DE2125309A1 - Composite materials - Google Patents

Description

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 22 33 41 TELEGRAMS: ZUMPAT POSTOCHECK ACCOUNT: MÖNCHEN SII39

BANK ACCOUNT! BANK H. AUFHSUSER

B MONKS 2,

Case RC 4825

DUNLOP HOLDINGS LIMITED, London, S.Y /. 1, England

Composite materials

The invention relates to composite materials, and more particularly it concerns the joining of composite materials, the layers of polyolefin rubbers and plastic materials contain.

The invention relates to a composite material or a composite structure comprising at least one layer of polyolefin plastic material with a melt index of not less than 0.25, which contains self-adhesive with at least a polyolefin rubber layer is connected.

The invention relates to a method for bonding a polyolefin rubber to a polyolefin plastic material which has a melt index which is not less than 0.25 . The method according to the invention is characterized in that the polyolefin rubber is vulcanized in contact with the polyolefin plastic material at a temperature which is above the softening point of the polyolefin plastic material.

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^mm ί— ^ ™

caned.

The polyolefin rubber can be saturated or unsaturated. Rubbers that can be used include olefin copolymers, i.e. ethylene / propylene copolymers, Olefin-diene copolymers, olefin-polyene copolymers or mixtures which one or more of these together with other rubbers, for example styrene butadiene rubber, Contain polybutadiene, polyisoprene, etc.

The polyolefin plastic materials used in accordance with the invention have melt indices or flow rates that are not less than 0.25. These melt indic.es or minimal Flow rates are determined under test conditions corresponding to the materials according to the ASTM standard D12J8-65T determined conditions specified.

These polyolefin plastic materials are preferably saturated and they can be homopolymers, such as polyethylene or polypropylene, or their copolymers, such as ethylene / propylene copolymers or ethylene / vinyl acetate copolymers be. These polyolefin plastic materials can contain any additives (i.e. fillers, etc.) that are normally found to such plastic materials. Desiccants can also be added to the polyolefin plastic material may be added to reduce the adverse effect on bond strength observed when the plastic material Absorbs moisture.

Although one generally uses continuous sheets of plastic material is used, filaments, cords, woven or non-woven films, etc. can be used as well.

The present invention can be used to make polyolefin wheels Use or disks with solid ethylene-propylene-diene copolymer tires Permanently connected or alas they can be used to make seals for car doors

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use vulcanized rubber sponge where it is common practice to be adhesively connected with rigid plastic extrusions. Other uses include joining of films made from ethylene-propylene-diene copolymer rubbers with the formation of, for example, linings for reservoirs, roofing felts and the formation of Polyolefin-reinforced rubber structures and laminates Materials that usually cannot be bonded together, for example a laminate of mild steel and polypropylene, with a thin intermediate layer of ethylene-propylene-diene copolymer used. f

The inventive polyolefin plastic material can be used as an intermediate layer to connect a polyolefin rubber with a plastic material that is usually not connected to the polyolefin rubber , but which can be connected to the polyolefin plastic material can be. Such plastic materials include nylon and terylene, and they may be in the form of reinforced members and so on.

The following examples illustrate the invention without, however, restricting it.

Examples 1 to 9

Foils 17.8 cm (7 inch) χ 7.6 cm (3 inch) x 2 mm made of polyethylene Low density films were in contact with 17.8 cm χ slides 7.6 cm χ 2 mm of various natural and synthetic rubber precursors brought. The compounds are detailed in Table I. One 17.8 χ 2.5 cm (7 χ 1 inch) strip made of Melinex polyester film was placed between the polyethylene and rubber components, along a Side of the structure to facilitate the adhesion tests. The composite rubber-plastic structure was 1 hour heated at the temperature given in Table II to vulcanize the rubber and bond the two layers. After cooling and removing from the mold, each

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Sample cut into 7.6 χ 2.5 cm (3 inch x 1 inch) wide strips covering an area of 6.45 cm (1 square inch) were not connected. The adhesion between the polyethylene and the vulcanized rubber composition was determined by examining the unconnected parts of the polyethylene and the Tucked rubber into clamps on an Instron device and removed the clamp at a speed of 50.8 cm (20 inches) separated per minute. The adhesion values are (kg / cm (lb / iiich)) given in Table II, the values given being the mean values of three determinations per sample.

Table I.

