Methods of treating textile fibres

Abstract

According to the invention there is provided a method of treating textile fibers including the steps of: providing 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).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 —R.sup.3-R.sup.5≡Y.sup.1, and R.sup.13 is C(O) or S(O).sub.2; coating the textile fibers with the polymeric precursor; and polymerizing the polymeric precursor so as to produce a polymeric coating on the textile fibers. ##STR00001##

Claims

1. A method of bonding textile fibers to a low surface energy elastomer including the steps of: providing a polymeric precursor which includes a group of sub-formula (I) ##STR00025## wherein: 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.10 CR.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, X.sup.1 is a group CX.sup.2X.sup.3, Y.sup.1 is a group CY.sup.2Y.sup.3, 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 —R.sup.3-R.sup.5═Y.sup.1, and R.sup.13 is C(O) or S(O).sub.2; coating the textile fibers with the polymeric precursor; polymerising the polymeric precursor so as to produce a polymeric coating on the textile fibers; and contacting the textile fibers with the low surface energy elastomer.

2. A method according to claim 1 in which the polymeric precursor is a compound of structure (II) ##STR00026## 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.

3. A method according to claim 2 in which the polymeric precursor is a compound of structure [III] ##STR00027##

4. A method according to claim 2 in which R.sup.6 comprises a straight or branched chain hydrocarbyl group, optionally substituted or interposed with functional groups.

5. A method according to claim 4 in which the straight or branched chain is interposed or substituted with one or more of an amine moiety, C(O) or COOH.

6. A method according to claim 5 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.

7. A method according to claim 5 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.

8. A method according to claim 7 in which the monomer is a compound of Formula (VI) ##STR00028## where v is 1 to 20.

9. A method according to claim 4 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.

10. A method according to claim 4 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.

11. A method according to claim 6 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.

12. A method according to claim 2 in which the polymeric precursor is a monomer of structure (VII) ##STR00029## where R.sup.6 is a straight or branched chain hydrocarbyl group, optionally substituted or interposed with functional groups, and r is an integer of 2 or more, or a pre-polymer obtained by pre-polymerisation of said monomer.

13. A method according to claim 1 in which the textile fibers are synthetic fibers.

14. A method according to claim 13 in which the textile fibers include aramid, nylon or polyester fibers.

Description

EXAMPLE 1 ADHESION PROMOTION OF M-ARAMID TO SILICONE AND FLUOROELASTOMER USING N,N-DIALLYL-3-(PROPYLAMINO)PROPANAMIDE AND N,N,N,N-TETRAALLYLETHANEDIAMIDE

(1) 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.

(2) 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.

(3) 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.

(4) ##STR00015##

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

(5) 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%.

(6) 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.

(7) 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%.

(8) ##STR00016##

Synthesis of N,N, N,N-Tetraallylethanediamide

(9) 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.

(10) 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.

(11) 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.

(12) 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

(13) 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)

(14) 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.

(15) 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.

(16) ##STR00017##

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

(17) 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%.

(18) ##STR00018##

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

(19) 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

(20) 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.

(21) 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.

(22) ##STR00019##

Synthesis of N,N-diallylhexanamide

(23) 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%.

(24) ##STR00020##

EXAMPLE 5 ADHESION PROMOTION OF ACID DYES TO M-ARAMID FABRIC USING AN ADHESION PROMOTION LAYER CONSISTING OF A COPOLYMER OF N,N-DIALLYL-2 (BUTYLDIALLYLCARBAMOYLMETHYLAMINO)ACETAMIDE AND N,N-DIALLYL-3-(PROPYLAMINO)PROPANAMIDE

(25) A mixture of N,N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (74.4 g) and N,N-Diallyl-3-(propylamino)propanamide (18.6 g) was pre-heated at 70° C. after which thermal initiator (DuPont Vazo67, 5.0 g) was added with constant stirring. The reaction mixture was maintained at 70° C. for 10 hours with continuous stirring to produce a viscous liquid, after which photoinitiator was added (Ciba Irgacure 819, 2.0 g) and dissolved fully into the mixture.

(26) This formulation was then coated onto m-aramid fabric using a reverse roller method to approximately 20 grams per square meter coat weight and cured under a 200 W/cm UV lamp using a gallium doped mercury bulb.

(27) Acid dyeing of the treated textile was performed by the application of a water based print paste, which contained the acid dye in solution. The paste was liberally applied to the textile, followed by heating of the dyed textile at 130° C. for 60 minutes followed by heating at 180° C. for 5 minutes. After cooling the dyed textile was washed in an alkaline solution of potassium carbonate (pH 10), rinsed in water and then dried.

