WO1989001950A1

WO1989001950A1 - Ethylene/polycyclic monomer copolymer and process for its preparation

Info

Publication number: WO1989001950A1
Application number: PCT/JP1988/000849
Authority: WO
Inventors: Yasuaki Sasaki; Tohru Matsuoka
Original assignee: Showa Denko Kabushiki Kaisha
Priority date: 1987-08-26
Filing date: 1988-08-26
Publication date: 1989-03-09

Abstract

A random copolymer comprising ethylene and units derived from a polycyclic monomer represented by general formula (I) (wherein q represents an integer and a methyl substituent or substituents may optionally exist) in a proportion of 90/10 to 10/90 shows well balanced optical, mechanical, thermal and chemical properties.

Description

Remarks Ethylene / polycyclic monomer copolymer and its production

The present invention relates to a random copolymer of ethylene and a polycyclic monomer and a method for producing the same.

This random copolymer has excellent transparency, is optically homogeneous, has low birefringence, and has well-balanced heat resistance, chemical resistance, dimensional stability, rigidity and other mechanical properties. Doing s landscape technology

As resins having excellent transparency, polystyrene, methyl polymethacrylate, polycarbonate, poly (41-methylpentene) -11 and the like have been known. Polystyrene has excellent transparency, good dimensional stability, and high rigidity, but has the problem of being easily attacked by ketones, esters, and aromatic hydrocarbons, and having low heat resistance. is there. Polymethyl methacrylate is very transparent and has high mechanical strength, but has low heat resistance and is easily attacked by ketones, esters, and aromatic hydrocarbons. Polycarbonate has excellent transparency, heat resistance, dimensional stability, and mechanical properties, but has problems such as weak optical strength and high optical anisotropy due to large birefringence. Poly-4-1-methylpentene-1 has problems such as poor dimensional stability and large birefringence due to its crystalline nature. Until now, there is no known resin material that can sufficiently satisfy the balance of transparency, optical properties, heat resistance, chemical resistance, dimensional stability, and mechanical properties.

In view of these circumstances, the present invention has excellent transparency. In addition to optical properties such as being optically homogeneous and having low birefringence, heat resistance, chemical resistance, and dimensional stability have been achieved. Another object of the present invention is to provide a resin material having excellent mechanical properties. Disclosure of the invention

The present invention, in one aspect,

(A) Ethylene and the following general formula (I)

(Where,, m, n and are 0 or 1 and q is an integer of 0 or more.)

A random copolymer having a repeating unit derived from a polycyclic monomer represented by the formula:

(B) the molar ratio of ethylene to the polycyclic monomer represented by the general formula (I) is 90 to 10 to 10 to 90,

(C) The position derived from the monomer represented by the general formula (I) is mainly represented by the following general formula (E): (Π)

(0Η ₃ ) ί (CH ₃ ) (CH ₃ )

(CH ₃ )

(Where £, m, n, p and q are as described above.)

(D) intrinsic viscosity measured in decalin at 135 ^e C [] is 0.2 to 15 <^ g,

Provide a random copolymer.

In another aspect, the present invention relates to a compound represented by the general formula (I) and ethylene in a hydrocarbon solvent in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organic aluminum compound. The present invention provides a method for producing the above random copolymer by copolymerizing the obtained polycyclic monomer. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an infrared absorption spectrum of the polystyrene monocyclic monomer copolymer of the present invention obtained in Example 1. BEST MODE FOR CARRYING OUT THE INVENTION In the random copolymer of the present invention, the polycyclic monomer represented by the general formula (I) copolymerized with ethylene is mainly represented by the general formula (Π) The following general formula

(X):

(In the formula, ,, m, η, ρ, and q are as described above.)

The structure caused by the ring-opening polymerization represented by the formula (1) is substantially not present, or is present in a very small amount. Therefore, the random copolymer of the present invention is chemically stable.

In the present invention, typical examples of the polycyclic monomer represented by the general formula (I) copolymerized with ethylene include the following general formula (UI):

(

(Where,, m and!) Are 0 or 1. )

1,4,5,8—Dimetano 1,2,3,4,4a, 4b, 5,8,8a, 9a—Decahydrofluorenes (DMDFs). The unit derived from this polycyclic monomer is mainly contained in the random copolymer of the present invention. The following general formula (IV): (IV)

(CH (CH ₃ ) _m (CH ₃ ) p

(Where,, m and p are as described above.)

And the structure resulting from ring-opening polymerization is not substantially present, or is present in a very small amount.

The DMDFs represented by the general formula (II) are obtained by hydrogenating two kinds of isomers of tricyclopentadiene in JP-A-52-62192, which is one of dihydrotricyclopentagen mixtures obtained. It is listed as an ingredient. DMDFs are partially hydrogenated dicyclopentagenes represented by the following general formula (K) and are 4,7-metano 3a, 5,6,7a —tetrahydro 1H— Indians and

(Here, P and m are 0 or 1.)

It is synthesized by a Diels-Alder reaction with cyclopentagens or by a reaction with dicyclopentadiene, which thermally decomposes under the reaction conditions to form cyclopentadiazines.

