KR101381879B1 - A preparation method for olefin-aromatic vinyl copolymer or terpolymer comprising polar groups - Google Patents

Abstract

The present invention relates to a method for producing an olefin-aromatic vinyl copolymer or terpolymer containing a polar group, and more particularly, to an aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; A polymer or terpolymer is prepared by polymerizing an alkenyldialkylaluminum compound, and then reacting the copolymer or terpolymer with oxygen, carbon dioxide or sulfur trioxide to hydrolyze a dialkylaluminum group to react with a hydroxyl group, a carboxyl group or a sulfone. Provided is a method for producing an olefin-aromatic vinyl-based copolymer or terpolymer having a polar group introduced at the side chain end by conversion to an acid group.

Description

A preparation method for olefin-aromatic vinyl copolymer or terpolymer comprising polar groups

The present invention relates to a method for producing an olefin-aromatic vinyl copolymer or terpolymer containing a polar group, and more particularly, to an aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; A polymer or terpolymer is prepared by polymerizing an alkenyldialkylaluminum compound, and then reacting the copolymer or terpolymer with oxygen, carbon dioxide or sulfur trioxide to hydrolyze a dialkylaluminum group to react with a hydroxyl group, a carboxyl group or a sulfone. Provided is a method for producing an olefin-aromatic vinyl-based copolymer or terpolymer having a polar group introduced at the side chain end by conversion to an acid group.

Coordination copolymerization between olefins and aromatic vinyl compounds, inter alia, copolymerization between aromatic vinyl compounds such as ethylene and styrene has been performed for the past 20 years. In the case of ethylene and styrene copolymerization using the first heterogeneous Ziegler-Natta catalyst, the yield of the resulting polymer was extremely low, and almost all of the polymers were homopolymers of polyethylene and polystyrene. The mixture consisted of (Polymer Bulletin , 1988, 20 (3), 237-241). In addition, in the case of a small amount of the copolymer produced, not only was the styrene content in the polymerization low, but also the uniformity of the copolymer was poor, making the application impossible.

Japanese Patent Laid-Open Nos. 3-163088 and 7-53618 use pseudo catalysts with constrained arrangements, and pseudo-randoms do not exist in the head-to-tail bond chain, which is a common styrene chain. -random) Ethylene / styrene copolymer is disclosed, and Japanese Patent Laid-Open No. 3-250007 uses a titanium complex having a phenol substituent (Ti complex) of at least 70 or more alternating degree (alternating degree) And, in more detail, nearly perfect alternating copolymers with very high levels of alternating degree of 90 or more were introduced. However, these copolymers have a disadvantage in that the composition of ethylene and styrene is fixed at about 50% to 50%, and thus the composition of the copolymer cannot be changed. The copolymer has a molecular weight of 20,000 or less, which is unsuitable in terms of physical properties, and has extremely low catalytic activity and copolymerization. In many cases, a large amount of homopolymers, such as syndiotactic polystyrene (sPS), are not suitable for practical commercialization.

On the other hand, International Publication No. WO 2007/139116 A1 introduced a cross copolymer and a resin composition having a lower mechanical crystallinity than the conventional ethylene aromatic vinyl copolymer, and having similar mechanical properties to soft PVC having improved flexibility, transparency, and compatibility. In particular, the polymerization method consisting of coordination polymerization and anion polymerization is a manufacturing method. In coordination polymerization, olefins, aromatic vinyl compounds and aromatic polyenes are copolymerized using a single site coordination polymerization catalyst to produce olefin-aromatic vinyl compounds. After synthesizing the terpolymer of an aromatic polyene, and then in the anionic polymerization step, an anionic polymerization initiator under coexistence of the terpolymer of the olefin-aromatic vinyl compound-aromatic polyene and the anionic polymerizable monomer. It is characterized in that to produce a cross copolymer.

