AD-A136 662 FLUONSALKYL SILOXANES AS LIQUID-REPELLENT FABRIC--FINISH-ES PANT 3 THE AURA..A S EFENCE RESEARCHESTABLISHMENT OTTAWA (ONTARIO S BOVENKAMP ET AL

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FLUOROALKYL SILOXANES AS LI QUID-REPELLENTFABRIC FINISHES

PART 111:THE DURABILITY OF THE COPOLYMERS AND

COMPARISONS WITH COMMERCIALLY AVAILABLEFINISHES

by

J.W. Bowenkarnp and I'V.. Lacroix

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N~ational Defense*~Defence nationale

FLUOROALKYL SILOXANES AS LIQUID-REPELLENTFABRIC FINISHES

PART I111:THE DURABILITY OF THE COPOLYMERS AND

COMPARISONS WITH COMMERCIALLY AVAILABLEFINISHES Accession F or

NIS ,GRA&DTIC TAB'Unannouncedby Justification~

i.W. Bovenk &fl and B.V. Lacroix ByProtective Sciences Division Distribution/_

Availability CodesAvail and/or -

Dist Special

DEFENCE RESEARCH ESTABLISHMENT OTTAWATECHNICAL NOTE 83-4

PCN SPeptr I=3

148 Otwa

ABSTRACT

-ln this report the durability of liquid repellency properties impartedto fibrics by solutions of the copolymers of fluoroalkyl-substituted silanesand non-fluorinated silanes is examined. The best available commercialfinishes were examined at the same time and the results compared with those ofthe experimental finishes. The durability testing encompassed wear, washing,dry cleaning, and weathering. Although the siloxane copolymers wear well,they are somewhat infcrior to the commercial finishes after a number ofwashes. Much better durability to washing was obtained when a small amount ofresin was added to the finish, following the normal commercial practice. Theproperties found for the siloxane finishes indicate that they could be usefulin some circumstances. -

R98UME

(.n examine dans ce rapport la durabilit des propietas hydrofuges etoleofuges des tissus trait~s avec des solutions de copolymeres contenant dessubstituts fluoroalkyles silanes et des silanes non fluores. Par la meme

occasion, on a fait 1'evaluation des meilleurs finis commerciaux disponibleset on en a compare les resultats avec ceux qui ont 6ti obtenus dans le cas desfinis expe'rimentaux. Les essais de durabilit englobaient l'usure, leblanchissage, le nettoyage a sec et la re'sistance aux intemperies. Quoiqueles copolymeres siloxanes sont assez efficaces contre lusure, ils sontquelque peu infdrieurs aux finis ccmmerciaux apres un certain nombre deblanchissage. L'addition de petite quantitt de resine aux finis augmentesensiblement la rtsistance au blanchissage, comme c'est le cas pour lea finiscommercials. Les proprifteg trouvees dans le cas des finis siloxanesindiquent qu'ils pourraient Atre utiles en certaines ciroonstances.

iii

:'S

INTRODUCTION

1he present Canadian Chemical Warfare (CW) protective overgarmentutilizes an outer layer of nylon/cotton (50/50 wt %) fabric which needs to betreated with a fluorocarbon finish to give it liquid repellent properties (oiland water repellency and resistance to penetration by liquid phosphorus esters(phosphate resistance)). In an earlier report (1), a state-of-the-artliterature review of these finishes was presented. The finish currently inuse is Zepel B (E.l. Dupont De Nemours & Co. (Inc.)). This and most othercommercial oil-and water-repellent finishes utilize a series offluoroalkyl-substituted acrylates and methacrylates having a carbon-carbonbackbone (2). Due to the importance of the liquid-repellent barrier in the CWsuit, it became desirable to evaluate and extend a number of publications onf'luorokyl-substituted siloxanes (3-9). It was felt that these inorganicpolymers having a silicone-oxygen backbone could have properties which wouldbe more in keeping with a multi-purpose finish for military use.

Ten fluoroalkyl silane monomers comprising the best of those found inthe literature as well as some new ones whose molecular structure appeared tohold promise were synthesized (1). Polymer solutions were then formed andapplied to nylon/cotton (50/50 wt 5) and to cotton (10). Copolymers of thefluoroalkyl silanes with non-fluorinated silanes were found to be especiallyeffective. It was indeed found (10) that the Initial liquid-repellency valuesof some of the experimental finishes were better than those obtainable fromthe best of the commercial finishes.

