JPH05295018A - Production of sulfonic acid group-bearing copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer which has excellent compatibility, adhesion and hydrophilic properties and is useful in ink by introducing sulfonic groups more than a prescribed mole % of the carbon-carbon double bonds of alkylidene groups in a specific unsaturated copolymer. CONSTITUTION:An alpha-olefin of 3 to 12 carbon atoms such as propylene and a cyclic olefin bearing an alkylidene or alkenyl group of the formula (R<1> is a 2 to 5 C alkylidene or a 2 to 5 C alkenyl; R<2> is a 1 to 5 C hydrocarbon or H; n is 0 to 2), for example, 5-ethylidene-bicyc1o[2,2,1]hept-2-ene are copolymerized to form an unsaturated copolymer (the concentration of the units originating from the cyclic olefin is 0.05 to 50 mole % in the copolymer). A complex of a sulfur trioxide donor and a Lewis base is allowed to react with an alkylidene group or an alkenyl group of the unsaturated copolymer to introduce sulfonic acid group into more than 5% of the carbon-carbon double bonds of said alkylidene or alkenyl groups whereby the objective copolymer is otabined.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to adhesiveness, printability, hydrophilicity, compatibility with polymer blends, etc. obtained by introducing a sulfonic acid group into a novel polymer having an olefinically unsaturated bond. The present invention relates to a method for producing an excellent sulfonic acid group-containing copolymer.

[0002]

2. Description of the Related Art α-Olefin homopolymers and their copolymers are inexpensive and have excellent mechanical strength,
Since it has gloss, transparency, moldability, moisture resistance, chemical resistance, etc., it is generally used alone or as a component of a polymer blend. However, since the α-olefin polymer has a non-polar molecular structure, it has a poor affinity with other substances, and is extremely inferior in adhesiveness, printability, and compatibility with polymer blends.

In order to make up for these drawbacks, a part of the polymer is oxidized by a chromic acid mixture or flame treatment, or a polar group-containing compound such as maleic anhydride, methyl methacrylate or acrylonitrile is used by a radical generator. Various modification methods such as graft modification and copolymerization with polar group-containing comonomers have been proposed.

Among the modification methods, sulfonation is very useful because it shows a unique reactivity different from other functional groups because of the strong acidity of the sulfonic acid group. As a polyolefin sulfonation method, a method of treating a polyolefin in fuming sulfuric acid is known, but this method is difficult to control the reaction, and it is difficult to obtain a homogeneous product. There is a limit.

Further, in order to control the sulfonation reaction, attempts have been made to use an unsaturated polymer and introduce a sulfonic acid group into an olefinically unsaturated bond in the unsaturated polymer. Examples of these include Japanese Patent Publication Sho 53
28-354 and JP-A-62-34906.

[0006]

However, these inventions are intended to sulfonate an elastomer such as a semi-crystalline EPDM elastomer or polybutadiene,
It is hard to say that the α-olefin polymer resin has physical properties such as excellent mechanical strength, heat resistance, and chemical resistance that are unique to the resin.

[0007]

[Means for Solving the Problems]

[Summary of the Invention] <Outline> The present invention is intended to solve these problems, and comprises a sulfonic acid group-introduced α-olefin and a specific cyclic olefin. The present invention aims to achieve this object by providing a modified copolymer of an unsaturated copolymer.

That is, in the method for producing a sulfonic acid group-containing copolymer according to the present invention, an α-olefin having 3 to 12 carbon atoms and an alkylidene group- or alkenyl group-containing cyclic olefin represented by the following general formula (I) are used. Comprising modifying an alkylidene group or an alkenyl group of an unsaturated copolymer (wherein the unit concentration based on the cyclic olefin occupying the copolymer is 0.05 to 50 mol%) obtained by polymerization, The modification is characterized by introducing a sulfonic acid group into 5% or more of carbon / carbon double bonds of the alkylidene group or alkenyl group.

[0009]

[Chemical 2]

(Wherein R ¹ represents an alkylidene group having 2 to 5 carbon atoms or an alkenyl group having ² to 5 carbon atoms, R ² represents a hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom, and n Is 0, 1 or 2.)