However, in the case of the conventional olefin-aromatic vinyl compound as described above, a copolymer having a low molecular weight and a non-uniform monomer composition has been produced under mild reaction conditions, especially in the case of coordination polymerization using a single site catalyst. When directly introducing a monomer having a polymer into the polymerization, the catalyst in the reaction tank is poisoned due to the polar group, the activity is lost, there was a limit in the production of a polymer containing a polar group on the main chain and side chain. Recently, a copolymerization method of directly introducing a polar group-containing monomer and ethylene into a polymerization reactor using a chelating complex composed of Ni and Pd, which is a low cycle affinity transition metal ( Sceience , 2000, 287 (5452), 460- ). 462) has been reported but produced polymers similar to polyethylene with very low monomer content containing polar groups ( Macromolelecules , 2003, 36 (26), 9731-9735) and also show little copolymerizability with α-olefins. Did. As a result, some of the olefin and aromatic vinyl compound copolymers do not contain polar groups on the cast iron and the side caps, despite having good flexibility, transparency, and workability, and thus have poor adhesion to other plastic materials and metals, and paintability. In addition, printability and compatibility with other resins were low, and there was much room for improvement.

Accordingly, the present inventors have been studied in view of the above points, first, an aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; Dialkylaluminum contained in the copolymer or terpolymer by polymerizing an alkenyldialkylaluminum compound to obtain a copolymer or terpolymer, and then reacting the copolymer or terpolymer in contact with oxygen, carbon dioxide or sulfur trioxide. The present invention was completed by confirming that olefin-aromatic vinyl-based copolymers or terpolymers having polar groups introduced at the side chain ends can be prepared by hydrolyzing the groups to convert to hydroxyl, carboxyl or sulfonic acid groups.

An object of the present invention is to provide a method for producing an olefin-aromatic vinyl-based copolymer or terpolymer in which a polar group is introduced at a high side ratio at a side chain end.

In order to solve the above problems,

1) an aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; Polymerizing an alkenyldialkylaluminum compound represented by the following Chemical Formula 2 to obtain a copolymer or a terpolymer comprising a unit of the following Chemical Formula 3; And

2) providing a method of preparing a copolymer or a terpolymer comprising a unit of the formula (1) comprising the step of reacting a copolymer or terpolymer comprising the unit of formula (3) in contact with oxygen, carbon dioxide or sulfur trioxide do.

In the above Formulas 1 to 3,

X represents OH, COOH, SOOH or SO ₃ H,

R ¹ and R ² are different from or equal to each other, and each independently represent a C _{1 -20} alkyl,

n represents the integer of 1-20.

Preferably, in the formula 2 and 3 R ¹ and R ² are different from or equal to each other, and each independently represent a C _{1 -8} alkyl group, more preferably represents a C _{1 -4} alkyl group;

In addition, n in the formulas (1) to (3) preferably represents an integer of 2 to 16, and more preferably, an integer of 4 to 12. If n is less than 1, it is difficult to secure the desired excellent flexibility, and if n exceeds 20, the glass transition temperature may be too low.

Step 1 may include an aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; Polymerizing the alkenyldialkylaluminum compound represented by the formula (2) to obtain a copolymer or terpolymer comprising the unit of formula (3), an olefin copolymer comprising an aromatic vinyl compound unit and a unit of formula (3), or It is a step of obtaining an olefin terpolymer comprising an olefin unit, an aromatic vinyl compound unit and a unit of formula (3).

Olefinic unsaturated monomers used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like, and cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3-methyl Cyclopentene, 3-methylcyclohexene, norbornene, and the like, and norbornene derivatives include 5-vinyl-2-norbornene, 5-butyl-2-norbornene, 5-methyl-2-norbornene , 5-hexyl-2-norbornene, 5-dimethylmethoxy norbornene, dicyclo pentadiene, cyclopentadiene, as a pendant functional group (polar group such as oxygen, chlorine, nitrogen, bromine, fluorine, etc.) Eggplants include various norbornene derivatives and the like.

The olefin monomer is copolymerized with an aromatic vinyl compound, and may be copolymerized using single or two or more kinds.

