JP3001691B2 - Novel amorphous polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel amorphous polymer which is excellent in mechanical properties such as transparency and rigidity, pulverizability, compatibility with other resins, moldability and heat resistance. And for the method of manufacturing the same,
The present invention relates to a novel amorphous polymer obtained by polymerizing a norbornene derivative or copolymerizing a norbornene derivative and a styrene derivative, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Low molecular weight polystyrene is known as a synthetic resin having excellent compatibility with other resins, pulverizability and transparency, and it is a tackifier for hot melt adhesives and a fluidity improver for resins. Used as a pigment dispersant, a vehicle for traffic paint or a binder for toner for electrophotography. However, the conventionally known low molecular weight polystyrene has a large problem that the glass transition temperature Tg is 100 ° C. or less and the heat resistance is lacking.

[0003] The applicant of the present application has disclosed in
In Japanese Patent Publication No. 109, a cyclic olefin random copolymer excellent in compatibility with other resins, pulverizability, transparency and heat resistance as shown below was proposed.

[0004] An aromatic vinyl compound (A) and at least one cyclic olefin (B) selected from the group consisting of unsaturated monomers represented by the following general formula [1] or [2]: (I) the aromatic vinyl compound (A) unit is in the range of 10 to 90 mol%, the cyclic olefin (B) unit is in the range of 10 to 90 mol%, and (ii) a temperature of 135 ° C. A cyclic olefin random copolymer having an intrinsic viscosity [η] measured in decalin of 0.005 to 1 dl / g.

[0005]

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In the formula [1], n is 0 or a positive integer, and R ¹ to
R ¹⁰ is a hydrogen atom, a halogen atom or a hydrocarbon,
Represents an elementary group.

[0007]

[0008]

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... [2] (In the formula [2], m is 0 or a positive integer, l is an integer of 3 or more, and R ¹ to R ¹⁰ are each a hydrogen atom, Represents a halogen atom or a hydrocarbon group).

The above cyclic olefin random copolymer comprises:
Produced in the presence of a catalyst formed from a hydrocarbon soluble vanadium compound and an organoaluminum compound. Incidentally, polynorbonadiene is known as a hydrocarbon-based non-crystalline polymer having a high glass transition temperature, and such a polynorbonadiene is described in JPKenny, JA Hinkly, Polymer, 6 , 133 (1965),
MBRoller, JKGillham, JPKennedy, Journal of Ap
plied Polymer Science, 17 , 2223 (1973).

In other words, these documents show that when cationic polymerization of norbonadiene is carried out at a low temperature of -123 ° C. using an aluminum chloride catalyst, the glass transition point becomes 320.
It is described that an amorphous polymer having a nortricyclene structure at 100 ° C. and 100% soluble in benzene is obtained.

This note recyclen structure is represented by the following equation.

[0013]

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However, a polymer obtained from such a norbornadiene becomes insoluble in a solvent such as benzene when the polymerization temperature exceeds -123 ° C. in the production thereof. Therefore, in order to produce such a polymer, the polymerization temperature must be maintained at an extremely low temperature such as -123 ° C., which is difficult for production on an industrial scale.

Furthermore, the glass transition point of the obtained polymer is as high as 320 ° C., and this temperature is close to the decomposition temperature of the obtained polymer, so that such polynorbonadienes are inferior in moldability.

Therefore, the inventors of the present invention have excellent mechanical properties such as transparency and rigidity, pulverizability, compatibility with other resins and moldability, and have a higher heat resistance than the above-mentioned cyclic olefin random copolymer. Intensive research to obtain a novel amorphous polymer excellent in the above, specific norbornene derivative and a specific styrene derivative were copolymerized in the presence of a cationic polymerization initiator, the obtained amorphous In the copolymer, the molar ratio of the structural unit derived from the norbornene derivative to the structural unit derived from the styrene derivative is 135.
It has been found that an amorphous copolymer having an intrinsic viscosity [η] measured in decalin at a temperature of 0 ° C. and a glass transition point measured by DSC in a specific range has excellent properties as described above, and thus completes the present invention. Reached.

