KR100880519B1 - Olefin-Acrylate-Maleic Acid Anhydride-Norbornene Four-Composite Copolymer and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer obtained by polymerizing a monomer mixture consisting of an olefin, an acrylate, maleic anhydride and a norbornene compound with a radical initiator in the presence of a metal oxide or a Lewis acid; The manufacturing method is disclosed. In the method for preparing an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer of the present invention, a metal oxide or a Lewis acid is used to polymerize an appropriate amount of an olefin monomer necessary for physical properties even under mild and low pressure mild reaction conditions. Copolymers can be prepared, and the solid type metal oxides used can be recovered and reused to ensure economical efficiency, and the problem of impurities in the polymers can be fundamentally solved to produce high purity polymers. The copolymer prepared by the above method is an amorphous polymer having a high content of polar groups, and has excellent transparency, and has a relatively high glass transition temperature because it simultaneously contains an olefin and a norbornene compound.

Olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, Lewis acid, metal oxide, glass transition temperature

Description

Olefin-Acrylate-Maleic Acid Anhydride-Norbornene Four-Composite Copolymer and Method for Preparing the Same}

1 is a graph showing the results of DSC experiments on the copolymers obtained in Comparative Examples 3 to 5 and Example 1. FIG.

2 is a graph showing the FT-IR measurement results for the copolymers obtained in Comparative Examples 3 to 5 and Example 1. FIG.

The present invention provides a process for preparing quaternary copolymers of olefins, acrylates, maleic anhydrides and norbornenes that are amorphous using Lewis acids or metal oxides, olefins, acrylates, maleic anhydrides and The present invention relates to an optical film comprising a tetrapolymer of norbornene and the tetrapolymer.

 Copolymerization of polar vinyl monomers with nonpolar α-olefins is expected to improve the range of polymer properties currently available. The two types of monomers are generally polymerized through different mechanisms. The polar vinyl monomers such as alkyl (meth) acrylates are free radical polymerization, and the nonpolar α-olefins are polymerized in the presence of a transition metal catalyst. have. In the case of α-olefins, free radical polymerization produces branched polymers only in harsh conditions. Thus, the general prior art of α-olefins and alkyl (meth) acrylate copolymers is a high temperature and high pressure reaction that increases the amount of comonomer incorporation under severe conditions of at least 1000 atm and at least 100 degrees. Therefore, there is a need for a radical polymerization method capable of copolymerizing them at low temperature and low pressure conditions.

On the other hand, α-olefin-alkyl (meth) acrylate-based copolymers do not break well as the ethylene content increases in the polymer chain, thereby improving film properties and increasing pyrolysis temperature, while lowering the glass transition temperature. have. The ethylene-acrylate copolymer is suitable for being used as an optical material because of its high transparency and adhesiveness, but in order to be used for the above purpose, the ethylene-acrylate copolymer should be excellent in heat resistance so that deformation is not caused by heat generated during operation of the optical device.

Representative monomers for improving heat resistance while maintaining transparency are norbornene, an aliphatic cyclic olefin. Polynorbornene obtained by homopolymerization is about 300 ℃ glass transition temperature can be improved heat resistance when forming a three-way copolymer with the monomers. However, norbornene is known as an olefin that is difficult to radically polymerize. Therefore, it is difficult to prepare a comonomer containing norbornene in an appropriate ratio by radical polymerization.

Therefore, it is required to develop a copolymer having improved physical properties such as heat resistance by solving the problems of the existing radical polymerization method and making the manufacturing process easy and the high norbornene content.

An object of the present invention is to provide an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer in which the problems of the prior art are overcome. The quaternary copolymer of the present invention can be particularly applied to an optical film because it has a high content of a polar group monomer and has excellent crystallinity and excellent adhesion with a material such as a metal. The α-olefin-alkyl (meth) acrylate copolymerized without the third monomer does not break well as the ethylene content increases in the polymer chain, thereby improving film properties and increasing thermal decomposition temperature (Td). There is a disadvantage that the temperature (Tg) is low. However, the present invention can provide a polymer resin having a glass transition temperature sufficient for application to an optical material by introducing maleic anhydride and norbornene as additional monomer components.

It is also an object of the present invention to provide a process for the preparation of the above olefin-acrylate-maleic anhydride-norbornene quaternary copolymers. According to the production method of the present invention, since the monomers are polymerized by a radical polymerization initiator in the presence of Lewis acid or a metal oxide, a copolymer can be produced even under mild reaction conditions at low temperature and low pressure, and particularly, a solid type metal oxide is used. In this case, there is an advantage in that the used metal oxide can be easily recovered and reused, and it is easy to separate and purify, that is, there is an advantage that a high purity polymer can be obtained without contaminating the produced polymer.

It is also an object of the present invention to provide an optical film comprising the olefin-acrylate-maleic anhydride-norbornene quaternary copolymer described above.

The present invention provides an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer in which an olefin monomer, an acrylate monomer, a maleic anhydride monomer and a norbornene monomer are polymerized.

As the content of monomers for the quaternary copolymer of the present invention, 1 to 48 mol% of olefin monomers, preferably 1 to 38 mol%, 50 to 97 mol% of acrylate monomers, preferably 60 to 97 mol% It is preferable that it is 1-48 mol% of maleic anhydride monomer, Preferably it is 1-38 mol%, and 1-48 mol% of norbornene monomer, Preferably it is 1-38 mol%. In addition, the quaternary copolymer of the present invention has a glass transition temperature (Tg) in the range of 90 to 300 ° C., a number average molecular weight in the range of 5,000 to 400,000, a weight average molecular weight in the range of 10,000 to 800,000, or an initial weight in the range of 300 to 500 ° It is preferred to have a temperature Td _{50 at} which 50% is decomposed.

The present invention also encompasses olefin-acrylate-maleic anhydride-norbornene comprising the step of polymerizing an olefin monomer, an acrylate monomer, a maleic anhydride monomer and a norbornene monomer with a radical polymerization initiator in the presence of a Lewis acid or a metal oxide. Provided are methods for preparing quaternary copolymers.

In the production method of the quaternary copolymer of the present invention, the Lewis acid or metal oxide to be used is preferably used in the range of 0.01 to 200 mol% based on the acrylate-based comonomer, and the content of each monomer used is As mentioned above, the content of the polymerization initiator used is preferably in the range of 0.01 to 10 mol% based on the acrylate monomer. In the case where the olefin monomer to be used is present in a gaseous state under the reaction conditions, particularly in the case of ethylene or propylene, preferably, at a reaction condition of 5 to 200 atm and 30 to 150 ° C, more preferably 20 to 50 The polymerization reaction is carried out at atmospheric pressure and reaction conditions of 50 ~ 80 ℃.