Specific examples of the aromatic vinyl compound include styrene, methyl styrene, ethyl styrene, butyl styrene, para-methyl styrene, para-t-butyl styrene, and dimethyl styrene. Halogenated styrene includes chlorostyrene, bromostyrene, and fluorostyrene. The halogen substituted alkyl styrenes include chloromethyl styrene, bromomethyl styrene, fluoromethyl styrene, and the like, and alkoxy styrene includes methoxy styrene, ethoxy styrene, butoxy styrene, and the like. And 4-vinyl biphenyl, 3-vinyl biphenyl, 2-vinyl biphenyl, and the like, and as vinyl phenyl naphthalene, 1- (4-vinyl biphenyl naphthalene), 2- (4-vinyl biphenyl naphthalene), 1 -(3-vinylbiphenylnaphthalene), 2- (3-vinylbiphenylnaphthalene), 1- (2-vinylbiphenylnaphthalene), and the like, and examples of vinylphenyl anthracene include 1- (4-vinylphenyl) anthracene, 2- (4-vinylphenyl) anthracene, 9- (4-ratio Nylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, and the like, and 1- (4-vinylphenyl) as vinylphenylpyrene. ) Pyrene, 2- (4-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2- (2-vinylphenyl Pyrene, and the like, and trialkylsilylvinylbiphenyl includes 4-vinyl-4-trimethylsilylbiphenyl and the like, and alkylsilylstyrene includes p-trimethylsilylstyrene, m-trimethylsilylstyrene, and o-trimethylsilylstyrene. , p-triethylsilyl styrene, m-triethylsilyl styrene, o-triethylsilyl styrene and the like.

In the present invention, specific examples of the alkenyldialkylaluminum compound include propenyldiethylaluminum, propenyldiisobutylaluminum, pentenyldiethylaluminum, pentenyldiisobutylaluminum, hexenyldiisobutylaluminum, hexenyldiethylaluminum, Octenyldiisobutylaluminum, octenyldiethylaluminum, dekenyldiisobutylaluminum, dodekenyldiisobutylaluminum and undekenyldiisobutylaluminum, and the like, among which hexenyldiisobutylaluminum and hexenyldiethyl Aluminum, octenyldiisobutylaluminum and octenyldiethylaluminum are preferred.

A commercially available compound may be used for the alkenyldialkylaluminum compound used by this invention, and it may be manufactured by a well-known method. For example, hydro-alumination reactions of nonconjugated dienes, cross-coupling reactions of alkenyl hydrides with organoaluminum compounds, organometallic compounds such as alkenyl lithium and alkenyl magnesium And a trans-metal reaction with an organoaluminum compound. Among these, a preferable method is the hydro-alumination reaction of a nonconjugated diene, and an alkenyldialkyl aluminum compound can be manufactured by making a nonconjugated diene and a dialkyl aluminum hydride react under mild conditions.

In the present invention, the catalyst used for the copolymerization of the aromatic vinyl compound and the alkenyldialkylaluminum or the terpolymerization of the olefin, the aromatic vinyl compound and the alkenyldialkylaluminum is not particularly limited. The coordination anion type catalyst which can be employed for polymerization can be used.

For example, a so-called metallocene catalyst or half metallocene catalyst can be used. Among these, in the present invention, it is preferable to use a half metallocene catalyst in consideration of the polymerizability with a relatively bulky alkenyldialkylaluminum compared to ethylene and propylene which are relatively existing olefins.

In the present invention, the monomer before polymerization and the solvent (when a solvent is used) can be purified by vacuum distillation or contact with alumina, silica or molecular sieve. Further, impurities can be removed by using a trialkylaluminum compound, an alkali metal, a metal alloy (particularly, Na / K) or the like.

In the present invention, as the half metallocene catalyst, in particular, transition metal compounds of group 4-6 of the periodic table having cyclopentadienes (conjugated 5-membered ring ligands) can be used.

In the present invention, the half metallocene catalyst is an activator for activating the catalyst, and an aluminoxane compound, a ionic compound which reacts with the catalyst to exchange a catalyst with a cation, a Lewis acid, and a cocatalyst such as an ion exchange layered silicate; It is more preferable to use together.

In addition, the alkenyldialkylaluminum compounds of the general formula (2) of the present invention may not only be used as comonomers but also act as cocatalysts.

