Composite articles and methods of producing same

Abstract

According to the invention there is provided a composite article including: a textile layer having a first and a second face, each of the first and second faces having a polymeric coating thereon; a first polymeric layer adhered to the polymeric coating on the first face of the textile layer; and a second polymeric layer adhered to the polymeric coating on the second face of the textile layer; in which the polymeric coatings on the first and second faces of the textile layer are each formed by polymerizing a polymeric precursor which includes a group of sub-formula (I) where R.sup.2 and R.sup.3 are independently selected from (CR.sup.7R.sup.8)n, or a group CR.sup.9R.sup.10, CR.sup.7R.sup.8CR.sup.9R.sup.10 or CR.sup.9R.sup.10CR.sup.7R.sup.8 where n is 0, 1 or 2, R.sup.7 and R.sup.8 are independently selected from hydrogen, halo or hydrocarbyl, and either One of R.sup.9 or R.sup.10 is hydrogen and the other is an electron withdrawing group, or R.sup.9 and R.sup.10 together form an electron withdrawing group, and R.sup.4 and R.sup.5 are independently selected from CH or CR.sup.11 where R.sup.11 is an electron withdrawing group, the dotted lines indicate the presence or absence of a bond, X.sup.1 is a group CX.sup.2X.sup.3 where the dotted line bond to which it is attached is absent and a group CX.sup.2 where the dotted line bond to which it is attached is present, Y.sup.1 is a group CY.sup.2Y.sup.3 where the dotted line bond to which it is attached is absent and a group CY.sup.2 where the dotted line bond to which it is attached is present, and X.sup.2, X.sup.3, Y.sup.2 and Y.sup.3 are independently selected from hydrogen, fluorine or other substituents, R.sup.1 is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or formula (II), and R.sup.13 is C(0) or S(0).sub.2.

Claims

1. A composite article including: a textile layer having a first and a second face, each of the first and second faces having a polymeric coating thereon; a first elastomeric polymeric layer adhered to the polymeric coating on the first face of the textile layer; and a second elastomeric polymeric layer adhered to the polymeric coating on the second face of the textile layer; in which the polymeric coatings on the first and second faces of the textile layer are each formed by polymerising a polymeric precursor which includes a group of sub-formula (I) ##STR00026## where R.sup.2 and R.sup.3 are independently selected from (CR.sup.7R.sup.8).sub.n, or a group CR.sup.9R.sup.10, CR.sup.7R.sup.8CR.sup.9R.sup.10 or CR.sup.9R.sup.10CR.sup.7R.sup.8 where n is 0, 1 or 2, R.sup.7 and R.sup.8 are independently selected from hydrogen, halo or hydrocarbyl, and either one of R.sup.9 or R.sup.10 is hydrogen and the other is an electron withdrawing group, or R.sup.9 and R.sup.10 together form an electron withdrawing group, and R.sup.4 and R.sup.5 are independently selected from CH or CR.sup.11 where R.sup.11 is an electron withdrawing group, the dotted lines indicate the presence or absence of a bond, X.sup.1 is a group CX.sup.2X.sup.3 where the dotted line bond to which it is attached is absent and a group CX.sup.2 where the dotted line bond to which it is attached is present, Y.sup.1 is a group CY.sup.2Y.sup.3 where the dotted line bond to which it is attached is absent and a group CY.sup.2 where the dotted line bond to which it is attached is present, and X.sup.2, X.sup.3, Y.sup.2 and Y.sup.3 are independently selected from hydrogen, fluorine or other substituents, R.sup.1 is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or ##STR00027##  and R.sup.13 is C(O) or S(O).sub.2.

2. A composite article according to claim 1 in the form of a hose, in which the textile layer and the first and second elastomeric layers are cylindrical, and wherein the first elastomeric layer is external to the textile layer and the second elastomeric layer is internal to the textile layer.

3. A composite article according to claim 1 in the form of a belt, a tyre or an air cushion.

4. A composite article according to claim 3 in the form of an endless belt, preferably a conveyor belt or a power transmission belt.

5. A composite article according to claim 1 in which at least one of the first and second elastomeric layers is a rubber.

6. A composite article according to claim 1 in which the first elastomeric layer is formed from a different material to the second elastomeric layer.

7. A composite article according to claim 2 in the form of a hose, in which the first elastomeric layer is formed from a silicone rubber and the second elastomeric layer is formed from a fluoro-silicone rubber.

8. A composite article according to claim 1 in which the first and second polymeric layers are formed from a thermosetting polymer.

9. A composite article according to claim 8 in which thermosetting polymer is a thermosetting epoxy resin.

10. A composite article according to claim 1 in which the textile layer is formed at least partially from polymeric fibres.