[0017]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and to provide mechanical properties such as transparency and rigidity, pulverizability, compatibility with other resins, and the like. An object of the present invention is to provide an amorphous polymer having excellent moldability and excellent heat resistance, and a method for producing the same.

[0018]

SUMMARY OF THE INVENTION An amorphous polymer according to the present invention comprises a norbornene derivative (a) represented by the following general formula [I] or [II] and a styrene derivative (b) represented by the following general formula [III]: Is a (co) polymer polymerized in the presence of a cationic polymerization initiator, wherein the structural unit derived from the norbornene derivative (a) is 20 to 100 mol% and derived from the styrene derivative (b). Structural unit is 80-0
Mol%, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 3.0 dl / g, and the glass transition point (Tg) measured by DSC at 100 ° C.
It is characterized by the above.

[0019]

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In the formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. Is also good.

When m = 0 and n = 0, R ¹⁵ .
R ¹⁸ is bonded to each other to form a monocyclic or polycyclic ring. ]

[0022]

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[II] [In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0.1 or 2, and R ^{1 to} R ¹⁹
Are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁹ (or R ¹⁰ ) and R ¹³ (or R ¹¹ ) each have 1 to 1 carbon atoms. The bond may be via an alkylene group 3 or directly without any group.

When n = m = 0, R ¹⁵ and R ¹² (or R ¹⁹ ) may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

[0025]

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[III] [In the formula [III], R ¹ and R ² independently represent a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. In addition, the method for producing an amorphous polymer according to the present invention is characterized in that, in the presence of a cationic polymerization initiator, a norbornene derivative (a) represented by the following general formula [I] or [II]; III] with a monomer supply ratio (molar ratio) of the norbornene derivative (a) and the styrene derivative (b) at a polymerization temperature of -80 ° C or higher.
20/80 is characterized by performing a cationic polymerization reaction.

[0027]

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[I] [In the formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. Is also good.

When m = 0 and n = 0, R ^15-
R ¹⁸ is bonded to each other to form a monocyclic or polycyclic ring. ]

[0030]

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[II] [In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0.1 or 2, and R ^{1 to} R ¹⁹
Are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁹ (or R ¹⁰ ) and R ¹³ (or R ¹¹ ) each have 1 to 1 carbon atoms. The bond may be via an alkylene group 3 or directly without any group.

When n = m = 0, R ¹⁵ and R ¹² (or R ¹⁹ ) may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

[0033]

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[III] [In the formula [III], R ¹ and R ² independently represent a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. The cationic polymerization initiator preferably used in the present invention includes:
It is a cationic polymerization initiator formed from (c) a metal halide and / or metal oxide, and (d) a compound having active hydrogen and / or an organic halogen compound.

The term "polymer" in the present specification is defined as
In some cases, both a homopolymer and a copolymer may be used, and in this case, the term “(co) polymer” may be used.

[0036]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the amorphous polymer according to the present invention and a method for producing the same will be specifically described.

First, the amorphous polymer according to the present invention will be described. The amorphous polymer according to the present invention includes (1) a polymer obtained by polymerizing a specific norbornene derivative (a) in the presence of a cationic polymerization initiator, and (2) a specific norbornene derivative (a). It is roughly classified into a copolymer obtained by polymerizing a specific styrene derivative (b) in the presence of a cationic polymerization initiator.

Norbornene Derivative (a) The norbornene derivative (a) used in the present invention is represented by the following general formula [I] or [II].

[0039]

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... [I] In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1.

Further, R ^{1 to} R ¹⁸ and R ^a and R ^b
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the hydrocarbon group independently include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

As a specific example of the cycloalkyl group,
And a cyclohexyl group. Further
In the above formula [I], R¹⁵And R¹⁶And R¹⁷And R
¹⁸And R ¹⁵And R¹⁷And R¹⁶And R¹⁸And R¹⁵When
R¹⁸And R¹⁶And R¹⁷And combine with each other
(In conjunction with each other) form a monocyclic or polycyclic group
And a single ring or a ring formed in this way.
May have a double bond in the polycyclic group.

Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

When m = 0 and n = 0, R ¹⁵ .
R ¹⁸ is bonded to each other to form a monocyclic or polycyclic ring. The norbornene derivative (a) represented by the general formula [I] can be easily produced by condensing cyclopentadiene with a corresponding olefin or a corresponding cyclic olefin by utilizing a Diels-Alder reaction. Can be.

Examples of the norbornene derivative (a) represented by the above general formula [I] used in the present invention include the following compounds and derivatives thereof.

[0047]

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[0048]

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[0049]

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The following are more specific examples of such compounds.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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... [II] In the above formula [II], p is 0 or a positive integer, preferably 0 to 3. In addition, the above formula [I
In I], m and n are 0, 1 or 2. In addition, q is 0 or a positive integer, and is preferably 0 or 1.

R ^{1 to} R ¹⁹ are each independently
An atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.

Specific examples of the alkyl group include methyl, ethyl, isopropyl, isobutyl, n-amyl, neopentyl, n-hexyl,
n-octyl group, n-decyl group, 2-ethylhexyl group and the like. Specific examples of the cycloalkyl group include a cyclohexyl group, a methylcyclohexyl group,
Examples thereof include an ethylcyclohexyl group, and specific examples of the aromatic group include a phenyl group, a naphthyl group, and a biphenyl group.

In the above general formula [II], R ⁹
And R ¹³ or R ¹⁰ and R ¹¹ may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group.

When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Preferred examples in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

[0073]

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In the above formula, q represents the above general formula [II]
Is the same as q in Specific examples of the norbornene derivative (a) represented by the general formula [II] include the following compounds and derivatives.

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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The norbornene derivative (a) represented by the general formula [II] is obtained by converting a cyclopentadiene with a corresponding olefin or a corresponding cyclic olefin.
It can be easily produced by condensation using the Diels-Alder reaction.

Styrene Derivative (b) The styrene derivative (b) used in the present invention is represented by the following general formula [III].

[0083]

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[III] In the above formula [III], R ¹ and R ² independently represent a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom.

Specific examples of the styrene derivative represented by the general formula [III] include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
α-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-ethylstyrene,
m-ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-
α-methylstyrene and the like.

In the amorphous polymer according to the present invention, the constitutional unit derived from the norbornene derivative is 20 to 100.
Mole%, preferably in the range of 30-100 mole%,
The constitutional unit derived from the styrene derivative is in the range of 80 to 0 mol%, preferably 70 to 0 mol%.

If the constitutional unit derived from the norbornene derivative is less than 20 mol%, only an amorphous polymer having low heat resistance can be obtained, which is not preferable. That is, if the amount of the structural unit derived from the styrene derivative exceeds 80 mol%, only an amorphous polymer having low heat resistance can be obtained, which is not preferable.

The amorphous polymer according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 3.
0 dl / g, preferably in the range of 0.05 to 2.5 dl / g.

When the intrinsic viscosity [η] is less than 0.01 dl / g, only an amorphous polymer having low heat resistance can be obtained.
When the intrinsic viscosity [η] exceeds 3.0 dl / g,
It is not preferable because compatibility with other resins is deteriorated.

The glass transition point (Tg) of the amorphous polymer according to the present invention measured by DSC is 100 ° C. or higher, preferably in the range of 120 to 300 ° C. Gel Permeation Chromatography (G
The molecular weight distribution (Mw / Mn) measured by (PC) is usually in the range of 1.0 to 10.0, preferably 1.5 to 7.0.

From the results of analysis by ¹³ C-NMR, the amorphous polymer according to the present invention is represented by the following general formulas [IV] and [V]
Alternatively, it is presumed to have a structural unit derived from the norbornene derivative (a) represented by [VI] and a structural unit derived from a styrene derivative (b) represented by the following general formula [VII].