As a preferred embodiment of the present invention, as the catalyst during the polymerization

A half metallocene compound represented by Formula 4 below; And

Aluminoxane or boron compounds can be used.

In Formula 4,

M represents Ti, Zr or Hf,

R ¹ , R ² And R ³ is different from or equal to each other, and each independently represent a C _{1 -5} alkyl group,

R ⁴ And R ⁵ are each the same or different and each independently represents a C _{1 -3} alkyl group or a halogen.

Specific examples of the half metallocene compound of Formula 4 include (i-PrNSiMe ₂ Flu) TiMe ₂ , (i-BuNSiMe ₂ Flu) TiMe ₂ , (t-BuNSiMe ₂ Flu) TiMe ₂ , (i-PrNSiMe ₂ Flu) TiCl ₂ , (i-BuNSiMe ₂ Flu) TiCl ₂ , (t-BuNSiMe ₂ Flu) TiCl ₂ , (i-PrNSiMe ₂ Flu) ZrMe ₂ , (i-BuNSiMe ₂ Flu) ZrMe ₂ , (t-BuNSiMe ₂ Flu) ZrMe ₂ , (i-PrNSiMe ₂ Flu) ZrCl ₂ , (i-BuNSiMe ₂ Flu) ZrCl ₂ , (t-BuNSiMe ₂ Flu) ZrCl ₂ , (i-PrNSiMe ₂ Flu) HfMe ₂ , (i-BuNSiMe ₂ Flu) HfMe ₂ , (t-BuNSiMe ₂ Flu) HfMe ₂ , (i-PrNSiMe ₂ Flu) HfCl ₂ , (i-BuNSiMe ₂ Flu) HfCl ₂ and (t-BuNSiMe ₂ Flu) HfCl ₂ , and the like. Examples include (t-BuNSiMe ₂ Flu) TiMe ₂ , (t-BuNSiMe ₂ Flu) ZrMe ₂ , and (t-BuNSiMe ₂ Flu) HfMe ₂ .

In the present invention, a titanium complex [(t-BuNSiMe ₂ Flu) TiMe ₂ ] represented by the following general formula (5) may be particularly preferably used.

In Formula 5,

Me represents a methyl group,

t-Bu represents a tertiary butyl group.

In the present invention, the aluminoxane is methyl aluminum oxane (PMAO) which is a condensation reaction of trimethyl aluminum (TMA) and water; And modified methylaluminum oxane (MMAO) resulting from the condensation reaction of a mixture of trimethylaluminum (TMA), triethylaluminum (TEA) or triisobutylaluminum (TIBA) with a small amount of trimethylaluminum (TMA) and water. One or more types selected from the group consisting of can be used.

The aluminoxane is characterized in that the chain or cyclic aluminum oxane containing a unit represented by the formula (6).

In Formula 6,

R is an alkyl group of C _{1 -6,}

m is an integer of 0-100.

In the present invention, the boron compound is a kind of uncoordinated Lewis acid, triphenyl carbenium tetrakis (pentafluorophenyl) borate ([Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]), N, One or more types selected from the group consisting of N-dimethyl aniline tetrakis (pentafluorophenyl) borate, ferrocerium tetrakis (pentafluorophenyl) borate, and tris (pentafluorophenyl) borate can be used.

In the present invention, it is also possible to change each of the monomers at the time of the polymerization in advance at a constant mixing ratio to react, or to change over time giving a time difference to the mixing ratio of the monomers to be supplied. Alternatively, a part of the monomer may be added separately in consideration of the copolymerization reaction ratio.

In the present invention, an object of formula (2), that is, an alkenyldialkylaluminum unit is aimed at introducing up to 50 mol%, preferably 10 to 50 mol%, of all units. In order to obtain a copolymer containing a large amount of such alkenyldialkylaluminum units, the copolymerizability of the catalyst used in the polymerization reaction and the type of the aluminum compound may be varied, but aromatic vinyl compound monomers or olefin-aromatic vinyl compound monomers and alkenes are used. The molar ratio of nildialkylaluminum is preferably 1: 0.001 to 1:10, more preferably 1: 0.001 to 1: 5, and even more preferably 1: 0.001 to 1: 2.

