FI59804C - AV ORGANISKA POLYMERFIBRER BESTAOENDE KOMPOSITION INNEHAOLLANDE EN BRANDHAEMMANDE BESTAONDSDEL - Google Patents

Description

| * Λ | §Τ * | [Β] (11) ANNOUNCEMENT r g η λ *

Ma 1 j *; utläggningsskrift 3 7oU4 fr: töni v (51) Kv.lk.3 / lnt.CI. C 0Ö I 5/5 ^ FINLAND - FINLAND (21) Ρ «·" «ι> '* ι <·'" «1 * - PaMntauuöknlng 1174/72 (22) H» k «miipllyi - Ansftknlngsdtg 2 5 · 04.72 ^ (23) Alkupilvl —Glltlghetsdag 25 · θ4 · 72 (41) Become Public - Bllvlt offentllg 26.10.73 _ *, (44) Nlhtivlkslpenon | a kuul.Julkalsun pvm. -, n

Patent · och registrstyrelsen 'Anaökan utlagd och utl.ikrlft * n publlcerad 30.06.81 (32) (33) (31) Requested Privilege — Begird prloritet (71) Mobil Oil Corporation, 150 East U2nd Street, New York, N.Y. 10017, USA (72) James Jeter Anderson, Metuchen, New Jersey, Wendell Mason Byrd, Jr., Charleston, South Carolina, Vasco Gomes Camacho, Iselin, New Jersey, USA (7 * 0 Berggren Oy Ah The present invention relates to a blend of organic polymeric fibers containing a flame retardant component. This invention relates to a blend of organic polymeric fibers containing a flame retardant component.

It has been recognized for many years that polymer preparations, whether natural, regenerated or synthetic, pose a fire hazard. This danger has been observed in textile components in particular, as numerous fatal accidents and serious injuries have resulted from the ignition of clothing and household furniture.

The difficulty of flame retardant textile blends has been recognized by many researchers (cf. Nametz, R.C., Ind. And Eng. Chem.,

Vol. 62, no. 3 ·, March 1970, pages 41-53; Endler, A.S. and Hurwitz, M.L. Amer. Dyestuff Reporter, Vol. 56, no. 19, September 11, 1967, pages 23-26; Liggett, R.W., Southern Research Institute Bulletin, Vol. XXI, no. 1, 1968, pages 3-6; Leblanc, R.B., Amer. Dyestuff Reporter, Dec. 30, 1968, pp. 35-38; Reeves, - W.A. et al., Textile Chemist & Colorist, Vol. 1, no. 17, 13 August 1969, pages 24/365, 366/25, 26/367, 368/27, 28/369) · The problem is particularly severe with a combination of carbonizing fiber such as rayon or cotton and fusible fiber such as polyester or nylon. When ignition of such combinations, carbonized residues of the second fiber keep the fusible fiber in the combustion zone. This phenomenon has been termed the "vaulting effect" and results in a more hot system than that observed with either fiber alone.

It was recently reported in the American Dyestoff Reporter (March 24, 1969, pages 21-23) that polyester fiber blends, which are self-extinguishing as a one-component fabric, burn when combined with cotton treated with a flame retardant. According to the notification, polyester / cotton blends can only be made flame retardant if both fibers are treated with a flame retardant.

Several compounds have been proposed for use as flame retardants, but to our knowledge none of them have been present or proposed in the compositions of the present invention. Flame retardants are disclosed, for example, in U.S. Patents: Coover et al., 2,875,229; Kolka, 2,866,808; Carpenter et al., 3,324,205; Taylor et al., 3,412,052 and Redfarn 3,471,318.

Therefore, the present invention is directed to fiber blends of organic polymers which contain, as flame retardant ingredients, a compound of the formula R 'r 1 "1, M f \?? V \

(XCHCHO) -β- (OCHCH) -O-) I

J w \ 1 / L Jz n.

or a mixture of such compounds wherein X is halogen, R is H, -CH 2 or CH 2 X provided that when one group R is other than H, the adjacent R is H, R * is X, alkyl, haloalkyl, alkoxy, aryl, haloaryl or arylalkyl group, a is 0, 1 or 2, n is 1, 2 or 3, w is 0, 1, 2 or 3, y is 1, 2 or 3j z is 0, 1 or 2 , and the sum y + z is 3, 59804 and the invention is characterized in that one of the organic polymers of the fiber mixture contains 2 to 50% by weight of a compound of formula I above or a mixture of such compounds.

Phosphorothioates The phosphorothioates of the formula I used herein are those disclosed in Finnish patent application ή: ο 1637/70. They contain halogen and are known from at least one P = S bond and the absence of a P = O bond.

Phosphorothioates can be prepared by reacting phosphorus trihalides with alkylene oxide to form tris- (haloalkyl) phosphites, and the latter can then be reacted with sulfur to form the corresponding phosphorothioates.

Another suitable process is described in U.S. Patent No. 2,724,719, which involves the reaction of an alkylene oxide and a thiophosphoryl halide in the presence of a phosphorus trihalide catalyst.

Another typical process involves the reaction of an alkylene oxide and a phosphorus trihalide in the presence of an amine catalyst followed by reaction with sulfur, as disclosed in U.S. Patent No. 2,866,808.

Other phosphonates can be formed by reacting halophenol, haloalcohol or a mixture of halophenoxyalcohol and haloalcohol with phosphorus trihalides and then reacting the resulting reaction product with sulfur.

Alternatively, phosphorothioates where z is 1 or 2 can be prepared by reacting a phosphorus trihalide with a halophenol or halophenoxy alcohol to form the corresponding phosphorus halodite or phosphorodihalodite and then reacting it with alkylene oxide to form a phosphite and then sulfur.

59804 4

Typical alkylene oxides or epoxides that can be used to form the desired phosphorothioates include ethylene oxide, propylene oxide, epichlorohydrin, and epibromohydrin.