Partially hydrogenated dicyclopentadiene compounds can be easily synthesized by using known dicyclopentadiene compounds as a starting material, for example, by a known method described in, for example, East German Patent No. 0154293. In the method of synthesizing DMDFs, the reaction ratio between the partially hydrogenated dicyclopentadiene and the cyclopentadiene or dicyclopentadiene is determined based on 1 mole of the partially hydrogenated dicyclopentadiene or cyclopentadiene or dicyclopentadiene. The proportion of dicyclopentadiene is 0.02 to: L 0 mol, preferably 0.05 to 0.5 mol.

The reaction temperature is 50 to 250'c when cyclopentadiene is used as a raw material, preferably 80 to 200, and 100 to 300'c when dicyclopentadiene is used as a raw material. , Preferably from 120 to 250. The reaction time varies depending on the reaction temperature, but is generally 30 minutes to 30 hours, preferably Ί to 20 hours. In the Diels-Alder reaction, it is preferable to add a polymerization inhibitor such as nitrodloquinone or tert-butylcatechol to suppress the formation of a polymer. In this reaction, low levels such as methanol or ethanol It is also possible to use hydrocarbons such as high-grade alcohol, toluene, and cyclohexane, or halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, and dichloroethane. In carrying out this reaction, either a notch process or a continuous process can be employed.

DMDFs can be separated and purified from the Diels ♦ Alder reaction product obtained under the above reaction conditions by means such as distillation.

In the present invention, other examples of the polycyclic monomer represented by the general formula (I) copolymerized with ethylene are shown in Table 1.

Dagger

table 1

Expression

Compound name

(a)} _Γί]) heptacyclo ^{^{^{[1 3 '6. 0''}}} 7, l, Zl' 5. Ο '. O 2' 7. 0 "', 6 ] one Ikosa 4 En

(b) Rimechiru to Butashikuro [1 ³ ^'6. ⁰ ^"1. ^{1, 2'} ^15. 0.0 ^2, ^7. 0"^'6] one Ikosa one 4- E down

(c) 0 "'"] 1—4—

CO

") ίΐ excitation Nonashikuro [1"''.. · l 5, fl, 1 13,20 1 15, 18 O 2 '10 0 4' 9 0 12,21 0 ".. '19 1 -. Peso々 1 Kosa 6

(e) {J jj)) > ^ methyl ^ 'Tashikuro [1 ³ ^R'6. ^{1, 0'} ^{^17.1, 2} ^'15. 0.0 ^2, ^7. 0 "'"] one Ikosa one 4- E N

CH ₃

Polycyclic mono mer as shown in Table 1, Pentashiku b ^{^{[6. 5 1 V 7 I 9 '}} 12 0 2.' 6 0 8 '13.. ] Ichipe Ntade force one 3 - E emissions such (g Li It can be easily obtained by a Diels-Alder reaction between cyclopentadiene (a partially hydrogenated product of cyclopentadiene) and cyclo π-pentane.

In the random copolymer of the present invention, the ratio of the unit derived from ethylene to the unit derived from the polycyclic monomer represented by the general formula (I) is from 10 to 90 to 10 (10). Molar ratio>, preferably 20 to 80 to 80.

It should be noted that other copolymerizable monomers may be copolymerized with the ethylene and the polycyclic monomer represented by the general formula (I) as long as the object of the present invention is not impaired. The amount of copolymerizable monomer will vary depending on the type.

A typical example of a copolymerizable monomer is represented by the following general formula (V):

(Where k is 0 or 1)

And a polycyclic monomer represented by the following general formula (VI)

C

(In the formula, k is the same as k in the general formula (V).)

This is a mixture with a monomer represented by the following formula. The ratio of both polycyclic monomers is (V) / (VI) = 5/95 to 20/80 (molar ratio).

A mixture of the polycyclic monomers represented by the above general formulas (V) and (VI) (ie, tricyclopentadiene) uses dicyclopentane as a starting material, and is disclosed in, for example, JP-A-49-49952. It is synthesized according to the method described. Note that these tricyclic pentagens are blocked as by-products in the synthesis of the DMDF represented by the above general formula (H), so that DHDFs and tricyclic pentagens are separated. The mixture can be used in the production of a polymer without any modification. By using the mixture as it is, the process of separating and purifying the MDFs can be simplified, and the unit price of the comonomer can be reduced, which is advantageous.

In the random copolymer, the tricyclopentagens represented by the general formulas (V) and

(W):

(K in the formulas is the same as k in the general formulas (V) and (VI)), and has substantially no structure resulting from ring-opening polymerization. Very little, if any. Therefore, the copolymer is chemically stable.

Ethylene, polymonomers represented by the general formula (I) (particularly, DMDFs represented by the general formula (H)), and tricyclopentagens (TCPDs) represented by the general formulas (V) and (VI) ), The proportion of each monomer unit in the copolymer is such that the ethylene units (molar ratio) are 10Z90 to 90Z10, preferably 20Z80 to 80/20, and TCPD DMDFs (molar ratio) 4 or less, preferably 15 to 85 to 80, more preferably 20 to 80/50/50.