Rubbery composition used in the examples 1 to 9 were used

example 1 SBR connection

Styrene butadiene rubber (Intöl 1500) 100.0

Sulfur 1.75

N-Cyclohexyl-2-benzthiazole sulfenamide 1.0

Stearic acid 1.0

Zinc oxide 3.0

Mineral oil 5.0

Santoflex IP 1.50

HAP Russ (Philblack 0) 50.0

"Santoflex IP" (trade name) is N-isopropyl-N'-phenyl-p-phenylenediamine.

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Example 2 Natural rubber connection

kneaded, ribbed, smoked gum in

Scroll 100.0

Sulfur 2.5

N-Cyclohexyl-2-benzothiazole sulfenamide 0.5

Stearic acid 2.0

Zinc oxide. 3.0

Mineral oil ■ 5.0

• Nonox HFN 1.0

HAP Russ (Philblack 0) 50.0

. "Nonox HPN" (trademark) is a mixture of aryl amines. "Philblack 0" is a trademark.

Example 3 PoIy i s o prenve binding

synthetic polyisoprene (Shell IR 305) 100.0

Sulfur 2.5

N-Cyclohexyl ~ 2-benzothiazole sulfenamide 0.5

Stearic acid '3.0

Zinc oxide 3.0

Mineral oil 5.0

Nonox HAi ¹ N 1,0

HAP Iluss (Philblack 0) 50.0

"Shell" is a trademark

Example 4 Polybutadiene compound Polybutadiene (Shell Oariflex BR 11) 100.0

Sulfur 1.75

N-Cyclohexyl-2-benzthiazole-sulfenamide 0.80 Stearic acid 2.0

Zinc oxide 3.0

Process oil (Sundex 53) - 15.0

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Example 4 (continued)

Santoflex IP 1.50

HAP Russ (Philblack 0) 60.0

Santoflex IP (trademark) is l '! ~ Isopropyl-l \ ^TI -phenylp-phenylenediamine

"Sundex" is a trademark

Example 5 Poly chloroprene compound, ¹ ?;

Chloroprene (Neoprene WRT) 100.0

Ethylene thiourea · 0.5

Sulfur 0.5

Tetramethylthiuram disulfide 0.5

1,3-diphenylguanidine 0.5

Zinc oxide 5 * 0

Stearic acid 2.0

N-phenyl-β-naphthylamine 1.0

HAF Russ (Philblack 0) 35.0

Example 6 Butadiene-acrylonitrile compound

Butadiene acrylonitrile (Butakon A3OO3) '100.0

Sulfur 1.5

H-Cyclohexyl-2-benzthiazole-sulfenarnide 1.0

Stearic acid 2.0

Zinc oxide ■ 5.0

Di-allyl phthalate 10.0

IT-phenyl-ß-naphthylamine 1.0

HAF Russ (Philblack 0) 50.0

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_ 7 - ■

Example 7 Butyl compound

Butyl (Polysar 301) 100.0

Sulfur 2.0

2-mercaptobenzothiazole 0.5

Tetramethylthiuram disulfide 1.0

Stearic acid 2.0

Zinc oxide 5.0

Mineral oil 5.0

HAF Russ (Philblack 0) 50.0

Example 8 Ethylenpropylen-Miscnpolymerisat-Verbinc'uiift

Ethylene propylene copolymer (Dutral N) 100.0

Sulfur 0.4

Dicuinyl peroxide 5.0

HAI ¹ Russ (Philblack 0) x 50.0

Example 9

Ethylene propylene terpolymer- 100.0

Rubber (Royalen 502)

Zinc oxide 5.0

Tetramethylthiuram disulfide 0.75 *

Dipentamethylene thiuram tetrasulfide 0.75

Tellurium diethyl thiocarbamate 0.75

2-mercaptobenzothiazole 1.50

Sulfur 2.0

Circosol 4240 oil 60.0

HAP Russ (Philblack 0) 90.0

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Table II

at
game
No. Chews
schuk temperature
at Ver
tie
(Hardening) average
Polyethylene /
Rubber adhesion
kg / cm (lb / inch) (2.6) Type of
Vereagens 1 Styrofoam
butadiene
rubber 15O ⁰ O • 0.46 (0.7) the bin
dung ver
says CVl Natural chew
schuk HO ⁰ C 0.12 (1.3) the bin
dung ver
says 3 Polyisoprene HO ⁰ C 0.23 (1.3) the bin
dung ver
says 4th Polybutadiene HO ⁰ C 0.25 (0.4) the bin
dung vcjr-
says 5 Polychloro
pren 150 ⁰ C 0.07 (0.2) the bin
dung ver
says 6th Butadiene
acrylonitrile 150 ⁰ C 0.035 (1.4)
(38.5) the bin
dung ver
says 7th
8th Butyl
Ethylene
per pylene
Mi s chpo Iy-
merisat 150 ⁰ C
150 ⁰ C 0.23
6.9 (33.0) the bin
dung ver
says
fail
des chews
schuks be
neighbors
binding 9 Ethylene propy-
wage mono- 150 ⁰ C 5.9 Kautsclrak
fails

meres

From these results it can be seen that the ethylene propylene and ethylene propylene human rubbers with their ability to bind polyethylene are unique, Examples 8 and 7 9.