The requirements for a good military finish, however, include that ofdurability. The literature contains very little information on this topic andthus, as described in this technical note, the best of the siloxane polymerswere submitted to extensive wear, washing, dry cleaning, and weathering tests.A brief summary of the results obtained at DREO for the durability of theoil-and water-repellency properties of the siloxane polymers has beenpublished recently in the open literature (11). In this technical note, thedurability of phosphate resistance is examined. Also, the sl1oxane-durabilityresults are compared with those obtained with some excellent commercialfinishes. The effects of added resin and of curing catalysts were assessed ina number of cases. Weathering tests were carried out.

Concluding statements are made regarding the usefulness of fluoroalkylsubstituted siloxanes as liquid-repellent fabric finishes.

I

I_________

2

EXPERINENTAL

The synthesis of the silanes _Lj2,nC1, and §2 (see Table 1 forstructures) have been described previously (1). The commercial finishes Zepelb and Zepel RN were obtained from E.l. Dupont De Nemours and Co. (Inc.) whileScotchgard FC 2'2 was obtained from 3M Co. The following were obtained fromCyanamid of Canada, inc. - Aerotex Resin MW, a melamine formaldehydecondensate; Aerotex Accelerator NX, a buffered magnesium salt; Aerotex ResinP-225, a hexamethoxymethylmelamine (solvent soluble); and Aerotex AcceleratorCycat 4040, an organic acid (solvent soluble). Mykon MRW-4 is a nonionicnon-rewetting surfactant obtained from Sun Chemical Corporation. The fabricused in this durability study was a nylon/cotton twist (50/50 blend, 170 gramsper square meter). It was designated as X74-438 (treated with olive green 107dye).

APPLICATION OF FINISH AND CURING OF FABRICS

Using a two-dip/two-nip procedure, fabric samples were padded on anAtlas padding machine (Type LW-5) to a wet pick-up of 70-100%. Afterpadding, the fabric samples were cured in a forced-air oven. For commercialfinishes, a 5 min drying time at 135C was used followed by a curing time of 3min at 171 0C. Fabrics treated with siloxanes were inserted into the oven atroom temperature and the oven temperature set at 1500C. Upon attaining 1500C,the samples were removed after 15 min. The treated fabrics were allowed tostand at room temperature overnight and then tested for oil-and waterrepellency and phosphate resistance.

DURABILITY TO WASHING, WEAR, DRY CLEANING, AND WEATHERING

Washing was carried out using an Atlas Launder-Ometer, Model B5,according to Canadian Standard Textile Test Methods, Method 19.1-h77, Washlest 1 (12). In this method, the samples (50 x 100 mm) are agitated In hotsoap solution containing stainless steel balls to provide mechanical action.One washing using this accelerated method approximates five launderings usinga domestic washing machine.

The effect of wear on fabric properties was examined using a wearmachine developed at DREO (13). Fabric samples (18 x 375 c) were sewn intoan endless belt and passed over the brushes and rollers of the machine underone-pound tension.

3

TABLE 1

Structures of the Silane Monomers and the FluorinatedComponent of the Commercial Finishes

A. Structures* of the Silane Monomers

Fluoroalkyl- Substituted MonomersEl CFs(CF2)eCONH(CH2) Si(OCaH5)s

F2 CFs(CF )sCONH(CH )$Si(OC2Hs)2(CS)3 CFs (CF2) COU(CUa) 3Si(OCifs) a

Non-fluorinated Co-monomers

Cl CHySi (OC2Hs)s

C2_ CHS (CHI) sSi(OC2HS)S

B. Structures of the Fluorinated Component of theCoumercial Finishes

~F3

* -l5am o nomers with three replaceable ethoxy sllax* eubstltuents formnetwork polymers whereas 12 with only two replaceable shlane substituent8forms linear polymers.

4

Dry cleaning was performed by slight modification of Canadian StandardTextile lest Method 29.1-H77 (12). The samples (6" x 6") were placedindividually in the containers of the Launder-Ometer. Perchloroethylene (150mL) and 100 steel balls were added. After running at 270C for 30 min thecontainer was drained and the samples were dried between two paper towels.After air drying, the samples were dried at 900C for 10 min.