[0092]

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... [IV]

[0094]

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... [V]

[0096]

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... [VI]

[0098]

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[VII] Since the amorphous polymer according to the present invention is produced by using a cationic polymerization initiator described below, the activity of the norbornene derivative (a) and the styrene derivative (b) is And the structural unit derived from the norbornene derivative completely enters the main chain of the amorphous polymer. Therefore, the amorphous polymer according to the present invention is described in the above-mentioned JP-A-1-31110.
As compared with the cyclic olefin random copolymer disclosed in Japanese Patent Publication No. 9-1997, the composition has the same composition, a high glass transition point, and excellent heat resistance.

Next, a method for producing an amorphous polymer according to the present invention will be described. The method for producing an amorphous polymer according to the present invention comprises the steps of: preparing a norbornene derivative (a) represented by the general formula [I] or [II] in the presence of a cationic polymerization initiator; Cationic polymerization of the represented styrene derivative (b) with a monomer supply ratio (molar ratio) of the norbornene derivative (a) and the styrene derivative (b) of 100/0 to 20/80 at a polymerization temperature of -80 ° C or higher. In this method, an amorphous (co) polymer is obtained by performing a reaction.

Cationic Polymerization Initiator The cationic polymerization initiator used in the present invention is listed in Chapter 2 of "Toshinobu Higashimura, Lecture Polymerization Reaction Theory, Vol. 3," Cation Polymerization ", Kagaku Dojin, 1974". Initiators include protic acids, metal oxides, halogens, metal halides, organometallic compounds and stable cations, of which protic acids, metal halides and metal oxides are preferred.

Particularly preferred cationic polymerization initiators are
A cationic polymerization initiator formed from a combination of (c) a metal halide and / or a metal oxide, and (d) a compound having active hydrogen and / or an organic halogen compound.

As the above protonic acid, specifically, H
₃ PO ₃ , H ₂ SO ₄ , HClO ₄ , HCl, HBr,
CCl ₃ CO ₂ H, CHCl ₂ CO ₂ H, CF ₃ CO ₂
H, H (CF ₂ ) ₆ CO ₂ H, ClSO ₃ H, FSO ₃
H, p-toluenesulfonic acid, CF ₃ SO ₃ H, CH ₃ C
OCO ₄ (acetyl perchlorate) and the like.

As the above-mentioned metal halide, specifically, Be, Mg, Zn, Cd, Hg, B, Al, Ga,
Ti, Zr, Sn, P, Sb, Nb, Bi, Ta, U,
Examples include halides of metals such as Re and Fe.

As the above metal oxide, specifically, C
Metal oxides such as r, Ti, Al, Co, Mn, Fe, V, Mo, W and the like can be mentioned. Examples of the halogenated metal include Be, Mg, Zn, Cd, Hg, B, Al, Ga,
Ti, Zr, Sn, P, Sb, Nb, Bi, Ta, U,
Examples include halides of metals such as Re and Fe. Of these, halides of B, Al, Ti, Sn, and Fe are preferable.

Specifically, boron trifluoride (BF ₃ ),
Boron trifluoride / diethyl ether complex (BF ₃ O (C
₂ H ₅ ) ₂ ), boron trifluoride-phenol complex (BF
₃ HOC ₆ H ₅ ), an organoaluminum compound represented by the general formula R _n AlX _3-n (X is any of chlorine, bromine, iodine or fluorine, n is a value satisfying 0 ≦ n <3, and R is Alkyl group), titanium tetrachloride (TiCl ₄ ), tin tetrachloride (SnCl ₄ ), iron trichloride (FeCl ₃ ), and the like.

Specific examples of the organoaluminum compound represented by R _n AlX _3-n include diethyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum dichloride, and ethyl aluminum dibromide. And aluminum trichloride. As long as the composition is R _n AlX _3-n, it may be a mixture of various organic aluminum compounds.

The above metal oxides include Cr, Ti, A
Oxides of metals such as 1, Co, Mn, Fe, V, Mo, W and the like are mentioned, and among these, Cr, Ti and Al are preferable.