Typical halophenols, haloalcohols, and halophenoxy alcohols used to prepare the desired phosphorothioates include: chlorophenols, bromophenols, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,4-dibromophenol, chloroethanol, bromoethanol, 1-chloro, 2-chloro chloro-1-propanol, 1,3-dichloro-2-propanol, 2,3-dichloro-1-propanol, 1,3-dibromo-2-propanol, 1-chloro-3 'bromo-2-propanol, 2- (chlorophenoxy) ethanol, 2- (2,4-dichlorophenoxy) ethanol, 1- (chlorophenoxy) -2-propanol, 2- (chlorophenoxy) -1-propanol and 2- (2,4-dibromophenoxy) ethanol.

Typical phosphorus halides used to form the desired phosphorothioates include: phosphorus trichloride, tribromide and triiodide, thiophosphoryl chloride, bromide and iodide.

It is to be understood that when alkylene oxides other than ethylene oxide react with a phosphorus halide, there are two distinct ways to open the epoxy ring to form the haloalkyl ester portion of the phosphorothioates. Just as the asymmetric alkylene oxide is reacted with phenol, two isomeric forms of phenoxyalkanols are formed, which in turn give two different forms of phenoxyalkyl ester group when further reacted to form phosphorothioates. The two possible structural variants A and B resulting from the alkylene oxide reaction are shown below:

Group Structure A Structure B

haloalkyl ester XCHoCHROP (S) --- RCHXCHnOP (S) ^ C.

phenoxyalkyl ester --- P (S) OCKRCH2Q- --- P (3) CCH2CKR0-

Typical phosphorothioates are shown below in Table I for purposes of illustration. The main manufacturing method is referred to as additional characters.

Table I

Compound No. Structure 1 / ch, (ck2ci) cho7T (? S

2 (C1CH2CH2O) 3PS

3 / rciCH2) 2CH073PS

4 _ / TclCIT2) 2CH072? (S) OCH (CH2Cl) CH2 + (C1CH2) 2-CHOPS - / _CH (CH2C1) Cl

5 (BrCII2CH2O) 3PS

5 59804

6 / CH3 (CH2Br) CH073PS

7 44% / Tcich2) 2cho72ps C1CH.CHO2 I CH2

25% (rClCH2) 2CH073PS

19 Ä (C1CH2) 2CHOP (S) (0 (pHCH2Cl) 2 ch3 3% (C1CH2CHO) 3PS CH3 and the remaining high-boiling products / -C19 Cl - <^> \ - OCH2CH2OP (S) / ÖCHCCH2Cl) - \ - ' ch3_7- / 5CH (CH2) 2-7

Polymeric

The flame retardant (PR) polymer preparation itself can be used as a flame retardant in blends they form with the same or other non-FR polymers with substantially similar results to distributing the same amount of flame retardant evenly throughout the blend.

Non-flame retardant materials suitable for blending with the FR polymer preparation may be natural, regenerated or synthetic. Natural materials include cotton, cellulose, paper, silk and wool. Regenerated polymers include viscose rayon and "copper ammonia rayon". Typical synthetic materials include cellulose ester such as cellulose acetate, cellulose acetate butyrate, polyurethane, polyvinyl alcohol, nylon type polycarboxamides, caprolactams, polyacrylonitrile, polyethylene, polypropylene and polyesters. Preferred polymeric materials include cotton, viscose rayon, cellulose, nylon-type polycarboxamides, caprolactams, polyacrylonitrile, cellulose acetate, silk, and modacrylics.

It has been found that the non-flame retardant polymeric material of the blends may be free of the flame retardant or may contain a flame retardant in an amount insufficient to provide any substantial flame retardant effect.

The polymeric preparations containing the flame retardants of the present invention can be used to improve the refractory properties of the various components of the above polymeric materials treated with the flame retardants.

The preferred physical form of the components used to make the compositions of this invention is fibrous in nature, but other forms such as films, flakes, and coatings may be used.

6 59804

Textile fiber blends can be made by any suitable manufacturing step, such as spinning, twisting, weaving, or knitting. The mixing of the fibers can also be performed during the manufacture of non-woven fabrics. Any method of bringing the components of the mixture into close contact with each other can be used. The blends can be made using one or more fiber forms well known in the art, including monofilaments, strands, ropes, staples, spun, or woven yarns to produce the desired flame retardant textile end product.

Consideration may also be given to the use of flame retardant fiber blends prepared by post-treating flame retardant-free fiber or fabric blends in which the phosphorothioate flame retardant is preferably absorbed or "attached" to a single fiber component.

Other flame retardant polymer blends, including blends of fibrous and non-fibrous or non-fibrous and non-fibrous polymeric forms, can be obtained by suitable methods such as coating, laminating, gluing or compression molding to achieve an effective degree of blending of the blend components.

Flame retardant cellulose preparations are recommended.

The following examples illustrate the compositions of this invention.

Example 1

Combustion properties of non-flame retardant polyester and viscose rayon blends

Mixtures were prepared by braiding (crochet chain loop) a total of four strands of 91.5 cm of commercial flame retardant polyester yarn weighing 0.37 g / m and / or commercial flame retardant viscose rayon yarn weighing 0.27 g / m. Each strand was first twisted open separately, placed as close together as possible, and twisted again before braiding to achieve maximum mixing of the different fibers. The approximate dimensions of the braids prepared in this way were 4.0-6.4 mm in diameter and 12.5-15 cm in length.

The combustion properties of each braided product were determined by the method described below:

Each braid sample was placed on a simple spring clamp. so that 5 cm of the braid extended over the fastener. The free end of the 5 cm overhang was ignited with a small gas burner. The fire resistance of the excess 7 59804 was tested in one or more of the following defined positions:

Direction of flame propagation after ignition of free end

Position 0 ° down, 90 ° to the horizontal 45 ° down, 45 ° to the horizontal 90 °. horizontally 135 ° upwards, 45 ° to the horizontal l80 ° upwards, 90 ° to the horizontal

The flame was held at the edge of the free end until the braid burned in the flame (usually a burning time of 5-10 seconds was required). The ignition flame was then removed. If the flame progressed to the fixture, the sample was considered to be self-extinguishing (NSE) in this position. If the sample self-extinguished (SE) before the flame reached the holder, it was re-ignited as originally. If the sample was SE before the flame reached the fixture after the second ignition, it was considered to be SE in this position.