On the other hand, the monomers that can be used in the present invention are as described below.

With respect to the Lewis acid and the metal oxide described herein, the metal oxide used in the present invention is conceptually included in the Lewis acid because it serves as a Lewis acid substantially providing an acid site in the polymerization reaction of the present invention. will be. However, compared to other Lewis acids in general, there is no change in structure or composition substantially after the polymerization reaction, and thus there is an additional advantage that it is not only simple to separate but also reusable. It will be called a metal oxide.

It is also to be understood that norbornene monomers described herein include norbornene as well as norbornene derivatives having substituents.

In addition, the acrylate monomers described in the present specification mean not only acrylates but also acrylate-based monomers, and should be understood as concepts including alkyl acrylates, alkyl methacrylates, and the like, which will be described in detail below.

It may also be understood that the maleic anhydride monomers described herein include maleic anhydride derivatives having substituents as well as maleic anhydride.

The olefin-acrylate-maleic anhydride-norbornene quaternary copolymer described herein refers to a copolymer formed by polymerization of an olefin monomer, an acrylate-based monomer, a maleic anhydride monomer and a norbornene monomer. The structure is expressed in these terms, and it will be readily understood by those skilled in the art that the double bond of monomers does not actually exist in the main chain chain of the copolymer of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer in which an olefin monomer, an acrylate monomer, a maleic anhydride monomer and a norbornene monomer are polymerized.

The olefin monomer used for the preparation of the copolymer of the present invention is not particularly limited as long as it is an olefin having a double bond in the terminal or the middle of the carbon chain. Examples of the α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Examples of the olefin having a bond include 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 2-octene, 2-nonene and the like.

The norbornene monomer used for the preparation of the copolymer of the present invention is a norbornene derivative or a norbornene derivative having a substituent, and representative examples thereof include a norbornene compound represented by the following Chemical Formula 1.

<Formula 1>

Where

m is an integer from 0 to 4,

R ₇ , R ′ ₇ , R ″ ₇ and R ′ ″ ₇ each independently represent a polar functional group or a nonpolar functional group;

R ₇ , R ′ ₇ , R ″ ₇ and R ′ ″ ₇ may be linked to each other to form a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms.

According to one embodiment of the invention, the nonpolar functional group is hydrogen; halogen; Linear or branched alkyl or haloalkyl having 1 to 20 carbon atoms; Linear or branched alkenyl or haloalkenyl having 2 to 20 carbon atoms; Linear or branched alkynyl or haloalkynyl having 2 to 20 carbon atoms; Substituted by linear or branched alkyl or haloalkyl of 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl of 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl of 2 to 20 carbon atoms, or halogen Or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted by linear or branched alkyl or haloalkyl of 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl of 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl of 2 to 20 carbon atoms, or halogen Or unsubstituted aryl having 6 to 40 carbon atoms; Or linear or branched alkyl or haloalkyl having 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl having 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl having 2 to 20 carbon atoms, or halogen Substituted or unsubstituted aralkyl having 7 to 15 carbon atoms;

The polar functional group is a non-hydrocarbonaceous polar group including at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron,

-R ⁸ OR ⁹ , -OR ⁹ , -OC (O) OR ⁹ , -R ⁸ OC (O) OR ⁹ , -C (O) R ⁹ , -R ⁸ C (O) R ⁹ , -OC (O ) R ⁹ , -R ⁸ C (O) OR ⁹ , -C (O) OR ⁹ , -R ⁸ OC (O) R ⁹ ,-(R ⁸ O) _k -R ⁹ ,-(R ⁸ O) _k -OR ⁹ , -C (O) -OC (O) R ⁹ , -R ⁸ C (O) -OC (O) R ⁹ , -SR ⁹ , -R ⁸ SR ⁹ , -SSR ⁹ , -R ⁸ SSR ⁹ , -S (= O) R ⁹ , -R ⁸ S (= O) R ⁹ , -R ⁸ C (= S) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C = S, -NCO, -R ⁸ -NCO, -CN, -R ⁸ CN, -NNC (= S) R ⁹ , -R ⁸ NNC (= S R ⁹ , -NO ₂ , -R ⁸ NO ₂ ,

이며,

Is,

In the polar functional group,

R ⁸ and R ¹¹ are each independently linear or branched alkylene or haloalkylene having 1 to 20 carbon atoms; Linear or branched alkenylene or haloalkenylene having 2 to 20 carbon atoms; Linear or branched alkynylene or haloalkynylene having 2 to 20 carbon atoms; Substituted by linear or branched alkyl or haloalkyl of 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl of 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl of 2 to 20 carbon atoms, or halogen Or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted by linear or branched alkyl or haloalkyl of 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl of 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl of 2 to 20 carbon atoms, or halogen Or unsubstituted arylene having 6 to 40 carbon atoms; Or linear or branched alkyl or haloalkyl having 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl having 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl having 2 to 20 carbon atoms, or halogen Substituted or unsubstituted aralkylene having 7 to 15 carbon atoms;

R ⁹ , R ¹² , R ¹³ and R ¹⁴ are each independently hydrogen; halogen; Linear or branched alkyl or haloalkyl having 1 to 20 carbon atoms; Linear or branched alkenyl or haloalkenyl having 2 to 20 carbon atoms; Linear or branched alkynyl, or haloalkynyl, having 2 to 20 carbon atoms; Substituted by linear or branched alkyl or haloalkyl of 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl of 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl of 2 to 20 carbon atoms, or halogen Or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted by linear or branched alkyl or haloalkyl of 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl of 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl of 2 to 20 carbon atoms, or halogen Or unsubstituted aryl having 6 to 40 carbon atoms; Or linear or branched alkyl or haloalkyl having 1 to 20 carbon atoms, linear or branched alkenyl or haloalkenyl having 2 to 20 carbon atoms, linear or branched alkynyl or haloalkynyl having 2 to 20 carbon atoms, or halogen Substituted or unsubstituted aralkyl having 7 to 15 carbon atoms; Linear or branched alkoxy or haloalkoxy having 1 to 20 carbon atoms; Carbonyloxy, or halocarbonyloxy;

It is preferable that each k is an integer of 1-10.