<Effect> The novel sulfonic acid group-containing copolymer according to the present invention has properties inherently possessed by an α-olefin polymer, such as excellent mechanical strength, transparency, moldability,
The properties based on sulfonic acid groups, such as the adhesiveness or dyeability of various inks and paints, and the hydrophilicity, are imparted without impairing the chemical resistance and the like. Further, the copolymer according to the present invention has a high affinity with other resins and exhibits an excellent compatibilizing effect in a polymer blend.

[Detailed Description of the Invention] << Unsaturated Copolymer to be Modified >><GeneralDescription> The unsaturated copolymer used in the present invention is a novel copolymer having 3 carbon atoms. ~ 12, preferably 3 ~
A copolymer of an α-olefin of 8 and a specific cyclic olefin represented by the above formula (I), wherein the cyclic olefin (I) content is 0.05 to 50 mol%, preferably 0.1 to 50 mol%.
.About.30 mol%.

In the copolymer, the cyclic olefin represented by the general formula (I) is mainly represented by the following general formula (II).
¹ H-NM is copolymerized with the structure
Confirmed by R, ¹³ C-NMR and IR analysis.

[0014]

[Chemical 3]

The unsaturated copolymer is crystalline. Crystallinity is 10% or more of crystallinity by X-ray analysis,
It is preferably 20% or more.
The unsaturated copolymer may further contain a small amount of comonomer up to about 15 mol% based on the total amount of both monomers.

The unsaturated copolymer should have a molecular weight and / or melting point sufficient to call it a resin. The molecular weight is represented by the number average molecular weight of 3,000 or more, preferably 5,000 or more, more preferably 8,000.
That is all. Alternatively, the melting point is 40 ° C. or higher. ¹³ C-
Triad [mm] fraction or [rr] measured by NMR
The fraction is 0.5 or more, more preferably 0.6 or more, and particularly preferably 0.75 or more.

Here, [mm] fraction of triad, [rr]
Fraction means three stereoisomeric structures that can be taken by “triad”, which is the minimum unit of a steric structure in a monomer unit in an α-olefin polymer, that is, “trimer unit”, that is, [mm] ( Isotactic), [mr] (heterotactic) and [rr] (syndiotactic) in total x, the ratio of the number y of triads having a [mm] structure (y / x), and [rr] It is the ratio (z / x) of the number z of triads having a structure. Note that ¹³
The C-NMR measurement was performed by JEOL. FX-20
0, measurement temperature 130 ℃, measurement frequency 50.1MH
z, spectrum width 8000 Hz, pulse repetition time 2.0 seconds, pulse width 7 μsec, number of integrations 10000 to 50
It was performed under the condition of 000 times. In addition, the analysis of the spectrum was carried out by A. Zambelli's Macromolecules 21 617 (198
8) and Tetsuro Asakura Proceedings of the Polymer Society of Japan 36 (8) 2408 (1987)
It was done based on.

The unsaturated olefin copolymer does not contain a gel component. Here, the gel content means an insoluble content when the copolymer is put into a wire mesh of 80 mesh and extracted with boiling xylene for 8 hours.

<Α-Olefin> Examples of the above α-olefin which is one of the constituents of the unsaturated copolymer include propylene, 1-butene, 1-hexene and 3-methyl-1.
-Butene, 3-methyl-1-pentene, 4-methyl-1
-Pentene, 3,3-Dimethyl-1-butene, 4,4-
Dimethyl-1-pentene, 3-methyl-1-hexene,
4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane 2-vinylbicyclo [2,2,2
1] -heptane and the like. Of these, preferred examples include propylene, 1-butene, 1-
Hexene, 3-methyl-1-butene, 3-methyl-1-
Pentene, 4-methyl-1-pentene, 3-methyl-1
-Hexene and the like, in particular propylene, 1-butene, 3-methyl-1-butene, and 4-
Methyl-1-pentene is preferred. These α-olefins may be used alone or in combination of two or more. Particularly, when the α-olefin is 1-hexene, it is preferably used in combination with at least one of propylene, 1-butene, 4-methyl-1-pentene and 3-methyl-1-butene. When two or more α-olefins are used, the α-olefins may be randomly distributed in the unsaturated copolymer, or may be distributed in blocks.