In general, all preparations were first tested at 9 ° C.

If they were found to be at an NSE angle of 90 °, they were tested sequentially at the 45 ° and 0 ° positions. If the sample was found to be SE at an angle of 45 °, this was considered to be the maximum angle at which the sample could be SE and this was marked as such. However, if the first sample tested at a 90 ° angle was found to be SE, the preparation was tested sequentially at the 135 ° and 180 ° positions. At the end of the combustion test in each position, the burnt end was cut off and the braid was placed back in the fastener so that a 5 cm protrusion was obtained for testing in the new position.

Every effort was made to prevent the sample from twisting or bending during the free combustion phase, which, if it occurred, could result in a change in the intended angle of combustion. This was accomplished by maintaining an appropriate burn angle while holding the unsupported end of the burning sample with metal pliers in an area that was not in the way of the advancing fire front.

To clarify the classifications of combustion properties in this and the following examples, the table below shows the combustion properties and overall classifications determined for each position.

Tested position (performance) Combustion classification 90 ° (NSE), 45 ° (SE) 45 90 ° (NSE), 45 ° (NSE), 0 ° (SE) · 0 8 59804

90 ° (NSE), 45 ° (NSE), 0 ° (NSE) NSE

90 ° (SE) *, 135 ° (NSE) 90 90 ° (SE), 135 ° (SE), 10 ° (NSE) 135 90 ° (SE), 135 ° (SE), 130 ° (SE) l80

An exception was made when the sample was found to be at an angle of SE 90, but the self-extinguishing of the flame was accompanied by a burning dripping of the molten mass, which moved the flame away. In this case, the braid was tested in all positions. If the sample burned at an angle of 0 °, it was given an NSE rating even though it was SE at an angle of 90 °. Preparations behaving in this way are provided with the relevant notes.

It is to be understood that the flame retardancy varied in relation to the numerical value reported in the flame classification. Thus, the flame retardancy is highest at 160 and lowest at NSE.

The compositions and burning properties of non-flame retardant polyester and viscose rayon braids prepared and tested according to the above methods are shown below:

Punos No. 1 2 3 4 5

Polyester filaments 4 3 2 1 0

Rayon fibers 01234 weight-3 polyester 100, 0 80, δ 56.7 31a2 0.0% by weight of rayon 0.0 19> 7 43.3 68.3 100.0

Palanis classification at 0 ° IISEa MSEs, e NSEs, e NSEs SEd at 45 ° angle NSEa NSEs, e NSEs, e N3Ed NSEs at 90 ° angle SEb NSEa, e NSEs, e NSEs NSEs at 135 ° angle MSEC NSEd, e NSEd'e NSEd MSEd at 180 ° NSEC NSEd, e. NSEd, e NSEd NSEd a) The sample appears to be NSE because the combustible molten mass flows downwards and strong distortion occurs.

b) Sample SE because the combustible molten mass drips away, moving the entire flame away.

c) Sample SE because the combustible molten mass drips away, moving only part of the flame away.

d) The specimen did not drip or warp. Charring occurred during combustion but the afterburn consumed the charred portion after the flames were extinguished.

e) Some melting was observed, but only a small movement (runoff) of the melted 9 59804 mass could be observed.

The results presented above generally support the reported vaulting effect of blends of thermoplastics and carbonizable fibers. The initial carbonization of the rayon prevented the molten polyester from dripping or dripping. Thus, in polyester-rayon blends, rayon prevented the self-extinguishing behavior and the associated melted polyester droplet at a 90 ° angle, and apparently the more flammable polyester prevented the normal self-extinguishing behavior of the rayon at an angle of 0 °.

Example 2

Braids were prepared and tested for burning properties in the same manner as in Example 1 from the flame retardant-free polyester yarn of Example 1 and viscose ion containing various amounts of flame retardant (CH 2 Cl 2) 2CHO 2 (PS 3 above) dispersed therein.

Viscose rayon fibers containing a flame retardant were prepared by injecting and dispersing Compound 3 in a xanthate spinning solution just before the spinning die. After the flame retardant-containing fiber was regenerated in a sulfuric acid bath, it was washed, treated with sodium sulfide, washed and dried.

After conditioning the viscose rayon fibers at 23 ° C and 507 relative humidity, they were braided together with polyester yarn.

The properties of the FR rayon fibers used in this or the following examples are shown below:

Fiber number Denier / Weight-7a Yarn weight g / m

thread / _TC1CH2 ^ CK07 ^ PS

A3 7.1 0.19 3 15 13.1 0.34 C 15 16.9 0.37 D 15 22.6 0.42 E 3 30.2 0.33? 1.5 31.6 0.22 G 15 to 0.37 H 15 to 0.34 I 15 to 0.13 a) Concentration of flame retardant calculated from P and / or Cl analyzes of the fiber.

The braiding compositions and combustion results are shown in Table II. Local melting was observed at radon concentrations of about 10-507. However, bending of the polyester was prevented at rayon concentrations as low as 10 59804. Permanent carbonization was formed in all cases while the amount of carbonization increased in proportion to the increase in the concentration of rayon and flame retardant. A short-term afterglow was observed only at low concentrations of flame retardant.

The overall results in Table II showed that the combustion classification of the mixture depended mainly on the concentration of flame retardant in the mixture and was almost completely independent of the concentration of flame retardant in the rayon fiber. The denier of the fiber or the thoroughness of the blending did not prove to be very significant.