Other examples of the monomer copolymerized with the ethylene and the polycyclic monomer represented by the general formula (I) include linear or branched -olefins having 3 to 10 carbon atoms. A cyclorefin having 5 to 18 carbon atoms is exemplified.

o — Examples of olefins are propylene, 1 — butene, hexene, 3 — methyl 1-butene, 4 — methylone 1-pentene, 1 — o Octene, 1-decane and the like. Or power, but with 3 or 6 carbon atoms is preferred.

Specific examples of cyclorefin include cyclopentene, cyclohexene, nonolebornane, methinolenolevonolenene, ethylnorbornane, 4,7-metano-3a, 5,6 , 7a — tetrahydro 1 H — indian.

Ethylene and a polycyclic monomer represented by the general formula (I) (particularly, In the case of a copolymer composed of a general formula (DMDFs represented by ΠΠ) and the above-mentioned olefin and Ζ or cycloolefin, the proportion of each monomer unit in the copolymer is determined by the ratio of ethyleneno DMDFs (molar ratio). ) Is 10 to 90 to 90, preferably 20 to 80 to 80, and the ratio of [α-olefin and / or cycloolefin] / DMDF (molar ratio) is 9 or less, preferably 90 no 10 to 15/85, more preferably 80/20 to 25-75.

In addition, another copolymerizable monomer in a smaller amount (less than 15 mol% of the monomer represented by the general formula (I) in the copolymer) may be used. Specific examples of such copolymerizable monomers include styrenes such as styrene and α-methylstyrene, norbornene such as norevozorenene, methyl / renozolevosolenene, and ethylenolebornen. , 4, 7 —methano 3a, 5,6,7a—tetrahide 1H—indene, 4,7—methano -2,3,3a, 7a—tetrahi Examples include norbornene-type compounds such as dro-1H-indene, and polyenes such as dicyclopentadiene, 5-ethylidene-12-norbornene, and 1,4-hexagen. The random warfare polymer of the present invention comprises ethylene, a polycyclic monomer represented by the general formula (I) and, if necessary, another monomer and a hydrocarbon-soluble vanadium compound in a hydrocarbon solvent. E, obtained by co-polymerization in the presence of a catalyst consisting of an organic aluminum compound

The vanadium compound used at this time is a vanadium halide such as VC ₄ , VC £ a or a general formula V0 (0 _t X ₃ _t 〔here! ? Is an alkyl group having at most 10 carbon atoms, X is a halogen, and 0 ≤ t ≤ 3.], a vanadium compound represented by the following formula: Examples of suitable compounds among these include:

V0C & a, V0Br ₃ ,

V0 (0CH ₃ ) C £ z,

V0 (0CH ₃ ) a, '

V0 (0C ₂ H ₅ ) C & 2,

V0 (0C ₂ H _s ) ₂ C &,

V0 (0CzH ₅ ) 3,

VO (OC ₃ H ₇ ) C a 2,

V0 (0C ₃ H ₇ ) ₂ C i,

V0 (0C ₃ H ₇ ) 3,

_{V0 (0 · n- C 4 .H} 9) C a 2,

V0 (0 · nC ₄ H ₉ ) _Z C &,-and the like. These compounds may be used alone or as a mixture of two or more.

The organic aluminum compound used in combination with the vanadium compound is represented by the general formula H'uA £ X'3-u (where R 'is an alkyl group having at least 10 carbon atoms and X' is a halogen. , 0 <u <3>. Among them, those in the range of 1 ≤ u ≤ 2 are preferably used. Examples of suitable are dimethylaluminum dichloride, methylaluminum dichloride, jetty Aluminum aluminum chloride, ethyl aluminum sesquique mouth light, ethyl aluminum dichloride, g-n-propyl aluminum chloride, n-pu α pill aluminum zinc mouth light, di-isobutyl aluminum π-ride And isobutyl aluminum dichloride. These compounds may be used alone or as a mixture of two or more dichlorides.

The use ratio of the vanadium compound and the organic aluminum compound having a haguchigen is 1 to 30 (preferably 2 to 20), preferably 2 to 20 (molar ratio).

The copolymerization is carried out in a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and kerosene; and aromatic hydrocarbons such as benzene, toluene, and xylene. Hydrogen or an alicyclic hydrocarbon such as cyclohexane is exemplified. These can be used alone or as a mixture.

In the copolymerization, the concentration of the vanadium compound used as a catalyst in the hydrocarbon solvent is from 0.1 to 30 millimoles, preferably from 0.2 to 10 millimoles.

The proportion of ethylene and the polycyclic monomer represented by the general formula (I) varies depending on the composition of the copolymer, the polymerization temperature or the type of the solvent. Ratio) is 1 to 1; L / 100. Also, ethylene, a polycyclic monomer represented by the general formula (I) (particularly, DMDF represented by the general formula (H)), and a tricyclopentene represented by the general formulas (V) and (W) In the case of copolymerization with tagenes (TCPD), in general, ethylene / DMDF (molar ratio)-1 to 1 to 1 and 100, TCPD

(Molar ratio) = 10 1 or less, preferably 1 to 100 to 10 1. In addition, ethylene and the polycyclic monomer represented by the general formula (I)

(Especially, when the DMDF represented by the general formula (（)) is copolymerized with —olefin and / or cycloolefin, generally, ethylene / DMDF (molar ratio) = 1 1 to 1 100, (a-olefin and cyclo or cycloolefin) DMDF

(Molar ratio) = 10 to 1 or less, preferably 1 to 50 to 10: 1. The polymerization temperature is usually between 1 and 60; 100'C, preferably between-30 and 50. The polymerization pressure is generally from 0 to 50 kg / hr, preferably from 0 to 30 kg / crf. In the present invention, hydrogen can be used for controlling the molecular weight of the copolymer.