Weathering was carried out on swatches (8 x 12 inches), exposed on astand on the roof of a three story building, inclined at 450 to the horizontaland facing south. They were fixed securely at each corner.

PAD FORMULATIONS

(i) Zeoel B

The padding emulsion consisted of 23 g of Zepel B (13% solids) to which77 g of water had been added with stirring.

(ii) Zepel B + Resin

This emulsion consisted of 23 g Zepel B, 3.75 g Aerotex Resin h, 0.75 g

Aerotex Accelerator MX, 0.3 g Mykon NRW-4, and 72.2 g water.

(iii) Zenel RN and Zenel RN + Resin

Same as above, except that Zepel B is replaced with Zepel RN emulsion(13$ solids).

(iv) Sootchgard FC 2_2

This finish consisted of 10 g FC 232 (30% solids) to which 90 g of waterhad been added with stirring.

(v) Scotchaard FC 2;2 + Resin

Added together with stirring were 10 g FC 232 (30% solids), 87.; gwater, 2.0 g Aerotex Resin HW, 0.4 g Aerotex Accelerator MX, and 0.3 g Mykon

(vi) Formulations of F1 Cl and F1 + C2

f1 (5.22 g) and R2 (0.78 g) (70/30 mole % ratio of L1/J, weights wereadjusted accordingly when 01 were used) were weighed into a 250 mL round-bottomflask. Tetrahydrofuran (120 mL) was added to dissolve the monomers. Sodiumhydroxide solution (3 mL, 40 mg NaOH/mL) was added dropwise during vigorous

I stirring. The solution was stirred for 24 h and then neutralized with 20%aqueous sulphuric acid solution. After filtering, the polymer solution wasapplied to the fabric.

•.4

5

(vii) Formulations of F2 + C1. F2 + C2. and F! . C1

As above for (vi) except that isopropanol was used as the solvent and astirring period of 2.5 h was utilized.

(viii) Formulations of Siloxanes + Resin

After polymerization of the copolymers in the usual fashion (5%wt/voiume solids), the solution was diluted with the polymerization solvent to4 g solids in 100 mL of solution. One gram of Aerotex Resin P-225 and 0.25 gol Aerotex Accelerator Cycat 4040 (active catalyst 40$ in isopropanol) wasthen added with stirring.

WATER AND OIL REPELLENCY TESTS

1he American Association of Textile Chemists and Colorists (AATCC) Testhethods 118-1966 (oil repellency) and 22-1967 (water repellency) (14) wereemployed in this study. The oil repellency test was modified to include halflevels. A short sumary of these tests has been included in ref. 10.

PHOSPHAIE RESISTANCE TESI

The resistance of treated fabrics to wetting by organo-phosphorusliquids was evaluated using a test developed at DREO by Hart and Fuoco (15).Small drops of the model test liquids trimethyl phosphate, triethyl phosphateand tri-n-propyl phosphate were placed on a flat fabric sample. After onehour, the appearance of each drop was noted visually and a rating assigned tothe fabric based on the overall appearance of the three types of droplets(rating scale 0-9). A rating of 7 or above is considered good and means thatonly one of the liquids exhibits spreading or wicking. A rating of 3 or lessindicates that all three of the liquids exhibit wetting to some extent.

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6

RESULTS AND DISCUSSION

Only the most promising experimental finishes (described in ref.10) weresubjected to durability testing. These were the copolymers of the fluoroalkylsubstituted silanes, fU, FU and FI with the non-fluorinated alkyl silanes C1and 2 (see Table 1 for structures). The exact structures of the commercialpolymeric finishes were proprietary information. From patents and reviews (2,16, 17), it was known that these are fluoroalkyl substituted esters as shownin Table 1. Generally x was 1 or 2 and y could be 5, 6, or 7. They could becopolymerized with or added to non-fluorinated acrylates.

