GB1590605A - Creation of Inventions and Patents with Artificial Intelligence

GB1590605A – Polyocyalkylene tetrahalophthalate ester as textile finishing agent
– Google Patents

GB1590605A – Polyocyalkylene tetrahalophthalate ester as textile finishing agent
– Google Patents
Polyocyalkylene tetrahalophthalate ester as textile finishing agent

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Publication number
GB1590605A

GB1590605A
GB365/78A
GB36578A
GB1590605A
GB 1590605 A
GB1590605 A
GB 1590605A
GB 365/78 A
GB365/78 A
GB 365/78A
GB 36578 A
GB36578 A
GB 36578A
GB 1590605 A
GB1590605 A
GB 1590605A
Authority
GB
United Kingdom
Prior art keywords
ester
fabric
flame retardant
ester mixture
polyoxyalkylene
Prior art date
1977-02-25
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB365/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Pennwalt Corp

Original Assignee
Pennwalt Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1977-02-25
Filing date
1978-01-05
Publication date
1981-06-03

1978-01-05
Application filed by Pennwalt Corp
filed
Critical
Pennwalt Corp

1981-06-03
Publication of GB1590605A
publication
Critical
patent/GB1590605A/en

Status
Expired
legal-status
Critical
Current

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Classifications

D—TEXTILES; PAPER

D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR

D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS

D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment

D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen

D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof

D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof

D—TEXTILES; PAPER

D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR

D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS

D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment

D06M13/224—Esters of carboxylic acids; Esters of carbonic acid

D—TEXTILES; PAPER

D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR

D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS

D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment

D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen

D06M13/402—Amides imides, sulfamic acids

D06M13/415—Amides of aromatic carboxylic acids; Acylated aromatic amines

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]

Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Y10T442/2279—Coating or impregnation improves soil repellency, soil release, or anti- soil redeposition qualities of fabric

Y10T442/2295—Linear polyether group chain containing

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]

Y10T442/2484—Coating or impregnation is water absorbency-increasing or hydrophilicity-increasing or hydrophilicity-imparting

Y10T442/2492—Polyether group containing

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]

