JPH0615218B2 - Composite with modified polyolefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a linear ethylene-α-olefin copolymer produced using an organometallic catalyst, usually by a vapor-phase / low-pressure method, to obtain an unsaturated carboxylic acid or an acid anhydride thereof. The present invention relates to a composite made by adhering or mixing a metal, an inorganic material, and a plastic with a polyolefin modified by grafting an object.

Conventional technology and its problems Conventionally, when a polyolefin is modified by grafting an unsaturated carboxylic acid or an acid anhydride thereof, a low pressure low density polyethylene (L-LD) is used as the polyolefin.
PE), high density polyethylene (HDPE), polypropylene (PP), ethylene ethyl acrylate copolymer (E
EA) and ethylene vinyl acetate copolymer (EVA) have been used. However, L-LDPE, HDPE, P
In the case of P, the modified polyolefin using these has a defect that when used as an adhesive resin for adhesion between metal and metal or between metal and plastic, the laminate becomes rigid. Further, in the case of EEA and EVA, the softening temperature is low, so that the laminate has a drawback of being modified at a low temperature.

In recent years, in place of the high pressure method, a linear ethylene-α-olefin copolymer having a density of 0.910 g / ml or less produced by the gas phase / low pressure method was developed by Union Carbide Co. As a result of intensive research by the present inventors, in order to improve the drawbacks of compound ginseng using the modified polyolefin,
Machine such as heat resistance of a composite made by adhering or mixing a modified polyolefin based on a linear ethylene-α-olefin copolymer by the gas phase / low pressure method with a metal, an inorganic material, or a heterogeneous plastic Unexpectedly found that the physical properties were greatly improved.

OBJECT OF THE INVENTION The present invention aims to provide composites with modified polyolefins with good mechanical properties.

Detailed Description of the Invention That is, according to the present invention, the density produced by the vapor phase / low pressure method is 0.9.
A linear ethylene-α-olefin copolymer of 10 g / ml or less is grafted with an unsaturated carboxylic acid or an acid anhydride thereof to modify a modified polyolefin, and the polyolefin is bonded or mixed with a metal, an inorganic substance or a different plastic to form a composite. The present invention relates to a composite made from a modified polyolefin characterized by the above.

In the present invention, various additives such as a different polymer, an antioxidant, a colorant, an organic peroxide and a crosslinking accelerator are blended with the above modified polyolefin as required.

In the present invention, the ethylene-α-olefin copolymer means ethylene having 50% or more, preferably 70% or more, and α-olefin having 3 to 12 carbon atoms. α
The olefin may be linear or branched, for example propylene, butene-1, pentene-1, hexene-1,
Heptene-1, octene-1,4-methylpentene-
1,4-methylhexene-1,4,4-dimethylpentene-1 and the like.

These ethylene-α-olefin copolymers are represented by Group IV to VIII transition metal compounds and Group I to VIII in the periodic table.
A catalyst produced by a combination of Group III organometallic compounds,
It is manufactured in the gas phase using a so-called Ziegler catalyst, and the manufacturing conditions can be carried out in the gas phase / low pressure as compared with the conventional high-pressure polyethylene.

More specifically, the linear ethylene-α-olefin copolymer of the present invention is (a) 0.35 at a temperature of 10 ° to 80 ° C and a pressure of 7,000 KPa or less in a fluidized bed reaction zone. 1-8.
Containing ethylene and at least one higher alpha-olefin having 3 to 8 carbon atoms in a molar ratio of 0: 1 higher alpha-olefin to ethylene, and b) at least 25 mol% of at least one diluent gas. A gas mixture having the formula: Mg _m Ti (OR) _n X _p [ED] _q [wherein R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR ′, Wherein R'is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I and mixtures thereof, and ED is an aliphatic or aromatic acid Is an organic electron-donating compound selected from the group consisting of alkyl esters, aliphatic ethers, cyclic ethers, and aliphatic ketones, m is 0.5 to 56, n is 0.1 or 2, and p is Is 2 to 116, and q is 2 to 8 In a] continuously contacted with the catalyst system of particles consisting of precursor composition having the formula with diluting the precursor composition with an inert Kiyariya _{materials: Al (R ') d X} ' e H f [ Wherein X ′ is Cl or OR ″, R ′ and R ″ are saturated hydrocarbon groups having 1 to 14 carbon atoms, e is 0 to 1.5, and f is 0 or 1 And d + e + f = 3],
It was prepared by a continuous process for producing an ethylene copolymer, characterized in that the activating compound was used in an amount such that the molar ratio of total aluminum to titanium in the reaction zone was 10: 1 to 400: 1. And is disclosed in JP-A-59-2.
It is described in detail in No. 30011.