All of the values discussed in this report were for nylon/cotton (50weight %) fabric. Table 2 gives the initial liquid repellencies obtained withthe siloxane copolymers and with the best of the commercial polymericfinishes. The siloxane copolymers P1, P2 and P3 all had equal or slightlybetter initial repellencies than the commercial finishes P8-P13. When 60% ofthe non-fluorinated alkyl silane §2 was utilized in P4, the phosphateresistance dropped from 9 to 4. When a linear siloxane was used, P5, thephosphate resistance dropped to zero while the water and oil repellencies wereunchanged at 100 and 6/7. This is an interesting finish since water and oilrepellency could be obtained while the wicking principlelcould be used withphosphate. This is the reason for the inclusion of this material in thisdurability study. When 60% Z1 was used, P6 (compare with P5), the oilrepellency remained at 6/7, however, the water repellency had degraded to 90.As observed before (10), when the fluoroalkyl substituent was shortened by twoF2 groups (M? (compare with P1)), the phosphate resistance dropped to zero

while the water and oil repellencies dropped to the next lower values.

Ihe commercial finishes Zepel B, Zepel RN, and FC 232 all had waterrepellencies of 100, oil repellencies of 5/6 and 6, and phosphate resistancevalues of 9. The use of a resin had no effect on the initial repellencies butwas important in providing durability (vide infra).

DURABILlT 10 WASHiNG

Table 3 gives the durability to washing of P1-PI3. The durability ofall of the siloxane copolymers, P1-P, to washing was unsatisfactory. By thesixth wash or earlier, water repellency had dropped to values as low as 0 andno values higher than 70 were obtained. The oil-repellency values after sixwashes for P1-P4 and P7 generally had dropped to the 1 or 2 level. The linearcopolymers, P5 and P6, on the other hand, maintained reasonable oil-repellencyvalues of 4/5-5/6. For the siloxanes, no values of phosphate resistancehigher than 1 were found after six washes.

'For the Canadian CW protective overgarment, the outer layer must be phosphateresistant. The CV protective garments of other countries utilize a wickingprinciple which requires that nerve agent droplets be spread to facilitate4 evaporation.

I

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7

TAN 2

Initial Liquid Repelleucies

Desiguation Couposition of z water Oil PhosphateCopolymer Mdd-on Repellency Repelency Resistance

A. 511oxaue- Copolpers-

P1 F1 701 - Cl 30Z 4.2 100 6/7-7 9P2 1 40 - 1 60% 4.4 100 6/7 9

"*1 P3 PI 70Z - C2 30% 2.4 100 6/7 9P4 401- C260 4.5 100 6 4PS # 70% - 30% 2.8 100 6/7 0P6 ' 4OZ - l602 2.8 90 6/7 0P7 i 70[ - C 130Z 2.8 90 6 0

B. Comercial _ltnjfes*

P8 Zepel B 4.0 100 5/6 9P9 Zepel B + resin 5.4 100 5/6 9PIO Zepel RN 4.2 100 5/6 9Pll Zepel Ri + resin 6.6 100 5/6 9P12 FC 232 4.7 100 6 9P13 FC 232 + resuin 5.2 100 6 9

* Zepel ] and Zepel RN are tirade nams of 39 1 . Dupeut Dt Nlxur.& Co. (Pnc.). IC 232 is a trade nam. of 3K Co.

:C4 Oaf In a~ 0 Op & 0 0 in1%O O'-- O.r4 P%.ll -4 innN 04 r *0 r.-. 0 u o 0 %O%

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in comparison, the commercial finishes, P8-P?, maintained waterrepeilencies of 100 in all cases and after six washes lost no more than onelevel of oil repellency. Zepel b maintained a perfect reading of 9 forphosphate resistance both with and without added resin. Zepel RN, however,suffered a degradation in phosphate-resistance to 6 (P1O) and 4 (P11) by thesixth wash. FC 2%2 alone had a phosphate resistance value of 6 (P12) at thesixth wash while a level of 9 was maintained if added resin was utilized

thus, in comparison to the commercial finishes, the siloxanes weredefinitely inferior when applied without added resin. As shown in lable 4,however, much better results were obtained for durability to washing whena small amount of resin was added to the siloxane copolymer solutions. Thevalues shown for P1'(Table 4) were a great improvement over that found forPi (Table ',). Water repellency was unchanged from 100 after 6 washes whileoil repellency dropped from 6 to only 5/6. These values were as good or betterthan those found for the commercial finishes P8-PI?:. The phosphate resistance,however, had degraded to 6 after six washes. This was better than that foundfor some of the commercial finishes but not as good as the value of 9 maintainedby P&, P9 and P1?:. Although P " was much better than P-- it was not as good asPFl. P5" was dramatically better than P5 and the values of 100 and 6/7 after sixwashes were the best of any in this study. The phosphate-resistance value waszero with or without resin. Even the values found for P7' were a considerableimprovement over the values found when no resin was used.