Y10T442/2631—Coating or impregnation provides heat or fire protection

Y10T442/2713—Halogen containing

Description

PATENT SPECIFICATION ( 11) 1590605
e ( 21) Application No 365/78 ( 22) Filed 5 Jan 1978 ( 31) Convention Application No772 043 ( 19) ( 32) Filed 25 Feb 1977 in ( 33) United States of America (US) If ( 44) Complete Specification Published 3 June 1981 ( 51) INT CL 3 C 07 C 69/80//C 08 G 65/32 ( 52) Index at acceptance C 2 C 220 227 22 Y 233 24 X 271 280 30 Y 314 31 Y 321 323 32 Y 338 339 342 34 Y 360 362 364 366 367 368 36 Y 491 583 62 Q 623 62 X 638 644 648 650 652 65 X 668 699 809 80 Y AA BS BT KN LS C 3 R 27 K 2 D 27 K 8 D 27 K 9 D C 3 Y B 310 F 112 ( 72) Inventor STANLEY R SANDLER ( 54) POLYOXYALKLYENE TETRAHALOPHTHALATE ESTER AS TEXTILE FINISHIING AGENT ( 71) We, PENNWALT CORPORATION, a corporation organised and existing under the laws of the State of Pennsylvania, United States of America, of Pennwalt Building, Three Parkway, Philadelphia, Pennsylvania 19102, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be 5
particularly described in and by the following statement:-
The present invention relates to polyoxyalkylene tetrahalophthalate esters and the application thereof to fabrics, such as 100 % polyester, to give the fabrics durable flame retardancy, with no added tendency to soil, and water wicking ability It also pertains to the finished fabric product with the polyoxyalkylene 10 tetrahalophthalate ester thereon.
Tetrahalophthalates are known in the prior art for flame proofing materials.
For example, United States Patent 3,775,165 (A) teaches the use of a tetrabromophthalate diester to make polyester fabric flame retardant and to improve the fabric’s dyeing properties A disadvantage of this compound is that it is not water 15 soluble, even with the aid of caustic, and must be applied with an organic solvent such as acetone This diester also leaves the fabric slightly stiff.
United States Patents 3,585,185 (B), 3,642,646 (C) and 3,929,866 (D) describe polyoxyalkylene tetrabromophthalates useful for flameproofing polyurethanes but not polyesters and since polyester fabric differs chemically and physically from 20 polyurethane, polyester would not be expected to respond to treatment in the same manner as polyurethane.
Finally, United States Patent 3,624,042 (E) describes a composition of polyoxyalkylene tetrabromophthalate that is used as a binder in propellant compositions 25 The present invention is based on the discovery of a group of polyoxyalkylene tetrahalophthalate esters that are useful in the treatment of fabrics, especially polyester fabrics, to give durable flame retardancy with no increased tendency to soil, and with water wicking ability, and which can readily be applied to the fabric from aqueous media Alternatively, they may be applied directly to the fabric or as 30 a solution in an organic solvent The compounds used in accordance with this invention cause little or no fabric discolouration and so may readily be used on white, dyed or printed fabrics.
The polyoxyalkylene tetrahalophthalate esters useful in accordance with this invention are compounds of the formula 35 ROOC O R? RI IIl CX Cú-X-(CCHCH 201 p Rl 11 I A 1 q where R is H, C,-C,0 alkyl, C 2-C,0 hydroxyalkyl or C 3-C 10 polyhydroxyalkyl; R’ is hydrogen or a mono or polyvalent group having a valency equal to q and selected from saturated hydrocarbon groups containing from 1-12 carbon atoms, such hydrocarbon groups optionally containing one or more hydroxy substituents, C 2-C,9 alkanoyl or hydroxyalkanoyl groups (including the corresponding polyfunctional acyl derivatives of di and polyfunctional alkanoic acid and hydroxyalkanoic acids), and groups of the formulae -lh -_/-, C Hm C Q CO O CH 2 z CH-CH 2 0 A A -C COOH COOH COOR CH 3 -CH 2-CH-NH-C A 10 R 3 R 4 R 3 R 4 R 3 R 4 -CHCHNR 5 R 6, (-CHCH)2 NR 5 and (-CHCH)3 N R 2 is H or CH 3-; R 3 and R 4 are each H of C 1-C,8 alkyl; Rs and Re are each H, C,-C,8 alkyl or C 6 Hs; p is an integer whose value or average value is from 4-50; 15 q is an integer of from 1-6; n is O or 1; m is 1, 2 or 3; X is O or NH; and A is Cl or Br.
In one aspect, therefore, the present invention provides a method of 20 flameproofing a polyester fabric, which comprises applying to the fabric, a polyoxyalkylene tetrahalophthalate ester of the formula defined above In another aspect, the invention provides compositions for the treatment of polyester fabrics to impart flame retardant properties thereto, comprising a polyoxyalkylene tetrahydrophthalate ester, as defined above, and an organic or inorganic solvent In 25 accordance with yet another aspect, the present invention provides a novel group of polyoxyalkylene tetrahalophthalate ester, being compounds of the formula defined above, where R’ is other than hydrogen.
The polyoxyalkylene tetrahalophthalate compounds (I) used in accordance with this invention can be applied to the fabric (e g a 100 % polyester fabric such as 30 polyethylene terephthalate) either in pure form or in the presence of a solvent.
Solvents such as water, a ketone, an alcohol, an organic ester or a halogenated hydrocarbon can be used When the compound (I) is applied to the fabric in the presence of a solvent, it is preferably applied as a composition containing 50 to 95 parts by weight of solvent and from 5 to 50 parts of the compound (I) In certain 35 instances an alkali metal hydroxide such as potassium and sodium hydroxide, ammonium hydroxide and an alkyl amine may be added in a sufficient amount to adjust the p H to the range of 3 to 7, preferably 4 to 5.