Furthermore, the linear ethylene-α-olefin copolymer of the present invention comprises ethylene alone or at least one C _3- .
About 10 ° C to about 11 in the gas phase together with C ₁₀ α-olefin.
(A) (1) Palladium trihalide (a) with chlorine, bromine or iodine at a temperature of 5 ° C. and an electron donor (b) which is a liquid organic Lewis base in which the vanadium trihalide is soluble. A vanadium compound which is a reaction product of (2) with the following formula MX _a (where M is either boron or AlR _(3-a) ,
Each R is each alkyl, provided that the total number of aliphatic carbon atoms in any R group does not exceed 14, X is chlorine, bromine or iodine, and a is 0, 1 or 2, A when M is boron
And a supported agent consisting essentially of a silica or alumina supported on a solid inert carrier, and (B) the following formula AlR ₃ (where R is Is as defined above) and (C) is of the formula _R'b CX ' _(4-b) where R'is hydrogen or unsubstituted or halogen-substituted lower alkyl. , X'is a halogen and B is 0, 1 or 2) and is prepared by a method for producing polyethylene comprising polymerizing a monomer by contacting it with a catalyst composition comprising a promoter having And is described in detail in JP-A-59-230006.

Examples of the unsaturated carboxylic acid or its acid anhydride used in the present invention include acrylic acid, maleic acid, itaconic acid, fumaric acid, hymic acid, citraconic acid, and acid anhydrides thereof. It is preferred to use maleic acid. When the amount of the unsaturated carboxylic acid or its acid anhydride to be added is less than 0.01 parts by weight with respect to 100 parts by weight of the linear ethylene-α-olefin copolymer, the adhesive strength is low and 3.0 parts by weight is added. If it exceeds, the pungent odor is strong and it is not preferable. Therefore, 0.01 to 3.0 parts by weight are used.

In the present invention, the organic peroxide used when adding the unsaturated carboxylic acid or its acid anhydride to the linear ethylene-α-olefin copolymer is benzoyl peroxide or di-t-butyl peroxide. , Dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane and the like. When the amount of the organic peroxide exceeds 0.5 parts by weight with respect to 100 parts by weight of the linear ethylene-α-olefin copolymer, a gel and a fisheye are generated when the modified resin obtained is a film. Not preferable. on the other hand,
If it is less than 0.01 parts by weight, the addition rate will be insufficient and the adhesive strength will be insufficient. Therefore, it is desirable to be in the range of 0.001 to 0.5 parts by weight.

The modified resin of the present invention can be produced by adding an unsaturated carboxylic acid or an acid anhydride thereof to the above-mentioned linear ethylene-α-olefin copolymer and applying various known modification methods. . For example, an unsaturated carboxylic acid or its acid anhydride and an organic peroxide such as benzoyl peroxide, di-t-butyl peroxide, or dicumyl peroxide are added to the above linear ethylene-α-olefin copolymer. , A Hensiel mixer, a ribbon blender, a tumbler, and other mixers, and this mixture is mixed with a Banbury mixer, a single-screw or multi-screw extruder for 150 to 300.
Melt and knead at ℃, preferably 180 ~ 250 ℃.

The modified polyolefin thus obtained is used alone, but an unmodified elastomer or polyolefin may be added to it. For example,
An elastomer such as ethylene-propylene copolymer (EPR), or high-pressure low density polyethylene, ethylene-acrylic acid copolymer (EEA), ethylene-vinyl acetate copolymer (E) is added to the modified polyolefin obtained above.
Polyolefins such as VA) can be used.