Examples 10 to H.

In a manner similar to that described in Examples 1 to 9,

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was opposed to the adhesion of low density polyethylene Rubber compounds of the following compositions are determined.

Examples ( parts by weight)

12 11 12 11 IA

Styrene

Butadiene

Rubber 100 75 50 25 0

(Intol 1500)

Ethylene propylene

terpolymer- _{n ot} - _Rr . _Πΐ - _1nn

Rubber (Intolan 170) ° ^{25 b0 75 10} °

Philblack 0 50 50 50 50 50

Zinc Oxide Stearic Acid Mineral Oil Sulfur N-Cyclohexyl-

2-benzothiazole

sulfenamide 11 1 1

IT-isopropyl-N '-

phenyl-p-phenylene-

diamine 1.5 1.5 1.5 1.5

VJ] 1 UI 1 5 1 Ul 1 5 1 1 1 1 1 5 5 5 Π " 5 1.75 , 75 , 75 , 75 , 75

The results obtained are shown in Table III. All examples were during 60 Wed:
Measurements were taken.

Examples were heated ^{to 150 0} C for 60 minutes before

Table III adhesion Type of failure example kg / cm (lb / inch) 0.18 (0.9) the bond fails 10 3.6 (19.8) the bond fails 11 • -7.9 (44) the rubber fails 12th > 7.9 1-44) Polyethylene fails 13th > 7.9 (> 44) Polyethylene fails H

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- ίο -

It is also possible to change the types of composite structures, to use those given in Examples 8 and 9 to bond polyolefin plastic to materials, those easily mixed with ethylene-propylene-diene or ethylene-propylene copolymer compositions, but not easily bonded to saturated polyolefin plastics.

Example 15

A mild steel plate was rubbed with Emery-l'uch before it with Chemlok 205, Qhemlok EX-B60-04 and finally with one 10bigen (weight / volume) solution of an ethylene-propylene-diene copolymer compound was coated in cyclohexane.

A low density polyethylene film was placed on top of the coated Mild steel was pressed and then the structure was heated at 150 ° C. for 1 hour. The polyethylene was obtained on cooling a strong bond. An average peel rate of 15.8 kg / cm (88 lb / inch) was obtained before the polyethylene failed. An average peel strength of 1.5 kg / cm (11 lb / inch) was obtained when the ethylene-propylene-dieri copolymer solution was left out. There is no adhesion between the polyethylene and the mild steel if that the former applied directly to the mild steel v.drd.

Alternatively, you can use a film made of dry ethylene-propylene-diene copolymer onto the Chemlok coated steel rather than depositing from solution.

The ethylene-propylene-diene copolymer composition, the used in this example was the following:

Parts

Ethylene-propylene terpolymer rubber "Nordel" 1070 (trademark) HAF Russ Zinc Oxide Mercaptoben ^ thiazole 109850/1817

1 00 50 5 , 0 1 , 5

Parts

Tetramethylthiuram disulfide 0.75

Tellurium diethyl dithiocarbamate 0.75

Sulfur 2.0

Dipentamethylene thiuram tetrasulfide 0.75

Chemlok 205 and Chemlok EX-B60-04 are protected adhesives, manufactured by Hughson Chemical Company, Division of Lord Corporation, Erie, Pennsylvania.

Example 16

A rubbery composition containing the following formulation was calendered to a thickness of 0.101 cm (0.040 inch) in contact with a polyethylene film 0.015 cm (0.006 inch) thick between. Where ^T white cloth tapes and by a Rotorcure (RotorhärtungSv ^. Ostracism) at 145 ^ is 150 ⁰ C added so that the polyolefin and the Kautschukzusammensetztuig by the pressure of the belt in direct contact were maintained and then the rubbery composition was vulcanized during 45 minutes .

After cooling, it was found that the polyethylene was firmly bonded to the rubber-like composition and that a composite Laminate was created. Attempts to separate the two components caused the whole to vulcanize Composition was torn.