The compounds (I) can be applied to the fabric in any convenient manner such as from an aqueous pad bath This bath can be in the form of a solution, an 40 emulsion, or dispersion The p H of an aqueous fabric-treating bath is generally about 3 to 7 The fabric is passed through the bath to get a sufficient wet pick-up (usually about 70-100 %) The bromine add-on will usually preferably be between I and 4 % in order to meet DOCFF-3-71 specifications The wet fabric is then dried for about 2-4 minutes at about 110 C and cured preferably at a temperature 45 of from 180-210 C, more preferably by heating for about 1/2 to 2 minutes at 190 to C Note that all percentages, unless otherwise stated, are based on the weight of the fabric.
The polyoxyalkylene tetrahalophthalate ester compounds (I) used in accordance with the present invention may be prepared by reacting a tetra 50 halobenzene dicarboxylic acid or anhydride with a molar equivalent of a polyoxyalkylene glycol or its monosubstituted derivative The tetrahalobenzene dicarboxylic acids or anhydrides used as starting materials in preparing the 1,590,605 compounds are either the tetrabromophthalic acid or anhydride or the tetrabromoisophthalic and tetrabromoterephthalic acids or anhydrides isomers Tetrachlorophthalic acid and its isomers can also be used for making the analogous chlorinated compounds.
Representative polyoxyalkylene derivatives useful as starting materials in 5 preparing the compounds used in accordance with this invention are as follows:
1 Polyoxyethylene glycols, HO(CH 2 CH 2 O)n H These glycols are sold under the trade names Carbowax (Registered Trade Mark) and Polyglycol E with a number as part of the trade name, such as: Carbowax 400, Carbowax 600, or Polyglycol E-2000 The number after the name denotes the average molecular 10 weight.
2 Polyoxyethylene methyl alcohols, HO(CH 2 CH 2),CH 3 These derivatives are sold under the trade name Methoxy Carbowax e g Methoxy Carbowax 350.
3 Polyoxyethylene alcohols, HO(CH 2 CH 2 O)n R These derivatives are made by the reaction of either ethylene oxide or the appropriate polyoxyethylene glycol 15 with proton reactive reagents such as carboxylic acid chlorides, phosphoryl chlorides, carboxylic acids or acid anhydrides, isocyanates, etc.
4 Polyoxyalkylene glycols CH 3 1 20 H±(-OCH 2 CH 2)u-OCH-CH) (OCH 2 CH Io OH where n, m, and o are integers, the sum of which results in molecular weights ranging from 150-2000, preferably 150 to 1000 These are mixed polyoxyethylene/polyoxypropylene glycols such as those available from BASF Wyandotte 25 under the trade names Pluracol and Pluronics (Registered Trade Mark).
Polyoxyalkylated polyols These derivatives are derived by reacting ethylene oxide and/or propylene oxide with polyols Straight and branched-chain polyols, sugars, and starches, are included in this class of compounds.
6 Polyoxyethylated fatty acids These derivatives are prepared by the reaction 30 of ethylene-oxide with fats or fatty acids to give, for example, polyoxyethylene fatty glycerides.
7 Polyoxyethylated amines These derivatives are prepared by the reaction of ethylene oxide with fatty amines or alkyl amines.
8 Polyoxypropylene amines, for example, CH 3 CH 3 l I NH 2 CH-CH 2 (OCH 2-CH)XNH These derivatives are sold under the trade name Jeffamines by Jefferson Chemical Co with a letter and number as part of the name, such as Jeffamine D-400 The 35 letter D denotes the compound has two primary amine groups per molecule (T would denote three amino groups per molecule) and the number denotes the average molecular weight.
Representative compounds used in accordance with this invention are as follows (where A is Br or Cl): 40 A A A -COOH A COOH A C Oa-COI CH 2 CH 2019 H A CO O (CH 2 CH 2017 CH 3 A A A A CH 3 A COOH A COOCH 2-CH-OH o 00 A C-NHIlH 2 CH 2 OJ 9 H A COOI(C lH 20)7 CH 3 A 11 A A A A COOH A COOH A COO CH 2 CM 20 14 H A l 01 CH 2 CH 20)SOW A A 1,590,605 1,590,605 COU A COO(CH 2 CH 2 M 6 M A ú 00 I CH 2 CH 2 ON C H 3 A A A COON A COON A 1 A A COO I CH 2 CH 20123 H COON A: O A A A CO O ( CH 2 C H 20 11 5 9 COON A A A O -) COO(CH 2 CM 2019 H A CH 3 1 COOCH 2 CH-ON A A A A COO(CH 2 CH 20)703 COOICH 2 CH 2019 CH 3 A A A A COON A AUB O 11 A COOICH 2 CH 2019-CCH 3 A A A A): 1111,3 CH 3 HOOC A A lyr-1 A A CONNICH-CH 2014-33 CP 2-CP-W A O A A -CH 2 A 111 H -CH 2 \ C-CP 5 A CONHIC 42-CW 20)4-50 CH 2/ A 3 A A COON ACOO(CH 2 CH 20 g-CH 2-CH 2 NICH 3 l 2 A A CW 2-CH 2 A COIN “\ 111 N ( CH 2 12 -17 CH 3 A COO (CH 2 ?-CHZ-0)4 -50 CH 2 CH 2 / A 2 A A 1111 CH 3 COO(CH 2-CH 2019 -CH 2 CH -N (CH 312 A to 1,590,605 5 A A COO I CH 2 CH 2 O WCH 2I CH) 4CHON A ON 0 A c A COON 1 t I HU 14 A COO I CH 2 CH 20)g A A A COO I EW 3 A COO I CH-CM 2013 (CO 2 CH 20110 H A COO (CH 2 CH 20 19 C H 2 CP 2 N (CH 3)2 AA A A COCH CH 3 ú 93 O A 1 1 11 A A COO CH 2 -CH04 MOCH CH 2 CC A A COO 1 CH 2 CH 20 14 -19 A 5 A COO I CH 2 CH 20 PCH 3 A A A A COIIIII A A A COO ICWZ-CM 20 17 C 43 CO O CP 2 CH -OH A 1 CH 3 A ACIII A COO 1 CH 2 CH 2 OM-CCH 2 h-16CH 3 A A A COOH COOH A COOICH 2 CHZO)9-ICI-1 CO O CH 2 CH-CM 2 0 ‘A ‘A CH 3 A 1 ACOOCH 2-CW-OH A O CONHICH 2 CH 2017 CH 3 A 1,590,605 A A >+COON C O H 5 A COO (C H 2 CH 2014-25 lH 2 CH 2 N (C 2 h 73173 A CH 3 A CH-CH 2 CH 3 X NCH 212-17 CH 3 A COOOO(CH 2z 20 1 tO -C CH 2 A -2 The preferred polyoxyalkylene tetrahalobenzene carboxylate esters used in this invention are those prepared by reacting the acid or anhydride with a polyoxyethylene glycol or its derivative having a molecular weight from about 200 to 1000 5 Examples of the preferred compounds of this invention are the polyoxyethylene tetrahalophthalates as follows:
A A COOR A COO Cú 2 CH 201 p R 1 A CH 3 where R is H or -CH 2-CH-OH R 1 is H or CH 3 10 A is Br or Cl p has a value or average value of from 4-23; A ACOON ICOOH Im A l CO (CH 2 C H 2 019 Co V C ADO O n where N is I or 2 and m is 1, 2 or 3 A AA C O CH 2 CP 20)9 jg CCOOCH 2 c H -CH 2 15 A O COOH A COIENA A A A A ClOOH 00 C A A O O ACOICC 2 CH 201 E-z C ‘ A A -E 1 -CH 2 A COONH C,2 C-C 2 H, A’CO c C”E 2 CH 2014-23, C,2 A j-E The compounds (I) used in this invention are clear, almost colorless and odorless viscous liquids They may be prepared in relatively pure form without side reactions or excess reagents remaining and have a halogen (bromine or chlorine) 20 content of preferably about 10 to 50 percent The compounds (I) are normally soluble in acetone, toluene, and perchloroethylene and are either soluble, self715 O O emulsifiable, or easily dispersible in water by the aid of caustic or with the use of 0.01 to 3 percent of a stabilizing surfactant Some typical surfactants include alkyl benzene metal sulfonates (such as Alcolac’s Siponate DS-10 which is dodecyl benzene sulfonate), polyoxyethylene ethers (such as Wyandotte’s Pluronic P 68, L 121, etc), polyoxyethylene or polyoxypropylene derivatives of fatty acid esters of 5 glycerol or other polyols e g those sold under the Registered Trade Marks Span and Tween, and polyoxyethylene derivatives of alkyl phenols e g those sold under the Registered Trade Mark Triton, such as Triton X-100 The alkyl benzene metal sulfonates alone or a mixture with nonionic surfactants are preferred.
The treated polyester fabric is evaluated for soil release (or stain removal) by 10 visual observation using Test Method 130-1974 as described in the Technical Manual of the American Association for Textile Chemists and Colorists (AATCC), Howes Publishing Co, 44 E 23rd Street, New York, with overhead lighting arranged as described in the test procedure The fabrics are stained with Nujol (Registered Trade Mark) according to the test method and additionally with butter, 15 Wesson Oil, and mustard as in the Sears Test TP-I 4; then they are washed according to Test Method 130-1974, placed on a black table top in front of a viewing board having “standard” specimens, and rated according to the criteria shown in the following Table:
TABLE I
Rating Appearance negligible or no staining (excellent cleanability) 4 slightly stained (good cleanability) 3 noticeably stained (fair cleanability) 2 considerably stained (poor cleanability) I heavily stained (very poor cleanability) The treated fabrics are evaluated for water absorbency by AATCC Test Method 79-1975.
The flame retardancy of the treated fabrics is evaluated according to DOC FF-3-71 (Federal Register, Vol 40, No 250, pp 59903-59917, Tuesday, December 30, 1975) Samples were laundered and dried according to AATCC Test 25 Method 124-1969 Samples passing this test have an average char length of not more than 7 0 inches with no individual specimen burning 10 0 inches Samples having a residual flame time greater than 10 seconds fail this test.
The intent of the following Examples is to illustrate the present invention and not to be a limitation thereof 30 Example I.
To 92 8 g ( 0 2 mole) of tetrabromophthalic anhydride is added all at once 80 g ( 0.2 mole) of Carbowax 400 and the mixture heated to 120-130 C for 2 5 hours.
The desired product is isolated in essentially quantitative yield as a clear yellow viscous liquid Calcd Mol Wt, 864; found 865 Calcd % Br, 37 1; found, 38 5 The 35 analytical data are consistent with the assigned structure:
Br Br COOH 0 Br COOICP 2 CH 2019 H Br ov.
Example 2.
To 240 g ( 024 mole) of the compound of Example I is added 45 3 g ( 0 24 mole) of trimellitic anhydride and heated at 155 C under nitrogen for about 7 hours The 40 infrared spectrum indicated the completion of the reaction by the substantial disappearance of the anhydride absorption band at 5 65 The product was isolated in essentially quantitative yield Anal Calcd: %Br, 30 3 %; Mol Wt, 1056; neutralization equivalent, 352; Found: %Br, 29 4; Mol Wt, 1014; neutralization equivalent, 351 The spectral data was consistent with-the structure: 45 1.590605 8 1,590,605 8 Br Br COO I COOH 0 Br cooi C CHCH 2019Cg COON Br av11 0 Example 3.
To 156 3 g ( 0 18 mole) of the compound of Example I is added 70 9 g ( 0 18 mole) 2,3-dibromopropyl trimellitate The mixture is heated at 130-140 C for 6 hours with stirring to give the product as a brown opaque oil Isolation afforded the 5 product in essentially quantitative yield and the analysis is consistent with the structure being:
Br Br COOH CO Ol Br ú 00 CH 2 c H 212019 -cc COOCH 2 C 1-C 2 (and isomers) Br O Br Br EAXMPLES 4 to 9 (The following preparations were carried out as in Example 1 using the reactants set forth below) Tetrabromophthalic Example No Anhydride Hydroxy Compound Product Structure Br Pr úOOH 4 1 0 mole H O CH Cl-1 OCH 2 CH 20 QT OCO(H 2 C 2) 0 V.
1.0 mole Br Br 1 O mole HO(CH 2 CHO 2),H Br I COON (Carbowax 200) Br COIC 2 C 2 04 1.0 mole 6 1 0 mole HO(CH CHO 2), H Br CO (Carbowax 600) pr COO(CH 2 CH 20113 H Br a 1.0 mole Br 7 1 0 mole HO(CH 2 CHP 2 O)H Br COON (Carbowax 1000) Or t O Ol CH 2 CH 20123 H Br OV.
1.0 mole .0 i.0 EXAMPLES 4 to 9 (Continued) (The following preparations were carried out as in Example 1 using the reactants set forth below) Tetrabromophthalic Example No Anhydride Hydrocy Compound Product Structure Br 8 1 0 mole HO(CH 2 CH 2 O)s 45 H r CO (Pelyglycol E-2000) r'” c O cc 20 sav 1.0 mole Or Br 9 2 0 mole HO(CH 2 CH 20),H 9 OH NOO gr’,’ COOICH 2 CH 201 g Br (Carbowax 400) Br aov Br 1.0 mole Example 10.
To 1,392 g ( 3 0 moles) of tetrabromophthalic anhydride is added 1,050 g ( 3 0 moles) of Methoxy Carbowax 350 in the presence of 22 0 g of sodium acetate The mixture is heated at 90 C for 8 hours in a nitrogen atmosphere The reaction mixture is filtered hot to remove the sodium acetate The analytical data are consistent with the assigned structure:
Br Br COOICH 2 CH 201 o 7 CH 3 0 ov.
Br COOH Br rL O b\ C C TABLE I I
Flame Retardancy-Soil Release and Water Wicking Results of Prior Art References and Examples 1 10 using % Undyed Broadcloth Polyester 3 1 oz/yd 2 % Solids Calculated Solvent Flame Retardancy Soil Released Water Wicking Prior Art Add-on % Br or (char length in Seconds b
References Compound or Example (owf) (owf) Application inihes) 50:Wash 5 Wash 10 Wash 5 Wash Fabric Blank BEL a 2.0 2 1 25.5 Br Brw C Oo CH 2 CH 2 OH Brv Y EOOCH 2 CHOH Br CH 3 Br r,COO(CH 2 CH 2019 H Br CO O CH 2 CHOH O Br CH 3 7.3 4 O Acetone 10.8 3.7 Acetone Br Br, CIOICH 2 CH 20)9 H Br COOIH Br A 2.7 2.8 2 O 5.3 B C 3.3 0 0 \ C) 2.4 3.3 TABLE II (Continued) Flame Retardancy-Soil Release and Water Wicking Results of Prior Art References and Examples 1 -10 using % Undyed Broadcloth Polyester 2 1 oz/yd 2 % Solids Add-on (owf) Compound or Example Calculated % Br (owf) Solvent or Applicatioi Flame Retardancy (char length in n inches) 50 Wash Soil Release d Wash 10 Wash Water Wicking Seconds b Wash 1.5 Water 3 1 2 5 2 5 6 3 2.8 2 7 2 5 2 6 11 3 3.8 3 3 2 8 2 6 3 3 Br Br ú COCú 2 CH-CH 20 H Br COOCH 2 C -CH 20 H Br OH Br \ Br ” COON Br 3 where N = 8-7 5 when m= 3 9.7 4 9 Acetone 16.3 2.6 Acetone Triol (polyoxy propylene)3 c Prior Art
References % % 13 % % % % 43.8 27.1 14.1 D E Lt.
O C b, O L/1 2.8 2.8 2.0 1 9 1.9 2 4 3.0 2.7 TABLE 11 (Continued) Flame Retardancy-Soil Release and Water Wicking Results of Prior Art References and Examples 1 10 using o Undyed Broadcloth Polyester 3 1 oz/yd 2 % Solids Calculated Solvent Flame Retardancy Soil Released Water Wicking Prior Art Add-on % Br or (char length in Seconds b
References Compound or Example (owf) (owf) Application inches) 50 Wash 5 Wash 10 Wash 5 Wash Example 1 9 2 3 3 Acetone 3 2 2 5 2 5 3 0 Example 1 16 2 5 9 Acetone 3 5 2 5 2 3 3 5 Example 1 7 2 2 8 Water e 3 7 2 6 2 9 5 7 Example 2 7 3 2 8 Acetone 2 6 2 4 2 1 4 5 Example 3 8 1 3 1 3 4 2 8 2 1 Example 4 6 1 3 4 3 1 3 3 2 3 65 3 Example 5 7 1 3 5 2 7 2 8 2 0 6 6 Example 6 9 0 2 8 Water 2 8 2 8 2 4 12 3 Example 7 10 5 2 3 Watere 3 2 3 3 2 8 4 5 Example 8 21 1 2 7 Water 2 5 2 6 2 5 9 0 Example 9 6 6 3 1 Acetone 2 4 2 8 2 5 7 0 Example 10 9 0 4 0 Water 2 8 2 5 2 4 4 0 Example 10 10 0 3 4 Water 2 7 3 1 2 6 4 0 a BEL signifies Burns Entire Length (Unacceptable) b The lower the number, the better it works.
c Triol starting material obtained from Dow Chemical Co under Registered Trade Mark Voranol (P 4701) mol wt 4830, hydroxyl number 34 7, equivalent wt 1610 d The higher the’number, the better it releases soil.
e Adjusted to p H 7 with ammonium hydroxide.
Example 11.
To 96 4 g ( 0 2 mole) of tetrabromoterephthalic acid is added all at once 160 g ( 0.2 mole) of Carbowax 400 and 300 g toluene containing 1 0 g P-toluene sulfonic acid The mixture is heated to reflux until 3 6 g ( 0 2 mole) water was collected The toluene is removed under reduced pressure to give a clear viscous liquid in 5 essentially quantitative yield The product COOH Br-K Br Brr-‘ Br COO(CH 2 CH 201)9 H o Cv.
gives flame retardant, soil release, and wicking results similar to that obtained for Example I.
Example 12.
To 86 4 g ( 0 1 mole) of the compound of Example I is added all at once 21 8 g 10 ( 0.1 mole) pyromellitic dianhydride and the mixture heated to 120-130 C for 2 5 hours to give the desired product Water, 1 8 g ( 0 1 mole), is added to open the remaining anhydride group and the analytical data are consistent with the assigned structure:
Br Br F CO Of CH 2 CH 20)9-1 0-COO O OV lit Br 0 COON The product gives flame retardant, soil release, and wicking results similar to that obtained for Example 2.
Example 13.
To 86 4 g ( 0 1 mole) of the compound of Example 1 is added all at once 10 9 g 20 ( 0.005 mole) of pyromellitic dianhydride and the mixture heated to 120130 C for 2.5 hours to give the desired product The analytical data are consistent with the assigned structure:
O Br ii Br COO -C 0 COO O Br COOICI 2 CH 201 g O (and isomers) Br Cv HOOC 2 -C I 1 o The product gives flame retardant, soil release, and wicking results similar to that 25 obtained for Example 2.
Example 14.
To 86 4 g ( 0 1 mole) of the compound of Example 1 is added all at once 21 8 g ( 0.1 mole) of phthalic anhydride and the mixture heated to 120-130 C for 2 5 hours to give the desired product The analytical data are consistent with the 30 assigned structure:
Br Br COOH HOOC Br/ COO(C 2 CH 209 C,Br or U The product gives flame retardant, soil release, and wicking results similar to that obtained for Example 2.
1,590,605 Example 15.
To 139 2 g ( 0 3 mole) of tetrabromophthalic anhydride is added all at once 122 9 g ( 0 1 mole) polyoxyethylated trimethylol propane of molecular weight 1229 and the mixture heated to 120-130 C for 2 5 hours to give the desired product.
The analytical data are consistent with the assigned structure: 5 Br CH 2 Br COOH PO -CH 2 \C-C 2 HS Br O C O (HZCH 20)9CH Br a 3 2 The product gives flame retardant, soil release, and wicking results similar to that obtained for Example 7.
Example 16.
To 139 2 g ( 0 3 mole) of tetrabromophthalic anhydride is added all at once 10 156 8 g ( 0 1 mole) polyoxypropylate trimethylol propane of molecular weight 1568 and the mixture heated to 120-130 C for 2 5 hours to give the desired product.
The analytical data are consistent with the assigned structure:
Br Br -COO N 0 o |C 3 -CH,-C-C 2 Hs Br COO(CH 2 CP 20)g Br av -CH 2 -3 The product gives flame retardant, soil release, and wicking when applied to 15 polyester.
Example 17.