These surprising results show that self-extinguishing (horizontally) non-drip, non-annealing polyester rayon mixtures can be prepared with amounts of rayon and flame retardants as low as 25% and 6%.

il 5 9804: θ

P

P

: 2

B

Wj I CO., LTD

P CO 2) —I * H 4-5 ac5 E · Η 20 CO 2 2 3 3 3 3 3 3 W m Ln ooooooo • hhown cq w oo co ooco ^ r- = r cr »m ο σ \ σ \ CO 2 2 2: 2: 2: 32: 2 2

P-t 1 — I

: 2

P

•B

C/O

2

• ' "S

Vi c • H 2 "

C -p CO

O p co • h 0 co co co t · - co co to ^ vo in to w 00 in in ^ 0 2 d 0 0 p— rG t · - ro - = r co 0 lo cm im m ^ ri m co h * (”1 CO Λ * N * Λ Λ ^ A ft Λ Λ Λ • h ρ 2 O 2 oo I — li — ti — I c \ j cm (M nm ^. = r and \ m mo vo vo t -

M (1) IXO

0 3 K O CD

0 2 3 2 CO

2 2 co co • H * H> 03

M C "H

M C · Η I in ή g ti o cr, m ιο o v- - = r cj ό o o vo o vo co m κη o Q O J JO Λ «S Λ Λ» N ft ft ft ft ft ΛΛί> # \ Λ * Λ

2: 2 00 O CO CD CO C7 \ tn m VO rH Γ— MO CO LT \ f— LO p— CM CM rH CD

2 ρ · Η d CD CD CO CO CO p- MO cv CD S in S ID CM VO C- in CD

2 I — I ε Ή> i rH

I — I: 2 o3 2 <—I

2 CO rH 2 0} O

<2 Ή CÖ P 3

£ h CO 3 C CO

CD CD

2 c ή to

P CD -P 22 P -P P O

0 co coc cocdcoo <co << 3 α ΰ <o q <o g ca 3 <

• H <D d · Η O rH LO LO CD IG MO CO Ρ "O CD ρ- Ο - = Γ Ρ- Ρ- P ^ O

2 CO 0 2 tC "" Λ "" n * * "* * **

D 3 d d O <—lOO IP Ki CO CM CO O LTM CM LT \ CM C— C— CM CD

2 P ε: 2 I rH rH rH CM ΙΉ rH CM LO CM CO P— P ~ \ CM P "CM O

2 · Η O: 2 2 r-1> 2 3 ε 2 P ~~

CO C

2 -H

3d 2 • H CD P I

3 P p -H

CO -H W

2 0 2 0 P> 3> 0 CO 3 2 2

• HO 2 CO

E 2 '· Η O r — ί I — f CT \ 1 — I 1 — C CMOrHiHCTi rH rH CT. MO rH CM 3 £> ft * * v «t #>« ι ^ Λ * N Λ Λ * \ f>, r \ r \ r * r \ f \ rH dd 2 O t> - ΚΛ MO C ~ - P - O CM ΡΛ t> - MO r-Π V- MO CM ΙΉ Ο t— 2: 2 0 Vi 0 1 — l 1 — I ΚΛ CM 1 — I 1 — I 1 — I 1 — I CM 1 — I ΓΌ 3 E 0 2

C n * H

• H: 2 C

2 d O

I: 2 -H

2: 2 2 3 E d

O

d

rH CM ΚΛ p- LO MO P— CO CM O rH CM KM P "LO MO f— OO

CO I — l r — I I — l I — t I — I I — i I — I I — I I — l 0 0

GO

12 59804

C

: θ C Λ

44 Φ O rH

O O O LT \ LO LPt 1_ίΛ LP \ OOO · Η Ό ϋ H

σ \ θΝ (^ ΐΛΚ1 (Λ (ΛΙΛ CO CO 03 CO · Η O Φ i — H rH r — I i — I i — f r — IrHr — I 440 4402 >> · Η 44

C to CO

0 C φ Φ • H φ: cd to cd E p C -H C cö

1 O · Η rH

04 CO »Hi — I

Ph O co 3 C 3

O 3 -HE

O O CP O * H £ 3 3 OJlO- = TVOC7 \ C - iHC \ i - = r CK MD 44 cc c O Λ Λ G ICÖ ΟΟΟΟΟΟΟΛΡΟΜΚΛΡ- d- Ό CM> $ * h xd

i — I rH pH rH rH i — I OJ "t / j« JH pH

CÖ * H rH

CO Ct Ct «H

co co co £ φ cd co (ti 4 Cd 3

P £ P

pc p

• H »H CCj» H

ϊ> · Η (- (Cd CP 3> CO ΝΛ O C '' - CM OO i — I OOO Cd .p coed »k * * \ Qj CMKKCMDC'-LP.OK'N KNOO P cd N CO W ΐ ( M LTN OJ C>;> · Η • h Kd cd φ

• H 44 rH

p cd cd p cd op

Φ * 1-3 CO

P O cd · Η

to C 44 E

sd · η co 3 44 cd O C- (X 44 e.

Sd Φ · Η

HQOCJQOCjW QOQ Ρ · Η "P

C \ l O- O ΚΛ CO O O C7 \ OOO -H sd cd

~ r h Φ CO C0C

C— Ό O KK (M 140 OO K- OO 44 coed (ΛΙΚΚΙιΛΚ-ΙΙΚΟ-Ο ^ Γ d— OOPC td 10 i — I i — li — i ted · · E co CO E rH cd co> s. £ 3 • H te 44 cd cd P CM C Cd

-P * · · I — I

• H -ST 0 3

CO I O CO

o ro co cd KO 3 co • H *> 44: cd co

cd o c / Ο sd O

P · PC

• C C -H C

3 C Φ · Η ET! Φ

CMOCKPVCCT \ PCM O CT \ Ό · ηφφ Φ CO

******** * * * IQCJCQ C0 # fC

OOJVOr *> C \ JVOrOO CM VO CM · Η cfl «H 3 CO <1>

fO OJ r — I rH OJ pH pH rO OJ rH OJ Ct · Η £ · Η O

P E cd -H O 44

3 ccd cd i — I O

Φ P co O C

44 · Η C C: cd C O 3 φ · Η: cd • H sd cd -p 44 co

C rH 44>, Φ CO

O P Ή CC0 · Η · Η se> 2 cd 3 p £

CKOPCMKKsrUKMD is CO CN Cd jO

i — ICMCMCMCMCMCMCM CMCMCM '-h i3 59804

Example 3

Braids were prepared in the same manner as in Example 1 from the flame retardant-free viscose rayon yarn of Example 1 and the flame retardant-containing viscose fibers of Example 2. The characteristics of the PR rayon used, the compositions of the mixtures and the combustion properties determined by the test method described in Example 1 are shown in Table III.