11. A composite article according to claim 10 in which the textile layer contains aramid fibres.

12. A method of producing a composite article including the steps of: providing a textile layer having a first and second face; providing at least one polymeric precursor which includes a group of sub-Formula (I) ##STR00028## where R.sup.2 and R.sup.3 are independently selected from (CR.sup.7R.sup.8).sub.n, or a group CR.sup.9R.sup.10, CR.sup.7R.sup.8CR.sup.9R.sup.10 or CR.sup.9R.sup.10CR.sup.7R.sup.8 where n is 0, 1 or 2, R.sup.7 and R.sup.8 are independently selected from hydrogen, halo or hydrocarbyl, and either one of R.sup.9 or R.sup.10 is hydrogen and the other is an electron withdrawing group, or R.sup.9 and R.sup.10 together form an electron withdrawing group, and R.sup.4 and R.sup.5 are independently selected from CH or CR.sup.11 where R.sup.11 is an electron withdrawing group, the dotted lines indicate the presence or absence of a bond, X.sup.1 is a group CX.sup.2X.sup.3 where the dotted line bond to which it is attached is absent and a group CX.sup.2 where the dotted line bond to which it is attached is present, Y.sup.1 is a group CY.sup.2Y.sup.3 where the dotted line bond to which it is attached is absent and a group CY.sup.2 where the dotted line bond to which it is attached is present, and X.sup.2, X.sup.3, Y.sup.2 and Y.sup.3 are independently selected from hydrogen, fluorine or other substituents, R.sup.1 is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or ##STR00029##  and R.sup.13 is C(O) or S(O).sub.2; polymerising the polymeric precursor or precursors to form a polymeric coating on each of the first and second faces of the textile layer; adhering a first elastomeric polymeric layer to the polymeric coating on the first face of the textile layer; and adhering a second elastomeric polymeric layer to the polymeric coating on the second face of the textile layer.

13. A method according to claim 12 in which the polymeric precursor is a compound of structure (II) ##STR00030## where r is an integer of 1 or more and R.sup.6 is one or more of a bridging group, an optionally substituted hydrocarbyl group, a perhaloalkyl group, a siloxane group, an amide, or a partially polymerised chain containing repeat units.

14. A method according to claim 13 in which the polymeric precursor is a compound of structure [III] ##STR00031##

15. A method according to claim 13 in which R.sup.6 comprises a straight or branched chain hydrocarbyl group, optionally substituted or interposed with functional groups.

16. A method according to claim 15 in which the straight or branched chain is interposed or substituted with one or more of an amine moiety, C(O) or COOH.

17. A method according to claim 16 in which the polymeric precursor is a monomer in which R.sup.6 is a straight or branched chain hydrocarbyl interposed with an amine moiety, or a pre-polymer obtained by pre-polymerisation of said monomer.

18. A method according to claim 16 in which the polymeric precursor is a monomer in which R.sup.6 is a straight or branched chain hydrocarbyl substituted with a COOH end group, or a pre-polymer obtained by pre-polymerisation of said monomer.

19. A method according to claim 15 in which the polymeric precursor is a monomer in which R.sup.6 is a straight or branched chain alkyl group having 1 to 30 carbon atoms, or a pre-polymer obtained by pre-polymerisation by said monomer.

20. A method according to claim 15 in which the polymeric precursor is a monomer in which R.sup.6 is a partially or per-halogenated straight or branched chain alkyl group having 1 to 30 carbon atoms, or a pre-polymer by pre-polymerisation of said monomer.

21. A method according to claim 17 in which the polymeric precursor is a monomer in which R.sup.13 is CO and R.sup.6 terminates in one or more amine moieties thereby forming a urea structure, or a pre-polymer obtained by pre-polymerisation of said monomer.

22. A method according to claim 12 in which the first and second faces of the textile layer are coated with the polymeric precursor or precursors prior to the step of polymerising the polymeric precursor or precursors.

23. A method according to claim 12 in which the polymeric precursor or precursors are polymerised by exposure to UV radiation.

Description

(1) Composite articles and methods in accordance with the invention will now be described with reference to the single accompanying FIGURE which shows

(2) (a) a plan view

(3) (b) a cross sectional view

(4) (c) a cutaway side view of a car hose of the invention.