DURABILI3Y IC WEAR

table 5 shows the values obtained when nylon/cotton fabrics treated withPi-PI were subjected to wear tests. All of the finishes suffered seriousdegraoation following wear. In terms of oil and water repellency, the resultsshowed degradation after 20 h wear time to values generally in the range of70-6C for water and 3/4-5 for oil repellency with the silanes retainingsomewhat better oil repellencies than the commercial samples. The commercialfinishes were superior in phosphate resistance, the best having degraded to 6(P9), 4 (11) and - (P1?:). The best siloxane finish, P1, still had a value of4 at 16 h wear time but had decreased to 1 at 20 h. No significantimprovement in durability to wearing was obtained when 1% of the siloxanecopolymer was replaced by resin.

DURABILITY T0 DRY CLEANING

As shown in lable 6, the siloxanes had good durability to dry cleaning.host values dropped only a level or two even after six dry cleanings. Theeffect of resin in both the commercial and the siloxane finishes was minimal.1he best siloxane, Pl', and the best commercial finishes P8 and Pg, had nearlyidentical values of 90, 4/5-5/6, and 8 after six dry cleanings.

, Im ' " . . . i - i ......... ......

TABLE 4

The Effect of Added Resin on the WashingDurability of Siloxane Copolymers

Designation Composition Z Number of Launder-Ometer Washingsof Copolymer Add-On 0 1 2 3 4 5 6

100 100 100 100 100 100 100Pit Fl 70%-Cl 30% 4.0 6 6 5/6 516 5/6 5/6 5/6

+ Resin 9 8 5 5 6 6 6

100 100 100 100 100 100 100P31 Fl 70%-C2 30% 3.9 6 6 5/6 5/6 5/6 5/6 5

+ Resin 9 6 6 6 5 5 4

100 100 100 100 100 100 100P51 F2 70%-Cl 30% 2.9 6/7 6/7 6/7 6/7 6/7 6/7 6/7

+ Resin 0 0 0 0 0 0 0

100 90 90 90 90 90 80P7' F3 70%-Cl 30% 5.6 5/6 5/6 5/6 5/6 5/6 5/6 5/6

+ -Resin 0 0 0 0 0 0 0

12

TABLE 5

Durability to Wear

Designation Composition of Wear Time (hours)Copolyi ,er 0 4 8 12 16 20

100 80 80 80 80 80P1 Fl 70%-Cl 30% 7 6 5/6 5 5 4/5

9 5 4 4 4 1

100 80 80 70 70 70P2 Fl 40%-Cl 60% 6/7 4/5 4/5 3 2 2

9 1 1 1 0 0

100 80 80 80 70 70P3 Fl 70%-C2 30% 6/7 6 5/6 5 5 4/5

9 4 4 1 1 1

100 80 80 70 70 70P4 Fl 40%-C2 60% 6 5/6 5 4/5 4/5 4

4 1 0 0 0 0

100 80 80 70 70 70115 F2 70%-Cl 30% 6/7 6/7 6 5/6 5/6 5

0 0 0 0 0 0

90 70 70 70 70 70P6 F2 40%-Cl 60% 6/7 6 516 5 5 4/5

0 0 0 0 0 0

90 80 80 70 70 70P7 F3 70%-Cl 30% 6 6 5/6 5 5 4/5

0 0 0 0 0 0

100 100 90 80 80 80P8 Zepel B 5/6 5 4/5 4 3/4 2

9 4 4 4 4 1

300 100 100 100 90 80119 Zepel B + Lesin 5/6 5/6 5 4 3/4 3/4

9 8 8 6 6 6

100 80 80 80 80 701110 Zvp#.l RN 5/6 5 4/5 4 3 3

9 6 5 5 5 2

100 100 100 90 80 80PI Zepel RN + Re, sin 5/6 5 4/5 4/5 4 3/4

9 7 5 5 5 4100 80 80 80 80 70

P12 FC 232 6 5 4/5 4/5 4 49 4 4 4 1 1

100 100 90 80 80 80

i'13 FC 232 + Rcaln 6 5/6 5/6 5 4 49 6 6 6 3 3

13

TABLE 6

Durability of Siloxanes, Siloxanes with Resinand Commercial Finishes to Dry Cleaning