<Cyclic olefin> The cyclic olefin used in the present invention is a compound represented by the following general formula (I).

[0021]

[Chemical 4]

(Wherein R ¹ is an alkylidene group or alkenyl group having 2 to 5 carbon atoms, R ² is a hydrocarbon group or hydrogen atom having 1 to 5 carbon atoms, and n is 0, 1 or 2). Examples of the alkylidene group having 2 to 5 carbon atoms represented by R ¹ include ═CH (CH ₃ ), ═CH (CH ₂ CH ₃ ), and ═C.
H (CH ₂ ) ₂ CH ₃ , = C (CH ₃ ) ₂ , = C (CH
₃ ) (CH ₂ CH ₃ ), ═C (CH ₂ CH ₃ ) _{2 and the} like, and as alkenyl having 2 to 5 carbon atoms, —CH═CH.
_{2, -CH 2 -CH = CH 2} , -CH 2 -C (CH 3)
_{= CH 2, -CH 2 -CH =} CH (CH 3), - CH 2
_{-CH = C (CH 3) 2} , -CH 2 -CH 2 -C (CH
_{3) = CH 2, -CH 2} -CH 2 -CH = CH (C
H _3), and the like can be given.

Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ² include alkyl groups such as methyl, ethyl, propyl and butyl. n is an integer up to 2, but 0 or 1 is preferable. Specific examples include the compounds listed in Table 1.

[0024]

[Table 1]

<Catalyst for Producing Unsaturated Copolymer> The unsaturated copolymer used in the present invention is obtained by contacting the catalyst comprising the component (A) and the component (B) with the above α-olefin and cyclic olefin. It is possible to produce by polymerizing. Here, “consisting of” does not mean that the ingredients are only those listed (ie, (A) and (B)),
Do not exclude the coexistence of other ingredients purposefully.

[0026] <Component (A)> Component (A) is a general formula _{Q a (C 5 H 5-} ab R 3 b) (C 5 H 5-ac R 4 c) a transition metal compound represented by Mexy. Where Q is
It is a bonding group that bridges two conjugated five-membered ring ligands. Specifically, (a) methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group, etc., divalent hydrocarbon residue having about 1 to 20 carbon atoms, (b) silylene group , A dimethylsilylene group, a phenylmethylsilylene group, a diphenylsilylene group, a disilylene group, a monomethyl or oligosilylene group which may have a hydrocarbon residue having about 1 to 20 carbon atoms as a substituent, such as a tetramethyldisilirene group, (C) a hydrocarbon group having about 1 to 20 carbon atoms containing germanium, phosphorus, nitrogen, boron or aluminum (specifically, (CH ₃ ))
₂ Ge group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group,
_(C 6 _H 5) P _group, (C _{4 H} 9) N _group, (C _{6 H} 5) N
Groups, _(CH 3) B _group, (C _{4 H} 9) B _group, (C _{6 H} 5)
B group, (C ₆ H ₅ ) Al group, (CH ₃ O) Al group, etc.) and the like. Preferred are alkylene groups and silylene groups. a is 0 or 1.