Norbornene compounds used as norbornene monomers in the present invention are 5-ethylester-2-norbornene, t-butyl-5-norbornene-2-carboxylate (NB-TBE), methyl-5-norbornene-2 One or more selected from the group consisting of -methyl-2-carboxylate (Nb-MMA), 5-methylene-2-norbornene, norbornene, and 5-n-butyl-2-norbornene.

The content of the olefin monomer and norbornene monomer used as the monomer for the copolymer of the present invention is 1 to 48 mol%, preferably 1 to 38 mol%, respectively. In addition, it is preferable that the sum of the content of the olefin monomer and the content of the norbornene monomer does not deviate greatly from the above range, and particularly preferably 10 mol% to 50 mol%. When the polymer consists of only the polar group monomer without the olefin or norbornene monomer, there is a problem of brittleness, especially when the sum of the olefin and norbornene monomer content is about 10 mol% or less, the copolymer of the present invention is brittle when forming the film. Due to the problem, it is inappropriate to be used as a laminated film of an optical material. However, the fragile problem may be applied to other applications where the physical properties do not have a significant effect. On the other hand, when the sum of the contents is more than 50 mol%, since the content of the polar monomers is small, the physical properties obtained from the polar group may not meet the required degree in some cases. Therefore, the copolymer of the present invention can control the physical properties by adjusting the content ratio of polar monomers and non-polar monomers can have a variety of adaptability.

The acrylate monomer used for the preparation of the copolymer of the present invention is sufficient as long as it has a compound having a double bond between the carbonyl group of the ester group and the conjugated (conjugated) carbon, and its substituent is not particularly limited. Examples of such acrylate monomers may include a compound represented by the following formula (2).

<Formula 2>

Where

R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms which may include a hetero atom; R ₄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As another example, wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom; A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 12 carbon atoms, an arylalkyl group having 6 to 18 carbon atoms, an alkylaryl group having 6 to 18 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; Carbamoyl group; Amino group; Or a silyl group.

As another example, in the above formula, the substituents (R ₁ , R ₂ and R ₃ ) to be substituted are preferably an amino group, an alkoxy group having 1 to 6 carbon atoms, a carbamoyl group or a silyl group.

As another example, the acrylate monomer may be an alkyl acrylate including a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl, or an alkyl methacrylate including a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl. Or alkyl butyacrylate containing a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl.

More specifically the acrylate monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, and 2- ethylhexyl acrylate with a C _5-12 alcohol Neo and the preferred acrylic acid esters such as the isomers, particularly preferred comonomers are n- alkyl methacrylate.

The content of such an acrylate monomer contained in the copolymer of the present invention as a repeating unit is 50 to 97 mol%, preferably 60 to 97 mol%.

When the content of the acrylate comonomer, which is the polar monomer, increases, it is possible to prevent crystallinity, which is inherent in olefins such as ethylene, and thus to prepare an amorphous copolymer. Such amorphous olefin-acrylate copolymers were difficult to manufacture in the prior art. The amorphous copolymer can be used as an optical material because of its high transparency and excellent adhesiveness. In particular, the amorphous copolymer has many polar functional groups, and thus has excellent adhesion to metals, and thus is advantageous for application as an electric device.

In the reaction, when the amount of the acrylate-based comonomer is less than 50 mol% based on the total amount of the monomers, there is a problem in bonding, and when it exceeds 97 mol%, there is a problem of brittleness. In addition, in order to apply the copolymer of the present invention to the laminated film for an optical material, the amount of the acrylate-based monomer needs to be adjusted to 95 mol% or less, more preferably 90 mol% or less in order to alleviate the fracture property during film formation. have.

The maleic anhydride monomer used for the preparation of the copolymer of the present invention may be a maleic anhydride compound selected from the group consisting of maleic anhydride, maleic anhydride derivative substituted with at least one or more substituents.

The content of such maleic anhydride monomer contained in the copolymer of the present invention as a repeating unit is 1 to 48 mol%, preferably 1 to 38 mol%. When the maleic anhydride monomer is introduced as a component of the copolymer of the present invention, since the copolymer of the present invention has a high glass transition temperature and excellent adhesion, etc., it can be used as an optical material, and especially includes a lot of polar functional groups. It is excellent in adhesion to metals and the like, which is advantageous for application as an electric device.

This copolymer of the present invention has a glass transition temperature (Tg) in the range of 90 ~ 300 ℃. In addition, the copolymer of the present invention preferably has a number average molecular weight in the range of 5,000 to 400,000 or a weight average molecular weight in the range of 10,000 to 800,000, and the temperature (Td50) at which 50% of the initial weight of the copolymer is decomposed is 300 to 500 ° C. It is preferable to have a range of.

Specific examples of the copolymer according to the present invention include an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer represented by the following formula (3).

<Formula 3>

Wherein each substituent and m are as mentioned above, and the structural formulas in square brackets [] indicate the basic arrangement of monomer repeat units of the copolymer of the present invention, and n means that the arrangement of the monomer repeat units is repeated. A, b, c and d are the minimum number determined by the content ratio (mol%) of the monomers, and may be expressed as real numbers if they have an integer in the arrangement of one repeating unit but average over the entire copolymer. have. Therefore, the copolymer of the present invention is that each monomer is copolymerized randomly.

Such a copolymer of the present invention is a random copolymer of the monomers as described above, since the content of the polar group is extremely high so that the crystallinity of the olefin such as ethylene does not exist, it is transparent even after processing into a polymer film or the like, norbornene and male Since it contains an acid anhydride, it has a relatively high glass transition temperature and improves adhesion compared to a copolymer in which olefins and acrylates are polymerized, and thus may be suitably used for applications such as optical materials.

The present invention also provides the above-mentioned olefin-acrylate-maleic anhydride- comprising the step of polymerizing an olefin monomer, an acrylate monomer, a maleic anhydride monomer and a norbornene monomer by a radical polymerization initiator in the presence of a Lewis acid or a metal oxide. Provided is a method for preparing a norbornene quaternary copolymer.

The type and amount of monomers used in the process of the invention and the structure and properties of the resulting copolymers are as described above.

The copolymer production method of the present invention is characterized in that the monomers are polymerized by a radical initiator in the presence of a Lewis acid or a metal oxide. The metal oxide used in the present invention is conceptually included in the Lewis acid because it serves as a Lewis acid which provides an acid site substantially in the polymerization reaction of the present invention. However, compared to other Lewis acids in general, there is no change in structure or composition substantially after the polymerization reaction, and thus there is an additional advantage that it is not only simple to separate but also reusable. It will be called a metal oxide.