The results in Table III again show that a surprisingly uniform level of flame retardancy is achieved with a given concentration of flame retardant in the mixture, but with large variations in the distribution of flame retardant in the mixture. For example, blends 15-18 containing 7.1-7.6 / 5 flame retardant have the same classification value of 90, although the actual weight percentage of flame retardant-containing fibers ranged from 24-100¾. In addition, the denier of the fibers in these examples ranged from 1.5 to 15. Similar comparisons can be made with other flame retardant concentrations and flame retardant concentrations.

Example 4

Braids were prepared according to the method of Example 1 from blends of the flame retardant viscosity fiber C of Example 2 and the other commercial flame retardant fibers listed below:

Fiber Yarn weight, w / w

Polypropylene 0.26 iJylon 0.45

Polyacrylonitrile 0.34

Polyester 0.43

Cotton 0.13

Viscose ray 0.27

Villa 0.34

As in the previous examples, multiple or partial strands of each yarn were used, as appropriate, to maintain poison dimensions and comparable concentrations of FR ray (and FR material) in the blends.

The braid compositions and the combustion classifications obtained according to the method of Example 1 are shown in Table IV.

Mixtures 1-7 in Table IV show the relative flame retardancy and burning behavior of the above flame retardant-free fibers as measured by this test method. The excellent flame retardancy in natural wool itself is particularly noteworthy.

Although a viscose crack containing a flame retardant effectively prevented combustion in all blends at two or more levels, large variations in concentration were required to achieve the same combustion properties with some fiber blends. This reflects the relative difference in the inherent level of flame retardancy of different textile polymers.

The combustion properties show that maximum concentrations of 20-35 $ viscose ion effectively eliminate dripping and cause some carbonized residue in all blends formed with the thermoplastic fibers.

i5 5 9804

I cq CO 3 • H -P £ * H JC

: ct3 CÖ ^ dOOOOO CO LOOP IP ooooooooomo .ρ ρ Ο - = r. = r cxr ff> C7NCTiCr \ c ^ cj \ (j \ CJNmiocT \

• H Cti 3 P

CQ CG H

P

03 (1)

• P TO

3 O c 3

• r-I CQ O C -H GJ O G

• H C G · »

Oj · Η -P 03 G £ -POT

• ho ¢) n k ο p cr \ cm lo o- vovoo ctn Lnt'-covoointpo ^ rinco

Cd CQ C <13 O O CP CM p- CO 3 · ^ O OJCMVOVOPCMPVOVOC'-OO

0 »P-j .f — I ζβ λ μ η η η λ *>« · »λ λ n O E G Js! O Ρ P CM CM CM ΙΡΓΌΡ - = J- inininUJSNSNCO mcr \ X 3 1C BH CC 0)

• H Oj pin CQ

> cc

G G

M: G CU * H

M> -P G

l — I: o3 ω Φ

Ρ O G P O

O rH φ Φ cq o P co oo lt \ vo> ~ pp ocgccvoovoo ^ tp · - P

C0 «H d) Λ * * A«> Λ Λ ^ r Λ ΛΛ C4 en Ρ>! o ir \ nr ο ο σν - = rccp c \ i ococpoop ^ vovopcmvo 3 · η cp: G po co co vo cd p coco> - - = r vovcrHvo .pc-— vo c— ρ p rH ui -h C ft O <- <3 G ¢: 3 (¾ G GO G: oj E-1 ρ · η O ε aj

P G Oh I G

CG £ VI O

G-H OI -H <sa <0 <Q tt3 <CQO <0 <CQfeQyOQ

• h oq ϋ O n) o p cm cm p ρ p P— vo ocmcmpopovovovoc— CO O CO C Λ iH ^ ΛΛΛΛΛ »Ν ^ ίΝΛΛΛΛΛΛ C \ * \

O O · Η I O "LTI H OLO PO [- OPOCPOPPPCOf— P

lie o lie 1 — IrHKVrH Ρ P HM LO PPCOPCPCMPCMPP

M CO H (0, ¾ rH

£> · Η G>

P I

CQ G ri o G: G GO 3 £ G ^ • H: o: G m

.G Ρ ε -H

P I>

G: G va. G

Ρ ε ^ CO

CQ: G G 3 G O Ρ Ρ P Cv rH VO CNH P PCVPCT \ PPVOVOCMC \ VO

% r ^ 0> Γ- | »\ Λ A *» * »*> Λ ^ rs # \ # \ Λ # Ν *» # \ # "ι« * ιΛΛ rs Λ ε p co> C o e-- p ip vo e— cvj cp tr- pvo> c-— vot— ppcmovocm G: cd G Ή O · —I (—I CM K "P i— | i — li — li — I p cm, - | f \ ji — I OQ Ή G Ή