(C ₅ H _5-ab R ³ _b ) and (C ₅ H
_The conjugated five-membered ring ligand represented by _5-ac R ⁴ _c ) is defined separately, but b and c and R ³ and R ⁴ are the same in definition (details later). It goes without saying that the two conjugated five-membered ring groups may be the same or different. One specific example of this conjugated 5-membered ring group is a cyclopentadienyl group of b = 0 (or c = 0) (without a substituent other than the bridging group Q). When this conjugated five-membered ring group is b ≠ 0 (or c ≠ 0) and has a substituent, one specific example of R ³ (or R ⁴ ) is a hydrocarbon group (C _1- ). C _20, preferably a C ₁ -C _12), the hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and two of which are when it is present a plurality It may be bonded at the other end and bonded together with the cyclopentadienyl group to form a ring. Typical examples of the latter are those in which R ³ (or R ⁴ ) shares a double bond of the cyclopentadienyl group to form a condensed 6-membered ring, that is, the conjugated 5-membered ring group is an indenyl group or A fluorenyl group. That is, a typical example of this conjugated five-membered ring group is
A substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ³ and R ⁴ are each the above C ₁
To C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon groups,
Halogen group (for example, fluorine, chlorine, bromine), alkoxy group (for example, C _{1 to} C ₁₂ ), silicon-containing hydrocarbon group (for example, silicon atom to —Si— (R ⁵ )).
(R ⁶ ) (R ⁷ ) group containing about 1 to 24 carbon atoms, a phosphorus-containing hydrocarbon group (for example, a phosphorus atom is -P.
-(R) (R) group containing about 1 to 18 carbon atoms),
A nitrogen-containing hydrocarbon group (for example, a nitrogen atom is -N (R)
(R ′) group containing about 1 to 18 carbon atoms or a boron-containing hydrocarbon group (for example, a boron atom containing —B—
(R) is a group containing about 1 to 18 carbon atoms in the form of (R). When b (or c) is 2 or more and a plurality of R ³ (or R ⁴ ) are present, they may be the same or different.

B and c are 0≤b≤ when a is 0.
5, 0 ≦ c ≦ 5, when a = 1, 0 ≦ b ≦ 4, 0 ≦ c ≦
4 is an integer that satisfies the requirement. Me is a group IVB transition metal of the periodic table selected from titanium, zirconium and hafnium, preferably titanium and zirconium, particularly preferably zirconium.

X and Y are each hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
An amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, for example, diphenylphosphine group), or 1 to 20 carbon atoms, preferably 1 carbon atom
.About.12, a silicon-containing hydrocarbon group (specifically, for example, a trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferable. Particularly, those in which X and Y are halogen are preferable.

Specifically, (1) bis (cyclopentadienyl) dimethylzirconium, (2) bis (cyclopentadienyl) diethylzirconium, (3) bis (cyclopentadienyl) methylzirconium monochloride, ( 4) bis (cyclopentadienyl) ethylzirconium monochloride, (5) bis (cyclopentadienyl) methylzirconium monobromide, (6) bis (cyclopentadienyl) methylzirconium monoiodide, (7) bis ( Cyclopentadienyl) zirconium dichloride, (8) bis (cyclopentadienyl) zirconium dibromide, (9) ethylenebis (cyclopentadienyl) zirconium dichloride, (10) ethylenebis (cyclopentadienyl) methylzirconium mono Chloride,

(11) ethylenebis (cyclopentadienyl) dimethylzirconium, (12) methylenebis (cyclopentadienyl) zirconium dichloride, (13) propylenebis (cyclopentadienyl) zirconium dichloride, (14) ethylenebis ( Indenyl) zirconium dichloride, (15) ethylenebis (indenyl) zirconium monochloride monohydride, (16) ethylenebis (indenyl) dimethylzirconium, (17)
Ethylenebis (indenyl) diphenylzirconium,
(18) Ethylenebis (indenyl) zirconium dibromide, (19) Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, (20)
Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride,

(21) Ethylenebis (4-methyl-1-indenyl) zirconium dichloride, (22) Ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, (23) Dimethylsilylbis (cyclopentadienyl) ) Dimethylzirconium, (24) Dimethylsilylbis (cyclopentadienyl) zirconium dichloride, (25) Dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride, (26) Dimethylsilylbis (dimethylcyclopentadienyl) zirconium dichloride , (27) bis (cyclopentadienyl) dimethyltitanium, (28) bis (cyclopentadienyl)
Methyl titanium monochloride, (29) bis (cyclopentadienyl) titanium dichloride, (30) ethylene bis (indenyl) titanium dichloride,

(31) ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride,
(32) Methylenebis (cyclopentadienyl) titanium dichloride, (33) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (34) Methylene (cyclopentadienyl) (3 4-dimethylcyclopentadienyl) zirconium chloride hydride, (35) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (36) methylene (cyclopentadienyl) (3,4 -Dimethylcyclopentadienyl) zirconium diphenyl, (37) methylene (cyclopentadienyl) (trimethylcyclopentadienyl)
Zirconium dichloride, (38) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (39) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, ( 40) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride,