To the composition of Example 10 ( 3 0 moles) are added 348 0 g ( 6 0 moles) of propylene oxide and 2 0 liters of toluene The mixture is heated at 60-100 C The solvent and residual propylene oxide are removed to give the product in almost 20 quantitative yield The analytical data are consistent with the assigned structure:
Br Br COOICH 2 CH 201 ov 7 CH 3 o O cv.
Br COOCH 2-CH-OH Br CH 3 Example 18.
To 93 1 grams of the composition of Example 17 is added and mixed thoroughly a solution of 1 7 grams of dodecylbenzene sulfonate in 5 2 grams water 25 Stable pad baths are prepared by adding 15 0 grams of the above composition mixture to 85 grams water Fabric samples are padded using 2 dips and 2 nips with the roll pressures adjusted to give 90-100 % wet pick-up The fabrics are then dried for 7 to 9 minutes (or until dry) at 100 C and then thermosolled for 90 seconds at 400 F Afterwashing is done in washing machine at the hottest water setting using 30 24 grams of Tide (Registered Trade Mark) detergent per 18 gallons of water and a minute wash cycle Fabrics are then rinsed and tumble dried.
Char lengths were measured (DOC FF-3-71) after 25 and 50 launderings using fabric samples that were restrained by stitching up the middle with a double seam of fire retardant spun polyester thread (Threads, Inc, “Sewkay FlameOut”, 35 size 100/2) Bromine analyses were performed after I and 50 launderings.
The fabrics were also evaluated for soil release and water wicking after several launderings The results are summarized in the Table III below.
1,590,605 TABLE III a,b,d Water Wickingb Soil Release c DOCFF-3-71 Total % % Bromine Char Length Fabric Add-on Initial a SW (secs) 5 W 10 W 50 W inches Commercial Fabric, 3 1 oz/yd 2 10 4 9 3 3 3 Undyed Broadcloth 0 O 90 2 2 BEL a Approx 50-60 % Br is retained after 50 washes.
b The lower the number, the better.
c The higher the number, the better d Average of 5 samples Example 19.
To 284 0 g ( 1 0 mole) of tetrachlorophthalic anhydride is added 350 0 g ( 1 O mole) of Methoxy Carbowax 350 in the presence of 7 0 g of sodium acetate The mixture is heated at 90 C for 8 hours in a nitrogen atmosphere The reaction 5 mixture is filtered hot to remove sodium acetate to give the expected product in nearly quantitative yield The analytical data are consistent with the assigned structure:
c L Cl ECOOICI 2 C)H 07 nv CH 3 cl cl Application of the above compound in an aqueous solution to polyester fabric 10 as described in Example 18 imparted flame retardancy.
0 ‘ l I s 7 Example 20.
To 634 0 g ( 1 0 mole) of the composition of Example 19 is added 116 g ( 2 0 moles) of propylene oxide in 200 ml of toluene The reaction mixture is heated from 60-100 C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield The analytical data are consistent with the assigned structure: 5 lI CI C’0 10 C’ 2 CH 2 C O 7 Hv CI 13 Cl-1 úO 00 H 2 CH-OH Cl CH 3 Application of the above compound in an aqueous solution to polyester fabric as described in Example 18 imparts flame retardancy.
Example 21 10
To 284 0 g ( 1 0 mole) of tetrachlorophthalic anhydride is added 200 0 g ( 1 0 mole) of Carbowax 200 in the presence of 7 0 g of sodium acetate The mixture is heated at 90 C for 8 hours in a nitrogen atmosphere The reaction mixture is filtered hot to remove sodium acetate to generate the expected product in nearly quantitative yield The analytical data are consistent with the assigned structure:
cl O co 15 C l COOH Cl Application of the above compound in an aqueous solution to polyester fabric as described in Example 18 imparts flame retardancy.
Example 22.
To 484 0 g ( 1 0 mole) of the product of Example 21 is added 116 0 g ( 2 0 mole) of propylene oxide in 200 ml of toluene The reaction mixture is warmed at 20 60-100 C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield The analytical data are consistent with the assigned structure:
cl Cl O COOICH 2 CH 20 I (,VH 0 C ‘COOCH 2-CH-OH CH 3 Application of the above compound in an aqueous solution to polyester fabric as described in Example 18 imparts flame retardancy 25 Example 23.
To 284 0 g ( 1 0 mole) of tetrachlorophthalic anhydride is added 400 0 g ( 1 0 mole) of Carbowax 400 in the presence of 7 0 g of sodium acetate The mixture is heated at 90 C for 8 hours in a nitrogen atmosphere The reaction mixture is filtered hot to remove sodium acetate to generate the expected product in nearly 30 quantitative yield The analytical data are consistent with the assigned structure:
rl CO Ol CH 2 CH 2 O Iv H El lDO Application of the above compound in an aqueous solution to polyester fabric imparted flame retardancy.
Example 24.
To 46 4 g ( 0 1 mole) of tetrabromophthalic anhydride is added all at once 44 1 35 g ( 0 1 mole) of the polyoxyethylated dimethylamine 1.590605 117 lCH 3)2 N(CH 2 CH 20),Hl dissolved in 100 ml of toluene The mixture was heated at 100-110 C for 45 hours and then concentrated to give the desired product in essentially quantitative yield The analytical data are consistent with the assigned structure:
Hoe per 5 I CU 3)2 Nl-C 2 CH 20 19 c, C Br I Br (CIH 3)2 Nl-Cw,2 CH 20- 19 v C, Br, B r Application of the above compound in an aqueous solution to polyester fabric imparts flame retardancy.
Example 25. To 92 8 g ( 0 2 mole) of tetrabromophthalic anhydride is added 80 0 g ( 0
2 mole) of 10 CH 3 CH 3 H 2 N-CH-CH 2 l(OCH 2 CH-l 5 8 v NH 2 (Jeffamine D-400) and the mixture heated to about 120 C The final product is obtained in almost quantitative yield The analytical data are consistent with the assigned structure:
Br Br COOH O C 3 CH 3 15 Br y CONHCH -CH 2 10 CH 2-CH-ls 6 Ev NH 2 Br Application of the above compound in an aqueous solution to polyester fabric imparts flame retardancy.