Polymerization can employ | adopt all polymerization methods, as long as a catalyst component and each monomer can be mixed efficiently. Specifically, a solution polymerization method using an inert solvent or a bulk polymerization method using an aromatic vinyl compound or an olefin-aromatic vinyl compound unit as a solvent can be employed. Moreover, the method of continuous polymerization, batch polymerization, or prepolymerization is also applied. In the case of solution polymerization, a single or mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene and toluene can be employed as the polymerization solvent. Polymerization temperature is 0-200 degreeC, and hydrogen and other molecular weight regulators can be used auxiliary as a molecular weight regulator.

Step 2 is a step of reacting a copolymer or terpolymer containing the unit of Formula 3 by contacting with oxygen, carbon dioxide or sulfur trioxide, and dialkyl in the copolymer or terpolymer comprising the unit of Formula 3 The aluminum group is hydrolyzed by contact with oxygen, carbon dioxide or sulfur trioxide to be converted into OH, COOH, SOOH or SO ₃ H.

More specifically, it is possible to convert the dialkylaluminum group to a hydroxyl group by hydrolysis by contacting with oxygen or a peroxide and reacting, thereby obtaining a copolymer containing a hydroxyl group.

It is also possible to obtain a carboxyl group-containing olefin-aromatic vinyl compound polymer by contacting carbon dioxide to convert the dialkylaluminum group to a carboxyl group.

The sulfonic acid group-containing olefin-aromatic vinyl compound polymer may also be obtained by contacting sulfur trioxide to convert the dialkylaluminum group into a sulfonic acid group.

The present invention can easily prepare olefin-aromatic vinyl compound copolymers or terpolymers containing polar groups under mild conditions other than harsh reaction conditions or using expensive reagents specifically for various uses requiring a polar group. have.

In addition, the present invention is capable of introducing a variety of reactive groups such as hydroxyl groups, carboxyl groups or sulfonic acid groups as polar groups of the copolymer and terpolymer, olefin unit, aromatic vinyl compound contained as a component of such a polymer The content of units, alkenes, and alkenes containing polar groups can be arbitrarily adjusted.

In addition, the introduction of a new reactive compound in the polymer side chain using the introduced polar group enables the development of various polymers having new functions through chain polymerization with oligomers or polymers possessing new monomers or terminal reactivity. do.

In addition, the present invention provides a copolymer with an aromatic vinyl compound or a ternary copolymer with an olefin-aromatic vinyl compound, which is prepared by the above production method, wherein the units of the following Chemical Formula 1 are 10 to 50 mol% in total units.

[Chemical Formula 1]

In Formula 1,

X represents OH, COOH, SOOH or SO ₃ H,

n represents the integer of 1-20.

The aromatic vinyl compound-alkenyldialkylaluminum copolymer or the olefin-aromatic vinyl compound-alkenyldialkylaluminum terpolymer of the present invention is an alkenyldialkyl of formula (2) in a structural unit leading to an aromatic vinyl compound or an olefin-aromatic vinyl compound. A structural unit derived from aluminum is randomly distributed, and 50 to 99.9 mol%, preferably 60 to 99.9 mol%, more preferably 65 to 99.9 mol%, of an aromatic vinyl compound or an olefin-aromatic vinyl compound unit. Aromatic vinyl compound-alkenyldialkylaluminum copolymer or olefin-aromatic vinyl compound-alkenyldialkylaluminum containing a unit of 0.1-50 mol%, Preferably 0.1-40 mol%, More preferably, 0.1-35 mol% Ternary copolymer.

In the present invention, when the structural unit of the general formula (1) derived from aluminum is less than 0.1 mol%, it is difficult to obtain an improvement effect such as dyeability, adhesiveness, and the like obtained when the alkenyldialkylaluminum group is converted into a polar group. Moreover, when larger than 50 mol%, it is hard to express the original characteristic of an aromatic vinyl compound or an olefin- aromatic vinyl compound polymer.