(28) Alternatively, the treated textile was simply treated with an acid dye in aqueous solution, for instance acid green 25 at 5% concentration, and then heated for 10 minutes at 70° C. The sample was then washed in water, then an alkaline solution of potassium carbonate (pH 10) and again rinsed in water before drying.

(29) ##STR00021##

Synthesis of N,N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide

(30) Chloroacetyl chloride (>98%, 212 g, 1.883 moles) and dichloromethane (397.5 g, 4.680 moles) were added to a reaction vessel and cooled to 5° C. N,N-diallylamine (freshly distilled, 402.57 g, 4.143 moles) was added to ichloromethane (397.5 g, 4.680 moles) and this mixture was then added dropwise to the chloroacetyl chloride mixture over several hours with constant stirring with the temperature kept below 10° C. The reaction mixture was then left to reach room temperature and then washed in water (1.5 l). The organic phase was washed again in water, followed by separation of the organic phase. Solvent and volatiles were then removed from the organic phase under vacuum to yield a yellow oil, which was further purified by column chromatography with ethyl acetate eluent and silica. Eluent was removed under vacuum to yield a yellow oil. Yield ˜78%.

(31) N,N-Diallyl-2-chloroacetamide (intermediate) (86.75 g, 0.500 moles), triethylamine (154.38 g, 1.500 moles) and tetrahydrofuran (222.25 g, 3.082 moles) were charged into a reaction flask with 1-butylamine (99%, 18.29 g, 0.250 moles) added dropwise over 15 minutes with constant stirring. The temperature of the reaction was brought to reflux and maintained for 4 hours. The reaction was then cooled to room temperature followed by filtration of the triethylamine hydrochloride salt from the reaction liquor. After removal of solvent under vacuum the product was added to dichloromethane (200 ml) and then washed twice in water (300 ml). The organic phase was separated, dried with magnesium sulfate and filtered. This was followed by removal of solvent under vacuum to yield a pale yellow oil. Yield ˜88%

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

(32) 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%.

(33) 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.

(34) 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%.

EXAMPLE 6 ADHESION PROMOTION OF ACID DYES TO M-ARAMID FABRIC USING AN ADHESION PROMOTION LAYER CONSISTING OF BENZENE-1,3,5-TRICARBOXYLIC ACID-TRIS-N,N-DIALLYLAMIDE

(35) Benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide was mixed with photoinitiator (ITX, 3% by weight) and amine synergist (4-Dimethylaminobenzoate, 2% by weight) and then applied by reverse roller method to an m-aramid fabric at 20 grams per square meter coating weight. This was cured under a focused 200 W/cm UV lamp using an Iron doped mercury bulb.

(36) Acid dyeing of the treated textile was performed by the application of a water based print paste, which contained the acid dye in solution. The paste was liberally applied to the textile, followed by heating of the dyed textile at 130° C. for 60 minutes followed by heating at 180° C. for 5 minutes. After cooling the dyed textile was washed in an alkaline solution of potassium carbonate (pH 10), rinsed in water and then dried.

Synthesis of Benzene-1,3,5-tricarboxylic acid-tris-N,N-Diallylamide

(37) A mixture of N,N-Diallylamine (>99%, 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 anhydrous 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%.

(38) Basic dyes may be applied in a similar way and may show enhanced dyeing when an acid group is present as part monomer structure.

EXAMPLE 7 ADHESION PROMOTION OF BASIC DYES TO M-ARAMID FABRIC USING AN ADHESION PROMOTION LAYER CONSISTING OF 4-(DIALLYLAMINO)-4-OXOBUTANOIC ACID AND N,N,N′,N′-TETRAALLYLETHANEDIAMIDE

(39) A mixture of 4-(Diallylamino)-4-oxobutanoic acid and N,N,N′,N′-Tetraallylethanediamide was prepared in the ratio 3:1 by weight respectively. To this photoinitiator was added (Ciba Irgacure 819, 3% by weight to total monomer) and stirred until fully dissolved. This formulation was then coated onto m-aramid fabric using a reverse roller method to approximately 20 grams per square meter coat weight and cured under a focused 120 W/cm UV source using a gallium doped mercury bulb.