The intrinsic viscosity [] of the copolymer of the present invention measured in 135′c decalin is 0.2 to 15 μg, and preferably 0.5 to 8 μg / g. [] Is preferably within the above range in order to balance heat resistance, mechanical properties and moldability. The novel random copolymer of the present invention is usually amorphous or low crystalline, but is preferably amorphous in order to exhibit excellent transparency. The crystallinity by X..rays is less than 5%, often 0%, and most of them have no melting point observed by differential scanning calorimeter (DSC). Further, the copolymer of the present invention has a high glass transition temperature, and the glass transition temperature by DSC is usually 80 to 230, and most of them are 100 to 200, and has excellent heat resistance. Of the polycyclic monomers represented by the general formula (I), q = l The copolymer obtained by using the above polycyclic monomer is compared with a copolymer obtained by using a polymeric monomer having q = 0 (that is, a DMDF represented by the general formula (IE)). The glass transition point is high if the ethylene ratio is the same. In addition, copolymers of ethylene and DMDF with a-olefin and Z- or cycloolefin are higher than copolymers of ethylene and DMDF only, even if the amount of DMDF is smaller. It indicates the glass transition point and can reduce the amount of DHDFs that are expensive.

The novel random copolymer of the present invention is formed into various shapes by a method such as a compression molding method, an extrusion molding method, an injection molding method, and a hollow molding method used in general synthetic resins. can do. At this time, additives such as light, heat, oxygen and ozone stabilizers, flame retardants, plasticizers, lubricants, antistatic agents, fillers, coloring agents, reinforcing agents, etc. are added as necessary. I can do it.

Further, the novel random copolymer of the present invention can be used in combination with various known polymers. Examples of these polymers include, for example, homopolymers of or olefins such as ethylene, propylene, butene-1. Hexene-1, 4-hexisopentene-11, and two kinds of these monomers. Polyolefins such as copolymers composed of the above, polystyrene, poly-α-methylstyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer Styrene-based polymers such as coalesced polymers, polybutadiene, polysoprene and other polygens, polyethylene terephthalate and polybutylene terephthalate and other polyesters, nylon 6, nylon Polyamides such as lon 66, nylon 11 and nylon 12 Halogen polymer such as polychlorinated vinyl and polyvinylidene chloride, polymethylacrylate, polymethylmethacrylate Examples include poly (meth) acrylates such as tacrylate, polycarbonate, and polyacetal.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

1,4,5,8—Dimetanol 1,2,3,4,4a, 4b: 5,8,8a, 9a-Decahydrofluorene (DMDF) combined stirrer, thermometer, additional In a 100-reactor equipped with a gas supply tube and a gas inlet tube, a nickel solution of nickel acetate tetrahydrate 5 ιηο £ in ethanol

Hydrogen gas was flowed from the gas injection pipe while 40 was charged and stirred vigorously. Here, a catalyst was prepared by adding dropwise 5 H of ethanol suspension of 5 mojg of sodium borohydride. The dicyclopentadiene lOOmojg was added and the hydrogenation reaction was continued until about 100mo of hydrogen was consumed. After the reaction, 6.5 g of acetate and 65 g of activated carbon (DARCO K-B) were added, and the mixture was stirred for 1 hour and filtered using purified diatomaceous earth (Celite) to give 8,9-dihydrocyclyl. An ethanol solution containing a mouth pentagen was obtained. Ethanol was distilled off from this solution under reduced pressure, and the boiling point was 178 to 180 at normal pressure. 11.8 kg of 8,9-dihydrid pentagen, which is a fraction of c, was collected. Next, the 8,9-dihydrocycline π-pentagen 70 m £ and the dicyclopentagen 15 m The mixture was heated to 230'c over 4 hours with stirring, and a simple reaction was carried out at that temperature for another 12 hours. The obtained reaction mixture was distilled under reduced pressure to obtain 2.15 kg of a fraction of NO2 at bp 115 to 118. This compound was identified by NMR and GC-MS to give 1,4,5,8—dimethano-1,2,3,4,4a, 4b, 5,8,8a, 9 a-It was confirmed that it was Deca Hydrofuroren.