(41) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(42) Isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (4
3) Isopropylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (44) Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) Zirconium dichloride, (45) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (46) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (47) ethylene (2, 5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (48) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(49) Diphenylmethylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (50) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride,

(51) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(52) Cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (53) dimethylsilylene (cyclopentadienyl) (3,4-dimethyl Cyclopentadienyl) zirconium dichloride, (54) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (5
5) Dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (56) Dimethylsilylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, (57) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (58) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopenta (Dienyl)
Zirconium dichloride, (59) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (60) dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,

(61) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (62) Dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (63) Dimethylsilylene ( 2,5-Dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (64) Dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (65) Dimethylsilylene (2,5-diethylcyclopentadiene (Enyl) (fluorenyl) zirconium dichloride, (66) dimethylsilylene (2-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Zirconium dichloride, (67) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-
Di-t-butylfluorenyl) zirconium dichloride, (68) dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (69) dimethylsilylene (diethyl) Cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (70) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,

(71) Dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (72) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (73) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (74) dimethylgermane (cyclopentadienyl) (fluorenyl) zirconium dichloride, (75) phenylamino (cyclopentadienyl) (fluorenyl) Zirconium dichloride,
(76) Phenylalumino (cyclopentadienyl) (fluorenyl) zirconium dichloride, and the like.

<Component (B)> The catalyst component used in the present invention is alumoxane. In the present invention, an organoaluminum compound represented by the following general formula (III) or (IV) can be used.

[0040]

[Chemical 5]

In this general formula, each R ⁸ is independently an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, and a methyl group is particularly preferred, and m Is 2 or more, preferably 4 or more 1
It is an integer of 00 or less. This component (B) is a product obtained by reacting one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, (a) methyl alumoxane, ethyl alumoxane, propyl alumoxane, butyl alumoxane, isobutyl alumoxane obtained from one type of trialkylaluminum, and (b) two types of trialkylaluminum obtained from water. Examples thereof include methyl ethyl alumoxane, methyl butyl alumoxane and methyl isobutyl alumoxane. Of these, methylalumoxane is particularly preferable.

A plurality of these alumoxanes can be used in combination in each group and between each group, and with other alkylaluminum compounds such as trimethylaluminum, toluethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is also possible to use together.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether, (b) a salt hydrate having trialkylaluminum and water of crystallization, such as copper sulfate or aluminum sulfate. Method of reacting with hydrate, (C) Method of reacting trialkylaluminum with water impregnated in silica gel, etc. (D) Mixing trimethylaluminum and triisobutylaluminum, and mixing with a suitable toluene, benzene, ether, etc. A method of directly reacting with water using an organic solvent, (e) a method of mixing trimethylaluminum and triisobutylaluminum, and reacting with a salt hydrate having water of crystallization, for example, copper sulfate, hydrate of aluminum sulfate, and heating. (F) Impregnate silica gel with water and use triisobutylaluminum. After the treatment, a method of additionally treating with trimethylaluminum, (to) a method of synthesizing methylalumoxane and isobutylalumoxane by a known method, mixing a predetermined amount of these two components, and reacting by heating, preferably (a) Is the method.

<Production of Unsaturated Copolymer> The copolymerization of α-olefin and cyclic olefin is usually carried out in a hydrocarbon solvent. Specific examples of the hydrocarbon solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane and kerosene, and aromatic hydrocarbons such as benzene, toluene and xylene. These can be used alone or as a mixture.

As the polymerization method, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method can be used. The polymerization temperature is -60 to 150 ° C, preferably -30 to 80 ° C.
The polymerization pressure is generally 0 to 50 Kg / cm ² , preferably 0 to 30 Kg / cm ² . In the present invention, hydrogen can be used for controlling the molecular weight of the copolymer.