Designation Composition of N Number of Dry CleaningsCopolyn-cr Add-On 0 1 2 3 4 5 6

100 100 90 90 90 90 90P1 F1 70%,Cl 30% 4.4 6 6 6 5/6 5/6 5/6 5

9 8 8 8 8 8 8

100 100 100 90 90 90 90P1' P1 + Resin 4.0 6 6 5/6 5/6 5/6 5/6 5/6

9 9 9 9 9 9 8

100 100 90 90 90 90 90P3 Fl 70%,C2 30% 4.2 6/7 6/7 5/6 5/6 5/6 5/6 5/6

4 4 4 4 4 4 4

100 100 100 90 90 90 90

P3' P3 + Kesin 3.9 6 5/6 5 5 5 5 59 9 9 9 5 5 5

100 100 90 90 90 90 90P5 F2 70%,CI 30% 3.1 6/7 6 6 6 6 6 6

0 0 0 0 0 0 0

100 100 100 100 100 100 100P5' P5 + Resin 2.9 6/7 6/7 6/7 6/7 6/7 6/7 6/7

0 0 0 0 0 0 0

90 90 80 80 80 80 80117 F3 70%,C] 30% 5.3 5/6 5/6 5/6 5/6 5/b 5/6 5/6

0 0 0 0 0 0 0

100 90 80 80 80 80 80P7' P7 + Resin 5.6 5/6 5/6 4/5 4/5 4/5 4/5 4/5

0 0 0 0 0 0 0

100 100 100 100 100 100 9018 Zepel B 4.0 5/6 4/5 4/5 4/5 4/5 4/5 4/5

9 8 8 8 8 8 8

100 100 100 100 100 100 90P9 Zepel II + Resin 5.4 5/6 4/5 4/5 4/5 4/5 4/5 4/5

9 9 8 8 8 8 8

100 100 90 90 80 80 80£1O Zepel RN 4.2 5/6 4/5 4/5 4/5 4/5 4/5 4

9 9 8 8 7 4 4

100 100 100 90 90 90 80PH1 Zepel RN + Resin 6.6 5/6 4/5 4/5 4/5 4/5 4 3/4

9 5 4 4 4 4 4100 100 90 90 90 90 80

I112 FC 232 4.7 6 6 5/6 5/6 5/6 4/5 4/59 9 9 9 9 6 6

100 100 100 100 100 100 100P13 FC 232 4 Resin 5.2 6 5/6 5/6 5/6 5/6 5/6 4

9 6 6 6 6 6 6

j .a

14

DURAblLITY TO WEATHERING

As shown in lable 7 noticeable degradation in both oil and waterrepellency was experienced by the treated fabrics when subjected toweathering. For the siloxanes, water repellencies generally fell from 100 to70 (P5 and P5' fell to 50) while oil repellency fell to 4 or 4/5 after threemonths. Note that nearly all of the degradation occurred during the firstmonth and the values were essentially stable after that. Phosphate resistancefor P1, PI', P3 and P3' fell from 9 to the medium range values of 4-6.Fabrics treated with siloxane finishes utilizing resin maintained the samewater repellencies and the same or slightly lower oil and water repellenciesthan those without.

In comparing the commercial finishes, P9 and Pl3, with the siloxanefinishes, P'' and Ps', it is seen that P9 maintained better values at the oneand two month stages, however, at the three month stage, the liquid-repellencyvalues were essentially the same. For P13, the results over the three monthperiod were comparable for water and oil repellency but were poorer forphosphate resistance, having dropped to 1-2 at three months.

INORGANIC CURING CATALYSTS

The inorganic curing catalysts zinc chloride (18), stannous octoate (18)ano tetrabutyl orthotitanate (19,20), upon occasion, have been used with bothfluoroalkyl and non-flucroalkyl substituted siloxanes. It was found in thiswork that the use of each of these catalysts with the copolymer solutions ofE Cl, LI + 1J, AND fU + C1 made little or no difference to the eventualproperties of the treated fabrics.

