JPS6218258A - Complex by denatured polyolefin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to the treatment of a linear ethylene-α-olefin copolymer produced using an organometallic catalyst, usually by a gas-phase, low-pressure method, with an unsaturated carboxylic acid or its This invention relates to a composite made by adhering or mixing a polyolefin modified by grafting an acid anhydride with a metal, an inorganic substance, or a plastic.

Conventionally, when polyolefins are modified by grafting with unsaturated carboxylic acids or their acid anhydrides, low pressure low density polyethylene (L-LD) is used as the polyolefin.
PE), high density polyethylene (HDPE), polypropylene (PP), ethylene ethyl acrylate copolymer (・
EEA) and ethylene vinyl acetate copolymer (ETA) have been used. However, L-LDPR, HDPE,
In the case of PP, modified polyolefins using these have the disadvantage of making the laminate rigid when used as an adhesive resin for adhesion between metals and metals or metals and plastics. Further, in the case of EEA and EVA, since the softening temperature is low, there is a drawback that the laminate is deformed at low temperature.

Recently, Union Carbide Co. has developed a linear ethylene-α-olefin copolymer with a density α of 910 g/- or less that is produced by a gas phase/low pressure method instead of a high pressure method. In order to improve the drawbacks of composites using the above-mentioned modified polyolefin, the present inventors conducted extensive research and found that
When a modified polyolefin based on a linear ethylene-a-olefin copolymer produced by the above-mentioned gas phase/low pressure method is adhered or mixed with a metal, an inorganic material, or a different type of plastic, the heat resistance of the composite produced is improved. It was unexpectedly discovered that the mechanical properties were significantly improved.

OBJECTS OF THE INVENTION The purpose of the invention is to provide composites with modified polyolefins having good mechanical properties.

Detailed Description of the Invention Namely, the present invention is characterized in that the density is α9 manufactured by a gas phase/low pressure method.
Polyolefin modified by grafting 10 g/- or less of a linear ethylene-α-olefin copolymer with an unsaturated carboxylic acid or its acid anhydride is bonded or mixed with a metal, inorganic substance, or different plastic. The present invention relates to a composite made of modified polyolefin, characterized in that it is made into a metal object.

In addition, in the present invention, various additives such as a different polymer, an antioxidant, a coloring agent, an organic peroxide, a crosslinking accelerator, etc. are blended with the above-mentioned modified polyolefin as necessary.

In the present invention, the ethylene-〇-olefin copolymer refers to one in which ethylene accounts for 50% or more, preferably 70% or more, and α-olefin has 3 to 12 carbon atoms. α
- The olefins may be straight or branched, for example propylene, butene-1, pentene-1, hexene-1,
heptene-1, octene-1,4-methylpentene-1
,4-methylhexene-1,44-dimethylpentene-
There is a first prize.

These ethylene-α-olefin copolymers contain transition metal compounds of groups IV to VIII in the periodic table,
It is produced in the gas phase using a catalyst produced by a combination of Group 1-1 organometallic compounds, the so-called Ziegler catalyst, and the production conditions can be lowered at lower temperatures and pressures compared to conventional high-pressure process polyethylene.

More specifically, the linear ethylene-α-olefin copolymers of the present invention can be prepared by (a)
ethylene and at least one higher alpha-olefin having from 3 to 8 carbon atoms in a higher alpha-olefin to ethylene molar ratio of from 35:1 to &0:1; (b) at least 2
A gas mixture containing 5 mol % of at least one diluent gas has the formula: % formula % () [wherein R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR] 'Ashi, here R
' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, X is selected from the group consisting of Cl5Brs I and mixtures thereof, and ED is an aliphatic or aromatic alkyl ester , aliphatic ether, cyclic ether, and aliphatic ketone, m is α5 to 56, n is α1 or 2, and p is 2S116. q is from 2 to 85], said precursor composition is diluted with an inert carrier material and has the formula: % formula % ( [Wherein, X' is CI or OR', nl and R1 are saturated hydrocarbon groups having 1 to 14 carbon atoms, e is 0 to t5, and f is 0 or 1 and d+e+f-5], and the activation compound is used in the reaction zone such that the total aluminum to titanium molar ratio is from 10:1 to 400:1. It is manufactured by a continuous manufacturing method of ethylene copolymer characterized in that it is used in such an amount.
No. 230011 describes this in detail.