It is preferable that the metal oxide used in the copolymer manufacturing method of this invention is a compound represented by following formula (4).

<Formula 4>

M _x N _y O _z

In the above formula

M represents at least one selected from the group consisting of alkaline earth metals, transition metals, group 13, and group 14 metals;

N represents a Group 5 or 6 atom;

O represents an oxygen atom;

x, y and z are values determined by the oxidation state of M and N,

x> 0, y> 0, and z> 0.

More specifically, the metal oxide may be aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ), silicon oxide (SiO ₂ ), boron oxide (B ₂ O ₃ ), cesium oxide (CeO ₂ ), dysprosium oxide (Dy ₂ O ₃ ), erbium oxide (Er ₂ O ₃ ), europium oxide (Eu ₂ O ₃ ), gadolinium oxide (Gd ₂ O ₃ ), Holmium oxide (Ho ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ), ruthetium oxide (Lu ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ), praseodymium oxide (Pr ₆ O ₁₁ ), samarium oxide (Sm ₂ O ₃ ), terbium oxide (Tb ₂ O ₃ ), thorium oxide (Th ₄ O ₇ ), thorium oxide (Tm ₂ O ₃ ), ytterbium oxide (Yb ₂ O ₃ ), tin oxide (SnO), and titanium oxide ( Metal oxides such as TiO ₂ ) and dysprosium aluminate (Dy ₃ Al ₅ O ₁₂ ), yttrium aluminate (Y ₃ Al ₅ O ₁₂ ), aluminum titanate (Al ₂ O ₃ ㆍ TiO ₂ ), aluminum silicate (3Al ₂ O ₃ ㆍ SiO ₂ ), calcium titanate (CaTiO ₃ ), calcium zirconate (Ca Composite metal oxides such as ZrO ₃ ), iron titanate (FeTiO ₃ ), magnesium aluminate (MgO.Al ₂ O ₃ ), cesium aluminate (CeAl ₁₁ O ₁₈ ), Al ₂ (SO ₄ ) ₃ , and AlPO ₄ It is preferably one or more selected from the group consisting of.

The metal oxide used in the present invention is not only economical because it can recover nearly 100% of the metal oxide even by a physical method using only a filtering device, and the recovered metal oxide can be used for polymerization again. It offers the advantage of high purity. The recovered metal oxide can generally be reused about 20 times.

Lewis acids used in the present invention are selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin a Lewis acid is preferred, and halides, triflate (triflate) which is formed to include one or more metal ^{_{cations, HPO 3 2-, H 3 PO}} 2 -, CF 3 COO -, C 7 H 15 OSO 2 - and SO ₄ ^{2 -} preferably comprises at least one anion selected from the group consisting of.

More specifically, the Lewis acid used in the method for preparing the olefin-acrylate-maleic anhydride-norbornene quaternary copolymer of the present invention is boron trifluoride, ethyl boron trichloride, boron trifluoride, boron tribo Chlorides such as romanide, boron triionide, aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, stanic chloride, zinc dichloride, copper dichloride, nickel chloride, and the like. Along with the fluoride-based Lewis acid, a trilate-based Lewis acid such as aluminum triflate, scandiqu triflate, copper triflate, yttrium triflate and zinc triflate can be used.

For example, Lewis acids suitable for the present invention include ZnBr ₂ , ZnI ₂ , ZnCl ₂ , ZnSO ₄ , CuCl ₂ , CuCl, Cu (O ₃ SCF ₃ ), described in US Patent Nos. 6,127,567, 6,171,996 and 6,380,421, and the like. ₂ , CoCl ₂ , CoI ₂ , FeI ₂ , FeCl ₃ , FeCl ₂ , FeCl ₂ (THF) ₂ , TiCl ₃ (THF) ₂ , TiCl ₄ , TiCl ₃ , ClTi (Oi-propyl) ₃ , MnCl ₂ , ScCl ₃ , AlCl ₃ , (C ₈ H ₁₇ ) AlCl ₂ , (C ₈ H ₁₇ ) ₂ AlCl, (iC ₄ H ₉ ) ₂ AlCl, (C ₆ H ₅ ) ₂ AlCl, (C ₆ H ₅ ) AlCl ₂ , ReCl ₅ , ZrCl ₄ , NbCl ₅ , VCl ₃ , CrCl ₂ , MoCl ₅ , YCl ₃ , CdCl ₂ , LaCl ₃ , Er (O ₃ SCF ₃ ) ₃ , Yb (O ₂ CCF ₃ ) ₃ , SmCl ₃ , B (C ₆ H ₅ ) ₃ and TaCl ₅ and the like. And metal salts such as ZnCl ₂ , CoI ₂ , SnCl ₂ , and the like described in US Patent Nos. 3,496,217, 3,496,218 and 4,774,353, RAlCl ₂ , RSnO ₃ SCF ₃ and R ₃ B, wherein R is an alkyl group or an aryl group. Organometallic compounds such as) are also suitable.

According to U.S. Patent No. 3,773,809, the anionic moiety is a halide such as fluoride, chloride, bromide and iodide, an anion of a lower fatty acid having 2 to 7 carbon atoms, HPO ₃ ^2- , H ₃ PO ^{2 _{-, CF 3 COO -, C}} 7 H 15 OSO 2 - or SO ₄ ^{2 -} may be selected from the group consisting of zinc, cadmium, beryllium, aluminum, gallium, indium, thallium, titanium, zirconium, hafnium, erbium, Germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt, preferably zinc, cadmium, titanium, tin, chromium, iron and cobalt It is also possible to use metals in cationic form.

U. S. Patent No. 3,773, 809 also discloses borohydrides, organoborohydrides and borate salts of the formula R ₃ B or B (OR) ₃ as suitable promoters, wherein R is hydrogen, having from 6 to 18 carbon atoms. From the group consisting of an aryl group substituted by an aryl group, an alkyl group having 1 to 7 carbon atoms, a cyano-substituted alkyl group having 1 to 7 carbon atoms, preferably triphenylborone Selected) is disclosed.

In the present invention, the term Lewis acid is used in the cocatalysts mentioned in US Patent Nos. 3,496,217, 3,496,218, 4,774,353, 4,874,884, 6,127,567, 6,171,996 and 6,380,421 in addition to the scope of the compounds described above. Include.