G P G G

CG CQ I G G

K .G · Η

Ph —- cq

O

e

i — I CM KV P LO. VO C — CQjv o PCMPPPVOPCOmOP

CQ r — I i — li — li — li — IPi — li — li — li — I CM OJ

o

QJ

C/O

16 5 9 8.0 4

G

ω Φ -Ρ ρ> 5

, G

LPt LO O LO LP \ OOOOOO G

κο ko oo ro ko co co co co co co cd

l — I (—l i — I r — I i — I i — I i — li — li — li — I r — I G P

• H CO Φ * H

co E G 0}

r "H

• h cd -ρ a

P

3 G I — I Φ

C \ J ΚΛ LTs ι — I VO VO O LO OV MD VO GTD

»3 ** Λ r Λ rt o n» \ ^ <r — 4

ΟΟΓνΙΚΛΚΛ ΚΛ VO VO VO CO C \ J O

i — li — li — li — li — I i — li — li — li — li — I C \ l G

.G

a> G G Ή • H (H 44 -H P CO

: cd 44 i-O O

iocmd — oco i_f \ ^ rmooo ω rt> * \ rti »> rti rt rt rt rt rt n» CO ·

vo p o o crv co σν lo> o co o G

vo cm vo κλ p - = r g- h <I) C- = r

G Ή G G: G> G G

G 0

G * H I — I CU * H i — I φ P G CO P

• · Η · Η · Η

U ffl pci CQ Q OfcWOQ M E G i — I

t- ~ COKOOOJ LTV VO LO O O O mG> o ******* # \ * \ * n rt n ^ r-Λοοσοοο o o g o c \ j o OGGco tP KV O VO CO LO LO O CO O 44 CU 3

i — I i — li — I 44 G G

G G G CO i — I Φ 44 · Η G Φ G O G co Φ P Ρ · Η G -H G · Η Cm "CG ^ -H rH G G CO: G Φ p 'G · ΐ“ 5 Φ G G

C \ J P VO P VC CV VO CM OV VO VO Φ> G · Η * * * * * n ft »\ Λ r

Ο ΓΟ i — l ΓΌ C \ l VO i — I O VO Γ0 PJ P G CO

K \ ρ ΚΛ p c \ J P IP KV P <\ | (M · Η> · Η G

> G G G G E G> ρ E p G G G G ρ co P co

• Φ> 3 G

P co G G G Ρ >> P

> M G G

cm kv g m vo p co cv o p cm G .o CO Cvj Cvl CM Cvl CO CM CM KV KV KV - r 59804

ί> 3 G G G

PC (d c C: it «GCGGCwJGadrG

HO) · Η · Η · Η · Η: αί I — I ί — I · Η Kti 34 Η: G ί — I 34 Ή ι — I

H C φ <D Φ 3> β Η Η> K G> .G H 3 H H

• H · Η · Η> i: c3> 5> ι >>: G H> ,: G >> · Η> 3> 3 κ ε κ χ:> 34 34 x:>, cx:> 34 x: 34 34

G

φ c

• H: ct3: G: G

G E Γ-t H I — I

φ G H ί — I r-H

K K> i> 3> 3 · Η · Η · Η H · Η · Η Η Η Η Η · Η • Η G 34 34 34 Φ Φ Φ Φ φ Φ Φ φ Φ Φ Φ G · Η ε & η «5 Ρ

* Ό Φ G

Φ Φ _

G G G CC

• H G H a a aj: 3 ϊΰ G: G G G G; G

CG E f — I rH ι — 1 ι — I iH K rH 34 H XCj <H

OHG ι — IH ι— (i — I * —f GHG ^ 33 '* • HG rH> 3> 3> 3> 5 · Η · Η> 1 · Η> 3 · Η >>: G · Η · Η> 3 gcg 34 34 34 34 φ φ 34 χ: 34χ: κ> φφ34

G · Η CO

• η ε

CO O

O CO I CO

O · Η CO G

34 ε -HP

CO G ε · Η JD XC JD

• h h G 34 ωωκωω ln «m en m W o ir \> G HO CO CO CQ CO CO O ΓΗ CO J J ^ n D ^

K GGKKKKK H K K H

G Ph H

xa c> φ

3>: G P G

H P co P

HO P

O: G Φ Φ G

34 co (O G co

^ .h 'h co md lt \ cm m rH oo rH

zs wc GO ooooooo cg ό oj m ih cm m φ ICO Λ O A ^ Λ ^ Λ ί \ 3 G-n> 03 34 OOOOOOO in ιλ 3 · lO ^

G P G fe O

£ h Ρ Ρ Φ

Φ · Η tÄ CO., LTD

G G

• H 34 G · Η · Η

G H H

G Φ · Η * H

G -H -H -H

> ε g g

G S3 HP HP

ρ p G H G G H G

COP Φ CO Φ CO

G: G GO H H Φ H H

OE G H H H G HHH G

H x3 P £ * 3 G P "3 G £ * 3 G ^ 3 G

KP H G. Φ> 3 G · Η G Φ> 3 G · Η

H G o- p G H G O P G r — t G

G: G G 34 G G 34 H O G G 34 H O

Pco G G ri Φ G H O G GCOGhOG

G H E G> 3 O> 3> 3> 34 H> 3 O> 3> 3> 34 H

H G G P HHHHGGH HHHHGGH

E P G O> 3 O O G H H O> 3 O O G H H

G x3 G G G G G G G>> G G G G G>> 1 — IP ο ε

CdH O OOOOOOO f- - = Γ O H - = T CO CM

P (A #S A #% * 1 O * 1 «* \ * \ *> A ^ Λ ooooooo - = x co lg γη - = r co ih era ooooooo co [h tn n e · - ό c- ~ -

φ G 1 — Ir — li — li — li — li — IH

G H

34 G

o o

0) H OOOOOOO ΓΠ CO o en O C \ l CO

Λ *> * \ · *! *> *>

G OOOOOOO IGHlTCOlTcHVO

1 (H C \ J CM CM C \ J ΓΗ C \ l cc (¾ G <<<<<<< OO h cm ih. = R lh o cm- ι — 1 era γη lo co e— Φ ··

CO G

is 59 80 4: cti «ti« ti «ti: cti« ti xö: cj * ^ j: ct: d: CvJ κΰ «ti

rH rH rH r — I f — f rH rH rH rH ι— (rH rH rH r-H rH

r — I rH rH i — I rH rH rH rH rH rH i — I t — I ι — I rH rH ·> i> 5> 5>,> 5> ΐ> 5> 2 >>> ϊ >>> 3 > 5> 2> 3 M tti 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44 M> rt