Furthermore, the linear ethylene-α-olefin copolymer of the present invention may contain ethylene alone or in combination with at least one type of am-
About 0°C to about 1 in the gas phase with CtOα-olefin
At a temperature of 15°C, (1) palladium trihalide (a) with chlorine, -bromine or iodine and 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 The total number of aliphatic carbon atoms in the group does not exceed 14, X is chlorine, bromine or iodine, a is 0.1 or 2, provided that when M is boron, a
3) supported on a solid inert support consisting essentially of silica or alumina; and C) a cocatalyst having the formula % (4) (where R1 is hydrogen or unsubstituted or herogen-substituted lower alkyl, and X' is a herogen substituted The polyethylene propagation process consists of polymerizing the monomers by contacting them with a catalyst composition containing a promoter having a polyethylene acetate, b is 0.1 or 2). , JP-A No. 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, or acid anhydrides thereof, but in particular acrylic acid or anhydride. Preferably, maleic acid is used. If the amount of unsaturated carboxylic acid or its acid anhydride to be added is less than 100 parts by weight of the linear ethylene-α-olefin copolymer, the adhesive strength will be low, and if it exceeds 3.0 parts by weight,
It has a strong pungent odor and is undesirable. Therefore, α01 to 50 parts by weight are used.

In the present invention, the organic peroxides used when adding an unsaturated carboxylic acid or its acid anhydride to the linear ethylene-α-olefin copolymer include 1-benzoyl peroxide and di-t-butyl peroxide. , dicumyl peroxide, Z5 dimethyl-2,5-di-t-butylperoxyhexane, tl-bis(1-butylperoxy)-3,5,5-)limethylcyclohexane, and the like. The amount of organic peroxide is linear ethylene-α
- If a film is made of a modified resin obtained by exceeding α5 parts by weight per 100 parts by weight of the olefin copolymer, it is not preferable because gel and finsinia will occur.

On the other hand, if α01 parts by weight or less, the addition rate will be insufficient and the adhesive force will be insufficient. Therefore, it is desirable that the content be in the range of α001 to 05 parts by weight.

The modified grease of the present invention can be produced by adding an unsaturated carboxylic acid or its pure hydrate to the straight-chain ethylene-α-olefin copolymer and applying various known modification methods. I can do it. 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 Henschel mixer, a ribbon blender, a tumbler, or other mixer, and the mixture was heated to 150 to 500°C using a Banbury Mixer 1 single-screw or multi-screw extruder.
, preferably melting and kneading at 180 to 250°C.

The modified polyolefin thus obtained can be used alone, but it can be used by adding an unmodified elastomer or polyolefin to it. for example,
The modified polyolefin obtained above is combined with an elastomer such as ethylene-propylene copolymer (EPR), high-pressure low-density polyethylene, ethylene-acrylic acid copolymer (ExA), ethylene-vinyl acetate copolymer (
Polyolefins such as EVA) can be used.

Examples of metals used in the present invention include aluminum, iron, stainless steel, brass, and lead. Examples of the inorganic material include aluminum hydroxide, and examples of the hydroxide include polyethylene, polyamide, and saponified EVA.

The composite in the present invention is obtained by adhering or mixing the modified polyolefin described above and a material selected from the metals, inorganic materials, or plastics described above in a molten state. The method of adhesion and mixing is not particularly limited, and for example, for adhesion, each is formed into a film or sheet, and then heat emulated, laminated outside the die, laminated inside the die, or extrusion coated. It is possible to use a known method such as the method. Further, for mixing, a known method such as melting and kneading the modified polyolefin and the metal or inorganic substance using a Banbury Mixer 1 single-screw or multi-screw extruder can be used.

The composite of the present invention basically has a two-layer structure in which a modified polyolefin is laminated to a material selected from the metals and plastics mentioned above for adhesion, and a three-layer structure in which a modified polyolefin is sandwiched between the modified polyolefin and the modified polyolefin. It is made by dispersing substances selected from the metals and inorganic substances mentioned above.

Therefore, the relative proportions of modified polyolefin and metal, inorganic or foreign 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 exhibits good adhesion to the metals, inorganic materials, or various plastics, and can produce a laminate with high adhesive strength, which is gas-impermeable and moisture-resistant. It can be used for packaging films, sheets, bottles, containers, etc. by taking advantage of its oil resistance and other advantages. Furthermore, by blending and kneading a large amount of the metals, inorganic substances, carbon black, etc. mentioned above with the modified polyolefin of the present invention, a composite with good mechanical properties can be made. It can be used for layers, conductive waterproof tapes, flame retardant materials, etc.

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples.

Polymers such as straight-headed ethylene-α-olefin copolymers, high-density polyethylene, EVA, and EE polymers with different densities and maleic anhydride, acrylic acid, and organic peroxide were mixed in a Henschel mixer in the proportions shown in Table 1. The mixture was mixed in a conventional manner, and the mixture was supplied to a vented extruder with a diameter of 50 sIII, and the mixture was mixed and extruded at 200° C. for denaturation to produce a cylindrical pellet.