FIRE RESISTANCE TESI1NG

Fabric samples treated with the siloxane copolymers P1-P7 (see Table 2)were tested for flame resistance using a vertical burning test (CanadianStandard Textile lest hethods, Method 27.1-M77 (12)).. It was found that atthese add-ons (2.8-4.5) little or no fire resistance was imparted to thefabrics. It must be noted that this test is a severe one because theprocedure creates conditions favourable to combustion.

1. lhc durability of the fluoroalkyl substituted siloxanes asliquid-repellent finishes on nylon/cotton (50/50 wt %) to washing, wear, drycleaning, and weathering has been examined. Several excellent commercialfinishes were examined at the me time.

* S __ ___,_

15

TABLE 7

Durability to Weatherin

Composition of 2 Wathering PeriodDesignation Copolymer Add-on Initial 17-06-80 21-07-80 26-08-80

17-07-80 21-08-80 26-09-80

P1 Fl 702, Cl 302 4.9 100 70 70 706/7 415 4 4

8 6 6 6

P1' P1 + Resin 4.7 100 70 70 706/7 4/5 4/5 4

9 5 5 5

P3 Fl 70%, C2 30% 4.8 100 70 70 706/7 4/5 4 4

9 6 6 6

P3' P3 + Resin 4.8 100 70 70 706/7 4/5 4/5 4

9 5 4 4

P5 F2 70%, Cl 30% 3.2 100 70 70 50617 415 4 4

0 0 0 0

P' P5 + Resin 3.2 100 70 70 506/7 4/5 4/5 4

0 0 0 0

P7 F3 70%, Cl 30% 3.0 90 70 70 705/6 5 4/5 4/5

0 0 0 0

P' P7 + Resin 3.5 100 70 70 705/6 4/5 4/5 4

0 0 0 0

P9 Zepel B + Resin 4.8 100 80 80 705 4/5 4 49 9 9 6

P13 FC 232 4 Resin1 5.2 100 70 70 705/6 5 4/5 49 6 3 1-2

1 The results for P9 and P13 in this table were provided by R.P. Fuoco andwere carried out in the same time periods indicated.

16

2. it has been found that the siloxanes do not exhibit satisfactorydurability to washing when used alone, but much better properties were foundwhen a resin was used. It is customary to use a resin with polymer finishes,and when a resin was used, the best network siloxane finish maintained aslightly better oil repellency but a slightly lower phosphate resistance thanthe best commercial finish. The linear siloxane maintained perfect waterresistance and the excellent oil repellency of 6/7 remained unchangedthroughout the six washings. This finish, however, had an initial phosphateresistance of zero.

All finishes, both experimental and commercial, experienced seriousdegradation of properties following wear. The best of the siloxanes retainedslightly better oil repellencies while the commercial finishes retained betterphosphate resistance.

4. The best experimental finishes and the best commercial finishes

exhibited identical liquid repellency values upon being subjected to repeateddry cleanings.

5. In terms of oil and water repellency, the linear siloxane finish (E270s, Ll -0W, when used with added resin, had nearly ideal values. Itmaintained unchanged values of 100 and 6/7 (water and oil repellenciesrespectively) upon repeated washings and dry cleanings and had values of 70and 4/5 after 20 h of severe wear. This finish, however, would not besuitable for use on the Canadian CU protective overgarment since the presentconcept requires a finish with phosphate resistance. The CW protectivegarments of other countries, however, utilize a wicking principle in which itis required that nerve agent droplets be spread to facilitate evaporation. Inthis circumstance, this could be an excellent finish. It could also be usedin commercial situations where only oil and water repellency is required.

6. In general, the experimental siloxane finishes are not significantlybetter than the commercial finishes currently in use. They could beconsidered desirable when either a disposable protective suit is utilizedand/or when only oil and water repellency are required.

4

.0!

17

ACKhOWLEDGEMIIS

The authors are grateful to Mr. R.P. Fuoco for helpful discussionsconcerning commercial finishes, resins and catalysts.

REFERENCES

a. J.h. bovenkamp. Defence Research Establishment Ottawa Report No. 802(1979) (U).