Rubber-like composition EPDM (Keltan 712)
EPDM (Intοlan 255)
FEF Russ

paraffinic extender oil, desiccant stearic acid
Zinc oxide
Zinc diethyl dithiocarbamate

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Weight point 25th 20th 5 10 0 40 20th 40 ο, 1,

Parts by weight

Mercaptobenzothiazole 0.25

Tetramethylthiuram disulfide 0.25

Dimorpholine disulfide 0.625

Sulfur 0.75

Keltan 712 and Intοlan 255 are ethylene-propylene-diene monomer rubbers, the approximately 40 and 25 hol? " Propylene and Contain 0.61 and 0.52 mol of ethylidene norbornene per kg of rubber.

The agent for dehydration that is used in the composition contained calcium oxide and is commercially available as "Rhenosorb C" from Rhein Chemie GmbH.

Example 17

Example 16 was repeated, instead of the polyethylene film a 0.015 cm thick (0.006 inch) film of ethylene vinyl acetate copolymer used the 10 to 13 $ vinyl acetate contained.

Again, such a strong bond was obtained between the two components of the laminate that attempts to close the laminate separate, brought with them that one or the other component tore.

Example 18

A 22.9 cm (9 inch) 7.6 cm (3 inch) x 2.5 mm sheet of ethylene-propylene-diene monomer rubber, its composition indicated below, a 22.9 cm χ 7.6 cm film of 500 gauge was in contact with the polyethylene side Nylon / polyethylene laminate sold by Smith & Nephew Ltd, as "Synthene" 5023, in a vulcanization mold was. Between the polyethylene and rubber compositions A 22.9 x 2.5 cm strip of Melinex polyester film was placed along one side for adhesion prevent and facilitate testing for adhesion. That

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Structure was heated for 60 minutes at 15O ⁰ G to vulcanize the rubber composition.

Rubber composition parts by weight

ΕΡΏΗ (Nordel 1070) 100

HAF Russ 50

Zinc oxide 5.0

Sulfur 2.0

Zinc dibutyl dithiocarbamate 2.0

Mercaptobenzothiazole - 1.5

Tetramethylthiuram disulfide 0.5 *

Nordel 1070 is an ethylene-propylene-1,4-hexediene - Terpol, γmeri- ■ sat rubber, at E.I. duPont de Nemours & Co is.

After the vulcanized structure has cooled down and out of shape removed, it was cut into 7.6 χ 2.54 cm strips covering an area of 6.45 cm (1 square inch) was not bonded and then became the strength of the bond between the plastic laminate and the vulcanized rubber composition determined according to the method described in Examples 1 to 9. The nylon and polyethylene J

ρ film separated under a load of 1.8 kg / cm (10 lb / inch) but the bond between the rubber composition and the laminate could not be destroyed.

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Claims (11)

Claims 1. Method of making a polyolefin rubber with a polyolefin • plastic material to connect that has a melting index, which is not less than 0.25, characterized in that the polyolefin rubber is in contact with the Polyolefin plastic material vulcanized at a temperature which is above the softening point of the Polyolefinfamst ™ Fabric material lies. 2. The method according to claim 1, characterized in that the polyolefin plastic material is a saturated polymer is. 3. The method according to any one of claims 1 and 2, characterized in that that the polyolefin plastic material'ein Is olefin homopolymer. 4. The method according to claim 3, characterized in that the polyolefin plastic material is polyethylene or polypropylene is. 5. The method according to claim 1 and 2, characterized in that the polyolefin plastic material is an Jlisehpolymerisat from zv / ei or more olefins. 6. The method according to claim 5, characterized in that the polyolefin plastic material is an ethylene / propylene copolymer or an ethylene / vinyl acetate copolymer. 7. The method according to any one of the preceding claims, characterized characterized in that the polyolefin plastic material is in the form of a continuous etolle or an Mlms. 8. The method according to any one of claims 1 to 6, characterized in that that the polyolefin plastic material is in the form of filaments, cords or ribbons, woven or non-woven Materials available. 9. The method according to any one of the preceding claims, characterized characterized in that the polyolefin rubber is an olefin copolymer is. 10. .The method according to claim 9, characterized in that the polyolefin rubber is an ethylene / propylene copolymer or an olefin / Men-Ivlischpolymerisat or an olefin / Polyene copolymer or a mixture of one or several of these materials are mixed with other rubbers. 11. Composite material or composite structure, characterized in that there is at least c ^ e layer of a saturated polyolefin impregnating material with a Schrielz index not less than 0.25, self-adhesive contains connected to at least one polyolefin rubber layer. 1098150/1817