Specifically, Cr_Two O_Three , CrO_Three , Cr
O_Two Cl_Two , TiO_Two , Al_TwoO_Three・ XCrO_Two , Al_Two 
O_Three ・ CoO, Al_Two O_Three ・ MnO, silica-alumina
(Al_Two O_Three ・ SiO_Two Is the main component), zeolite (Na
_Two O ・ SiO_Two ・ Al_Two O _Three Is the main component)
Noxane [(MeAlO)_n ], Cr_Two O_Three , Fe _TwoO_Three
 , MoO_Three , V_Two O_Three , WO_Two Cl_Two Etc.
You.

In the method for producing an amorphous polymer according to the present invention, the compound having active hydrogen and / or the organic halogen compound is used as a co-initiator (co-catalyst) of the above-mentioned metal halide or metal oxide, respectively. You.

Examples of the compound having active hydrogen include:
Examples include water, alcohols, phenols, organic acids and inorganic acids. As alcohols, aliphatic, alicyclic and aromatic alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, cyclohexanol and benzyl alcohol are used.

The phenols include phenol,
Cresol or the like is used. Examples of the organic acid include carboxylic acids such as acetic acid, trichloroacetic acid, propionic acid, fumaric acid, and benzoic acid; sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid; and inorganic acids such as sulfuric acid, phosphoric acid, and hydrochloric acid. Is used.

Examples of the organic halogen compounds include aliphatic, alicyclic, and aromatic organic halogen compounds. Specifically, second halogen compounds such as isopropyl chloride, sec-butyl chloride, cyclohexyl chloride, cyclohexyl bromide, and 1-phenylchloroethane; tertiary halogen compounds such as tert-butyl chloride, tert-amyl chloride, and triphenylchloromethane Compound; Acid chlorides such as acetyl chloride, acetyl bromide and benzoyl chloride are preferably used.

Among the above compounds having active hydrogen and / or organic halogen compounds, water or organic halogen compounds are preferable in consideration of the reaction rate, easiness of post-treatment, corrosion of the apparatus, economy and the like.

In the present invention, the polymerization reaction between the norbornene derivative (a) and the styrene derivative (b) is usually performed in a solution. As a solvent used for such a polymerization reaction, a solvent that does not inhibit cationic polymerization of a carbon-carbon double bond is used.

Examples of such a solvent include aromatic compounds such as benzene, chlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene;
Saturated aliphatic compounds having 5 to 18 carbon atoms such as hexane; saturated alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, and methylethylcyclohexane; methylene chloride, chloroform;
Examples include halides such as carbon tetrachloride, dichloroethane, and trichloroethane.

Of course, the solvents that can be used in the present invention are not limited to the above-mentioned solvents. Note that two or more solvents can be used as a mixture. Also, depending on the type of the solvent, the above-mentioned norbornene derivative (a) and styrene derivative (b)
, The rate of the polymerization reaction, the reaction rate and the like can be changed. For example, when a polar solvent such as a solvent composed of a halide is used, the polymerization reaction between the norbornene derivative (a) and the styrene derivative (b) proceeds rapidly, and a copolymer having a relatively high molecular weight can be obtained. it can.

In producing the amorphous polymer according to the present invention, the total concentration of the norbornene derivative (a) and the styrene derivative (b) in the reaction system is adjusted to 0.3 to 5.0 mol / l. preferable.

If the total concentration is less than 0.3 mol / liter, the molecular weight of the produced polymer may not be increased. Conversely, if the total concentration of these exceeds 5.0 mol / l, the viscosity of the polymerization system will increase significantly,
The temperature of the polymerization system may become abnormally high due to the heat of reaction.

The molar ratio of the norbornene derivative (a) to the styrene derivative (b) in the reaction system is 100 /
It is desirable to be 0/20/80, preferably 100 / 0-30 / 70. When this molar ratio is less than 20/80, the resulting polymer does not have a glass transition temperature (T _g ) of 100 ° C. or more, and thus has reduced heat resistance.

Further, the concentration of the metal halide or metal oxide used as the cationic polymerization initiator component in producing the amorphous copolymer according to the present invention is preferably 1 to 100 mmol / L. .

The total concentration of the compound having active hydrogen and / or the organic halogen compound which is the metal halide co-initiator (co-catalyst) is adjusted to 0.5 to 50 mmol / L. Is preferred.

