CA1195043A - Polyethylene composition comprising lldpe and rubber - Google Patents

Polyethylene composition comprising lldpe and rubber

Info

Publication number
CA1195043A
CA1195043A CA000400585A CA400585A CA1195043A CA 1195043 A CA1195043 A CA 1195043A CA 000400585 A CA000400585 A CA 000400585A CA 400585 A CA400585 A CA 400585A CA 1195043 A CA1195043 A CA 1195043A
Authority
CA
Canada
Prior art keywords
composition
ethylene
olefin
alpha
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000400585A
Other languages
French (fr)
Inventor
Kazuo Sei
Hiroshi Inoue
Masaaki Isoi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tonen General Sekiyu KK
Original Assignee
Toa Nenryo Kogyyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toa Nenryo Kogyyo KK filed Critical Toa Nenryo Kogyyo KK
Application granted granted Critical
Publication of CA1195043A publication Critical patent/CA1195043A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • C08L2203/202Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

ABSTRACT
An improved polyethylene composition is disclosed.
The composition comprises linear low density polyethylene (an ethylene/alpha-olefin copolymer) and a synthetic rubber.
In one embodiment the composition includes a synthetic rubber reacted with a carboxylic acid. The polyethylene compositions are particularly useful in environments requiring stress crack resistance, such as in coverings of electrical wire, cables, steel wires, pipes, and similar uses.

Description

-- 1 ' 1 The presen-t invention relates to a polyethylene
2 composition comprising linea~ low density polyethylene and
3 synthetic rubber.
4 Heretofore, hi.gh-pressure low density polyethyl-ene (LDPE) and medium- and low-pressure high density poly-6 ethylene (HrPE) have been used for moldings, films,la~linates, 7 wire and ~able coverings, and s~eel pipe coating by injec-8 tion moldi.n~, extrusion molding, blow molding, and the likeg by virtue of their outstanding chemical resistance, elec-1~ trical insulation, and moldability. Recently, linear low 11 density polyethylene (L-LDP~), which is produced by coPoly-12 meri.zation of ethylene and an alpha-olefin under low pres-13 sur~, is attracting attention because it is superior to 14 LDPE in mechanical strength and durability.
L-L~PE is still deficient in environmental stress-16 cracki.ng resistance (ESCR) when used for certain coverings 17 of electric wires and cables, steel wires, and steel pipes.
18 In accordance with the invention, it has heen 19 found that when L-LDPE is incorporated with synthetic rub-ber, the resulting composition exhibits improved ESCR.
21 Thus, the present invention provides a polye-thyl-22 ene composition which comprises linear low density poly-23 ethylene and synthetic rubber, said linear low density poly-24 ethylene being a copolymer of ethylene and alpha-olefin, having a density of 0.915 to 0.935, and having a rati.o for 26 weight-average molecular weight to number-avera~e molecular 27 weight (abbreviated as Mw/Mn hereunder) o~ 3 to 12.
28 The L-I,DPE used in this invention i9 produced ~y 29 copolymeri.z,ing ethylene with an alpha-olefin selected from butene-l, pentene-l, hexene-l, heptene-l, octene-l, and 4-31 methylpentene-l, at a ratio of 3 to 14 wt.~ in the presence 32 of a chromium catalyst or Ziegler catalyst by the gas phase 33 method, liquid phase method, or solution method. L-LDPE
34 thus pxoduced has a density of 0.915 to 0.935, an Mw/Mn ratio of 3 -to 12, and an MI of 0.1 to 50 [as measured by 36 ASTM D 1238E (19OQC, 2160 g); the same shall apply here-37 under]. Preferable among them is one which is produced by 38 the gas phase method. ;