(5) The Figure shows an example of a composite article which may be produced in accordance with the invention, which in this example is a hose 10 for a car. The car hose 10 comprises a main tubular section 12 having suitable connections 14, 16 disposed at either end in a manner which is well known to the skilled reader. The tubular section is of a three-ply structure which is produced in accordance with the invention. As shown best effect in FIGS. 1(b) and (c), the tubular section 12 comprises an inner rubber layer 12a, an outer rubber layer 12b and a reinforcing textile layer 12c which is disposed intermediate the inner and outer rubber layers 12a, 12b. The textile layer 12c has polymeric coatings of the type described herein on both of its inner and outer faces. These polymeric coatings promote adhesion of the textile layer 12c to the inner and outer rubber layers 12a, 12b. The invention can be used to produce hoses and other composite articles formed from many combinations of rubbers and textiles. For example, the inner rubber layer 12a may be formed from an oil resistant rubber such as a fluoro-silicone rubber (FSR/FVMQ), and the outer rubber layer 12b may be formed from a suitable material such as silicone rubber (VMQ/HCR). Although the invention is not limited in this regard, it is advantageous that the textile layer may be an aramid fabric such as Nomex®. Examples of suitable polymeric coatings in accordance with the invention will now be described.

(6) Unless otherwise stated, all percentages described below are wt %.

EXAMPLE 1

Adhesion promotion of m-aramid to silicone and fluoroelastomer using N,N-Diallyl-3-(propylamino)propanamide and N,N,N,N-Tetraallylethanediamide

(7) To a mixture of N,N-Diallyl-3-(propylamino)propanamide and N,N,N,N-Tetraallylethanediamide (in the ratio of 9:1 by weight) a thermal initiator was added (Vazo 67, DuPont, 5% weight of total monomer mixture) and stirred until fully dissolved. The mixture was then maintained at 70° C. for 8 hours with constant stirring to produce a viscous yellow oil, to which a photoinitiator was added (Ciba Irgacure 819, 2% by weight) and mixed thoroughly.

(8) This formulation was then applied onto each side of a strip of m-aramid cloth (DuPont Nomex) at a coating weight of approximately 5 grams per square meter. The coating was cured sequentially after each layer was deposited using focused 200 W/cm UV source with an iron doped mercury bulb.

(9) Strips of fluoro-elastomer and silicone compounds containing initiators or other curing agents were placed on each side of the adhesion promoted textile and then treated at 190° C. at 65-80 psi for 15 minutes to cure fluoro-elastomer and silicone rubber and bond them to the textile.

(10) ##STR00018##

N,N-Diallyl-3-(propylamino)propanamide

Synthesis of N,N-Diallyl-3-(propylamino)propanamide

(11) 3-bromopropionylchloride in dichloromethane (1:1 v/v) was added drop wise to a slight molar excess of diallylamine in dichloromethane (DCM) at ˜10° C. over 2 hours with constant stirring. This was then washed in dilute HCl and dichloromethane and the organic fraction retained. The solution of product in DCM was then purified by column chromatography using silica (60 A) and the DCM removed to yield the 3-bromo-N,N-diallylpropylamide intermediate; a yellow liquid. Yield 70%.

(12) The 3-bromo-N,N-diallylpropylamide intermediate (30 g, 129 mmoles) was added to THF (1:1 v/v). This was then added dropwise over 2 hours into a stirred, refluxing mixture of 1-propylamine (43.1 g, 0.730 mmoles), potassium carbonate (90 g, 0.652 mmoles) and THF (133.6 g, 1.850 mmoles). The reflux was then left to cool over 1 hour with constant stirring.

(13) The cooled reaction mixture was washed in water (400 ml), dissolving the potassium carbonate and leaving a clear, yellow organic top layer, which was decanted off. This layer was then washed again in water, separated and dried to yield a yellow liquid N,N-Diallyl-3-(propylamino)propanamide product. Yield ˜65%.

(14) ##STR00019##

N,N,N,N-Tetraallylethanediamide

Synthesis of N,N,N,N-Tetraallylethanediamide

(15) Fresh, dry oxaloyl chloride (ClOOCCOOCl) (200 mmoles) was placed into a 3-necked round bottomed (RB) flask with 200 ml of dry dichloromethane. Freshly distilled diallylamine (400 mmoles) was added to triethylamine (400 mmoles), further diluted (1:1 v/v) in dry dichloromethane then added into a dropping funnel and placed onto the reaction flask. Nitrogen gas was pumped through the vessel through the other two necks. To neutralise HCl produced, the waste gas was bubbled through a CaCO.sub.3 solution. The reaction vessel was then placed into a salt water/ice bath and once the contents were cooled the diallylamine/triethylamine/DCM was added dropwise to the acid chloride solution with continual magnetic stirring of the mixture. The temperature was monitored and maintained between 5-10° C. The dropping of the diallylamine and triethylamine was stopped after three hours and the reaction was left to stir for another hour.

