JPH0617465B2 - Novel ethylene copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ethylene copolymer and a method for producing the same. More specifically, ethylene copolymers having photodegradability and biodegradability suitable for films, sheets, electrical insulating materials, polymer modifiers, coating materials or dispersants such as pigments and inorganic fillers. Furthermore, the present invention provides an ethylene copolymer suitable for modification utilizing a polymer reaction and a method for producing the same.

(Prior Art) Ethylene polymers are excellent in various properties such as mechanical properties, processability, and electrical properties, and are economically inexpensive. Therefore, ethylene polymers are used as materials such as electrical insulating materials and foam materials, or as films and pipes. It is used in various fields as processed products such as containers.

Further, ethylene copolymers in which a functional group is introduced into the ethylene polymer in order to improve the performance of the ethylene polymer are also well known.

Further, ethylene polymers and ethylene copolymers having a relatively low molecular weight are also known and are used as coating materials, paint additives, polymer modifiers and the like.

Further, modified ethylene (co) polymers obtained by modifying these ethylene polymers and ethylene copolymers by utilizing a polymer reaction are also known.

However, these ethylene copolymers, modified ethylene (co)
Most of the polymers have a functional group in the side chain, not in the polymer main chain, and have a drawback that they are poor in photodegradability and biodegradability, which have recently been desired from the standpoint of environmental problems.

Furthermore, when obtaining a modified ethylene copolymer having various functions by modification utilizing a polymer reaction, an excellent ethylene copolymer for modification having high reactivity with various modifiers is obtained. Polymers are desired.

Also, for example, J. Polym. Sci. Polym. Lett. Ed., 21, 43
3 (1983) Pain discloses a homopolymer of 2-substituted-3-vinyloxiranes, but the homopolymer has drawbacks such as extremely low moldability and low solvent resistance. It is difficult to use it as a material as described above.

(Problems to be Solved by the Invention) As a result of intensive studies in view of the above points, the present inventors have a chemical structure that has never been known, and have excellent moldability.
The present invention has been completed by succeeding in the development of a novel ethylene copolymer having light and biodegradability and having excellent reactivity to modification utilizing various polymer reactions.

(Means for Solving the Problem) The present invention is essentially composed of a repeating unit represented by the formula (I) and has an intrinsic viscosity in decalin at 135 ° C.
A novel ethylene copolymer having a weight ratio of 0.04 to 1.2 is provided.

[However, x and y represent the number of each repeating unit when x + y = 100, x is 50 to 99.9, and y is 0.
It is a value of 1 to 50.

Also X is; (However, R ₁ and R ₂ are a hydrogen atom and a carbon number of 1 to 4 respectively.
Represents an alkyl group, a methoxy group, a nitrile group, an amino group, a nitro group, or a halogen atom), α-naphthyl group, β-naphthyl group, nitrile group, (However, R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), (However, R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), (However, R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Furthermore, the present invention provides ethylene and at least one formula (II)
Is copolymerized in the presence of a radical polymerization initiator to be substantially composed of the repeating unit represented by the formula (I), and the intrinsic viscosity in decalin at 135 ° C. is 0.04 to 1.2. It is intended to provide a method for producing a novel ethylene copolymer.

(However, X in the formula (II) is the same as the formula (I).) In the above (I), y is 0.1 to 50, and preferably y.
0.3 to 20 is suitable. Further, the intrinsic viscosity of the ethylene copolymer is suitably 0.04 to 1.2, preferably 0.05 to 1.0.

When y is less than 0.1, the excellent performance of the copolymer is hardly seen, and when it exceeds 50, it becomes economically expensive and the above-mentioned 2-substituted-3-vinyloxirane homopolymer is obtained. Defects appear.

When the intrinsic viscosity of the copolymer is less than 0.04, it becomes unsuitable for the above various uses. On the other hand, when it exceeds 1.2, the moldability is lowered.

The repeating unit in formula (I) Is derived from the comonomer represented by the formula (II).

Examples of the comonomer represented by the above formula (II) include 2-phenyl-3-vinyloxirane, 2-tolyl-3-vinyloxirane, 2-xylyl-3-vinyloxirane, 2
-Ethylphenyl-3-vinyloxirane, 2-diethylphenyl-3-vinyloxirane, 2-methoxyphenyl-3-vinyloxirane, 2-dimethoxyphenyl-3-vinyloxirane, 2-chlorophenyl-3-vinyloxirane, 2- Dichlorophenyl-3-vinyloxirane, 2-chlorotolyl-3-vinyloxirane,
2-nitrilephenyl-3-vinyloxirane, 2-dinitrilephenyl-3-vinyloxirane, 2-aminophenyl-3-vinyloxirane, 2-diaminophenyl-3-vinyloxirane, 2-nitrophenyl-3-
Vinyloxirane, 2-3,4-methylenedioxyphenyl-3-vinyloxirane, 2-α-naphthyl-3-
Vinyloxirane, 2-β-naphthyl-3-vinyloxirane, 2-nitrile-3-vinyloxirane, 2-acetoxy-3-vinyloxirane, 2-formyloxy-3-vinyloxirane, 2-propionyloxy-3
-Vinyloxirane, 2-formamide-3-vinyloxirane, 2-acetamido-3-vinyloxirane,
2-propionamido-3-vinyloxirane, 2-acetyl-3-vinyloxirane, 2-formyl-3-vinyloxirane, 2-propionoyl-3-vinyloxirane and the like.