Examples of the metal used in the present invention include aluminum, iron, stainless steel, brass and lead. Examples of the inorganic material include aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass fiber, silica, talc, carbon black, and the like. Further, as the plastic,
Examples include polyethylene, polyamide, saponified EVA, and the like.

The composite in the present invention is obtained by adhesion or mixing in a molten state with the above-mentioned modified polyolefin and one selected from the above-mentioned metals, inorganic materials or plastics. The method of adhering and mixing is not particularly limited. For example, regarding adhering, each of them is formed into a film or a sheet and thermocompression bonded, laminated outside the die, laminated inside the die, or extrusion coated. A known method such as a method can be used. For the mixing, known methods such as melting and kneading the modified polyolefin and the metal or inorganic substance with a Banbury mixer or a single-screw or multi-screw extruder can be used.

The composite of the present invention has a two-layer structure in which a modified polyolefin is laminated on a material selected from the above-mentioned metals and plastics for adhesion, and a three-layer structure in which modified polyolefin is further laminated. It is a dispersion of one selected from the above-mentioned metals and inorganic materials.

Therefore, the relative proportions of modified polyolefin and metal, inorganic or heterogeneous plastic in the composites of the present invention can vary widely depending on the end product application.

As described above, the modified polyolefin according to the present invention shows good adhesion with the above-mentioned metal, inorganic material or various kinds of plastics, and it is possible to form a laminate having high adhesive strength, which is gas impermeable, moisture resistant, It can be used for packaging films, sheets, bottles, containers, etc. by taking advantage of its oil resistance. Further, the modified polyolefin according to the present invention can be mixed with a large amount of the above-mentioned metal, inorganic material, carbon black, etc. and kneaded to make a composite having good mechanical properties. It can be used for layers, conductive water-blocking tapes, flame-retardant materials, etc.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Examples 1 to 4 and Comparative Examples 1 to 4 Polymers such as linear ethylene-α-olefin copolymers having different densities, high density polyethylene, EVA and EEA, and maleic anhydride, acrylic acid and organic peroxides, respectively. The proportions shown in Table 1 were mixed by a conventional method with a Henschel mixer, and the mixture was supplied to an extruder with a vent and a diameter of 50 mm, kneaded and extruded at 200 ° C. to be modified to produce a cylindrical beret.

Each modified polyolefin pellet obtained here was molded into a sheet having a thickness of 0.5 mm, a length of 150 mm, and a width of 180 mm by a hot press molding machine at 165 ° C. under 100 kg / cm ² for 2 minutes. An aluminum foil, a modified polyolefin, and an aluminum foil were laminated in this order on each sheet and an aluminum foil having a thickness of 0.2 mm, and pressure-bonded at a temperature of 180 ° C. and a pressure of 30 kg / mm ² for 2 minutes to obtain a three-layer laminate.

The above-mentioned three-layer laminate is cut into a test piece having a width of 10 mm and a length of 150 mm, and JIS K test is performed by an Instron universal tensile tester.
A peel test was performed according to 6854 to measure the adhesive strength between the modified polyolefin and the aluminum foil. However, the pulling speed is 100 mm / min for T-shaped peeling, and
The measurement temperature was changed to ℃, 50 ℃ and 70 ℃. The results are shown in Table 2.

In addition, each modified polyolefin described above is molded by a hot press molding machine to obtain a thickness of 0.5 mm, a length of 150 mm,
A test piece having a width of 6 mm and a length of 100 mm was cut out from a sheet having a width of 180 mm, and the folding endurance specified in JIS P 8115 was measured for each of the test pieces. The results are also shown in Table 2.

A sheet of 1.0 mm in thickness, 150 mm in length and 180 mm in width was formed from each of the above modified polyolefins using a hot press molding machine, and a die C punched out from the sheet according to ASTM D 638 was used to make a test piece. To do. For these test pieces, the stiffness was also measured according to ASTM D638, and the results are shown in Table 2.

