₂ (PPh ₃ ) ₃ , Ni (NCN) Br, and the like. Among the catalysts exemplified above, one obtainable and preferred is CuX (X = Br, Cl). Ligands used accordingly are 2,2'-bipyridine and derivatives thereof, 2-iminopyridine, a chelate compound of nitrogen, and aliphatic. Aliphatic polyamines and the like, with 2,2'-bipyruidine, dNbipy (4,4'-di- (5-nonyl) -2,2'-dipyridyl), and dHbipy (4,4 '). -di- (n-heptyl) -2,2'-dipyridyl), PMDETA (N, N, N ', N', N "-pentamethyldiethylene triamine), etc. The ratio of catalyst and ligand is 1-4.

In the present invention, ATRP proceeds using a bulk polymerization, a solution polymerization, and the like, which are generally performed in a polymerization reaction. The solvents used for the reaction may include benzene, toluene, xylene, dimethoxylbenzene, and anisole. , Diphenylether, ethylene carbonate, propylene carbonate, cyclohexanone and the like.

In the present invention, the hydrolysis proceeds under a basic catalyst, and the basic catalyst used is potassium hydroxide, sodium hydroxide, sodium ethoxide, potassium ethoxide, and the like. The amount is 1 to 20 in terms of molar ratio with the vinyl alcohol precursor.

The reaction temperature is different from telomerization reaction, ATRP, and hydrolysis reaction. The reaction temperature of the telomerization reaction depends on the initiator used and is generally 0 to 90 ° C. The polymerization temperature of ATRP is 50-150 ° C. and depends on the catalyst / ligand used. The reaction temperature of the hydrolysis reaction is from room temperature to 100 ℃, and the catalyst and reaction time used must be properly adjusted according to the temperature so that the hydrolysis reaction can proceed completely.

As described above, the vinyl alcohol-styrene block copolymer has a vinyl alcohol chain length controlled by an amount of a molecular weight modifier, and the syndiotactic of vinyl alcohol is controlled by using different monomers or a composition ratio of monomers. And the chain length of styrene depends on the molarity ratio of telomer and catalyst and polymerization time.

As described above, the vinyl alcohol-styrene block copolymer prepared by the present invention has various block chain lengths and syndiotactic properties, and has excellent self-assembly performance, and thus may be applied to various areas.

The following examples are illustrated to specifically illustrate the present invention, but the present invention is not limited to these examples.

<Example 1>

25 ml of vinylfiberate, 25 ml of acetone, 27.8 mg of AIBN (initiator), and 0.49 ml of CCl ₄ were added to a 100 ml round bottom flask, and nitrogen was passed through a predetermined time to remove oxygen, followed by reaction at 50 ° C. for 6 hours. After the reaction was completed, precipitated in methanol / water, followed by a filter, washing, and vacuum drying to obtain a telomer (macromer). The telomer obtained was placed in a round bottom flask with CuCl, bipyruidine and styrene in a ratio of 1: 1: 2: 300, and passed through a predetermined time to remove oxygen, followed by reaction at 130 ° C. for 6 hours. After the reaction was completed, precipitated in methanol / water, and then filtered, washed and dried in vacuo to obtain a vinylfiberrate-styrene block copolymer. The obtained block copolymer and THF were placed in a round-bottomed flask equipped with a reflux condenser, and passed through nitrogen for a predetermined time to remove oxygen, and reacted while slowly dropping a 25% KOH / methanol solution at room temperature. After dropping all of the KOH / methanol solution, the reaction was continued at 60 ° C. for 15 minutes, and when the reaction was completed, precipitated in methanol, followed by a filter, washing, and vacuum drying to obtain a vinyl alcohol-styrene block copolymer.

The composition, the syndiotacticity of the vinyl alcohol-styrene block copolymer prepared above, the composition and the degree of hydrolysis of the vinylfiberrate-styrene block copolymer, the structure confirmation and the molecular weight of the telomer were measured by ¹ H-NMR and GPC. . The measurement results are shown in Table 1.

TABLE 1

Polymer GPC ¹ H-NMR M _n M _w / M _n M _{n, NMR} Composition (styrene content mole%) Syndiotactic (%) Telomer 4560 1.55 4760 - - Vinyl feverrate-styrene 14730 1.38 17550 77.4 - Vinyl alcohol-styrene - 14380 74.3 61.0

Determination of molecular weight, composition and syndiotacticity of the polymer by ¹ H-NMR: The molecular weight of the telomer is δ4.9 ppm absorption peak area / δ 3.0 ppm absorption peak area ratio; The molecular weight and composition of the vinylfiberrate-styrene polymer were determined by the ratio of δ 0.9-1.3 ppm absorption peak area / δ 6.3-6.8 ppm absorption peak area; The molecular weight and composition of the vinyl alcohol-styrene polymers include the δ4.1-4.8 ppm absorption peak area / δ 6.3-6.8 ppm absorption peak area ratio; The syndiotacticity of the vinyl alcohol block was calculated by the absorption peak area ratio (δ4.3ppm + 0.5 × δ4.5ppm) / (δ4.3ppm + δ4.5ppm + δ4.7ppm).