These comonomers can be prepared by known methods, for example J. Polym. Sci. Po.
lym.Chem.Ed., 23, 1931 (1985).

Examples of the radical polymerization initiator referred to in the present invention include peroxides, hydroperoxides, azo compounds, amine oxide compounds, oxygen and the like.

The radical copolymerization of the present invention is carried out in the presence or absence of a solvent, optionally using a chain transfer agent, at a pressure of 1 to 400.
0 atm, preferably 30-3500 atm, temperature 20-4
It can be carried out in a tank type or tubular reactor under the condition of 00 ° C, preferably 50 to 350 ° C.

Examples of the chain transfer agent include propylene, butene-1,
C ₁ -C ₂₀ or higher saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons such as methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C ₁ -C ₂₀ or higher saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol, C ₁ -C ₂₀ or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone and aromatic compounds, Examples include compounds such as toluene, diethylbenzene and xylene.

As the solvent, various solvents that do not inhibit the polymerization reaction can be used. Aromatic solvents such as benzene and chlorobenzene are typical.

Further, if necessary, the copolymerization may be carried out in the presence of at least one ethylenically unsaturated monomer.

The ethylenically unsaturated monomer is, for example, propylene,
Butene-1, hexene-1, 4-methylpentene-1,
Octene-1, olefins having 3 to 10 carbon atoms, such as decene, styrene, vinyl esters of C ₂ -C ₃ alkanoic acid, acrylics or methyl methacrylate, acrylic acid or meth acrylate, acrylic Acid or propyl methacrylate, acrylic acid or methacrylic acid esters such as glycidyl acrylate or glycidyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid and ethylenically unsaturated carboxylic acid such as maleic anhydride or the like Anhydrides,
Examples thereof include ethylenically unsaturated carboxylic acid amides such as acrylic acid amide and methacrylic acid amide. These ethylenically unsaturated monomers can be copolymerized with the copolymer of the present invention up to 10 mol%.

(Function and Effect of Invention) The novel ethylene copolymer of the present invention is a film, a sheet,
Excellent as an electrical insulation material, polymer modifier, coating material, dispersant for pigments and inorganic fillers, etc.
Provides a material that is biodegradable. Furthermore, it is a polymer suitable for modification utilizing a polymer reaction.

For example, when the ethylene copolymer of the present invention is heated in the presence of oxygen, a carbonyl group is generated in the polymer molecule very quickly. The polymer having this carbonyl group in the molecule is itself a polymer having functions such as photodegradability,
Further, various functional groups can be introduced into this polymer by reacting a reagent that reacts with a carbonyl group and hydrogen at the α-position of the carbonyl group.

For example, hydrazine and substituted hydrazines act on carbonyl groups in polymer molecules to form hydrazones, ammonia and amines act on condensation to cause semicarbazides to act to form semicarbazones, and bisulfite. Reaction to add sodium, reaction to add hydrogen cyanide to produce cyanohydrin,
Reaction of condensing ammonium cyanide to produce α-amino acid nitrile, reaction of so-called Grignard reagent to produce alcohol by dehydration, reaction to act reducing agent such as lithium aluminum hydride to produce alcohol , A reaction that produces a carboxylic acid by the action of an oxidizing agent such as potassium permanganate, α
-Reaction to form α, β-epoxy ester by addition of halogen ester, reaction to add aldehydes, reaction to add hydrazoic acid, reaction to add acid anhydride, reaction to add diazomethane and polymer molecule Polymer molecule utilizing reactions such as halogen substitution on the hydrogen at the α-position of the carbonyl group, reaction to condense the hydrogen at the α-position with a carboxylic ester, oxidation of the hydrogen at the α-position, etc. Various functional groups can be introduced into.