Among the above-mentioned Lewis acids, in particular metal salts, particularly preferably metal halides such as fluorides, chlorides, bromide and iodides, in particular chlorides, aluminum (III) chloride, zinc chloride, iron (II) chloride And iron (III) chloride are particularly preferred.

In the production method of the present invention, the metal oxide or the Lewis acid is preferably used 0.01 to 200 mol% based on the acrylate-based comonomer.

The present invention can appropriately control and control the content of the monomers included in the repeating unit in the copolymer produced by using a metal oxide or Lewis acid according to the required physical properties. Particularly when the olefin monomer present in the gas phase under the reaction conditions such as ethylene or propylene is partially dissolved in the solvent to participate in the polymerization reaction, the metal oxide or Lewis acid may be polymerized in an appropriate amount of the olefin monomer necessary for the required physical properties of the copolymer to be produced. It may serve to control, and also as described below, serves to make the polymerization reaction at a low temperature low pressure as compared to the prior art.

The radical initiator used in the production method of the present invention is preferably a peroxide, an azo compound or the like. More specifically, examples of the peroxide compound include hydrogen peroxide, decanonyl peroxide, t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, 3,5,5-trimethyl hexanoyl peroxide, diethyl peroxide t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxy isobutyrate, benzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxy benzoate, di-t-butyl peroxide, t Amyl peroxy neodecanoate, t-amyl peroxy pivalate, t-amyl peroxy-2-ethyl hexanoate and 1,1,3,3-tetramethyl butyl hydroperoxide; Alkali metal persulfates, perborates and percarbonates, and examples of azo compounds include 2,2'-azo-bis (isobutyronitrile) (AIBN) (2,2'-azo-bis (isobutyronitrile) Azo compounds such as Preferred initiators are azo compounds. Mixtures of such initiators may also be used.

The initiator may be added to the reaction stream in any suitable manner, such as in pure form, in dissolved form in a suitable solvent, and / or mixed with a monomer or comonomer feed stream. Regarding the amount of radical initiator used in preparing the copolymer of the present invention, the ratio of the mole number of the radical initiator to the mole number of the acrylate monomer is preferably 1: 0.0001 to 1: 0.1, but is not necessarily limited thereto. It can be used accordingly.

The polymerization reaction of the invention is preferably carried out in a solvent, in particular an organic solvent. Examples of such solvents are preferably, but not necessarily limited to, one or more solvents selected from the group consisting of toluene, chlorobenzene, n-hexane, heptane, tetrahydrofuran, ether, methanol, ethanol, chloroform, and methylene chloride. . That is, the solvent that can be used in the technical field of the present invention is not particularly limited.

In the polymerization reaction of the present invention, norbornene monomer, acrylate monomer and maleic anhydride monomer are generally present in the liquid phase under the reaction conditions, so that they are dissolved in a solvent and participate in the polymerization reaction. Therefore, the reaction pressure is not particularly limited as long as the monomers used in the present invention can exist in the liquid phase under the reaction conditions.

On the other hand, since the olefin monomer is generally present in the gaseous state under the reaction conditions, especially in the case of ethylene and propylene, in order to contain the olefin monomer in an appropriate amount in the repeating unit of the copolymer of the present invention, a high pressure reaction condition is required. The reaction pressure is not particularly limited if it is present in the liquid phase.

The polymerization reaction of the present invention can be carried out under mild conditions of 200 atm and 150 ° C. or less, preferably 100 ° C. or less, unlike the prior art requiring harsh reaction conditions of at least 1000 atm and 100 ° C. and high temperature and high pressure. There is a simple process, it is easy to control the physical properties of the copolymer produced. In addition, the metal oxide according to the present invention is particularly excellent in water safety, efficient and recyclable.

The manufacturing method of the present invention, unlike the prior art by using a metal oxide or Lewis acid can avoid the harsh conditions of high temperature and high pressure, the process is simple. In addition, since the used metal oxide can be easily recovered and recycled 100% with only the filtering device after polymerization, the manufacturing cost can be significantly reduced. In addition, it has high water and air stability, high efficiency, and can simplify the polymerization process.

Specifically, the reaction conditions for the polymerization of the present invention, when the olefin monomer is gaseous under the reaction conditions, the polymerization reaction is preferably made at a pressure of 5 to 200 atm and temperature conditions of 30 to 150 ℃, particularly preferably The reaction is carried out at a pressure of 20 to 50 atm and temperature conditions of 50 to 80 ℃.

If the pressure is less than 5 atm, there is a problem that the olefin content is lowered, if the pressure exceeds 200 atm it is necessary to install additional equipment in the process. And if the temperature is less than 30 ℃ there is a problem that the initiator is not activated, if it exceeds 150 ℃ there is a problem of excess unreacted monomer generation and process control.

One specific embodiment of the present invention uses ethylene as an olefin monomer, norbornene as a norbornene monomer, methyl methacrylate or methyl acrylate as an acrylate monomer, maleic anhydride as a maleic anhydride monomer, and aluminum oxide as a metal oxide. To polymerize AIBN as a polymerization initiator at a pressure of 5 to 60 atm and a temperature of 50 to 80 ° C.

The olefin-acrylate-maleic anhydride-norbornene quaternary copolymer produced by such a polymerization reaction of the present invention can be particularly suitably used for the production of an optical film. Since the optical film including the copolymer of the present invention is manufactured using a copolymer resin having high light transmittance, glass transition temperature, and toughness, the optical film has high light transmittance and has high adhesive content due to high content of monomer having polar functional groups. It is suitable for use as a laminated film such as a polarizing plate. Therefore, it is also possible to produce a polarizing film through post-treatment with a retardation compensation film having a birefringence and an iodine solution through stretching, or other various optical films.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are only for illustrating the present invention, the present invention is not limited to these.

The organic reagents and solvents required for the polymerization were purified by a standard method by Aldrich, and ethylene was polymerized after passing a high purity product of Applied Gas Technology through a water and oxygen filtration device.

In order to obtain a monomer content ratio in the copolymer, spectra were obtained using 500 MHz NMR manufactured by Varian. The glass properties, Tg, which is a thermal property of the obtained polymer, were measured in DSC Q100 from TA Instrument, and Td_50 (50% pyrolysis temperature) was used for TGA of the same company.

Molecular weight and molecular weight distribution were obtained by gel permeation chromatography (GPC) analysis from Waters. The analytical temperature was 25 ° C., tetrahydrofuran (THF) was used as the solvent, and standardized with polystyrene to obtain the number average molecular weight (Mn) and the weight average molecular weight (Mw).