Copolymerization of ethylene and DMDF

Stirrer, thermometer, dropping low bets and thoroughly purged with nitrogen for 1 0 & four Rrofurasuko having a gas blowing tube, ₀ one charged with anhydrous toluene 5 &! In DMDF 700 gヽV0C & ₂ (OEt) 1 0 mmo £ were charged into a flask, the dropping low preparative was charged Toruen solution 2 0 nil containing _{_{_{Et 3 a £ 2 C £ 3}}} 2 0 mmo. A mixed gas of ethylene 140 {1} and nitrogen 100 hr was passed through a gas injection pipe through a flask cooled to 10 ° C. with ice water for 15 minutes. By the dropping low preparative added dropwise Et ₃ A ^ ₂ C _3, to start the copolymerization reaction was carried out for 30 minutes copolymerization reaction 1 0 hand. During the Copolymerization Reaction—The inside of the polymerization system was uniform, and no copolymer folding was observed. <60 mL of methanol was added to stop the copolymerization reaction. The copolymer was deposited by pouring the polymerization solution into a large amount of methanol, washed with methanol, and dried in vacuo at 50 to obtain 280 g of the copolymer. Obtained.

The ethylene content in the copolymer was 51 mol% according to ¹³ C-MR analysis, 135. c The intrinsic viscosity [?] measured in decalin was 1.1. The iodine value which is a measure of the unsaturated bond is 0.8.

The transparency was measured according to ASTM D1003-52 using a disk having a diameter of 50 «i« and a thickness of 1 produced by injection molding, and as a result, Haze was 8%. The birefringence was 5 nm when measured by the ellipsometer method (light source wavelength: 830 nm) using the same test piece.

In addition, no. When the melting point Tm and the glass transition temperature Tg were measured by Kinelma Co., Ltd., Type 7 DSC, the melting curve was not observed in the range of 30 to 400'C, and the Tg was 170 ° C.

The flexural modulus and yield strength were 2.4 x 10 g / ci. 840 kg / crf, respectively, as measured using a 2 mm thick press sheet according to ASTM D790.

To further evaluate chemical resistance, a 1 ™ thick press sheet was soaked in acetone, acetyl acetate, sulfuric acid (98%), and ammonia water (28%) for 20 hours at room temperature. Observation of the change in appearance showed that there was no change in color, transparency, etc., and no deformation, cracking, etc. were observed.

Example 2 ~ Ί

A copolymerization reaction was carried out in the same manner as in Example 1 except that the copolymerization conditions in Example 1 were changed as shown in Table 1, and the results in Tables 2 and 4 were obtained. Table 2

Examples 8 and 9

Methyl 1—1,4, _5, —8—dimetano_1,2_, 3 ^,

Synthesis of 4a, 4¾, 5,8,8a, 9a-decahydrofluorene (methyl-DMDF)

In Example 1, a methyl-DMDF was synthesized in exactly the same manner as in Example 1 except that methyl dicyclopentadiene was used instead of dicyclopentadiene when synthesizing the partially hydrogenated dicyclopentene.

Copolymerization of ethylene and methyl-DMDF

In Example 1, the copolymerization of ethylene and methyl-DMDF was carried out in the same manner as in Example 1 except that methyl DMDF was used instead of DMDF and the copolymerization conditions were as shown in Table 3. The results in the table were obtained. Examples 10 to 12

Dime chiru 1, 4, 5, 8-dime tano 1, 2, 3, 4,

4a, 4b, 5,8,8a, 9a —Synthesis of Decahydrofluorene (Dimethyl-DMDF)

In Example 1, dimethyl-DMDF was synthesized in the same manner as in Example 1, except that dimethyl-cyclopentagen was used instead of dicyclopentene when synthesizing the partial hydrogenated dicyclopentagen. did.

Copolymerization of ethylene and dimethyl-DMDF

The copolymerization of ethylene and dimethyl-DMDF was carried out in the same manner as in Example 1 except that dimethyl-DMDF was used instead of DMDF in Example 1 and the copolymerization conditions were changed as shown in Table 3. 3. The results in Table 4 were obtained.

Table 3

* 1 Methyl-DMDF

* 2 Dimethyl Table 4

Example 13

Synthesis of tricyclopentadiene (TCPD; polyreducible monomer represented by formulas (V) and (VI))

4.5 kg of dicyclopentagen and 2 kg of xylene were charged into a nitrogen-substituted 10-piece clove, and the mixture was heated with stirring and reacted at 195'C for 2 hours. Xylene was distilled off from the obtained reaction product by atmospheric distillation, and then 1.2 kg of TCPDs were obtained as a 112 to 120'C fraction by vacuum distillation. These TCPDs contained 90% of the TCPD of the general formula (VI) and 10% of the TCPD of the general formula (V).

Copolymerization of ethylene, DMDF and TCPDs

The 10 £ four-necked flask equipped with a stirrer, thermometer, dropping funnel and gas inlet tube was sufficiently purged with nitrogen, and dehydrated toluene 5 was charged. Then, DMDF500 g synthesized similarly to Example 1, TCPD class 200 g, V0 (0Et) C & 2 1 0 mmojg narrows specifications in flasks, the dropping low _{_{DOO, Et 3 A jg 2 C £}} a 2 0 mmojg was charged. A mixed gas of 140 hr of ethylene and nitrogen / hr of nitrogen was passed through a gas inlet pipe through a flask cooled to 10 with ice water for 15 minutes. By the dropwise addition of Et _₃ A _J e ₂ C ₃ from dropping low bets, initiate the copolymerization reaction, such Oko the 3 0 min copolymerization reaction in at 1 0 ivy. During the copolymerization reaction, the inside of the polymerization system was uniform, and no precipitation of the copolymer was observed. The copolymerization reaction was stopped by adding methanol 60. The copolymer is deposited by pouring the polymerization solution into a large amount of methanol, washed with methanol, and dried in vacuum at 50 ° C to obtain the copolymer. 310 g was obtained.