• H rH

44 rt 44 C, S4 • H · Η · Η · Η Ή · Η · Η · Η · Η · Η · Η · Η Ή · Η “Η 04 Ο φφφφφφφ φφφφφφφ φ ε 44 • Η Ο co 44 φ rt C« 44 CC rt GCO co

• H x * 44 · Η: rt O

> 43 rt> 43 C 44 £> 3 CCj * H rH: rt · Η Ή · Η · Η · Η · Η Ή · Η · Η Ή · Η · Η Ο 43> 43 43> ΦΦΦΦ φφφφφφφ φ · Η «rt rt? 3 φ

• H CO

C0 · Η Ο Ε lt> oooomo lc m lt \ m ο ο σ ο Ο> η c'1 σ \ σ \ σ \ ιλ co κι nn rA οο ο co co 44 rt I — II — II — II — II— II — I t — II — I ι — I 1 — i CO 44

•B

> c xti o> o

O LH 3Γ LC O> LO: rt CTN

o so - co m rH co c-— OC -— OCOSOO σι p #V Λ Λ #v #v «V» V r \ * \ rr \ r> rv rv ¢ - · (-_) O c— oo oo co c · - co ro c \ i cm ro cm ro re so: rt rt

i— (I — I (—I I — I I — I rH I — I (—I 1 — I CO P

•B

co rt • Η * H ’r-3 1 — I I — t rt • Η · Η -P in

• Η · Η P HT

C U Φ • HP -HP c rt rt -H c rt -H C · Η> φ rt ο φ. c o rtrtco Φ · Η · Η Φ · Η · Η Ε · Η

ι — I · Η rH rt rH · Η t — I rt rt E O

iHrtinrt tn c: >> c rtrtcrt

Crt Φ> 1 ci Ή C, Φ> 3 rt -rt> CQ

O POrHCO O pfnrHCO «JO -H

rt CO 44 rH O rt C044I-HO PDOrt C4Crtrt-HOrt c-Cort-HOrt co pc,> 3 O> 3> 3> 44 rH>, O>)> J> XH rt · Η £ 4 rH i— (i —I rH rt CO f — I <—I i — I rH rH rt CO i — ί 'φ · Η

O>, O O rt · Η · Η, O> 5 O O rt · Η · Η · Η CO P

C, S3 C, O. C,>> C, S3 O, C, C,>> 44 rt 44 rt cot'-oC'-p'OO co> - o cc - = r and \ rn o rt coco rv rv r \ r »rv rv rv rv rv rv rv rv rv« vr> φ o - = 3- o c-- σν c— e— co co in γλ 3 · cv c ^ o co ca

^ TLOcn ^ r- ^ rirs ^ r pcmcsicmcmpcm · η E

E p rt p rt

rH> 3 rH

rt; rt rt O-, s co c \ j rc o cc co - = r p- lh mcp A * n * nnn rt «> *> -ir rt rt o in o cm oc \ jc \ i ρ m lo vo crv c vo or—, r-, m 4 · ιλ in in 3 · φ co c ~ - c— cp cp cc [> - o rt o rH ^ v · - '

CQ 43 CQ C3 CQ D3 33 O O O O O O O

P (M C-Λ 3Γ Ι4Λ VO lp P CM ΓΗ P "LO VO CP CO

19

Example 5

Combustion experiments were prepared and performed according to the above methods from mixtures of the viscous ion containing the flame retardant of Example 2 or the polyester fibers without the flame retardant of Example 1 and a viscous ion containing various phosphorothioates. Flame retardant and rayon compositions are shown below:

Fiber% FR material Compound Yarn weight designation (observed) a number g / m 0 15.9 1 0.57 H 16.1 7 0.3¾ C 16.9 3 0.42 1 18.1 9 0.13 (a) Concentration calculated from P and / or Cl analysis of rayon fiber.

Mixture compositions and combustion classifications are shown in Table V. The results do not show significant differences in flame retardant efficiencies when the concentrations are nearly the same in the corresponding mixtures. All rayon fibers containing the flame retardant were substantially similar in terms of dripping, melting and post-glow prevention.

20 59804

I CO

co rt • H -P cd e · η ω cd X oo o o lo o in o in in in o in f — i o o tn p- -a- mmm

Cd rt P P

CL P

cd Ό C -P <Ö H Φ 4-5

C 03 P

o rt φ cd • h rt c co

CtiCQ -rt CO LO O CO O C— L £ ~ N CXJ LO CM LO

rt · Η Cda> CO CT \ C— CM (T \ CT \ t— i — I rHCrtd- «P ^ ζφ I CO rs« «Λ Λ r» nr »rs rs r \ coC CC X cc cj in in ro ro p- en cc cl

O * rt pL O

O E Φ x o vt co rt CO CO ‘rt

• rt * rt C

> E o cd ccd «rt rt i — I * rt Cd * rt» rt * rt: cd rt E-. f. rt rt rt> rt, CD -rt Φ Φ Φ

: cd -P 00 P P P

+5 rt CO O CO CO CO

> P Φ ΦΟ C C C C ΦΦΦ rt C C

: cdP >> X OOCO>;>) >> O O O

O CO CO i — I CO * rt »rt * rt 'rt i — I t — I i — I · γΗ · γΗ · γΗ rti> rtO O * rt cd cd cd rt ooo cdrtcd X CO Φ rt c,> rt rt rt rt rt.rt.rt, rt rt rt rt CO 44) rH cd · Η OO CC HC in O C'- O 4a LO P- ^ £ ζ / 3 ^ 5 r »rs rs rs Λ rs r \ rs rs rs rs rs cd · η Φ rt E oo co o co c— LO lo im cm p- cm Ei φ · ο> E oo vo c— Ό of— r— f- p- - = r p- C rt rt vl pp

• H P P

cd · η co rt o cd x o

• h X

> C

co φ c cd 4-5 * H Φ · Η

co E PC

cd: o co O

op o -h odcop u x o o x o

• H D t) cd CM CM CM LO O rO O LO P "LO

r- · * rH ro Lj II rs r> rs rs rs rs rs rs #s ·> £ I i — I On i — 1 C \ l LO KL LO f- LO C— cd κΰ X ro CM ro ro CM cm cm 10 lo lo pp Cl