Further, the ratio of the co-initiator to the metal halide or metal oxide is preferably adjusted to 0.1 to 20 in terms of molar ratio. The polymerization temperature is −80 ° C. or higher, preferably from −50 ° C. to around room temperature. If the polymerization temperature is lower than -80 ° C, this is not only economically unfavorable but also unfavorable because the insoluble component in the polymer tends to increase.

In the method for producing an amorphous polymer according to the present invention, the polymerization reaction between the norbornene derivative (a) and the styrene derivative (b) involves adding a small amount of alcohol such as methanol to such an extent that the polymer does not precipitate. Can be stopped by

Next, a high-purity amorphous polymer according to the present invention can be obtained by performing the following operations. (1) Water is added to the solution containing the produced polymer, and deashing and washing are repeated several times. (2) Next, after performing oil-water separation, the mixture is poured into a poor solvent such as alcohol or acetone to precipitate a polymer. (3) Thereafter, the polymer is removed by filtration, and the obtained polymer is dried.

The amorphous polymer obtained as described above is excellent in mechanical properties such as transparency and rigidity, pulverizability, compatibility with other resins and fluidity, and has a high glass transition point (Tg). ) Having excellent heat resistance, for example, a tackifier or a heat resistance imparting agent for a hot melt adhesive,
It can be used in fields such as resin fluidity improvers, resin modifiers such as pigment dispersants, traffic paint vehicles, and electrophotographic toner binders.

[0127]

The amorphous polymer according to the present invention comprises a structural unit derived from a specific norbornene derivative (a) and a structural unit derived from a specific styrene derivative (b). Since the molar ratio of the units is within the specific range defined by the present invention and the structural unit derived from the norbornene derivative (a) is completely contained in the main chain of the amorphous polymer, the transparency and Excellent in mechanical properties such as rigidity, pulverizability, compatibility with other resins and moldability, as well as excellent heat resistance.

According to the method for producing an amorphous polymer according to the present invention, the (co) polymer reaction can be carried out at a temperature around room temperature in the presence of a cationic polymerization initiator. Thus, the production of an amorphous polymer having the above-described effects on an industrial scale can be economically performed.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

[0130]

Example 1 500 m capacity equipped with a stirring blade and a cooling pipe
flask l, 169.5Ml dichloromethane, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 15.8ml the Table 1 of the compound (A)], styrene 11.5ml and 1 mmol N / ml containing tert-butyl chloride
-1 ml of the decane solution was added, and the flask was cooled to -50 ° C.

Next, 2.2 ml of an n-decane solution containing 0.89 mmol / ml ethylaluminum dichloride was added to the flask to initiate polymerization. The total volume of the polymerization reaction system was 200 ml, and the initial concentration of each component was [compound (a)] ₀ = 0.5 mol / l, [styrene] ₀ = 0.5 mol / l, [tert-
Butyl chloride] ₀ = 5.0 mmol / l, [ethyl aluminum dichloride] ₀ = 10.0 mmol / l
Liters.

While maintaining the polymerization temperature at −50 ° C., the polymerization reaction was carried out in a nitrogen atmosphere. 60 minutes after the start of the polymerization, 3.0 ml of methanol was added to the polymerization reaction system,
The polymerization reaction was stopped.

The solution containing the polymer thus obtained was washed with water to remove catalyst residues in the solution. This operation was further repeated three times. Next, a solution containing the polymer was added to a large excess of a poor solvent (acetone / methanol = 50 /
(50% by volume) to precipitate a polymer, followed by filtration to separate a copolymer.

The copolymer was further washed with acetone,
Dry at 100 ° C and 200 mmHg for 12 hours.
2.4 g of a copolymer (polymer yield: 47.0%) was obtained. Structural units derived from the norbornene derivative in the copolymer thus obtained [hereinafter, sometimes referred to as norbornene structural units] and structural units derived from the styrene derivative [hereinafter, sometimes referred to as styrene structural units] Was measured by ¹ H-NMR, and the molar ratio of [norbornene structural unit] / [styrene structural unit] =
48.8 / 51.2.