According to 13 C—NMR analysis, the ethylene content in the copolymer was 53 mol%, and was 135. The intrinsic viscosity [] measured in decalin was 1.3. '

When the 兵 property of the soldier polymer was measured in the same manner as in Example 1, Haze was 7% and the birefringence was 5 nra. The melting curve was not observed in the range of 30'C to 400'c, and the glass transition point Tg was 176. The flexural modulus ^{2. 6 X 1 0 4 kg /} crf. Descending茯強degree

The weight was 910 kg. 1 The press sheet was immersed in acetone, ethyl acetate, sulfuric acid (98%), and ammonia (28%) for 20 hours at room temperature and observed for changes in appearance. There was no change and no deformation or cracking was observed. Examples 14 to 20

A copolymerization reaction was carried out in the same manner as in Example 13 except that the copolymerization conditions were changed as described in Table 5, and the results in Tables 5 and 6 were obtained. Example 2 1

Of a mixture of urea and TCPDs

30 mol of 8,9-dihydroxycyclopentadiene obtained in Example 1 and 20 mol of pentadiene pentadiene obtained in Example 1 were charged into a nitrogen-purged 30 autoclave, and humidified to 230'c over 4 hours with stirring. The reaction was carried out at that temperature for another 8 hours. The resulting reaction mixture was distilled under reduced pressure to remove the unreacted J-core 8,9-dihydroxycyclopentadiene and dicyclopentane, and then the fraction having a boiling point of 110 to 118'C (2 mmHg) was removed. 8 kg was obtained. This was analyzed by NMR and GC-MS. The mixture was identified as a mixture of about 70% DMDF and about 30% TCPDs. Note that these TCPDs contained 8% and 92% of the TCPD. Of general formula (V) and general formula (VI), respectively.

Co-residence of ethylene, DMDF and TCPDs

A copolymer was produced in exactly the same manner as in Example 13 except that 700 g of the mixture of DMDF and TCPD obtained above was used instead of DMDF and TCPDs. The results are shown in Tables 5 and 6. Table 5

* Used as a mixture

Table 6

Π

Ethylene ["] Tg Tm Haze Bend Bend Kenkan Resistance

Composition 135 -C (DSC) (DSC)

No. Acetone Tori Echiru IJIt βί

(mo sound Cc) O (%) (10 kg / crtD (kg / cnO (98%) water (28¾)

13 52 1.1 175 fitt 7 2.6 930 5

14 65 1.6 138 10 2.0 950 10

15 63 1.5 143 lfi £ 8 2.1 880 10 C en

16 56 1.0 163 8 2.5 910 6

17 63 1.6 145 ilEE 9 2.2 1000 9

18 60 1.2 150 fin 7 2.3 890 6

19 70 1.9 130 ¾ £ 8 1.8 760 9

20 49 1.4 178 M 6 2.7 9705

21 51 1.2 175 M '", 6 2.6 820 5

ooooooooo

o oooooooo

ooooooooo Example 22

Copolymerization of ethylene, DMDF and propylene

A 10-neck four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a gas inlet tube was sufficiently purged with nitrogen, and dehydrated toluene 5 was charged. Then, charged DMDF500 g, V0 (0Et) C & z 1 0 mmojg synthesized in the same manner as in Example 1 in a flask, the dropping low _{bets, Ε "Α 2 (:.} 3 2 0 were charged Mmojg gas injection A mixture of ethylene 140 / hr, propylene 180-111 "and nitrogen 1000 / hr was passed through a tube through a flask cooled to 10'C with ice water for 15 minutes. Et ₃ A & The copolymerization reaction was started by dropping zZ & z, and the copolymerization reaction was performed at 10'C for 30 minutes.During the copolymerization reaction, the inside of the polymerization system was uniform, and the copolymer The copolymerization reaction was stopped by adding methanol 60. The copolymer was deposited by pouring the polymerization solution into a large amount of methanol. After washing with methanol and vacuum drying at 50, 260 g of a copolymer was obtained.

According to 13 C—NMR analysis, the ethylene content in the copolymer was 44 mol%, and the intrinsic viscosity () measured in decalin at 135 ° C. was 2.1.

When physical properties of the copolymer were measured in the same manner as in Example 1, Haze was 6% and birefringence was 1 O nm. The melting curve was from 130 to 40 (not observed in the range of TC, the glass transition temperature T g was 125. The flexural modulus was 1.7 X 10 ⁴ kgZon 'and the yield strength was 780 kgrZoi. Press the 1-me thick press sheet at room temperature. It was immersed in acetonitrile, ethyl acetate, sulfuric acid (98%), and ammonia (28%) at 20 o'clock, and observed for changes in appearance. No outbreaks were observed.