In the copolymerization, the concentration of the transition metal atom used as the catalyst component in the hydrocarbon solvent is from 10 ⁻⁵ to
1 milligram atom / liter, preferably 10 ⁻⁴ to 10
^-1 mg atom / liter. The concentration of alumoxane in the hydrocarbon solvent is 10 ⁻¹ to 10 ² milligram atom / liter of aluminum atom, preferably 5 × 10 ^{−1 to} 5 × 10 milligram atom / liter. After the completion of the polymerization reaction, the unsaturated olefin copolymer is obtained by treating the polymerization reaction solution by a conventional method.

<< Modification of Unsaturated Polymer >> In the present invention,
The above olefinically unsaturated polymer is modified to introduce a sulfonic acid group into the unsaturated bond of R ¹ derived from a cyclic olefin. In the present invention, preferred specific examples of the method for introducing a sulfonic acid group into an olefinic unsaturated bond include sulfuric acid such as concentrated sulfuric acid, fuming sulfuric acid, and anhydrous sulfuric acid, and a sulfur trioxide donor such as sulfur trioxide; Acetic acid, acetic acid, dioxane,
This is a method using a complex with a Lewis base such as tetrahydrofuran, pyridine, dimethylaniline, dimethylformamide, N-methylpyrrolidone, triethyl phosphate, and triethylamine.

The reaction is carried out in a state where the unsaturated polymer is swollen or dissolved in a solvent or in a molten state. Reaction in the dissolved or molten state is preferred. The solvent to be used should be appropriately selected depending on the type of reaction, but is an aliphatic, alicyclic or aromatic hydrocarbon and its halides, esters having 6 or more carbon atoms, ketones, ethers, and carbon disulfide. Often selected from the above, it can be used as a mixed solvent of two or more kinds. The reaction in the molten state can be carried out by using, for example, an ordinary granulator, a twin-screw kneader, a plastomill or the like. The selectivity of the reaction does not necessarily have to be 100%, and the product of the side reaction may be mixed in if the sulfonic acid group is substantially introduced.

The amount of the sulfonic acid group introduced is 5% or more, preferably 8% of the olefinic unsaturated bond in the unsaturated polymer.
Or more, and more preferably 10% or more. If the amount introduced is less than 5%, the resulting sulfonic acid group content is low and the modification effect is poor.

<< Modified Polymer >> The sulfonic acid group-containing copolymer according to the present invention is a novel sulfonic acid group-containing copolymer obtained by introducing a sulfonic acid group into a novel unsaturated olefin copolymer. , and the fact that sulfonic acid groups are introduced into the olefinic unsaturated bond by reaction of above ¹ H-
NMR method, ¹³ C-NMR method, ion chromatography method and I
Confirmed by R analysis. It has also been confirmed by GPC that the molecular weight and molecular weight distribution of this sulfonic acid group-containing copolymer are almost the same as those of the unsaturated olefin copolymer before the introduction of the sulfonic acid group. It can be seen that molecular cleavage, cross-linking, etc. at the time of introducing the group hardly occur. The gel content measured by the above method is not included.

The modified copolymer according to the present invention has a characteristic property because it has a sulfonic acid group in the branched chain. For example, it has excellent adhesion to various printing inks and paints, and is more hydrophilic than ordinary polyolefins. Since it has excellent adhesiveness with other resins, it is advantageous to use it as a binder between incompatible resins, and in particular, polyolefin resin and polystyrene, polyamide, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, etc. It can exhibit excellent physical properties as a compatibilizing agent for resins.

[0052]

【Example】

[Unsaturated Copolymer Production Example-1] <Synthesis of ethylenebis (indenyl) zirconium dichloride> A 300 ml glass flask sufficiently replaced with nitrogen was charged with 5.16 g of bis (indenyl) ethane and 150 ml of tetrahydrofuran, Then, it cooled to -78 degreeC. 25 ml of Aldrich butyl lithium
(1.6 mol / liter concentration) was added dropwise over 1 hour, the temperature was gradually raised to the reflux temperature, and then the mixture was refluxed for 2 hours.