CO P

• H: cd feL

E CO cd · Η p co cd rt, -Hd i cd p co co

• rH »H Cd * H CO

rt · Η P> * H

WC PC

Φ O

rt rt -h clpop opcl cl p co <r ^ (¾ If rs rs rs rs r \ rs ♦> rs rs rs

ΙΠ VO VO CO LO VO VO m νΰ VO

I «H · Η rH r — i i — i rH i — J i—) * -)» —I rH i — I

X cd co

X> O

a o vi x x CO o <c <<c O ·· i — t CM to pr LO LO E ~ - CO CL (O a n φ c co 59804 21 en

•B

O

e-

•B

3 O, & LOGO OOO LPvOl-Π OOO · Η σ \ ολ cococo ιλ oo ^ cccoco +2 1 — I ι — I rH 1 — I 1 — t ι — I ι — I 1 — I 1 — t cd ra ra cd ε cd I — 1 3 ra m cm m cd CO O -¾- ra! - M3 GiC— C— CO rH CO> fti ^ Λ Λ Λ Λ Λ Λ ^ ^ ζ \ 3

CC ΟΟ CM CM (Λ rH CM C \ l L · ^ O U3 ι — I

1 — I (—ti — I 1 — ti — ti — I ι — tl — li — t cd S3 o 44

O

44 cd jv; • 1 — t · Η · Η · Η · Η · Η ra

3 3 3 3 3 3 O

0 O) 0 CL) 0 3 44

-P P P -P P P

ra ra ra ra ra "000 CdC 000 3> ^; >> >> 000> i> j> 3 ra

r — j 1 — H rH · Η · Η · Η ι — I rH ι — I CO

OOC aS aS d OOO as SL C, C, 333 Si ft ft ε

I-I

o VO O COOLTi OOG OOO 3 o n ·> «Λ Λ Λ Λ Λ * N V 'o ^ ro co ^ = r co in H in ooo tO- = rLr \ rHr-HCMCMCM c o o

C/O

C 34 O 03X0 Oftdo 0340 CO

0-3 "0 CM O LO OOO OOO

* \ «· * # \ Λ Λ ft» r \ r \ r \ * \ olpio ocr \ o m o m ooo 3 n n m co n ra t— - c ^ - ooo 44 rH rH rH K3

O

• o 0

P

: cj O ', H O') on Η σ> CTN ^ H CTn ον η o rt Λ η Λ ft Λ ft Λ ft ft ft ft / ->, ΙίΛΌΟ LPi M3 M3 LO M3 Ό LO M3 M3 Cd ι — I 1 — I 1 — I 1 — ti — Ir — I 1 — IrHi — I ι — ti — li — I '-' <<< QCQCQ a 3 a e-- co co mj · in r ~ - co <0 Oi -hcm I-1 I-1 Ii 22 5 980 4 The novel polymer blends of this invention have several advantageous features.

Flame retardant compositions can be prepared by incorporating one flame retardant component. This method inherently provides excellent economic advantages over the higher capital and manufacturing costs associated with the manufacture of two or more flame retardant components.

A simple flame retardant polymer preparation can be used to provide different flame retardant levels of the blends. Likewise, a virtually unlimited amount of flame retardant compositions can be prepared from a single flame retardant polymer preparation together with one or more flame retardant-free polymers.

Several degrees of freedom are available to maintain the desired level of combustion resistance while varying the concentrations of the components to achieve other desired physical and chemical properties of the mixture. This is possible because the effect of the flame retardant mainly depends only on its concentration in the mixture.

The cost of incorporating a flame retardant into many polymers, such as cotton, cellulose, wood, wool, silk, and other natural polymers, by "attaching", impregnating, blending, and other methods the flame retardant is usually much higher than incorporating the flame retardant during spinning. a particular flame retardant for different polymers usually varies widely due to differences in solubility, miscibility, perspiration, extractability, absorbency, thermal stability, chemical stagnation, and other important chemical and physical inhibitors. component is obvious.

It is common practice in the textile industry to blend fibers to achieve a certain combination of properties. thus, the greatest advantages can be obtained by incorporating the FR substance into one of the fibers (or an acceptable substitute) normally by the cheapest method. A judicious choice of the component to be "carried" by the flame retardant can provide the desired properties in the mixture, such as good weather resistance, washability, etc., which cannot be achieved by incorporating the same flame retardant or different

Claims (4)

59804 23 flame retardants for other components. The advantages obtained by (a) eliminating dripping and (b) eliminating or reducing the melting properties when blending a carbonizable flame retardant polymer preparation with thermoplastic polymers are shown in the above examples. A blend of organic polymeric fibers comprising a compound of the formula: R'a Γ 1 RRSRR / p \ ti Ji l 1 // Vv (XCHCHO) - P - (OCHCH) “- o - ^ y X is J 2 or a mixture of such compounds wherein X is a halogen atom, R is H, -CH 2 or -CH 2 X provided that when one group R is other than H, the adjacent R is H, R 'is X, alkyl, haloalkyl -, alkoxy, aryl, haloaryl or arylalkyl group, a is 0, 1 or 2, n is 1, 2 or 3, w is 0, 1, 2 or 3, y is 1, 2 or 3, z is 0 , 1 or 2, and the sum y + z is 3, characterized in that one of the organic polymers of the mixture contains 2 to 50% by weight of a compound of the formula I or a mixture of such compounds. Fiber mixture according to Claim 1, characterized in that it consists of a synthetic polymer and a regenerated polymer, the compound of the formula I being incorporated into the regenerated polymer. Fiber mixture according to Claim 2, characterized in that the regenerated polymer is a viscose rayon. Fiber mixture according to one of Claims 1 to 3, characterized in that 5 to 95% by weight of the mixture consists of a polymer in which the compound of the formula I is incorporated.