Preparation of Polymer

Comparative Example 1

56.1 mmol of norbornene was added to an argon atmosphere reactor. And 0.274 mmol of initiator AIBN dissolved in toluene was added. The reactor temperature was then raised to 70 ° C. and polymerization was carried out for 20 hours.

Comparative Example 2

28.1 mmol of methyl methacrylate and 28.1 mmol of norbornene were added to an argon atmosphere reactor. Then, 9.3 mmol of aluminum chloride as Lewis acid and 1.4 mmol of initiator AIBN dissolved in toluene were added thereto. Subsequently, 30 bar of ethylene was charged to the reactor and the reactor temperature was raised to 70 ° C. and polymerization was carried out for 20 hours.

Comparative Example 3

28.1 mmol of maleic anhydride and 28.1 mmol of norbornene were added to an argon atmosphere reactor. Then, 1.4 mmol of the initiator AIBN dissolved in toluene was added. The reactor temperature was then raised to 70 ° C. and polymerization was carried out for 20 hours.

Comparative Example 4

Into an argon atmosphere, 18.7 mmol of methyl methacrylate, 18.7 mmol of maleic anhydride, and 18.7 mmol of norbornene were added. Then, 1.4 mmol of the initiator AIBN dissolved in toluene was added. The reactor temperature was then raised to 70 ° C. and polymerization was carried out for 20 hours.

Comparative Example 5

Into an argon atmosphere, 18.7 mmol of methyl methacrylate, 18.7 mmol of maleic anhydride, and 18.7 mmol of norbornene were added. Then, 9.3 mmol of aluminum chloride as Lewis acid and 1.4 mmol of initiator AIBN dissolved in toluene were added thereto. The reactor temperature was then raised to 70 ° C. and polymerization was carried out for 20 hours.

Example 1

Into an argon atmosphere, 18.7 mmol of methyl methacrylate (MMA), 18.7 mmol of maleic anhydride (MAH), and 18.7 mmol of norbornene were added. Then, 9.3 mmol of aluminum chloride (AlCl ₃ ), which is a Lewis acid, and 1.4 mmol of the initiator AIBN dissolved in toluene were added thereto. Subsequently, 30 bar of ethylene was charged to the reactor and the reactor temperature was raised to 70 ° C. and polymerization was carried out for 20 hours.

The polymerization conditions and results of Comparative Examples 1 to 5 and Example 1 are shown in Tables 1 and 2. FT-IR measurement results demonstrating that the DSC graph and the maleic anhydride copolymerized the results of the polymerization analysis of Comparative Examples 3 to 5 and Example 1 are shown in FIGS. 1 and 2, respectively.

In the above table, the molar ratio for norbornene and ethylene in Example 1 is a value relating to the total content of norbornene and ethylene, and means for calculating the corresponding data values.

In Comparative Example 1, no polymer was synthesized. From the above results, it was confirmed that norbornene was difficult to be homopolymerized under free radical polymerization conditions. In Comparative Example 2, when norbornene and methyl acrylate were added in a 1: 1 molar ratio in the presence of Lewis acid, norbornene was not copolymerized, and only an ethylene-methyl methacrylate copolymer having an ethylene content of 11 mol% was obtained. lost.

In Comparative Example 3, a norbornene-maleic anhydride alternating copolymer was obtained and the glass transition temperature was as high as 260 ° C. In Comparative Example 4 and Comparative Example 5, methyl methacrylate-norbornene-maleic anhydride terpolymer was obtained, and the glass transition temperatures were 145.7 ° C and 136.3 ° C, respectively.

In Example 1, an ethylene-methyl methacrylate-norbornene-maleic anhydride quaternary copolymer was obtained and a glass transition temperature was obtained at 112.4 ° C. It is believed that the glass transition temperature is lower than that of Comparative Example 4 and Comparative Example 5 because ethylene is contained, and that the glass transition temperature is higher than that of Comparative Example 2 because norbornene / maleic anhydride is contained.

That is, an ethylene-methyl methacrylate moiety copolymer containing norbornene / maleic anhydride was synthesized using maleic anhydride in the presence of Lewis acid, and the quaternary copolymer was added to the existing ethylene-methyl methacrylate copolymer. Compared with the heat resistance.

Comparative Example 6

56.1 mmol of methyl methacrylate was added to an argon atmosphere reactor. Then, 14 mmol of Lewis acid aluminum chloride and 0.274 mmol of initiator AIBN dissolved in toluene were added. Subsequently, 30 bar of ethylene was charged into the reactor and the reactor temperature was raised to 60 ° C. and polymerization was carried out for 20 hours.

Comparative Example 7

56.1 mmol of methyl methacrylate, 16.8 mmol of maleic anhydride, and 16.8 mmol of norbornene were added to an argon atmosphere reactor. Then, 14 mmol of Lewis acid aluminum chloride and 0.274 mmol of initiator AIBN dissolved in toluene were added. The reactor temperature was then raised to 60 ° C. and polymerization was carried out for 20 hours.

Example 2

56.1 mmol of methyl methacrylate, 16.8 mmol of maleic anhydride, and 16.8 mmol of norbornene were added to an argon atmosphere reactor. Then, 14 mmol of Lewis acid aluminum chloride and 0.274 mmol of initiator AIBN dissolved in toluene were added. Subsequently, 30 bar of ethylene was charged into the reactor and the reactor temperature was raised to 60 ° C. and polymerization was carried out for 20 hours.

Example 3

The polymerization was carried out in the same manner as in Example 2, except that 56.1 mmol of methyl methacrylate, 11.22 mmol of maleic anhydride and 11.22 mmol of norbornene were added.

Example 4

The polymerization was carried out in the same manner as in Example 2, except that 56.1 mmol of methyl methacrylate, 8.41 mmol of maleic anhydride and 8.41 mmol of norbornene were added.

The polymerization conditions and results of Comparative Examples 6 to 7 and Examples 2 to 4 are shown in Tables 3 and 4 below.

Through Comparative Examples 6 to 7 and Example 2, the reaction temperature was lowered to 60 ° C, Lewis acid and the amount of initiator was reduced to change the polymerization conditions, and then the copolymer was polymerized. By lowering the reaction temperature and reducing the amount of initiator, a polymer having a number average molecular weight of 40,000 to 60,000 could be obtained.