(40) The treated fabric was then dyed by immersion of the fabric in a solution of basic blue 26 (3 wt % solution) in water at 70° C. for 10 minutes. This was followed by washing of the fabric in a dilute acetic acid solution, rinsing in thoroughly in water and drying with warm air.

(41) ##STR00022##

Synthesis of 4-(Diallylamino)-4-oxobutanoic acid

(42) A solution of diallylamine (>99%, 24.5 g) in dichloromethane (50 ml) was added drop-wise over 1 hour to a solution of succinic anhydride (>98%, 25.3 g) in dichloromethane (200 ml) with constant stirring. The temperature throughout the addition of the diallylamine was maintained between 10-20° C. and with constant stirring throughout the reaction. After all the diallylamine was added the reaction was allowed to proceed for 30 minutes, after which the mixture was washed once with HCl (100 ml, 3 molar), once with saturated potassium carbonate solution (200 ml) and then twice in water (200 ml). The organic phase was dried over MgSO.sub.4, filtered and the solvent then removed in vacuum to yield a pale yellow oil.

(43) ##STR00023##

EXAMPLE 8 ADHESION PROMOTION OF AN ACID DYE TO NYLON 6,6 FABRIC USING AN ADHESION PROMOTION LAYER CONSISTING OF A COPOLYMER OF N,N-DIALLYL-2 (BUTYLDIALLYLCARBAMOYLMETHYLAMINO)ACETAMIDE AND N,N-DIALLYL-3-(PROPYLAMINO)PROPANAMIDE

(44) A mixture of N,N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (56.0 g) and N,N-Diallyl-3-(propylamino)propanamide (14.0 g) was pre-heated to 75° C. To this mixture a solution of thermal initiator (DuPont Vazo 67, 3.0 g) in N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino) acetamide (21.6 g) and N,N-Diallyl-3-(propylamino)propanamide (5.4 g) was added over 10 hours with temperature maintained at 75° C. with constant stirring and under a nitrogen atmosphere. After the 10 hours reaction time the solution was left to cool and the photoinitator 2-isopropyl thioxanthone (ITX) (2.0 g) and synergist ethyl 4-(dimethylamino)benzoate (EDB) (3.0 g) were added. Both additives were fully dissolved and mixed into the monomer mixture prior to use.

(45) This formulation was then coated onto nylon 6,6 fabric using a reverse roller method to approximately 20 grams per square meter coat weight and cured under a 200 W/cm UV lamp using a gallium doped mercury bulb.

(46) Acid dyeing of the treated textile was performed by the application of a water based print paste, which contained the acid dye in solution. The paste was liberally applied to the textile, followed by heating of the dyed textile at 130° C. for 60 minutes followed by heating at 180° C. for 5 minutes. After cooling the dyed textile was washed in an alkaline solution of potassium carbonate (pH 10), rinsed in water and then dried.

EXAMPLE 9 ADHESION PROMOTION OF AN ACID DYE TO M-ARAMID FABRIC USING AN ADHESION PROMOTION LAYER CONSISTING OF A POLYMER MADE WITH N,N-DIALLYL-2(-BUTYL-DIALLYLCARBAMOYLMETHYLAMINO)ACETAMIDE

(47) N,N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (70.0 g) was pre-heated to 75° C. after which a mixture of thermal initiator (DuPont Vazo 67, 3.0 g) in N,N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (27.0 g) was added over 10 hours with the temperature maintained at 75° C. with constant stirring and under a nitrogen atmosphere. After the 10 hours reaction time the solution was left to cool and the photoinitator 2-isopropyl thioxanthone (ITX) (2.0 g) and synergist ethyl 4-(dimethylamino)benzoate (EDB) (3.0 g) were added. Both additives were fully dissolved and mixed into the monomer mixture prior to use.

(48) This formulation was then coated onto m-aramid fabric using a reverse roller method to approximately 10 grams per square meter coat weight and cured under a 200 W/cm UV lamp using an iron doped mercury bulb.

(49) Acid dyeing of the treated textile was performed by the application of a water based print paste, which contained the acid dye in solution. The paste was liberally applied to the textile, followed by heating of the dyed textile at 130° C. for 60 minutes followed by heating at 180° C. for 5 minutes. After cooling the dyed textile was washed in an alkaline solution of potassium carbonate (pH 10), rinsed in water and then dried.

EXAMPLE 10 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

(50) A mixture of N,N-Diallyl-3-(propylamino)propanamide (85.5 wt %), 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.

(51) 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.

(52) ##STR00024##

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

(53) 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.

(54) 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%).