On the other hand, 100 ml of tetrahydrofuran was charged into a 200 ml glass flask that had been sufficiently replaced with nitrogen, and then-
Cooled to 78 ° C, and 4.7 g of zirconium tetrachloride
Was added and the temperature was gradually raised to room temperature. This zirconium tetrachloride solution was added all at once to the previously prepared lithium salt solution of bis (indenyl) zirconium at 0 ° C., then the temperature was raised to the reflux temperature and the reaction was continued at the reflux temperature for 16 hours. Then, the produced yellow solid was filtered off, the solid was washed with methanol, and dried under reduced pressure. 1.9 g of ethylenebis (indenyl) zirconium dichloride was obtained. <Alumoxane> Methyl alumoxane manufactured by Tosoh Akzo (degree of polymerization 20) was used.

<Polymerization> After sufficiently drying an induction stir type stainless steel autoclave having an internal volume of 1 liter,
It was thoroughly replaced with dry propylene. Purified toluene 500
ml and 5-vinylbicyclo [2,2,1] hept-2-
1.5 ml of ene was put into this autoclave under a propylene gas stream, and then methylaluminoxane was added in an amount equivalent to 11 mg atom in terms of aluminum atom, and ethylenebis (indenyl) zirconium dichloride was 1.1 × 10 in terms of zirconium atom. Amounts corresponding to ^-3 milligram atoms were added in this order to the autoclave at room temperature, pressurized with propylene gas to 5 kg / cm ² G, and copolymerized at 50 ° C for 2 hours. After the polymerization, the residual gas was purged, and the polymer solution was poured into a large amount of methanol to precipitate the polymer.

Thereafter, it is dried under reduced pressure at 80 ° C., and after drying 6
0.5 g of copolymer was obtained. The activity per unit zirconium was 27,500 g polymer / milligram atom Zr · hr. The content of 5-vinylbicyclo [2,2,1] hept-2-ene in the obtained polymer was ¹³ C-N.
The result of MR analysis was 0.5 mol%, the number average molecular weight (Mn) of the obtained polymer was 14,000 in terms of polystyrene, and the weight average molecular weight (Mw) was 28,000. NMR
The tacticity measured in step 9 was 90.1% for mm, 7.0% for mr, and 2.9% for rr. This is designated as resin A.

[Unsaturated Copolymer Production Example-2] In the polymerization of the unsaturated copolymer Production Example-1, the compound N shown in Table 1 was used.
Copolymerization was carried out in the same manner as in Unsaturated Copolymer Production Example-1, except that 1.5 ml of o.3 of cyclic olefin was used. As a result, 78.5 g of a copolymer was obtained,
The polymerization activity was 700 g polymer / milligram atom Zr · hr. The comonomer content of the polymer obtained, Mn,
Mw, mm, mr and rr are 0.5 mol% and 1 respectively
3,000, 24,000, 90.8%, 6.7%,
It was 2.5%. This is referred to as resin B.

Example 1 10 g of Resin A, 200 ml of chlorobenzene and 6.8 ml of acetic anhydride were added to a separable flask of 500 ml, the temperature was raised to 100 ° C., and then cooled to room temperature. To this was added 2.9 g of concentrated sulfuric acid, and the reaction was carried out at room temperature for 3 hours. After the reaction, the content in the flask was poured into a large amount of cold acetone to precipitate a polymer, and the polymer was filtered. Further, after washing with acetone and water by filtration twice, each was dried under reduced pressure to obtain a modified copolymer. The obtained modified copolymer was uniformly white, and it was confirmed by infrared spectroscopy and ion chromatography that a sulfonic acid group was introduced into the polymer, and the olefinic unsaturated bond in the copolymer was confirmed. The conversion rate to sulfonic acid groups was 98%. The molecular weight measured by GPC was the same as that before the introduction of the sulfonic acid group. There was also no gel.

Example-2 The reaction was carried out in exactly the same manner as in Example-1 except that 10 g of Resin B was used. The obtained modified copolymer was uniformly white, and it was confirmed by infrared spectroscopy and ion chromatography that a sulfonic acid group was introduced into the polymer, and the olefinic unsaturated bond in the copolymer was confirmed. The conversion rate to sulfonic acid groups was 100%. GPC
The measured molecular weight was the same as before the introduction of the sulfonic acid group. There was also no gel.