Polyolefins obtained by modifying linear ethylene-α-olefins having a density of 0.910 g / ml or less with maleic anhydride or acrylic acid in Examples 1 to 23 have a temperature of 23 to 70 ° C.
Has good adhesion to aluminum foil at each temperature of
It has a high flexibility because it has a small staying strength, but it also has a feature that it has a large folding endurance and is hard to break. This characteristic is also observed in a polyolefin obtained by modifying a linear ethylene-α-olefin with another polyolefin, for example, EEA in combination with maleic anhydride, as shown in Example 4.

In the case where the density of the linear ethylene-α-olefin shown in Comparative Example 1 is higher than 0.910 g / ml and the case of the high-density polyethylene shown in Comparative Example 2, the folding endurance is small and the flexibility is poor. Showing the performance, EVA and E of Comparative Examples 3 and 4
In the case of EA, although the flexibility is good, it is recognized that the adhesive strength sharply decreases as the temperature rises.

Examples 5 to 8 and Comparative Examples 5 to 6 The modified polyolefins of Examples 1 and 3 and Comparative Examples 2 and 3 shown in Table 1 were mixed with iron oxide, magnesium hydroxide and calcium carbonate in the ratio shown in Table 3. The mixture was kneaded at 165 ° C. for 15 minutes using a Banbury mixer.

Each kneaded product was heated to 150 using a hot press molding machine.
Pressed at 100kg / cm ² for 2 minutes, thickness 1.0mm and 2.
A 0 mm sheet was molded. From a sheet with a thickness of 1.0 mm to JI
A dumbbell-shaped test piece specified by SK 6760 was punched out, and the tensile strength and elongation were measured at a tensile speed of 100 mm / min.

In addition, from a sheet with a thickness of 2.0 mm, JIS K 7216
A rectangular test piece having a width of 6.0 mm and a length of 38.0 mm specified in 1. was punched out, and the embrittlement temperature was measured.

The above results are shown in Table 4. As can be seen from Examples 5 to 8, linear ethylene-α-olefins produced by the gas phase low pressure method with a density of 0.910 g / ml were treated with maleic anhydride or acrylic acid. The modified polyolefin, kneaded with a metal, an inorganic substance and the like have sufficiently large tensile strength, elongation and low temperature embrittlement, but the high density polyethylene and EVA shown in Comparative Examples 5 and 6 are mixed with maleic anhydride. All of those modified by (1) have low tensile strength and insufficient low temperature brittleness.

Examples 9 to 12 and Comparative Examples 7 to 9 The modified polyolefins of Example 1 and Comparative Example 2 shown in Table 1 were mixed with EVA, EEA, carbon black and calcium carbonate in the ratios shown in Table 4, and a Banbury mixer was used. And kneaded at 165 ° C. for 15 minutes.

The obtained mixture was subjected to the same operations as in Examples 5 to 8 and Comparative Examples 7 to 8 to obtain dumbbell-shaped test pieces for measuring tensile strength and elongation and rectangular test pieces for measuring embrittlement temperature.

Tensile strength, elongation and embrittlement temperature were measured for the above test pieces, and the results are shown in Table 5. As can be seen from Examples 9 to 12, the gas phase density of 0.910 g / ml / low pressure was obtained. A linear ethylene-α-olefin produced by the method of the present invention and a mixture of a polyolefin modified with maleic anhydride and an unmodified EVA or EEA, or a mixture obtained by further adding carbon black or calcium carbonate to it has a sufficiently large tensile strength. It has strength, elongation and low temperature brittleness. On the other hand, the polyolefins obtained by modifying the high-density polyethylenes shown in Comparative Examples 7 to 9 with maleic anhydride and unmodified EVA or EEA
Or a mixture of carbon black and calcium carbonate added thereto has low tensile strength and elongation and insufficient low temperature brittleness.

As described above, the present invention has a density of 0.910 g / ml or less and is a linear ethylene-α-produced by the gas phase / low pressure method.
Metallic polyolefin modified by grafting an unsaturated carboxylic acid or its acid anhydride onto an olefin copolymer,
It relates to the formation of composites by adhering or mixing with inorganic substances or different types of plastics, and has adhesive strength at high temperatures, good folding endurance, sufficient flexibility, tensile strength that cannot be obtained with conventional modified polyolefins. Strain, elongation and low temperature brittleness are imparted, and their industrial value is extremely high.