In general, when a long branch chain (Branched Long Chain) is coupled to the main chain of a polymer, the three-dimensional volume of the lamellar structure in the molecule is known to be more flexible than a single molecule. In addition, in the case of hydrocarbon-based polyolefins such as PE and PP, there is a limitation in application to a wide range of applications because of poor adhesiveness and printability due to lack of structural polar groups.

The polymer obtained by the present invention has not only transparency, which is a basic characteristic of polyolefin resin, but also a long branched chain in the main chain, which has flexibility and low crystallinity. Printability and the like are improved. In addition, excellent compatibility can be usefully used as a modifier when mixing two or more different resins.

In addition, the polymer of the present invention possesses low crystallinity, flexibility, transparency, low specific gravity, molding processability, and chemical resistance, and has electrical, mechanical, and appearance characteristics, and can control the monomer magnification in the resin to form an amorphous resin and an amorphous polymer. Provided is an olefin / aromatic vinyl compound copolymer, particularly preferably an ethylene / aromatic vinyl compound copolymer, capable of arbitrarily controlling the properties of the resin.

In addition, in order to enhance transparency and flexibility of the olefin / aromatic vinyl compound copolymer, the polymer of the present invention introduces an alkenyldialkylaluminum compound capable of expressing a ductile long branched structure as a comonomer to form a copolymer. A olefin copolymer or terpolymer of molecular structure having a long branch having a polar group at the end is finally provided by hydrolysis of the dialkylaluminum group contained thereafter.

Conventional olefin / aromatic vinyl compound copolymers have a lot of room for improvement because of poor adhesion to other plastic materials and metals, poor paintability, printability, and poor compatibility with other resins. The polymer of the present invention is a comonomer having a molecular structure containing a polar functional group such as a hydroxyl group, a carboxyl group or a sulfonic acid group that can solve these disadvantages.

The present invention also provides an aromatic vinyl compound unit, or an olefin unit and an aromatic vinyl compound unit; And it provides a copolymer or a terpolymer comprising a unit represented by the following formula (3).

(3)

In Formula 3,

R ¹ and R ² are different from or equal to each other, and each independently represent a C _{1 -20} alkyl,

n represents the integer of 1-20.

In the present invention, the aromatic vinyl compound unit, or an olefin unit and an aromatic vinyl compound unit; And a copolymer or ternary copolymer comprising a unit represented by Formula 3 may be converted into a polar group of OH, COOH, SOOH, or SO ₃ H by reacting with oxygen, carbon dioxide, or sulfur trioxide to include a polar group. It can be usefully used as an intermediate for the preparation of an olefin copolymer.

The present invention is to prepare an aromatic vinyl compound-alkenyldialkylaluminum copolymer or an olefin-aromatic vinyl compound-alkenyldialkylaluminum terpolymer having a long branched structure and then convert the copolymer or terpolymer into oxygen, carbon dioxide or Hydrolysis of the dialkylaluminum groups by contact with sulfur trioxide to convert to hydroxyl, carboxyl or sulfonic acid groups to produce olefin-aromatic vinyl compound coordination copolymers or coordination terpolymers containing hydroxyl, carboxyl or sulfonic acid groups. can do. The coordination copolymer or coordination terpolymer has some long branches in the molecule to exhibit flexibility, and also contains polar groups such as hydroxyl groups, carboxyl groups or sulfonic acid groups contained in the long branch end portions, thereby reducing conventional olefins and aromatic vinyls. In addition to transparency, processability, and mechanical / electrical properties, which are advantages of the compound copolymer resin, it may further possess adhesiveness, paintability, and printability with other plastic materials and metals expressed due to polar groups. Therefore, the coordination copolymer or coordination terpolymer prepared according to the manufacturing method of the present invention having the above characteristics is a melt extrusion and injection method used in the field of medical materials, as well as IT fields such as flexible displays and solar cell devices. It is expected to be useful as a material produced by the company.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples.

Materials and methods

Measurement of physical properties

The molecular weight and molecular weight distribution were measured by gel permeation chromatography method. The measurement temperature was 140 ° C., orthodichlorobenzene was used as the solvent, and the molecular weight was calculated based on a standard polystyrene column.