1 The synthetic rubber used in the present inven-2 tion includes a copolymer rubber of ethylene and an alpha-3 olefin selected from propylene, butene-l, pen~ene-l, hexene-4 1, 4-methylpen-tene-1, and octene-l; ethylene~propylene non-conjugated diene xubber (EPDM), isoprene rubber (IR), butyl 6 rubber (BR), and styrene-butadiene thermoplastic rubber 7 (SBR). Preferable among them is ethylene-alpha-olefin co-8 polymer rubber, and most preferab]e is ethylene-butene~l 9 copolymer rubber (EBR). These synthetic rubbers should pre-ferably have a Mooney viscositv of 10 to 150 (MLl+4 100C, 11 JIS K6300 [the same shall apply hereunder]), and a crystal-12 lization degree less than 30~. Such ethylene-alpha-olefin 13 copolymer rubbers usually have a density lower than 0.9.
14 The composition of the present invention can be obtained by incorporating L~LDPE with synthetic rubber, fol-16 lowed by melting and mixlng. More specifically, L-L~PE and 17 synthetic rubber are mixed by a Henschel mixer or ribbon 18 blender and the mixture is melted and kneaded at a temper~
19 ature higher than the melting point of polyethylene but low-er than 250C using a Banbury mixer or single screw or mul 21 tiscrew extruder. For synthetic rubber in the form of bale, 22 a Banbury mixer or roll mill is suitable for heatiny, melt-23 ing, and mixin~. The blending ratio of L-LDPE and synthe-24 tic rubbex should preferably be 70 to 98 parts by weight for L-LDPE and 30 to 2 parts by weight for synthetic rubber.
26 If the synthetic rubber is less than 2 parts by weight, no 27 improvement is made in ESCR; and conversely, if it is more 28 than 30 parts by weight, ESCR is improved but mechanical 29 strength decreases.
The synthetic rubber in the composition of this 31 invention may be replaced by a modified synthetic rubber or 32 a mixture of an unmodiEied synthetic rubber and such a mod-33 ified synthetic rubber. This modified synthetic rubber can 34 be produced by adding to a synthetic rubber an unsa-turated carboxylic acid or a derivative ther-eof e.g., maleic anhy-36 dride, acrylic acid, methacrylic acid, or endo-bicyclo 37 [2,2,1]-5-heptene-2~3 dicarboxylic acld anhydride; in an 38 amount of 0.05 to 3 wt.~ in the presence of an organic per-39 oxide such as 2.5-dimethyl~2,5~di(t butylperoxy)-hexene~3 1 and di-t-butyl peroxide. If such a modified synthetic rub-2 ber is incorporated, the resulting compo~ition is im~roved 3 not only in ESCR, tensile strength, elongation, etc. but 4 also in adhesion. Therefore, such a composition can be used to make laminates with a metal or a thermoplasticresin 6 such as polyamide, polyolefin, polyvinylformal (Vinylon)~
7 polyester, and polyvinyl chloride.
8 As mentioned above, the composition of this in-9 vention has high ESCR, tensile strength, and elongation, and films produced from the composition have greatly im-Ll proved heat-sealability, transparency, and glos~. Thus, 12 the composition of this invention is suitable for films, 13 stretched films, sheets, and coverings of electric wires 14 and cables, steel pipes, metal plates and steel wires.
The composition of this invention may be incor-16 porated, as required, with a weathering agent, antioxidant, 17 heat stabilizer, molding aid, colorant, and the like.
18 The invention is described in detail by the fol-19 lowing examples. In Examples and Referential Examples, "parts" means "parts by weight," and ESCR and high-speed 21 tensile elongation were evaluated by the following test 22 methods~
23 (1) T3SCR: (in conformity with ASTM D-1693) 24 (A) Test Piece: 38 x 12.7 x 2 mm (~) Surface active agent: 10% aqueous solution Igepal 26 (C) Test temperature: 50C
27 (2) fIigh-speed tensile elongation (JIS TC-6760) ~8 (A) Rate of pulling: 500 mm/min +10%
29 r~ les : t~ ' The compositions of this invention were prepared 31 by mixing L-LDPE and ethylene-butene-l copolymer rubber 32 (MIo 4.0, density: 0.88) in the ratios shown in Table 1 33 uslng an extruder at 220C. The physica] properties of the 34 resulting compositions are shown in Table 1.

~ ~c7~ ~

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~5~3 1. Referential Exam~les l_to 7 2 For the purpose of reference, L-LDPE alone, LDPE
3 alone, HDPE alone, and a composition of LDPE and ethylene~
4 butene-l copolymer rubber prepared as in Example 1 wereeval-uated for their physical properties. The resul~s are shown 6 in Table 2~

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5~

1 Example 8 and Referential Exa~
2 A 30 micron thick film was produced from the com-3 position of Example 5 using a T-die film extrusion machine 4 for thermoplastic resin. For the purpose of reference, a 30 micron thick film was produced from the L-LDPE Of Refer-
6 ential Example 2. The resulting films were evaluated for
7 gloss (ASTM D~523, incident angle of 45), haze (ASTM D-1003),
8 and heat seal strength. The heat seal strength was deter-
9 mined by measuring with an Instron type universal tester at heat sealing temperature the peel strength of the heat-11 sealed part formed under a pressure of 2 kg/cm and for a 12 period of 1 second using Toyo Seiki's heat inclination tes-13 ter. The results are shown in Table 3.