The pellets of each modified polyolefin obtained here were put into a hot press molding machine at 165°C at 100 KP/cr,
Thickness rJ, 5scaa, hlj 50 under conditions of 2 minutes
A sheet with m=1801 in width was molded. These sheets and aluminum foil with a thickness of 12 m were layered in the order of aluminum foil, modified polyolefin, and aluminum foil, and the temperature was 1.
80℃, pressure 30 odor/c! The above three-layer laminate was cut into test pieces with a width of JQw+ and a length of 150cm, and tested using an Instron universal tensile tester according to JIS K 685.
A peel test was conducted according to 4, and the adhesive strength between the modified polyolefin and the aluminum foil was measured. However, the tensile rate was T-shaped peeling at jQQw/min, and the measurement temperature was changed to 25°C, 50°C, and 70°C. The results are shown in Table 2.

In addition, a thickness of 0.5 m obtained by molding each of the above-mentioned modified polyolefins with a hot press molding machine, Jii j
Cut out test pieces of width 6 cm and length 100 cm from a sheet of 5 Q m and width 180 cm, and test these with JI8.
The folding strength specified by F8115 was measured. The results are also shown in Table 2.

Each of the modified polyolefins described above is molded into a sheet with a thickness of tQm, a length of 15Qm, and a width of 180mm using a hot press molding machine, and a test piece is prepared by punching the sheet with a die C specified in ASTM D 638.

ASTM D 65 for these specimens
The stiffness was measured according to B, and the results are shown in Table 2.

(Note 1): Density [19001/Wtt, melt index 0.8y/10 min, manufactured by Union Carbide (linear ethylene-α-olefin copolymer disclosed in JP-A No. 11559-230006) (Note 2) ): Density αtp 061/lags Melt index 5.0 g/10 min, manufactured by Union Carbide (linear ethylene-α-olefin copolymer disclosed in JP-A-59-250011) (Note 5): Density 0.924Ji'/go, melt index 4.8g/10 minutes, manufactured by Union Carbide (Note 4): Density α945 fi/rat, melt index 4.5y/10 minutes, manufactured by Union Carbide (Note 5): VA Content 15%, )lk index x
1ag71a minute Nippon Unicar Co., Ltd. Note 6): EA content 20%, Melt Intex 20g/10 minutes, Nippon Unicar Co., Ltd. (Note 7): 2@5 dimethyl-λ5-di-t-butyl peroxyhexane Example In 1 to 5, the polyolefin modified with maleic anhydride or acrylic acid to a linear ethylene-α-olefin having a density of arplal/lrt or less is 23 to 5.
It has good adhesion to aluminum foil at various temperatures of 70° C., and has low stiffness, making it highly flexible, but it also has extremely high bending strength, making it difficult to break. This feature, as shown in Example 4, shows that linear ethylene-α
-Olefins in combination with other polyolefins, such as ERA, are also recognized as polyolefins modified with maleic anhydride.

The case where the density of the linear ethylene-α-olefin shown in Comparative Example 1 is higher than αtp1aji/sd, and the case where the density of the linear ethylene-α-olefin is larger than αtp1aji/sd, and the case where the density of the linear ethylene-α-olefin is higher than
In the case of high-density polyethylene shown in FIG.
In the case of ASEEA, although the flexibility is good, it is recognized that the adhesive strength rapidly decreases as the temperature rises.

Examples 5 to 8, 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 ratios shown in Table 3. The mixture was kneaded at 165° C. for 15 minutes using a Banbury mixer.

Using a hot press molding machine, each kneaded material was molded into 150
Press at 100 KP/d for 2 minutes at °C to a thickness of tQ.
Sheets of wm and lQm were molded. A dumbbell-shaped test piece specified by JIS K 6760 was punched out from a sheet having a thickness of tQm, and the tensile strength and elongation were measured at a tensile rate of 100 as/min.

Also, from a sheet with a thickness of zom, JI8 K7216
[6.0111%] Rectangular test pieces with a length of 38.0 m were punched out and the embrittlement temperature was measured for them.

The above results are shown in Table 4, and as can be seen from Examples 5 to 8, the density α910 p/m/! Polyolefins made by modifying linear ethylene-α-olefins with maleic anhydride or acrylic acid produced by the gas-phase, low-pressure method, and metals, inorganic materials, etc., have a sufficiently high tensile strength, elongation, and low temperature. Although they have brittleness, the high-density polyethylene and EVA modified with maleic anhydride shown in Comparative Examples 5 and 6 both have low σ1 tensile strength and insufficient low-temperature brittleness.

Examples 9 to 12, 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 the mixture was mixed in a Banbury mixer. The mixture was kneaded for 15 minutes at 165°C.

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.