Copolymer Comonomer  Content measurement

The content of the comonomer contained in the copolymer prepared in the present invention was measured by ¹³ C-NMR, the measurement temperature was 120 ℃, 1, 1, 2, 2-tetrachloroethane-d2 as a solvent Was used. In addition, the pulse angle was 45 °, the number of scans was 10000, and the pulse interval was 7 seconds.

Of half metallocene catalyst  Produce

As a half metallocene catalyst, [t-BuNSiMe ₂ Flu] TiMe ₂ was manufactured and used based on the description of "Macromolecules, Vol. 31, p. 3184, 1998". The prepared catalyst was purified by recrystallization in hexane at -20 ° C and used for polymerization. As a promoter, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] was obtained from Tosoh Finechem Co., Ltd. in Japan and used as it is.

Manufacturing example  One: Of octenyldiisobutylaluminum  synthesis

1,7-octadiene (20ml: 0.114mol) and diisobutylaluminum hydride (2.5ml: 0.014mol) were added to 50 ml of each half-glass attachment reactor, and it was made to react at 60 degreeC for 6 hours. Thereafter, the remaining 1,7-octadiene was removed under reduced pressure to obtain a reaction product. The reaction product was analyzed by gas chromatography and NMR. 0.5 ml of reaction product was diluted with 2 ml of Normal-decane, after which distilled water and hydrochloric acid were added to decompose and used for the analysis. As a result, it was confirmed that octenyl diisobutylaluminum was produced quantitatively.

Example  1: aromatic vinyl compound or olefin-aromatic vinyl compound Alkenyl Dial Copolymerization of Kiel Aluminum

Toluene and octenyldiisobutylaluminum (0.007 mol), an aromatic vinyl compound or an olefin-aromatic vinyl compound (0.036 mol) were added to a 100 ml glass reactor with half-cells. The addition amount of toluene was adjusted so that the total volume of octenyl diisobutyl aluminum (0.007 mol), an aromatic vinyl compound or an olefin-aromatic vinyl compound, and toluene might be 30 ml. After adjusting the reactor temperature to 40 ° C., 20 μmol of triphenyl carbenium tetrakis (pentafluorophenyl) borate ([Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]) as a catalyst, dimethyl silylene flu Orene amido dimethyl titanium ([t-BuNSiMe ₂ Flu] TiMe ₂ ) was added as a toluene solution to 20 mol, and polymerization was carried out at 40 ° C. for 10 minutes. After 10 minutes, a small amount of methanol and hydrochloric acid were added directly to terminate the polymerization reaction. The reaction product was separated and dried under reduced pressure at 60 ° C. for 6 hours to obtain a copolymer. The weight and physical properties of the copolymer were measured and shown in Table 1 below.

Alkenylalkyl Aluminum Supply Quantity Mn (× 10 ⁴ ) Mw / Mn Formula 3
unit mol g - - mol% Example 1 0.007 0.67 7.08 2.56 9 Example 2 0.014 0.74 5.02 2.87 12 Example 3 0.028 0.93 4.39 3.32 19

Example  2-3: aromatic vinyl compound or olefin-aromatic vinyl compound Alkenyl Dialkyl  Copolymerization of Aluminum

The copolymerization was carried out in the same manner as in Example 1 except that the addition amount of octenyldiisobutylaluminum to be added was changed as shown in Table 1 above. The number and physical properties of the polymer and the polymer of the produced aromatic vinyl compound or olefin-aromatic vinyl compound copolymer are as shown in Table 1.

Example  4-6: Olefin-Aromatic Vinyl compound  Introduction of polar groups into the copolymer

To the polymer obtained in Examples 1 to 3 above, dry oxygen was introduced at room temperature in an amount of 200 ml / min for 1.5 hours. Thereafter, the reaction product was fractionated and dried under reduced pressure at 60 ° C. for about 6 hours to obtain an aromatic vinyl compound or an olefin-aromatic vinyl compound copolymer containing a hydroxyl group. Physical properties of the copolymers are shown in Table 2 below.