14 Table 3 15 Film Properties Example 8 Ref. Ex. 8 16 Gloss (~) 145 128 17 Haze (~) 1.5 3.6 18 Heat seal strength 19 (g/15 mm) 20Seal Temp. 100C 180 0 22~.10C 500 (-~) 100 23l:L5C 500 (~) 420 241~0C 500 (~) 450 _ _ _ _ _ ~
Example 9 A compositlon was prepared by mixlng the L-LDPE
26 used in Example 1, at the ratio shown in Table 4, with a 27 modified synthetic resin prepared as follows: To 100 parts 28 of ethylene~butene-l copolymer rubber used in Example 1 29 were added 1.1 parts of maleic anhydride ancl 0.025 yar-t of 2,5-dime-thyl-2,5-di-(t-butyl peroxide)~hexene-3 (initiator)O
31 The mixture was kneaded u~ing an extruder at 220C so that 1 1.0 wt.~ of acid was added to the synthetic xubber. The re-2 sulting composition was measured ~or physical properties, 3 and evaluated for adhesion by measuring peel stren~th o~
4 laminates produced from the composition.
The peel strength and melt tensile strength were 6 measured according to the following methods.
7 (l) Peel strength 8 Preparation of test piece 9 (A) Aluminum laminate A three-layered laminate consisting of two alumi-11 num sheets (0.1 mm thick) sandwiching an inter-12 mediate layer (0.1 mm thick) of the composition, 13 was cut into a 25 mm wide specimen.
14 (B) Iron laminate A two-layered lamina~e consisting of a bonderized 16 iron plate (3.2 mm thick) and a layer (2 mm thick) -17 of the composition, was cut into a 10 mm wide 18 specimen.
19 (C) Nylon laminate A three-layered lamlnate consisting of two nylon 21 6 layers (0.1 mm thick) sandwiching an intermedi-22 ate layex (0.1 mm thick) of the composition, was 23 cut into a 25 mm wide specimen.
24 These specimens were measured for 90 peel strength on an Instron type universal tester.
26 (2) Melt tensil strength 27 The flowability was evaluated by measuring the tensile 28 force required to pull at a constan~ rate the molten 29 resin extruded from the orifice of a melt indexer un-der the followin~ conditions.

31 (A) Orifice: 2.095 mm~ x 8 mm 32 (B) Test temperature: 190~C
33 (C) Extrusion rate of resin: 10 mm/min.
34 (D) Take-up rate of resin: 5.5m/min.

-Table 4 .
2 Example No. 1 9 .. ~
3 ~LDPE ( par ts ) 90 4 l~c,dified syntnetic rubber (parts) lO
~_ Prcperties 6 Quan~ity of acid added ~wt%~ O.lO
7 MI ( g/lO min ) 7 . O
8 Density (g/cc) 0~ 922 9 ESCR Fso (time) ~lOOO
High~speed elongation ~ 96 ) 700 ll ~1e1 t pulliny force (G) 0.7 ].2 Peel strength :L 3 I ron ( kg/'cm) 4 . S
l4 Aluminum ( lcg/~ . 5 cm) 4 ~ O
t1ylon- 6 ~ lcg/2 . 5 cm ) ~ . O
___ __ _ .

Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polyethylene composition which comprises:
(a) from 70 to 98 parts by weight of linear low density polyethylene comprising a copolymer of ethylene and an alpha-olefin having a density of 0.915 to 0.935 and Mw/Mn ratio of 3 to 12; and (b) from 2 to 30 parts by weight of an ethylene-butene-1 copolymer rubber having a density lower than 0.9.
2. A thermoplastic coating composition for wire, cable or pipe which exhibits improved environmental stress cracking resistance, said coating comprising:
(a) from 70 to 98 parts by weight linear low density polyethylene comprising a copolymer of ethylene and an alpha-olefin and having a density of 0.915 to 0.935 and Mw/Mn ratio of 3 to 12; said alpha-olefin constituting from 3 to 14 weight percent of the copolymer and being selected from butene-1, pentene-1, hexene-1, heptene-1, octene-1, and 4-methylpentene;
(b) from 2 to 30 parts by weight of an ethylene-butene-1 copolymer rubber having a density lower than 0.9.
3. A composition as set forth in claim 1, in which the alpha-olefin is an olefin selected from the group consisting of butene-1 pentene 1, hexene-1, heptene 1, 4-methylpentene-1, and octene-1.
4. A composition as defined in claim 1, wherein the synthetic rubber is reacted with from 0.01 to 3.0 weight percent of an unsaturated carboxylic acid or derivative thereof in the presence of an organic peroxide.
5. A composition as defined in claim 2, wherein the copolymer comprises from 3 to 14 weight percent of the alpha-olefin.
6. The composition of claim 3 wherein the linear low density polyethylene is produced by a low pressure process.
7. The composition of claim 6 wherein the linear low density polyethylene produced by a gas phase process.
CA000400585A 1981-04-07 1982-04-06 Polyethylene composition comprising lldpe and rubber Expired CA1195043A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP56051099A JPS57165436A (en) 1981-04-07 1981-04-07 Polyethylene composition
JP51099/81 1981-04-07

Publications (1)

Publication Number Publication Date
CA1195043A true CA1195043A (en) 1985-10-08

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ID=12877358

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000400585A Expired CA1195043A (en) 1981-04-07 1982-04-06 Polyethylene composition comprising lldpe and rubber

Country Status (3)

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US (1) US4426498A (en)
JP (1) JPS57165436A (en)
CA (1) CA1195043A (en)

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Also Published As

Publication number Publication date
US4426498A (en) 1984-01-17
JPS57165436A (en) 1982-10-12
JPS6333783B2 (en) 1988-07-06

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