[Application Example-1] Polypropylene resin (MA8 manufactured by Mitsubishi Petrochemical Co., Ltd.), terminal aminated polyphenylene ether obtained as described below, and sulfonic acid group-containing α-obtained in Example-2 An olefin polymer and an internal volume of 60
The composition was as shown in Table 2 and melt-kneaded for 6 minutes under the conditions of 230 ° C. and a rotation speed of 180 rpm in a plast mill manufactured by Toyo Seiki Co., Ltd. The obtained mixture was press-molded under the condition of 280 ° C. to prepare a sheet having a thickness of 2 mm. Various test pieces were cut out from this sheet and evaluated for physical properties.

Example of the preparation of terminally aminated polyphenylene ether Poly (2,6-dimethyl-1,4-phenylene ether) (PPE, intrinsic viscosity measured in chloroform at 30 ° C .: 0.30 dl / g) 20.0 g and 200 ml of toluene was charged into the reactor and heated and stirred at 80 ° C. to dissolve the polyphenylene ether. Subsequently, 7.0 g of a 50% aqueous sodium hydroxide solution as a basic catalyst and 2.0 g of trioctylmethylammonium chloride as a phase transfer catalyst were added, the temperature of the reaction mixture was raised to 90 ° C., and stirring was continued for 30 minutes. Subsequently, 3.5 g of 2-chloroethylamine was added as an aqueous solution over 15 minutes. Furthermore, after heating and stirring for 7 hours, the reaction mixture is mixed with methanol 1.5
The modified resin produced was poured into liter to precipitate. After filtering this off, it was washed with 1 liter of water and methanol 1
Washed with liters. It was dried by heating under reduced pressure at 80 ° C. to obtain terminal aminated polyphenylene ether. 100% yield
Then, the reaction rate of the polyphenylene ether end is 100%,
Proton nuclear magnetic resonance absorption spectrum revealed that the number of primary amine halides added was one molecule.

<Measurement and Evaluation Method> (1) Flexural Modulus A test piece having a width of 25 mm and a length of 80 mm was cut and processed in accordance with JIS.
It measured using the Instron tester based on K7203. (2) Izod impact strength The impact resistance was measured according to JIS K7110 by stacking three test pieces each having a thickness of 2 mm and measuring the notched Izod impact strength at 23 ° C.

<Results> Table 2 shows the results obtained by the above method. As is clear from Table 2, the composition using the sulfonic acid group-containing α-olefin copolymer according to the present invention exhibits high impact strength.

[0063]

[Table 2]

[0064]

The sulfonic acid group-containing copolymer according to the present invention, without impairing the properties inherently possessed by the α-olefin polymer, such as excellent mechanical strength, transparency, moldability and chemical resistance, Properties based on sulfonic acid groups, such as adhesiveness or dyeability of various inks and paints, and hydrophilicity are imparted, and the copolymer according to the present invention has high affinity with other resins and is a polymer blend. That the excellent compatibilizing effect is exerted in the above is as described above in the section of "Outline of the Invention".

Claims (2)

[Claims] 1. An unsaturated copolymer obtained by copolymerizing an α-olefin having 3 to 12 carbon atoms with an alkylidene group- or alkenyl group-containing cyclic olefin represented by the following general formula (I) The unit concentration based on the cyclic olefin in the coalescence is 0.05 to 50 mol%) of the alkylidene group or alkenyl group, and the modification comprises carbon-carbon double bonds of the alkylidene group or alkenyl group. A method for producing a sulfonic acid group-containing copolymer, which comprises introducing a sulfonic acid group into 5% or more of bonds. [Chemical 1] (In the formula, R ¹ is an alkylidene group having 2 to 5 carbon atoms or an alkenyl group having ² to 5 carbon atoms, and R ² is 1 to 5 carbon atoms.
Represents a hydrocarbon group or a hydrogen atom, and n is 0, 1 or 2. ) 2. The method for producing a sulfonic acid group-containing copolymer according to claim 1, wherein the modification is carried out by reacting the unsaturated copolymer with a complex compound of a sulfur trioxide donor and a Lewis base.