<Example 2>

A vinyl alcohol-styrene block copolymer was prepared under the same conditions as in Example 1 except that the ATRP reaction time was performed for 47 minutes, 120 minutes, and 240 minutes, respectively. The results are shown in Table 2.

TABLE 2

Example 1 Example 2 ATRP polymerization time (min) 47 120 240 Vinyl Feverrate Blocks (M _{n, NMR} ) 4760 4760 Conversion of styrene (%) 45.0 9.9 26.0 43.9 Styrene Block (M _{n, th} ) ^* 14040 3090 8110 13700 Vinyl feverrate-styrene M _{n, th} ^** 18800 7850 12870 18460 M _{n, GPC} 14730 7480 10413 13990 M _w / M _n 1.38 1.32 1.29 1.33 Vinyl Alcohol Block (M _{n, NMR} ) 1580 1580 Syndiotacticity (%) 61.0

* M _{n, th} = [Styrene] / [Telomer] × MW (styrene) × Conversion (%) (styrene)

** M _{n, th} = [Styrene] / [Telomer] × MW (Styrene) × Conversion (%) (Styrene) + M _{n, NMR} (Telomer)

<Example 3>

The telomerization reaction proceeds for 1 hour by a bulk polymerization method, except that the telomer is prepared using 0.13 ml, 0.16 ml, 0.20 ml, and 0.23 ml of CCl ₄ , respectively, and the preparation conditions are the same as those in Example 1. The results of the telomerization reaction are shown in Table 3.

TABLE 3

Polyvinyl Feverrate (Telomer) CCl ₄ Volume (ml) 0.13 0.16 0.20 0.23 M _{n, NMR} 7580 6810 5020 4380 M _{n, GPC} 7940 7560 6580 5750 M _w / M _n 1.66 1.62 1.63 1.64

As can be seen from the above results, according to the present invention, the manufacturing method is simpler and more advantageous in terms of economics than the conventional manufacturing method, and the vinyl alcohol-styrene block copolymer in which the molecular weight of the two blocks and the syndiotacticity of the vinyl alcohol block are controlled. Can be prepared.

Claims (12)

In the method for producing a vinyl alcohol-styrene block copolymer using atomic transfer radical polymerization, (a) adding a molecular weight regulator to telomerize the vinyl alcohol monomer, (b) block copolymerization with styrene and atom transfer radical polymerization in the presence of a transition metal compound catalyst after the formation of the telomer; (C) a method for producing a vinyl alcohol-styrene block copolymer, characterized in that it comprises the step of hydrolyzing the block copolymer produced by step (b). The method of claim 1, The vinyl alcohol monomer is a method of producing a vinyl alcohol-styrene block copolymer, characterized in that it comprises at least one selected from vinyl acetate, vinyl acetate substituents and vinyl ethers. The method of claim 1, Method for producing a vinyl alcohol-styrene block copolymer, characterized in that the molecular weight modifier used in the telomerization reaction is a polyhaloalkane represented by the following general formula. CX _n R _4-n (n = 2, 3 and 4; X = Cl, Br; R is -CH ₂ OCOC (CH ₃ ) ₃ , -CH ₂ CH ₂ OCOCH ₃ , -CH ₂ CH ₂ CH ₂ OCOCH ₃ , -CO ₂ CH ₃ , -CF ₃ , -CH ₂ OH or an alkyl group) The method of claim 1, Method for producing a vinyl alcohol-styrene block copolymer, characterized in that 10 to ³ to 10 ² moles of the molecular weight regulator is used per 1 mole of the monomer. delete The method of claim 1, The transition metal compounds include CuX (X = Cl, Br), RuCl ₂ (PPh ₃ ) ₃ , RuH ₂ (PPh ₃ ) ₃ , FeCl ₂ (PPh ₃ ) ₃ , NiBr ₂ (PPh ₃ ) ₃ , Ni (NCN) Br Method for producing a vinyl alcohol-styrene block copolymer, characterized in that it comprises at least one selected from the like. The method of claim 1, The ligand of the atomic transfer radical polymerization reaction contains at least one selected from 2,2'-bipyruidine and derivatives thereof, and a nitrogen chelate compound selected from 2-iminopyruidine, aliphatic polyamine, and the like. Method for producing vinyl alcohol-styrene block copolymer The method of claim 1, Method for producing a vinyl alcohol-styrene block copolymer, characterized in that the ratio of the catalyst and ligand in the atomic transfer radical polymerization reaction is 1 to 4. The method of claim 1, The catalyst used in the hydrolysis reaction is a method of producing a vinyl alcohol-styrene block copolymer, characterized in that the basic catalyst The method of claim 9, The basic catalyst comprises at least one selected from potassium hydroxide, sodium hydroxide, ethoxide sodium, ethoxide potassium and the like. The method of claim 1, The catalyst for the hydrolysis reaction is a method for producing a vinyl alcohol-styrene block copolymer, characterized in that 1 to 20 in a molar ratio with the vinyl alcohol precursor. The method of claim 1, wherein the reaction temperature Method for producing vinyl alcohol-styrene block copolymer, characterized in that the tellerization reaction is carried out at 0 ~ 90 ℃, atomic transfer radical polymerization reaction is 50 ~ 150 ℃, hydrolysis reaction at room temperature ~ 100 ℃