Alkenylalkyl Aluminum Supply Quantity Mn (x10 ⁴ ) Mw / Mn Formula 3
unit Formula 1
unit mol g - - mol% mol% Example 4 0.007 0.78 5.12 4.25 2 6 Example 5 0.014 0.89 3.23 5.11 4 9 Example 6 0.028 0.96 2.07 4.67 5 15

Claims (9)

In the method for producing a copolymer or a terpolymer comprising a unit of the formula (1),
An aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; Polymerizing an alkenyldialkylaluminum compound represented by the following Chemical Formula 2 to obtain a copolymer or a terpolymer comprising a unit of the following Chemical Formula 3; And
Contacting the copolymer or terpolymer comprising the unit of Formula 3 with oxygen, carbon dioxide or sulfur trioxide for reaction;
Half metallocene compound represented by the following formula (4) as a catalyst during the polymerization; And aluminoxane or boron compounds.
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Formulas 1 to 3,
X represents OH, COOH, SOOH or SO ₃ H,
R ¹ and R ² are the same as or different from each other, and each independently represent a C _1-20 alkyl group,
n represents an integer of 1 to 20;
In Formula 4,
M represents Ti, Zr or Hf,
R ¹ , R ² and R ³ are the same as or different from each other, and each independently represent a C _1-5 alkyl group,
R ⁴ and R ⁵ are the same as or different from each other, and each independently represent a C _1-3 alkyl group or a halogen.
According to claim 1, wherein the alkenyldialkyl aluminum compound is propenyl diethyl aluminum, propenyl diisobutyl aluminum, pentenyl diethyl aluminum, pentenyl diisobutyl aluminum, hexenyl diisobutyl aluminum, hexenyl diethyl aluminum, At least one selected from the group consisting of octenyl diisobutyl aluminum, octenyl diethyl aluminum, dekenyl diisobutyl aluminum, dodekenyl diisobutyl aluminum, and undekenyl diisobutyl aluminum.
delete The method of claim 1, wherein the half-metallocene compound of Formula 4 is (i-PrNSiMe ₂ Flu) TiMe ₂ , (i-BuNSiMe ₂ Flu) TiMe ₂ , (t-BuNSiMe ₂ Flu) TiMe ₂ , (i-PrNSiMe ₂ Flu) TiCl ₂ , (i-BuNSiMe ₂ Flu) TiCl ₂ , (t-BuNSiMe ₂ Flu) TiCl ₂ , (i-PrNSiMe ₂ Flu) ZrMe ₂ , (i-BuNSiMe ₂ Flu) ZrMe ₂ , (t-BuNSiMe ₂ Flu) ZrMe ₂ , (i-PrNSiMe ₂ Flu) ZrCl ₂ , (i-BuNSiMe ₂ Flu) ZrCl ₂ , (t-BuNSiMe ₂ Flu) ZrCl ₂ , (i-PrNSiMe ₂ Flu) HfMe ₂ , (i-BuNSiMe ₂ Flu) HfMe ₂ , (t-BuNSiMe ₂ Flu) HfMe ₂ , (i-PrNSiMe ₂ Flu) HfCl ₂ , (i-BuNSiMe ₂ Flu) HfCl ₂ and (t-BuNSiMe ₂ Flu) HfCl ₂ Production method that is one or more.
According to claim 1, wherein the aluminoxane is methyl aluminum oxane (PMAO) which is a condensation reaction of trimethyl aluminum (TMA) and water; And modified methylaluminum oxane (MMAO) resulting from the condensation reaction of a mixture of trimethylaluminum (TMA), triethylaluminum (TEA) or triisobutylaluminum (TIBA) with a small amount of trimethylaluminum (TMA) and water. At least one production method selected from the group consisting of.
The boron compound of claim 1, wherein the boron compound is triphenyl carbenium tetrakis (pentafluorophenyl) borate ([Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]), N, N-dimethyl aniline tetrakis (Pentafluorophenyl) borate, a ferrocerium tetrakis (pentafluorophenyl) borate, and a tris (pentafluorophenyl) borate.
The method of claim 1, wherein the aromatic vinyl compound monomer or a mixture of an olefin monomer and an aromatic vinyl compound monomer; The molar ratio of the alkenyldialkylaluminum compound is 1: 0.001-1: 10.
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