In addition, olefin polymers (including copolymers) other than the ethylene copolymer of the present invention, polyacrylonitrile, polyamide, polycarbonate, ABS resin, polystyrene, polyphenylene oxide, as long as the properties of the ethylene copolymer are not significantly impaired. Thermoplastic resin such as polyvinyl alcohol resin, vinyl chloride resin, vinylidene chloride resin, polyester resin, thermosetting resin such as petroleum resin, coumaroindene resin or phenol resin, melamine resin, ethylene-propylene copolymer Rubber (EP
R, EPDM, etc.), SBR, NBR, butadiene rubber,
It can be used as a mixture with at least one kind of synthetic rubber such as IIR, chloroprene rubber, isoprene rubber, styrene-butadiene-styrene block copolymer or natural rubber.

When using the ethylene copolymer of the present invention, organic / inorganic fillers, antioxidants, lubricants, various organic / inorganic pigments, ultraviolet inhibitors, antistatic agents, dispersants,
Additives such as copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, antifoaming agents, flame retardants, cross-linking agents, flowability improvers, weld strength improvers, nucleating agents and the like may be added.

(Example) An example is described below.

Examples 1 to 18 In each Example, a metal autoclave type reactor equipped with a stirrer and having an internal volume of 320 ml was sufficiently replaced with nitrogen and ethylene, and then a predetermined amount of ethylene was charged to prepare a comonomer and a polymerization initiator. A certain di-tert-butyl peroxide (DTBP) was injected with 39 g of a 2: 1 mixed solution of benzene and n-hexane, and polymerization was carried out at a predetermined temperature for 4.5 hours.

When the average molecular weight of the produced polymer was relatively high, the polymer was dissolved in heated toluene and then poured into a large amount of methanol to precipitate the polymer, which was filtered, washed, and then vacuum dried for purification.

When the average molecular weight of the produced polymer was relatively low, the polymer was purified by removing the unreacted monomer and the benzene / n-hexane mixed solution by evaporation under heating and reduced pressure.

The intrinsic viscosity [η] of the purified polymer in decalin at 135 ° C. was measured. The measuring method is as follows. The polymer is dissolved in heated decalin at a concentration of 40 mg / 20 ml and the relative viscosity (η _r ) at 135 ° C. is measured by an Ubbelohde viscometer. From this relative viscosity, the intrinsic viscosity [η] is calculated using the following formula.

(C is the concentration of the polymer solution, g / 100 ml) The purified polymer is heated and compressed to a thickness of about 100
Molded into a sheet of μm or dissolved in heated carbon tetrachloride, dropped this solution on rock salt plate and volatilized carbon tetrachloride to form a polymer thin film on the rock salt plate, and analyzed by infrared spectroscopy. .

Further, the purified polymer was used as an orthodichlorobenzene solution and analyzed by ¹³ C-NMR spectrum at 80 ° C. to confirm the ethylene copolymer of the present invention.

Table 1 shows the results of each example.

The infrared absorption spectrum of the polymer obtained in Example 6 showed the following absorptions.

700, 760, 1500, 1600 cm ^-1 [phenyl group] 1060 cm ^-1 [ether bond] 1670 cm ^-1 [C = C-O-C = C bond].

Furthermore, the following signals were found in the ¹³ C-NMR spectrum.

126.0, 144.1 ppm [phenyl group] 80.5, 83.0 ppm [C—O—C bond] The other examples were analyzed and confirmed in the same manner.

Claims (4)

[Claims] 1. A novel ethylene copolymer which is essentially composed of a repeating unit represented by the formula (I) and has an intrinsic viscosity in decalin at 135 ° C. of 0.04 to 1.2. [However, x and y represent the number of each repeating unit when x + y = 100, x is 50 to 99.9, and y is 0.
It is a value of 1 to 50. Also X is; (However, R ₁ and R ₂ are a hydrogen atom and a carbon number of 1 to 4 respectively.
Represents an alkyl group, a methoxy group, a nitrile group, an amino group, a nitro group, or a halogen atom), α-naphthyl group, β-naphthyl group, nitrile group, (However, R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), (However, R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) or (However, R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). ] 2. The novel ethylene copolymer according to claim 1, wherein X in the formula (I) is a phenyl group. 3. Copolymerizing ethylene and at least one comonomer represented by the formula (II) in the presence of a radical polymerization initiator to substantially constitute a repeating unit represented by the formula (I). And the intrinsic viscosity in decalin at 135 ° C is 0.
A method for producing a novel ethylene copolymer which is 04 to 1.2. [However, x and y represent the number of each repeating unit when x + y = 100, x is 50 to 99.9, and y is 0.
It is a value of 1 to 50. In formulas (I) and (II), X is; (However, R ₁ and R ₂ are a hydrogen atom and a carbon number of 1 to 4 respectively.
Represents an alkyl group, a methoxy group, a nitrile group, an amino group, a nitro group, or a halogen atom), α-naphthyl group, β-naphthyl group, nitrile group, (However, R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), (However, R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) or (However, R ₅ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). ] 4. The method for producing a novel ethylene copolymer according to claim 3, wherein X in the formulas (I) and (II) is a phenyl group.