(16) Thin layer chromatography using ethyl acetate and an alumina was used to monitor the reaction comparing starting material to the product. Iodine was used to develop the plate and the reaction product could be seen as a spot that had been eluted much further than the starting material.

(17) To remove the amine chloride and excess diallylamine the reaction liquor was washed in 3M HCl. The monomer stayed in the DCM fraction and was removed using a separating funnel. Two washes of 100 ml HCl were used. The solvent was then removed in a rotary evaporator.

(18) The product was added to dichloromethane (1:1 v/v) and passed through a silica gel (Merck, grade 60 for chromatography) column with dichloromethane as the eluent.

EXAMPLE 2

Adhesion promotion of m-aramid to EPDM rubber using N,N-Diallyl-3-(propylamino)propanamide and N,N,N′,N′-Tetraallylethanediamide

(19) The same formulation coating method as used in example 1 was used with a woven m-aramid fabric but instead placed between two sheets of EPDM rubber compound. The m-aramid fabric was bonded to the EPDM under elevated pressure (45-75 psi) and temperature (190° C.) for 15 minutes.

EXAMPLE 3

Adhesion promotion of m-aramid to silicone rubber and fluoroelastomer using benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide and 2,2′,2″,2′″-(ethane-1,2-diylbis(azanetriyl))tetrakis(N,N-diallylacetamide)

(20) A mixture of benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide and 2,2′,2″,2′″-(ethane-1,2-diylbis(azanetriyl))tetrakis(N,N-diallylacetamide) was made in a 9:1 ratio by weight, respectively. Photoinitiator (Ciba Irgacure 127) was added at 3% of total weight of monomer mixture and dissolved by maintaining gentle heating of the mixture. This formulation was then applied onto each side of a strip of m-aramid cloth (DuPont Nomex) at a coating weight of approximately 10 grams per square meter and the coating was cured sequentially after each layer was deposited using focused 200 W/cm UV source with an iron doped mercury bulb.

(21) Strips of fluoro-elastomer and silicone compounds containing initiators or other curing agents were placed on each side of the adhesion promoted textile and then treated at approximately 175° C. in a 40 tonne upstroking press for 25 minutes to cure the fluoro-elastomer and silicone rubber and bond them to the textile.

(22) ##STR00020##

benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide

Synthesis of Benzene-1,2,4-tricarboxylic acid-tris-N,N-Diallylamide

(23) A mixture of N,N-Diallylamine (128.26 g, 1.32 moles) and dichloromethane (106.0 g, 1.248 moles) was added to a funnel and added dropwise over 75 minutes to a reaction vessel containing a cooled mixture (10° C.) of 1,3,5-trimesoyl chloride (53.1 g, 0.200 moles) in dichloromethane (530.0 g, 6.24 moles) with constant stirring. The temperature was maintained at <10° C. for the duration of the addition of the diallylamine solution and then left to return to room temperature over another 60 minutes with constant stirring. The organic reaction product was then washed with an excess of water (1×600 ml and 2×300 ml) to remove the hydrochloride salt of the diallylamine, followed by drying over MgSO.sub.4. Solids were then filtered off and the solvent removed under vacuum. The crude product was then purified by column chromatography using a silica column and dichloromethane as eluent. The dichloromethane was again removed under vacuum to yield a pale yellow, viscous product. Yield 60.2%.

(24) ##STR00021##

2,2′,2″,2′″-(ethane-1,2-diylbis(azanetriyl))tetrakis(N,N-diallylacetamide

Synthesis of 2,2′,2″,2′″-(ethane-1,2-diylbis(azanetriyl))tetrakis(N,N-diallylacetamide)

(25) A mixture of 4-dimethylamino pyridine (0.5 g), dicyclohexylcarbodiimide (103.0 g), ethylenediamine tetraacetic acid (36.0 g), diallylamine (53.0 g) and dichloromethane (250 g) was added to a reaction vessel and maintained at approximately 20° C. for 120 hours with constant stirring. Solids, including urea formed in the reaction, were then removed by filtration followed by the removal of amine and solvent under vacuum. After removal of impurities a clear, viscous oil was obtained (˜65%).

EXAMPLE 4

Adhesion promotion of a poly(ester) textile to silicone rubber and fluoroelastomer using N,N-diallyl hexanamide and N,N,N′,N′-Tetraallylethanediamide

(26) To a mixture of N,N-diallyl hexanamide and N,N,N′,N′-Tetraallylethanediamide in the ratio of 9:1 by weight a thermal initiator (Vazo 67, DuPont) was added initially at 1% weight of total mixture and increased by 1% after each hour of reaction until 5% was added with a total reaction time of 8 hours; reaction temperature was maintained at 70° C. over the whole reaction period. A viscous yellow oil was produced. To this a photoinitiator (Ciba Irgacure 819) was added at 2% by weight of total solution and mixed thoroughly. This formulation was then applied onto each side of a strip of knitted poly(ester) fabric at a coating weight of approximately 5 grams per square meter with UV curing performed sequentially after each layer was deposited.