2. b.. Lichstein. Chapter 1-, 'Stain and hater Repellency of Textiles'in 'Surface Characteristics of Fibers and Textiles'. Part 11. Ed.K.J. Schick, Marcel Dekker lnc. N.Y. (1977).

'. h.L. hasley and A.G. Pittman. U.S. Patent 4,029,867 (1977).

4. A.G. Pittman and h.L. haslcy. British Patent 1,344,3'6 (1974).

5. halco Chcmical Co. British Patent 1,267,224,(1972).

6. A.G. Pittman and h.L. Wasley. British Patent 1,178,743 (1970).

7. A.G. Pittman and h.L. hasley. U.S. Patent -,422,131 (!969).

6. G.h. holbrook and C.h. Steward. U.S. Patent 3,015,565 (1962).

9. G.h. holbrook and C.h. Steward. U.S. Patent 3,012,006 (1961).

iW. J.W. bovenkamp. Defence Research Establishment Ottawa Reportbo. 0C4 (1979) (U).

11. J.h. bovenkamp and b.V. Lacroix. Ind. Eng. Chem. Prod. Res.Dev. 2, l30 (1981).

12. lextile lest Methods. National Standard of Canada. CAN 2-4.2-K77. Published by Canadian Government Specifications board,Lttawa, Gntario KIA OS5 (1977).

1,. J.A. Hart. Defence Research Establishment Ottawa. Unpublishedresults.

14. Technical Manual of the American Association of Textile Chemistsand Colorists. Vol. A6 (1970).

I Ii . ' - V j

18

15. J.A. hart and R.P. Fuoco. Defence Research Establishment Ottawa.Unpublished results.

16. John h. Palmer. lextile Processing and Finishing Aids. RecentAdvances. Noyes Data Corporation, New Jersey (1977).

17. C.S. Sodano. %ater and Soil Repellents for Fabrics. Noyes DataCorporation, hew Jersey (1979).

16. J.A.C. Watt. J. lextile 1nst. 51, T1 (1960).

19. bradford Dyers' Association Limited. British Patent 708,821 (1954).

20. honsanto Chemicals Ltd. british Patent 723,989 (1955).

,;-. .

19

UNCLASSIFIDS~euity Claselifatren

DOCUMENT CONTROL DATA R A 0ISec'utity classifiscation of litl., body of jatract aid indesoft antratn most hem entered whvien the overall dricustbot si classifued)

)GIAIING ACTIVITY 20a. OCUME NT SECURITY CL ASSIFWSAT00ONI' ile~ece Research Establishment Ottawa i GROU

3. DOCUMENT TITLEFluoroalkyl Siloxanes As Liquid-Repellent Fabric Finishes. Part Ill.* TheDurability of the Copolymers and Comarisons with Commercially Availabi. Finishe

4. DESCRIPT IVE NOTES (Type of report anid incls"v duata)Technical Note

bt AUTHOR(S) MLast name. first name, middle initial)

BOVENKAWE, John W. and LACROIX, Benoit V.

6. DOCUMENT DATE 7a. TOTAL NO. OF PAGES 7b. NO 1 REFSSEPTEMBER 1983 181Ba. PROJfCT OR GRANT NO.9. ORIGINATOR*S DOCUMENT NUMBERIS

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13. ABSTRACT

In this report the durability of liquid repellency properties Impartedto fabrics by solutions of the copolymers of fluoroalkyl-substituted silanesand non-fluorinated silanes is examined. The best available comrcialfinishes were examined at the sam time and the results compared with those ofthe experimental finishes. Th, durability testing encompassed waring,washing,, dry cleaning, and weathering. Although the siloxane copolymers wearwell, they are somewhat Inferior to the comrcial finishles after a number ofwashes. Mu~ch better durability to washing yas obtained when a small amountof resin was added to the finish, as is the usual commercial practice. Theproperties found for the siloxmne finishes indicate that they could beuseful in some circumstances.

77 "l

20

UNCIASSIFIDSecurty Cteshifhetite

Fluoroalkyl 81lomanesCopolymersLiquid RepellencyWater RepellencyOil RepellencyFabric FinishesCoumercial FinishesPhosphate ResistanceWeatheringWearing

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