Examples 23-34

A copolymerization reaction was carried out in the same manner as in Example 22 except that the copolymerization conditions were changed as described in Table 7, and the results shown in Tables 7 and 8 were obtained. Example 3 5

Combination of ethylene and methyl-DMDF with norbornane

Copolymerization of ethylene, methyl-DMDF and norbornane was performed in exactly the same manner as in Example 26 except that methyl-DMDF synthesized in the same manner as in Example 8 was used instead of DMDF. The results are shown in Tables 7 and 8. '

Table 7

CO

* Methyl—DMDF

Methyl norbornene

σ

H

1 1 S SS 1 1 1 1 1 1

M *

! cn I! ¾SS¾ I ¾ 1 ί ta

V? 1— w

Crq '

; P55 * * pj * ^ around 2 ~ around ■ »* g * g * ^-3

= s co n «* at« -a <incncr nco--3C005cn I 1 g (/) k) (cin28%

Small rooster toatiasenjemornni

Elasticity

删 bending

§§Gi ii§ii g § Plan i% P H (f oooooooooooooo a

oooooooooooooo

OS

6fr800 / 88df / XDd 0S610 / 68 OM Example 3 6

Copolymerization of ethylene with the polycyclic monomer (a) in Table 1

A 10 L four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a gas inlet tube was sufficiently purged with nitrogen, and 5 L of dehydrated toluene was charged. Then, 700 g of the compound of (a) in Table 1,

V0 (0Et) were charged C i 2 1 0 mmo flask, the dropping low bets, was charged with _{_{_{Et 3 A i 2 C 3 2}}} 0 mmo. From a gas injection pipe, a mixed gas of ethylene 140 hr and nitrogen 1000 hr was added using ice water. Pass the cooled flask through c for 15 minutes. The copolymerization reaction was started by dropping Ε "Α ₂ (: £ ₃ from the dropping funnel, and the copolymerization reaction was carried out at 10 for 30 minutes. The copolymer was homogeneous and the copolymer was not precipitated.The polymerization reaction was stopped by adding methanol 60. The polymerization solution was poured into a large amount of methanol. To make the copolymer luminous, and after washing with methanol,

By vacuum drying at 50, 210 g of a copolymer was obtained. The ethylene composition in the copolymer was determined by 13 C-NMR analysis.

The intrinsic viscosity C V) measured in decalin was 0.9 at 63 mol%.

The physical properties of the copolymer were measured in the same manner as in Example 1. As a result, Haze was 10%, and the birefringence was 8 nm. The melting curve is from 30 to 400. It was not observed in the range of c, and the glass transition point T g was 145. The flexural modulus was 2.4 × 10 ⁴ kg / α £, and the yield strength was 980 kg. 1 Thick pressed sheet was prepared at room temperature with acetate, ethyl acetate, sulfuric acid (98%), ammonia (28%). %) For 20 hours and observed changes in appearance. As a result, there was no change in color, transparency, etc., and there was no deformation or cracking.

Examples 37-45

Table 9 and Table 10 were obtained in the same manner as in Example 36 except that the monomer components and the copolymerization conditions were changed as described in Tables 9 and 10. Table 9

* Show view Same as 1

Table 10

Industrial applicability

The random copolymer of the present invention exhibits balanced optical properties, mechanical properties, thermal properties, and chemical properties that cannot be obtained with conventional resin materials. That is, the polymer of the present invention has excellent transparency, is optically homogeneous, has small birefringence, and has excellent mechanical properties such as heat resistance, chemical resistance, dimensional stability, and rigidity. I have.

The copolymers of the present invention include, for example, optical materials such as optical discs, optical fibers, plastic lenses, optical filters, etc .; · Can be used in the chemical field.

Claims

1. (A) Ethylene and the following general formula (I)

Blue

(Where &, m, n, and!) Is 0 or 1, and q is an integer of 0 or greater. )

(B) ethylene The molar ratio of the polycyclic monomer represented by the general formula (I) is 90Z10 to 1090,

(C) The unit derived from the polycyclic monomer represented by the general formula (1) is mainly represented by the following general formula (Π):

(Where, m, η, ρ and q are as described above)

Take the structure shown by

(D) Intrinsic viscosity measured in decalin at 135'C [J?] Force 0.2 to 15 ng, Random copolymer.

2. The polycyclic monomer has the following general formula (m)

(Equations φ, ί, m and p are 0 or 1.)

1,4,5,8—Dimethanol 1,2,3,4,4a, 4b, 5,8,8a, 9a—decahydrofluorenes represented by the formula: The unit is mainly the following general formula (W) t

(In the formula,! Ί, m and ρ are as described above.)

2. The random copolymer according to claim 1, wherein the random copolymer has a structure represented by the formula:

3. Substantially, ethylene and 1,4: 5,8—dimethano-1,2,3,4,4a, 4b, 5,8,8 represented by the general formula (ΠΙ)

3. The random copolymer according to claim 2, comprising only repeating units derived from 8a9a-decafluorofluorenes.

4. (A) Ethylene, polycyclic monomer represented by the general formula (m): The following general formula (V): (V)

(CH 3) k (CH 3) k (CH 3) k

(Where k is 0 or 1.)