Claims (19)

WHAT WE CLAIM IS:-

1 A polyoxyalkylene tetrahalophthalate ester or ester mixture of the formula:
ROOC O 01 R 2 l C Hzlp R’ (II 20 wherein: R is hydrogen, C 1-Co alkyl, C 2-C,0 hydroxyalkyl or C 3-C 10 polyhydroxyalkyl; R’ is a group having a valency equal to q and selected from saturated hydrocarbon groups of from 1-12 carbon atoms and optionally containing one or more hydroxy substituents, C 2-C 19 alkanoyl or 25 hydroxyalkanoyl (including polyfunctional alkanoyl and hydroxyalkanoyl), and groups of the formulae:
lCOO Hlm O -C l( COOCH 2 CH-C Hi 2 -CO X A A ( )n COOH ( O)n IH COOH O COOR CH 1 N0 A)& Aj 1,590,605 R 3 R 4 R 3 R 4 I I I (-CHCH)NR 5 R 8, (-CHCH)2 NRB and R 3 R 4 l l (-CHCH)3 N, where R 2 is H or CH 3-; R 3 and R 4 are each H or C,-C,8 alkyl; W’R and R’ are each H, C,-C,8 alkyl or C,,H; 5 p is an integer whose value or average value is from 4 to 50; q is an integer of I to 6; n is 0 or 1; m is 1, 2 or 3; X is O or NH, and 10 A is Cl or Br-.

2 An ester or ester mixture according to claim 1, which is of the formula:
A A, COOR A CO CIH 2 CH 201 p R 1 A where A is Cl or Br; CH 3 R is H or -CH 2-CH-OH; 15 R’ is H or CH 3; and p has a value or average value of from 4-23.

3 An ester or ester mixture according to claim 1, which is of the formula:
A C 00 Hl OOH IM A CO IC 1 CH 2 CH 2 O g 19 o m -C 4 i A O o n where A is Cl or Br; 20 n is I or 2, both being the same; m is 1, 2 or 3.

4 An ester or ester mixture according to claim 1, which is of the formula:
A A COOH A’CO( CH 2 C 201901 C 9 OOCH 2 C 1 H CH 2 A O O O RH A A where A is Br or Cl.

An ester or ester mixture according to claim 1, which is of the formula: 25 A 4 Atr COOH HO Ot A A’ COICH 2 CH 209 a&C A A R d A where A is Br or Cl.

6 An ester or ester mixture according to claim 1, which is of the formula:
1,590,605 A ‘ COOH CH 2 C C 2 H 5 A < CO I CH 2 CH 2 014-23 Gv_ H/ A 2 7 A method of imparting flame retardant properties to polyester fabrics, which comprises depositing on the fabric a flame retardant composition comprising a polyoxyalkylene tetrahalophthalate ester or ester mixture of the formula set out in claim 1, where R, R', R 2, R 3, R 4, R 5, RM, p, q, n, m, X and A are as defined in 5 claim 1, with the proviso that R' may also represent hydrogen. 8 A method according to claim 7, wherein the flame retardant composition comprises a polyoxyalkylene tetrahalophthalate ester or ester mixture as claimed in any one of claims 2-6. 9 A method according to claim 7 or 8, wherein sufficient flame retardant com 10 position is deposited on the fabric to provide a bromine or chlorine content of from I to 4 % based on the weight of the fabric. A method according to claim 7, 8 or 9 which comprises impregnating fabric with a solution or dispersion of the polyoxyalkylene tetrahalophthalate ester or ester mixture in a liquid medium, drying the impregnated fabric and curing the 15 dried fabric at a temperature in the range 180 to 210 'C. 11 A method according to claim 10, wherein the polyoxyalkylene tetrahalophthalate ester is applied to the fabric from an aqueous medium. 12 A polyester fabric containing, as a flame retardant, a polyoxyalkylene tetrahalophthalate ester or ester mixture of the formula set out in claim 1, wherein 20 R, R', R 2, R 3, R 4, R 5, RW, p, q, n, m, X and A are as defined in claim 1, with the proviso that R' may also represent hydrogen. 13 A polyester fabric according to claim 12, wherein the flame retardant is an ester or ester mixture as claimed in any one of claims 2-6. 14 A polyester fabric according to claim 12 or 13, wherein the flame retardant 25 agent is sufficient to provide a bromine or chlorine content of from 1-4 % based on the weight of the fabric. A composition for the treatment of polyester fabrics to impart flame retardant properties thereto, said composition comprising a solution or dispersion of an ester or ester mixture of the formula set out in claim 1, wherein R, R', R 2, R 3, 30 R 4, R 5, R", p q n, m, X and A are as defined in claim 1, with the proviso that R' may also represent hydrogen, in a solvent selected from water, acetone, toluene or perchloroethylene, said composition containing from 50-95 parts by weight of solvent and 50-5 parts by weight of said ester or ester mixture. 16 A composition according to claim 15, wherein the ester or ester mixture is 35 as defined in any one of claims 2-6. 17 A composition according to claim 15 or 16, which is an aqueous composition having a p H of from 3-7. 18 A composition according to claim 17, wherein said p H is from 4-5. 19 A composition according to claim 17 or 18 which contains from 0 01 to 3 % 40 by weight of a surfactant. For the Applicants, D YOUNG & CO, Chartered Patent Agents, 9 Staple Inn, London, W C I. Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981. Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained. I 1,590,605 GB365/78A 1977-02-25 1978-01-05 Polyocyalkylene tetrahalophthalate ester as textile finishing agent Expired GB1590605A (en) Applications Claiming Priority (1) Application Number Priority Date Filing Date Title US05/772,043 US4098704A (en) 1977-02-25 1977-02-25 Polyoxyalkylene tetrahalophthalate ester as textile finishing agent Publications (1) Publication Number Publication Date GB1590605A true GB1590605A (en) 1981-06-03 Family ID=25093727 Family Applications (1) Application Number Title Priority Date Filing Date GB365/78A Expired GB1590605A (en) 1977-02-25 1978-01-05 Polyocyalkylene tetrahalophthalate ester as textile finishing agent Country Status (4) Country Link US (1) US4098704A (en) CA (1) CA1147744A (en) DE (2) DE2759028A1 (en) GB (1) GB1590605A (en) Families Citing this family (36) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title US4298517A (en) * 1978-12-22 1981-11-03 Pennwalt Corporation Tetrahalophthalates as flame retardant plasticizers for halogenated resins US4239635A (en) * 1979-06-11 1980-12-16 Cincinnati Milacron Inc. 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