As can be seen from the DSC results of the three polymers, the quaternary copolymer of Example 2 had a higher glass transition temperature than the ethylene-methyl methacrylate copolymer synthesized in Comparative Example 6 containing no norbornene, and Comparative Example 7 The glass transition temperature was lower than that of the methyl methacrylate-norbornene-maleic anhydride terpolymer synthesized at. The higher the ethylene content, the lower the glass transition temperature of the polymer chain, and the higher the norbornene content, the higher the glass transition temperature of the polymer chain. The comparison confirmed that the quaternary copolymer was polymerized.

Examples 5-8

The experiment was carried out in the same manner as in Example 1 except that the metal oxides shown in Table 5 below were used instead of the aluminum chloride used as the Lewis acid. After the polymerization, the solid metal oxide was removed by a strainer, and the polymerization solution was added to ethanol and stirred to obtain a polymer.

In the table, the molar ratios for norbornene and ethylene in the examples are values relating to the total content of norbornene and ethylene, and represent means for calculating the corresponding data values.

As shown in the tables, it can be seen that the copolymer obtained by the above examples has similar physical properties to the copolymer obtained by using aluminum chloride which is Lewis acid.

According to the present invention, a copolymer can be prepared even under mild conditions of low temperature and low pressure by using Lewis acid or a metal oxide, so that the process is simple and the physical properties of the copolymer are easily controlled. In addition, the α-olefin-acrylate-maleic anhydride-norbornene quaternary copolymer of the present invention prepared by the above method has a relatively high glass transition temperature because it includes norbornene and maleic anhydride. Since the α-olefin such as ethylene is included, the film properties are remarkably improved by compensating for the disadvantages of high hygroscopic and brittle acrylic resin.

Claims (27)

Olefin-acrylate-maleic acid polymerized with 1 to 48 mol% olefin monomer, 50 to 97 mol% acrylate monomer, 1 to 48 mol% maleic anhydride monomer and 1 to 48 mol% norbornene monomer As an anhydride-norbornene quaternary copolymer, The olefin monomers are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene and 2-butene, 2-pentene, 2-hexene, 3 -At least one selected from the group consisting of hexene, 2-heptene, 2-octene and 2-nonene, The acrylate monomer is represented by the following formula (2) <Formula 2>

(Wherein, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms which may include a hetero atom; R ₄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) It is an acrylate compound represented by The maleic anhydride monomer is maleic anhydride or a maleic anhydride derivative substituted with a substituent that does not participate in the polymerization reaction, The norbornene monomer is the following <Formula 1> <Formula 1>

Wherein m is an integer of 0 to 4, and R ₇ , R ₇ ^′ , R ₇ ^'' and R ₇ ^'' are substituents that do not participate in the polymerization reaction, and are each independently a polar functional group or a nonpolar functional group. R ₇ , R ₇ ^′ , R ₇ ^'' and R ₇ ^'' may be linked together to form a saturated or unsaturated cyclic group of 4 to 12 carbon atoms, or an aromatic ring of 6 to 24 carbon atoms; Nonpolar functional groups include hydrogen; halogen; linear or branched alkyl of 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl, haloalkynyl of 3 to 20 carbon atoms ( alkynyl); cycloalkyl of 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl Of 6 carbon atoms unsubstituted or substituted with haloalkenyl, or haloalkynyl Aryl of 40; or aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; As a non-hydrocarbonaceous polar group including the above oxygen, nitrogen, phosphorus, sulfur, silicon, or boron, -R ⁸ OR ⁹ , -OR ⁹ , -OC (O) OR ⁹ , -R ⁸ OC (O) OR ⁹ , -C (O) R ⁹ , -R ⁸ C (O) R ⁹ , -OC (O) R ⁹ , -R ⁸ C (O) OR ⁹ , -C (O) OR ⁹ , -R ⁸ OC (O) R ⁹ ,-(R ⁸ O) _k -OR ⁹ ,-(OR ⁸ ) _k -OR ⁹ , -C (O) -OC (O) R ⁹ , -R ⁸ C (O ) -OC (O) R ⁹ , -SR ⁹ , -R ⁸ SR ⁹ , -SSR ⁸ , -R ⁸ SSR ⁹ , -S (= O) R ⁹ , -R ⁸ S (= O) R ⁹ ,- R ⁸ C (= S) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C = S, -NCO, R ^8- NCO, -CN, -R ⁸ CN, -NNC (= S) R ⁹ , -R ⁸ NNC (= S) R ⁹ , -NO ₂ , -R ⁸ NO ₂ ,

In the polar functional group, each of R ⁸ and R ¹¹ is linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene having 1 to 20 carbon atoms; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Arylene having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Or aralkylene having 7 to 15 carbon atoms, unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, and each of R ⁹ , R ¹⁴ , R ¹² and R ¹³ is Hydrogen; halogen; Linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl having 1 to 20 carbon atoms; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Or alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy; Each k is an integer of 1 to 10) Olefin-acrylate-maleic anhydride-norbornene quaternary copolymer. The method of claim 1, The copolymer is an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that it has a glass transition temperature (Tg) in the range of 90 ~ 300 ℃. The method of claim 1, The copolymer is an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that it has a number average molecular weight in the range of 5,000 to 400,000 or a weight average molecular weight in the range of 10,000 to 800,000. The method of claim 1, The copolymer is an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that it has a temperature (Td ₅₀ ) 50% of the initial weight in the range of 300 ~ 500 ℃. delete delete delete The method of claim 1, The acrylate comonomer is an alkyl acrylate containing a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl, an alkyl methacrylate including a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl, or alkyl An olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that it is an alkyl butacrylate containing a straight or branched alkyl group having 1 to 12 carbon atoms. delete The method of claim 1, The copolymer is an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that used for the optical film. A monomer mixture consisting of 1 to 48 mol% olefin monomer, 50 to 97 mol% acrylate monomer, 1 to 48 mol% maleic anhydride monomer, and 1 to 48 mol% norbornene monomer is used as the acrylate monomer. Polymerizing with a radical polymerization initiator at 5 to 200 bar and 30 to 150 ° C. in the presence of 0.01 to 200 mol% of metal oxide or Lewis acid on a basis of The olefin monomers are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene and 2-butene, 2-pentene, 2-hexene, 3- At least one selected from the group consisting of hexene, 2-heptene, 2-octene and 2-nonene, The acrylate monomer is represented by the following formula (2) <Formula 2>

(Wherein, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms which may include a hetero atom; R ₄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) It is an acrylate compound represented by The maleic anhydride monomer is maleic anhydride or a maleic anhydride derivative substituted with a substituent that does not participate in the polymerization reaction, The norbornene monomer is the following <Formula 1> <Formula 1>