Claims (6)

[Claims] 1. A straight-chain ethylene-α-olefin copolymer produced by a gas-phase / low-pressure method having a density of 0.910 g / ml or less is modified by grafting an unsaturated carboxylic acid or an acid anhydride thereof. A composite by a modified polyolefin, characterized in that a composite is prepared by adhering or mixing the above-mentioned polyolefin with a metal, an inorganic material or a different kind of plastic. 2. The number of carbon atoms constituting the α-olefin is 3 to.
A linear ethylene-α-olefin copolymer produced by a gas phase / low pressure method within the range of Claim 8.
The compound according to the item. 3. A catalyst, a so-called Ziegler, produced by combining a linear ethylene-α-olefin copolymer with a transition metal compound of groups IV to VIII and an organometallic compound of groups I to III in the periodic table. The composite according to claim 1, which is produced by a gas phase / low pressure method using a catalyst. 4. A straight chain ethylene-α-olefin copolymer produced by a gas phase / low pressure method having a density of 0.910 g / ml or less, is modified by grafting an unsaturated carboxylic acid or an acid anhydride thereof. A composite according to claim 1 which comprises a mixture of an unmodified elastomer or a polyolefin added to said polyolefin. 5. A linear ethylene-.alpha.-olefin copolymer having a temperature of 10.degree.-80.degree. C. and 7,000 in a fluidized bed reaction zone.
At pressures below 0 KPa, (a) ethylene and 3 at a molar ratio of higher α-olefin to ethylene of 0.35: 1 to 8.0: 1.
At least one higher alpha-olefin having from 8 to 8 carbon atoms, and (b) at least 25 mol% of at least 1
A gas mixture containing a diluent gas of the formula: MgmTi (OR) _n X _p [ED] _q [wherein R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR]. Is R ', where R'is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, X is selected from the group consisting of Cl, Br, I and mixtures thereof, and ED is a fatty group. An organic electron-donating compound selected from the group consisting of alkyl esters of aromatic or aromatic acids, aliphatic ethers, cyclic ethers and aliphatic ketones, m is 0.5 to 56, n is 0.1 or 2 and p is 2 to 116 and q is 2 to 85] are continuously contacted with particles of a catalyst system comprising a precursor composition, and the precursor composition is an inert carrier material. Dilute and formula: Al (R ′) _d X ′ _e H _f [ Wherein X ′ is Cl or OR ″, R ′ and R ″ are saturated hydrocarbon groups having 1 to 14 carbon atoms, e is 0 to 1.5, and f is 0 or 1 And d + e + f = 3],
It was prepared by a continuous process for producing an ethylene copolymer, characterized in that the activating compound was used in an amount such that the molar ratio of total aluminum to titanium in the reaction zone was 10: 1 to 400: 1. The composite according to claim 1, which is a composite. 6. The linear ethylene-α-olefin copolymer comprises ethylene alone or at least one C ₃ -C ₁₀ α.
(A) (1) Palladium trihalide (a) with chlorine, bromine or iodine and a liquid in which the vanadium trihalide is soluble at a temperature of about 10 ° C to about 115 ° C in the gas phase together with an olefin. And a vanadium compound which is a reaction product with an electron donor (b) which is an organic Lewis base of (2) the following formula MXa (where M is either boron or AlR (3-a), R is each alkyl, provided that the total number of aliphatic carbon atoms in any R group does not exceed 14, X is chlorine, bromine or iodine, a is 0, 1 or 2, and M is A is boron
Is a 3) and a supported precursor consisting essentially of a silica or alumina supported on a solid inert carrier consisting essentially of (B) the following formula AlR ₃ (where R Is as defined above), and (C) is of the formula _R'b CX '(4-b) where R'is hydrogen or unsubstituted or halogen-substituted lower alkyl. , X'is a halogen, and b is 0, 1 or 2) prepared by a process for producing polyethylene from polymerizing the monomer by contacting with a catalyst composition containing a promoter having The composite according to claim 1, which is a composite.