The tensile strength, elongation, and embrittlement temperature of the above test pieces were measured, and the results are shown in Table 5.As can be seen from Examples 9 to 12, the density was 0. A mixture of polyolefin obtained by modifying linear ethylene-α-olefin with maleic anhydride produced by the gas phase/low pressure method of 91097M and unmodified EVA or EEA, or to which carbon black or calcium carbonate is further added. The mixture has sufficiently high tensile strength, elongation and low temperature brittleness. on the other hand,
Polyolefins obtained by modifying high-density polyethylene with maleic anhydride shown in Comparative Examples 7 to 9 and unmodified EVA or E
Mixtures of EA or mixtures in which carbon black or calcium carbonate is added have low tensile strength and elongation, and insufficient low-temperature brittleness.

(Note 1): Dutral-Co 055, Mo
Manufactured by nte-Edlson (Note 2): EA content 20%
, Melt Index ,91o#/rL
Adhesion of polyolefin modified by grafting unsaturated carboxylic acid or its acid anhydride to a linear ethylene-α-olefin copolymer produced by a gas phase/low pressure method with a temperature of t or less, to metals, inorganic materials, or different plastics. or relating to making a composite by mixing;
It provides adhesive strength at high temperatures, good bending strength, sufficient flexibility, tensile strength, elongation, and low-temperature brittleness that cannot be obtained with conventional modified polyolefins, and its industrial value is extremely large. .

Claims (1)

[Scope of Claims] (1) An unsaturated carboxylic acid or its acid anhydride is added to a linear ethylene-α-olefin copolymer produced by a gas phase/low pressure method and has a density of 0.910 g/ml or less. 1. A composite made of a modified polyolefin, which is obtained by adhering or mixing a polyolefin modified by grafting with a metal, an inorganic substance, or a different type of plastic. (2) Linear ethylene-α- produced by a gas phase/low-pressure method in which the number of carbon atoms constituting the α-olefin is in the range of 3 to 8.
The composite according to claim 1, which is an olefin copolymer. (3) Linear ethylene-α-olefin copolymers are classified as transition metal compounds in groups IV to VIII and group I in the periodic table.
The composite according to claim 1, which is produced by a gas-phase, low-pressure method using a catalyst produced by a combination of group III organometallic compounds, a so-called Ziegler catalyst. (4) Polyolefin modified by grafting an unsaturated carboxylic acid or its acid anhydride to a linear ethylene-α-olefin copolymer produced by a gas phase/low pressure method and having a density of 0.910 g/ml or less 2. A composite according to claim 1, comprising a mixture in which an unmodified elastomer or polyolefin is added. (5) The linear ethylene-α-olefin copolymer is heated at a temperature of 10° to 80°C and 7,000 K in a fluidized bed reaction zone.
At a pressure of Pa or less, (a) 0.35:1 to 8.0:1
ethylene and at least one higher alpha-olefin having from 3 to 8 carbon atoms in a molar ratio of higher alpha olefins to ethylene of
A gas mixture containing an olefin and (b) at least 25 mol % of at least one diluent gas has the formula: Mg_mTi(OR)_nX_p[ED]_q [wherein
R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR^1, where R^1 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 selected from the group consisting of alkyl esters of aliphatic or aromatic acids, aliphatic ethers, cyclic ethers and aliphatic ketones. m is 0.5 to 56, n is 0.1 or 2, p is 2 to 116, and q is 2 to 85. The precursor composition is diluted with an inert carrier material and has the formula: Al(R^1)_dX^1_eH_f, where X^1 is Cl or OR^ ■, R^1 and R^■ are saturated hydrocarbon groups having 1 to 14 carbon atoms, e is 0 to 1.5, f is 0 or 1, and d+e+f=3 completely activated with an organoaluminum compound having
A process for the continuous production of ethylene copolymers, characterized in that the activation compound is used in an amount such that the molar ratio of total aluminum to titanium in the reaction zone is from 10:1 to 400:1. Claim 1 which is
Compounds described in Section. (6) The linear ethylene-α-olefin copolymer contains ethylene alone or at least one type of C_3 to C_1_0
About 10°C to about 115°C in the gas phase with α-olefin
(A) (1) palladium trihalide (a) with chlorine, bromine or iodine and an electron donor (b) which is a liquid organic Lewis base in which the vanadium trihalide is soluble; The reaction product vanadium compound and (2) the following formula MX_a (where M is boron or AlR_(_3_-_a_)
each R is 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, with the proviso that when M is boron, a is 3) supported on a solid inert support consisting essentially of silica or alumina. (B) a promoter having the formula AlR_3, where R is as defined above; and (C) a cocatalyst having the formula R^1_bCX^1_(_4_-_b_), where R^1 is hydrogen or unsubstituted or halogen-substituted lower alkyl, X^1 is halogen, and b is 0, 1 or 2). 2. The composite according to claim 1, which is produced by a method for producing polyethylene, which comprises polymerizing polymers.