Wherein m is an integer of 0 to 4, and R ₇ , R ₇ ^′ , R ₇ ^'' and R ₇ ^'' are substituents that do not participate in the polymerization reaction, and are each independently a polar functional group or a nonpolar functional group. R ₇ , R ₇ ^′ , R ₇ ^'' and R ₇ ^'' may be linked together to form a saturated or unsaturated cyclic group of 4 to 12 carbon atoms, or an aromatic ring of 6 to 24 carbon atoms; Nonpolar functional groups include hydrogen; halogen; linear or branched alkyl of 1 to 20 carbon atoms, haloalkyl, alkenyl, haloalkenyl; linear or branched alkynyl, haloalkynyl of 3 to 20 carbon atoms ( alkynyl); cycloalkyl of 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl Of 6 carbon atoms unsubstituted or substituted with haloalkenyl, or haloalkynyl Aryl of 40; or aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; As a non-hydrocarbonaceous polar group including the above oxygen, nitrogen, phosphorus, sulfur, silicon, or boron, -R ⁸ OR ⁹ , -OR ⁹ , -OC (O) OR ⁹ , -R ⁸ OC (O) OR ⁹ , -C (O) R ⁹ , -R ⁸ C (O) R ⁹ , -OC (O) R ⁹ , -R ⁸ C (O) OR ⁹ , -C (O) OR ⁹ , -R ⁸ OC (O) R ⁹ ,-(R ⁸ O) _k -OR ⁹ ,-(OR ⁸ ) _k -OR ⁹ , -C (O) -OC (O) R ⁹ , -R ⁸ C (O ) -OC (O) R ⁹ , -SR ⁹ , -R ⁸ SR ⁹ , -SSR ⁸ , -R ⁸ SSR ⁹ , -S (= O) R ⁹ , -R ⁸ S (= O) R ⁹ ,- R ⁸ C (= S) R ⁹ , -R ⁸ C (= S) SR ⁹ , -R ⁸ SO ₃ R ⁹ , -SO ₃ R ⁹ , -R ⁸ N = C = S, -NCO, R ^8- NCO, -CN, -R ⁸ CN, -NNC (= S) R ⁹ , -R ⁸ NNC (= S) R ⁹ , -NO ₂ , -R ⁸ NO ₂ ,

In the polar functional group, each of R ⁸ and R ¹¹ is linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene having 1 to 20 carbon atoms; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Arylene having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl; Or aralkylene having 7 to 15 carbon atoms, unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, and each of R ⁹ , R ¹⁴ , R ¹² and R ¹³ is Hydrogen; halogen; Linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl having 1 to 20 carbon atoms; Linear or branched alkynyl, haloalkynyl having 3 to 20 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; Or alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy; Each k is an integer of 1 to 10). The metal oxide is represented by the following formula (4) <Formula 4> M _x N _y O _z (M represents at least one selected from the group consisting of alkaline earth metals, transition metals, Group 13, and Group 14 metals; N represents a Group 5 or 6 atom; O represents an oxygen atom; x, y and z represent A value determined by the oxidation state of M and N, wherein x> 0, y ≥ 0, and z> 0). The Lewis acid is at least one metal cation and halide selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin, wherein, C ₇ H ₁₅ OSO ^2- and a compound consisting of one or more anions selected from the group consisting of SO ₄ ^{2- -} triflate ^{_{(triflate), HPO 3 2-,}} H 3 PO 2-, CF 3 COO The manufacturing method of the olefin acrylate-maleic anhydride norbornene quaternary copolymer which is made. delete delete The method of claim 11, The metal oxide may be aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ), silicon oxide (SiO ₂ ), boron oxide (B ₂ O ₃ ), cesium oxide (CeO ₂ ), dysprosium oxide (Dy ₂ O ₃ ), erbium oxide (Er ₂ O ₃ ), europium oxide (Eu ₂ O ₃ ), gadolinium oxide (Gd ₂ O ₃ ), holmium oxide (Ho ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ), lutetium oxide (Lu ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ), praseodymium oxide (Pr ₆ O ₁₁ ), samarium oxide (Sm ₂ O ₃ ), With terbium oxide (Tb ₂ O ₃ ), thorium oxide (Th ₄ O ₇ ), thulium oxide (Tm ₂ O ₃ ), ytterbium oxide (Yb ₂ O ₃ ), tin oxide (SnO), and titanium oxide (TiO ₂ ) Metal oxide group and dysprosium aluminate (Dy ₃ Al ₅ O ₁₂ ), yttrium aluminate (Y ₃ Al ₅ O ₁₂ ), aluminum titanate (Al ₂ O ₃ ㆍ TiO ₂ ), aluminum silicate (3Al ₂ O _{3 and} SiO _2), calcium titanate (CaTiO _3), calcium zirconate (CaZrO _3), iron Titanate (FeTiO _3), magnesium aluminate (MgO and Al ₂ O _3), cesium aluminate _{(CeAl 11 O 18), Al} 2 (SO 4) 3, and AlPO a selected complex metal oxide group consisting of ₄ or more A process for producing an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that delete delete delete The method of claim 11, The copolymer has a glass transition temperature (Tg) in the range of 90 ~ 300 ℃ olefin-acrylate-maleic anhydride-norbornene quaternary copolymer production method. The method of claim 11, The copolymer has a number average molecular weight in the range of 5,000 to 400,000 or a weight average molecular weight in the range of 10,000 to 800,000. The method of producing an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer. The method of claim 11, The copolymer has a temperature (Td ₅₀ ) at which 50% of the initial weight of the range of 350 ~ 550 ℃ decomposition (Td ₅₀ ) characterized in that the manufacturing method of the olefin-acrylate-maleic anhydride-norbornene quaternary copolymer. delete The method of claim 11, The olefin is a method for producing an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that ethylene or propylene. delete delete The method of claim 11, The acrylate comonomer is an alkyl acrylate containing a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl, an alkyl methacrylate including a straight or branched alkyl group having 1 to 12 carbon atoms of alkyl, or alkyl A method for producing an olefin-acrylate-maleic anhydride-norbornene quaternary copolymer, characterized in that the alkyl butyacrylate comprises a straight or branched alkyl group having 1 to 12 carbon atoms. delete An optical film comprising the olefin-acrylate-maleic anhydride-norbornene quaternary copolymer of any one of claims 1 to 4, 8 or 10.

Images