And a polycyclic monomer represented by the following general formula (VI)

(

(In the formula, k is the same as k in the general formula (V).)

A random copolymer comprising repeating units derived from a polycyclic monomer represented by the formula:

(B) the mole ratio of ethylene / polycyclic monomer represented by the general formula (ΠΙ) is 90 10 to 10/90,

(C) (Polycyclic monomer represented by general formula (V) + polycyclic monomano represented by general formula (VI) The molar ratio of polycyclic monomer represented by general formula (ΙΠ) is 4 or less. ,

(D) a polycyclic monomer represented by the general formula (V), wherein the molar ratio of the polycyclic monomer represented by the general formula (VI) is from 5 to 95 to 20 to 80,

(Ε) The unit derived from the polycyclic monomer represented by the general formula (1Π) mainly has a structure represented by the general formula (IV),

(F) The units derived from the polycyclic monomers represented by the general formulas (V) and (VI) are mainly represented by the following general formulas (W) and (W), respectively:

(Where k in the formula is the same as k in the general formulas (V) and (VI)).

3. The random copolymer according to claim 2.

5. (A) Ethylene, a multimer represented by the general formula (m), and selected from an orifice having 3 to 10 carbon atoms and a cyclo-olefin having 5 to 18 carbon atoms A random warfare polymer consisting of repeat units derived from at least one monomer,

(Β) Ethylene / multimers represented by the general formula (m) have a mole ratio of 90 to 10 to 10 to 90,

(C) the molar ratio of at least one polycyclic monomer represented by the general formula (m) selected from monoolefin and cycloolefin is 9 or less;

(D) The position derived from the polycyclic monomer represented by the general formula (m) mainly has a structure represented by the general formula (W).

3. The random copolymer according to claim 2.

6. (A) Hydrocarbon soluble vanadium compounds and halogens In a hydrocarbon solvent in the presence of a catalyst formed from the organic aluminum compound containing

(B) Ethylene and the following general formula (I):

(Where,, m, n and p are 0 or 1, and q is an integer of 0 or more.)

By copolymerizing the polycyclic monomer represented by

(C) the ethylene / polycyclic monomer represented by the general formula (I) has a molar ratio of 90/10 to 10/90,

(D) The unit derived from the polycyclic monomer represented by the general formula (I) is mainly represented by the following general formula (Π):

(In the formula, m, n, p and q are as described above.)

Take the structure shown by

(E) the intrinsic viscosity [] measured in decalin of 135'C is 0.2 to 15 <^ / g,

A method for producing a random copolymer. The following general formula (m)

(In the formula, &, m and p are 0 or 1.)

1,4,5,8—dimethano 1,2,3,4,4a, 4b, 5,8,8a, 9a—decahydrofluorenes represented by The unit derived from the polycyclic monomer is mainly represented by the following general formula (IV):

(

(In the formula, J2, m and p are as described above.)

7. The method for producing a random copolymer according to claim 6, wherein a copolymer having a structure represented by the following formula is obtained.

8. Substantially, ethylene and a general formula (1, 4, 5, 8—dimethanone 1, 2, 3, 4, 4, 4a, 4b, 5, 8, 8,

8. The method for producing a random copolymer according to claim 7, wherein a monomer mixture comprising only 8a, 9a-decahydrofluorenes is copolymerized.

9. (A) Ethylene, a polycyclic monomer represented by the general formula (Π): The following general formula (V):

(Where k is o or l.)

And a polycyclic monomer represented by the following general formula (VI)

(In the formula, k is the same as k in the general formula (V).)

By copolymerizing the polycyclic monomer represented by

(B) Ethylene: The polycyclic monomer represented by the general formula (BI) has a molar ratio of 90 to 10 to 10Z90,

(C) (polycyclic monomer represented by general formula (V) + polycyclic monomer represented by general formula (VI)) No general formula (molar ratio of polycyclic monomer represented by ΠΠ is 4 Below,.

(D) a polycyclic monomer represented by the general formula (V): a molar ratio of the polycyclic monomer represented by the general formula (VI) is from 5 to 95 to 20 to 80;

(E) The unit derived from the polycyclic monomer represented by the general formula (m) mainly has a structure represented by the general formula (IV),

(F) The units derived from the polycyclic monomers represented by the general formulas (V) and (VI) are mainly represented by the following general formulas (W) and (¾), respectively:

(Where k in the formula is the same as k in the general formulas (V) and (VI).)

A method for producing the random copolymer according to claim 7.

-10. (A) Ethylene, selected from polycyclic monomers represented by the general formula (m), and C3 to C10 olefins and C5 to C18 cycloolefins By copolymerizing at least one monomer,

(B) ethylene: the molar ratio of the polycyclic monomer represented by the general formula () is 90 to 10 to 10Z90,

(C) at least one monomer selected from the group consisting of α-olefin and cycloolefin; the molar ratio of the polycyclic monomer represented by the general formula (H) is 9 or less;

(D) a unit derived from the polycyclic monomer represented by the general formula (II) is mainly obtained as a unit polymer having a structure represented by the general formula (IV) T,

A method for producing a random copolymer according to claim 7.