(27) Strips of fluoro-elastomer and silicone compound were placed on each side of a knitted poly(ester) fabric coated with the adhesion promoting layer and then treated at 190° C. at 45-75 psi for 25 minutes to cure fluoro-elastomer and silicone rubber and bond them to the textile.

(28) ##STR00022##

N,N-diallyl hexanamide

Synthesis of N,N-diallylhexanamide

(29) A mixture of diallylamine (>99%, 70.85 g), dichloromethane (265.0 g) and triethylamine (>98%, 73.4 g)) was added dropwise to a stirred mixture of hexanoyl chloride (>98%, 96.15 g) and dichloromethane (530.0 g) over 195 minutes with temperature maintained between 0-10° C. Following this the reaction vessel was allowed to warm to room temperature with stirring of the mixture maintained for a further 60 minutes. The resulting reaction liquor was washed in HCl (3M, 600 ml) and the organic phase separated and dried over anhydrous MgSO.sub.4. After filtration, volatiles including the dichloromethane, were removed under vacuum and the crude product further purified by column chromatography using silica and ethyl acetate as eluent. Ethyl acetate was removed from the product under vacuum to yield a yellow oil, yield 64%.

(30) ##STR00023##

N,N,N′,N′-Tetraallylethanediamide

EXAMPLE 5

Adhesion promotion of a poly(aramid) textile to silicone rubber and fluoroelastomer using a mixture of N,N-Diallyl-3-(propylamino)propanamide, benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide and the fluorinated monomer, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-N,N-di(prop-2-en-1-yl)octanamide

(31) A mixture of N,N-Diallyl-3-(propylamino)propanamide (85.5wt %), benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide (9.5 wt %), 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-N,N-di(prop-2-en-1-yl)octanamide (2 wt %) and the photoinitiator Irgacure 127 (3 wt%, Ciba SC) was applied onto each side of a strip of m-aramid cloth (DuPont Nomex) at a coating weight of approximately 10 grams per square meter. The coating was cured sequentially after each layer was deposited using focused 200 W/cm UV source with an iron doped mercury bulb.

(32) Strips of fluoro-elastomer and silicone compounds containing initiators or other curing agents were placed on each side of the adhesion promoted textile and then treated at approximately 175° C. in a 40 tonne up-stroking press for 25 minutes to cure the fluoro-elastomer and silicone rubber and bond them to the textile.

(33) ##STR00024##

2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-N,N-di(prop-2-en-1-yl)octanamide

(34) Synthesis of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-N,N-di(prop-2-en-1-yl)octanamide

(35) A mixture of perfluorooctanoyl chloride (20.0 g) and dichloromethane (1.6 g) was added drop-wise over 1 hour to a stirring mixture of diallylamine (9.88 g, >99%) and dichloromethane (1.72 g), cooled to 0° C. The reaction was allowed to warm to room temperature with continuous stirring for a further hour.

(36) The product was washed with water (500 ml) twice, followed by the removal of the dichloromethane under vacuum to yield a very low viscosity orange-yellow liquid (yield 79%).

EXAMPLE 6

Synthesis of 1,1-Diallyl-3-(6-{3,5-bis-[6-(3,3-diallylureido)-hexyl]-2,4,6-trioxo-[1,3,5]-triazinan-1-ylhexyl)urea

(37) N,N-diallylamine (Freshly dried, 30.60 g) was added dropwise to a mixture of the isocyanate Tolonate HDT-LV2′ (Rhodia) (50.4 g) in dichloromethane (>99.5%, 132.50 g) over 2 hours with the temperature maintained to below 30° C. and with constant stirring. After the addition of the diallylamine the mixture was maintained for a further 30 minutes at room temperature. Solvent and excess diallylamine were removed under vacuum to yield a high viscosity, amber liquid with a yield of 80.1%. This monomer can be used to adhere a textile layer to elastomers such as NBR rubber and FKM fluoroelastomers using the principles described herein.

1,1-Diallyl-3-(6-{3,5-bis-[6-(3,3-diallyl-ureido)-hexyl]-2,4,6-trioxo-[1,3,5]-triazinan-1-yl-hexyl)urea

(38) ##STR00025##