The Tg measured by the DSC method was 163 ° C. Table 2 shows the results.

[0136]

Examples 2 to 7 and Comparative Examples 1 and 2 Copolymers of norbornene derivatives and styrene were produced using the norbornene derivatives shown in Table 1 under the polymerization conditions shown in Table 2 in the same manner as in Example 1. did.

Table 2 shows the results. However, in Comparative Example 1, VO (OC ₂ H ₅ ) Cl ₂ / A as a Ziegler polymerization initiator was used instead of ethyl aluminum dichloride / tert-butyl chloride as a cationic polymerization initiator.
The reaction was started by adding l (C ₂ H ₅ ) _1.5 Cl _1.5 at a concentration of 0.5 mmol / L and 5 mmol / L in the system, respectively.

[0138]

[Table 1]

[0139]

[Table 2]

As is clear from Table 2, the polystyrene polymer having no structural unit derived from the norbornene derivative (Comparative Example 2) has a glass transition point (Tg) of 100.
It is low at less than ° C. and inferior in heat resistance. In addition, when a copolymer comprising a norbornene derivative and styrene was produced using a Ziegler polymerization catalyst (Comparative Example 1), it was found that the yield of a copolymer comprising a norbornene derivative and styrene was reduced.

On the other hand, the copolymers according to the present invention all have glass transition points (Tg) as high as 100 ° C. or higher,
It turns out that it is excellent in heat resistance and also economical in terms of yield.

Claims (3)

(57) [Claims] (1) A norbornene derivative (a) represented by the following general formula [I] or [II] and a styrene derivative (b) represented by the following general formula [III] are reacted in the presence of a cationic polymerization initiator. A polymerized (co) polymer, wherein the structural unit derived from the norbornene derivative (a) is 2
0 to 100 mol%, the structural unit derived from the styrene derivative (b) is present at a ratio of 80 to 0 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.0
An amorphous polymer characterized by having a glass transition point (Tg) of not less than 100 ° C. and a glass transition point (Tg) measured by DSC of 1 to 3.0 dl / g. Embedded image ····· [I] [In the formula [I], n is 0 or 1, and m
Is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Also, m = 0 and n = 0
In the case of R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. ] ... [II] [In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0.1 or 2, and R ^{1 to} R ¹⁹ are each independently A hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein R ⁹ (or R ¹⁰ ) and R ¹³ (or R ¹¹ ) are an alkylene group having 1 to 3 carbon atoms. May be connected via
Also, they may be directly bonded without any group. Also,
When n = m = 0, R ¹⁵ and R ¹² (or R ¹⁹ ) may combine with each other to form a monocyclic or polycyclic aromatic ring. ] ... [III] [In the formula [III], R ¹ and R ² independently represent a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. ] 2. A norbornene derivative (a) represented by the following general formula [I] or [II] and a styrene derivative (b) represented by the following general formula [III] in the presence of a cationic polymerization initiator. A cationic polymerization reaction at a polymerization temperature of −80 ° C. or higher with a monomer supply ratio (molar ratio) of the norbornene derivative (a) and the styrene derivative (b) of 100/0 to 20/80. For producing an amorphous polymer. Embedded image ····· [I] [In the formula [I], n is 0 or 1, and m
Is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Also, m = 0 and n = 0
In the case of R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. ] ... [II] [In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0.1 or 2, and R ^{1 to} R ¹⁹ are each independently A hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein R ⁹ (or R ¹⁰ ) and R ¹³ (or R ¹¹ ) are an alkylene group having 1 to 3 carbon atoms. May be connected via
Also, they may be directly bonded without any group. Also,
When n = m = 0, R ¹⁵ and R ¹² (or R ¹⁹ ) may combine with each other to form a monocyclic or polycyclic aromatic ring. ] [III] [In the formula [III], R ¹ and R ² independently represent a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. ] 3. The cationic polymerization initiator is formed from (c) a metal halide and / or metal oxide, and (d) a compound having active hydrogen and / or an organic halogen compound. The method for producing an amorphous polymer according to claim 2, wherein: