GB1588642A – Flame-retardant fibres and filaments of linear thermoplastic polyesters
– Google Patents
GB1588642A – Flame-retardant fibres and filaments of linear thermoplastic polyesters
– Google Patents
Flame-retardant fibres and filaments of linear thermoplastic polyesters
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Publication number
GB1588642A
GB1588642A
GB41784/77A
GB4178477A
GB1588642A
GB 1588642 A
GB1588642 A
GB 1588642A
GB 41784/77 A
GB41784/77 A
GB 41784/77A
GB 4178477 A
GB4178477 A
GB 4178477A
GB 1588642 A
GB1588642 A
GB 1588642A
Authority
GB
United Kingdom
Prior art keywords
filaments
fibers
polyester
flame
brominated
Prior art date
1976-10-09
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
GB41784/77A
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.)
BASF SE
Original Assignee
BASF SE
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.)
1976-10-09
Filing date
1977-10-07
Publication date
1981-04-29
1977-10-07
Application filed by BASF SE
filed
Critical
BASF SE
1981-04-29
Publication of GB1588642A
publication
Critical
patent/GB1588642A/en
Status
Expired
legal-status
Critical
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Classifications
D—TEXTILES; PAPER
D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
C08K3/00—Use of inorganic substances as compounding ingredients
C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
C08K3/20—Oxides; Hydroxides
C08K3/22—Oxides; Hydroxides of metals
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
C08K5/00—Use of organic ingredients
C08K5/02—Halogenated hydrocarbons
C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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
Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y10S260/00—Chemistry of carbon compounds
Y10S260/24—Flameproof
Description
PATENT SPECIFICATION ( 11) 1 588 642
r ( 21) Application No 41784/77 ( 22) Filed 7 Oct 1977 19 t ( 31) Convention Application No 2645711 ( 32) Filed 9 Oct 1976 in ( 33) Fed Rep of Germany (DE) ( 44) Complete Specification Published 29 Apr 1981 tn ( 51) INT CL 3 C 08 K 5/03 ( 52) Index at Acceptance C 3 K 200 201 ED C 3 W 317 ( 54) FLAME-RETARDANT FIBERS AND FILAMENTS OF LINEAR THERMOPLASTIC POLYESTERS ( 71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, 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 particularly described in and by the following Statement:-
The present invention relates to flame-retardant fibers and filaments of linear 5 thermoplastic polyesters.
Processes for flameproofing fibers of linear polyesters have been disclosed For example, it has been proposed to introduce halogen-containing or phosphoruscontaining monomers into the molecular chain as integral constituents of the chemical structure The principal disadvantage of this approach is that the molar concentration of the comonomers required 10 to achieve the desired degree of non-flammability is generally so high that the end product has entirely different physical properties from those of conventional polyesters and is therefore less suitable for the manufacture of fibers.
It has also been proposed to admix halogen-containing organic compounds to the polyester Such compounds however mostly act as pigments and thus adversely affect the 15 mechanical properties of the fibers A further disadvantage of such additives is that when washing or drycleaning is necessary, such treatment easily removes the additives from the fibers Furthermore, such additives are frequently substances of high melting point (for example the melting point of decabromodiphenyl ether = 306 ‘C), which presents problems in using them for relatively low-melting polymers In addition, such compounds tend to be 20 very volatile at high temperature, leading to the known plate-out effect.
The present invention seeks to provide flame-retardant polyester filaments and fibers with improved properties compared to the prior art.
According to the present invention, there are provided filaments and fibers of a linear, thermoplastic polyester which contain a halogen compound as flameproofing agent, 25 wherein the fibers and filaments contain a chlorinated and/or brominated oligomeric styrene containing up to 100 monomer units as the flameproofing agent.
Fibers and filaments within the invention have the advantage that their flame-retardant finish is durable and that they do not lose this property even after repeated cleaning They have the further advantage that the flameproofing agent does not migrate out and has little 30 effect on the dyeability Furthermore, there is little effect on the textile properties of the filaments and fibers.
The degree of polymerization of the oligomers is especially from 3 to 20 and cyclic oligomers may also be used According to a preferred embodiment of the invention, the chlorinated and/or brominated oligomeric styrenes to be employed have the formula I 35 shown below, where X = Cl or Br (individual X’s being identical or different), R = H or an aliphatic radical, especially an alkyl radical, e g CH 3 or C 2 H 5, m is an integer from 1 to 5, and n, the degree of polymerization, is from 3 to 100.
40) 40 4 C-CH 54 R _n 45 1 588 642 The oligomeric styrenes may of course contain chlorine and bromine simultaneously.
Amongst the halogen substituents X, bromine is particularly preferred; advantageously, the oligomeric styrenes contain from 40 to 80 % by weight of bromine They may be manufactured by, for example, bromination of hydrogenated oligomeric styrenes.
Brominated oligomeric styrenes produced from naturally occurring oligostyrenes may also 5 be used, though their heat stability is lower than that of the firstmentioned brominated oligomeric styrenes The flame-proofing agents obtainable by polymerizing bromostyrenes can also be used, as can the brominated oligostyrenes obtainable from styrene and bromine by a single vessel process.
The fibers and filaments may contain a synergistic agent for the flameproofing agent 10 Virtually all conventional synergistic agents may be used as the synergistic agents for the brominated oligomeric styrenes; oxides of metals of group Vb of the periodic table, especially antimony trioxide, Sb 203, are particularly preferred Antimony trioxide which has been precipitated on suitable inorganic carriers, e g finely divided kaolin, calcined kaolin or talc, is particularly active 15 The amount of brominated oligostyrenes required for the flameproofing of polyester fibers depends on the bromine content of the oligostyrenes; the bromine content in the fibers or filaments of the invention may be, for example, from 2 to 20 %, preferably from 5 to 15 %, by weight The amount of Sb 2 03 is suitably from 2 to 10 %, preferably from 3 to 6 %, by weight In addition, conventional anti-drip additives, e g colloidal Si O 2, may also 20 be added.
The preferred linear saturated polyester is polyethylene terephthalate, which may be modified with up to 15 mole% of one or more other dicarboxylic acids or diols.
Examples of suitable modifiers are aliphatic dicarboxylic acids of up to 20 carbon atoms, cycloaliphatic dicarboxylic acids or aromatic dicarboxylic acids with 1 or 2 aromatic rings 25 Specific examples are adipic acid, sebacic acid, cyclohexanedicarboxylic acid, isophthalic acid and 2,7 and 2,6-naphthalenedicarboxylic acid Suitable alcoholic modifiers are in particular aliphatic and cycloaliphatic glycols of 2 to 20 carbon atoms Examples are propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol and 1,4-bishydroxymethylcyclohexane 30 The chlorinated and/or brominated oligostryenes can be introduced into the linear, saturated polyester fibers or filaments at any stage of their process of manufacture in order to produce the compositions of the present invention In general, they are added before production of the fiber, toward the end of the manufacture of the polyester, or during the spinning process In a preferred process of manufacture, the brominated oligostyrenes are 35 added to the molten polyester during melt spinning and the molten mixture is spun in the conventional manner to give filaments or fibers.
The relative viscosities flrcl of the polyesters in the Examples which follow were determined in a 3:2 mixture of phenol and o-dichlorobenzene.
The LOI test is used below as a criterion for assessing the flameretardant properties of 40 the fibers and filaments of the invention This test is carried out as follows: a vertically arranged sample, in a combustion tube through which a mixture of oxygen and nitrogen flows at a defined velocity, is ignited at the top by means of a gas flame The ratio of oxygen to nitrogen in the mixture is then varied until the sample burns away uniformly with a minimal flame The LOI value is then calculated as follows 45 Lol 2 l 2 20 50 According, the LOI value indicates the percentage proportion of oxygen, in an oxygen/nitrogen mixture, which is just sufficient to allow the vertically clamped sample to burn away uniformly from top to bottom.
The test used below to determine the non-extractability of flameproofing additives was carried out as follows: 10 g of the fibers to be examined were boiled in 350 ml of an organic 55 solvent (e g trichloroethylene) for 6 hours under reflux.
The filaments and fibers according to the invention include those which can be used for the manufacture of textiles of low flammability, e g carpeting or curtains.
The Examples which follow illustrate the invention.
60 Example 1
Dried polyethylene terephthalate (K value 56) is mixed, in a mixing extruder, with the particular amount of brominated oligostyrene at from 280 to 300 C and the melt is extruded, into a water bath, as strands which are then granulated The polyester chips thus obtained are then melt-spun by conventional processes 65 1 588 642 Example 2
In a modified procedure, the relevant amount of brominated oligomeric styrene is added to a molten polyethylene terephthalate (K value 60) in a spinning extruder, and the melt is spun to give fibers or filaments.
The results obtained are set out in the following Table as compared with other halogen-containing additives introduced in the same way.
The procedures in the two Examples give essentially similar results.
TABLE I
Extraction test Polyethylene terephthalate fibers with brominated additive oligostyrenes as a flameproofing Br content of the fibers LOI value of before extraction after extraction the fibers 2.5 % 2 1 % 24 5 5.6 % 4 4 % 26 O 6.3 % 5 2 % 26 5 9.4 % 6 4 % 28 12.6 % 8 1 % 29 13.5 % 8 5 % 29 5 15.7 % 9 5 % 30 COMPARATIVE EXPERIMENTS Polyethylene terephthalate fibers with other halogen-containing additives Type of additive Halogen content of the fibers before extraction after extraction 3.4 % Br O 5 % Br Hexabromodiphenyl 8 5 % Br O 8 % Br 11.5 % Br O 9 % Br Cl Cl cl cl cllcl Cl 7 9 % Cl O 6 % Cl Cl Cl 10 8 % Cl O 8 % Cl Cl Cl
Claims (1)
WHAT WE CLAIM IS:-
1 Fibers and filaments of a linear, thermoplastic polyester containing a halogencontaining flameproofing agent which is a chlorinated and/or brominated oligomeric styrene containing up to 100 monomer units.
2 Polyester fibers and filaments as claimed in claim 1, which contain, as chlorinated 1 588 642 and/or brominated oligomeric styrene, material of the formula I 5 C-CH 2 R 10 where X is chlorine or bromine, individual X’s being identical or different, R is hydrogen or an aliphatic radical, N is a integer from 3 to 100 and m is an integer from 1 to 5.
3 Polyester fibers and filaments as claimed in claim 1 or 2, in which the chlorinated and/or brominated oligomeric styrene has a degree of polymerization of from 3 to 20 15 4 Polyester fibers and filaments as claimed in any of claims 1 to 3, in which a brominated oligomeric styrene containing from 40 to 80 % by weight of bromine is used as flame-proofing agent.
Polyester fibers and filaments as claimed in any of claims 1 to 4, in which a brominated oligomeric styrene is used as flame-proofing agent in an amount such that the 20 bromine content of the fibers is from 2 to 20 % by weight.
6 Polyester fibers and filaments as claimed in any of claims 1 to 5, in which the polyester is polyethylene terephthalate.
7 Polyester fibers and filaments as claimed in any of claims 1 to 6, which also contain antimony trioxide as synergistic agent for the flameproofing agent 25 8 Polyester fibers and filaments as claimed in claim 7, in which the antimony trioxide is present in an amount from 3 to 6 % by weight.
9 Polyester filaments and fibers as claimed in any of claims 1 to 8, in which the flameproofing agent is added to molten polyester during melt spinning and the molten mixture is then spun to give filaments or fibers 30 Polyester filaments and fibers as claimed in claim 1 and substantially as hereinbefore described.
11 Fabrics comprising polyester filaments or fibers as claimed in any of claims 1 to 10.
J Y & G W JOHNSON, 35 Furnival House, 14-18 High Holborn, London, WC 1 V 6 DE.
Chartered Patent Agents, Agents for the Applicants 40 Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1981.
Published by The Patent Office 25 Southampton Buildings, London, WC 2 A l AY from which copies may be obtained.
GB41784/77A
1976-10-09
1977-10-07
Flame-retardant fibres and filaments of linear thermoplastic polyesters
Expired
GB1588642A
(en)
Applications Claiming Priority (1)
Application Number
Priority Date
Filing Date
Title
DE2645711A
DE2645711C3
(en)
1976-10-09
1976-10-09
Fibers and threads made from linear, thermoplastic polyesters and containing halogen-containing flame retardants
Publications (1)
Publication Number
Publication Date
GB1588642A
true
GB1588642A
(en)
1981-04-29
Family
ID=5990110
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
GB41784/77A
Expired
GB1588642A
(en)
1976-10-09
1977-10-07
Flame-retardant fibres and filaments of linear thermoplastic polyesters
Country Status (11)
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US
(1)
US4151223A
(en)
JP
(1)
JPS5349124A
(en)
AT
(1)
AT351143B
(en)
BE
(1)
BE859463A
(en)
CA
(1)
CA1111165A
(en)
CH
(1)
CH629854A5
(en)
DE
(1)
DE2645711C3
(en)
FR
(1)
FR2367126A1
(en)
GB
(1)
GB1588642A
(en)
IT
(1)
IT1086069B
(en)
NL
(1)
NL7711055A
(en)
Cited By (1)
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Priority date
Publication date
Assignee
Title
EP0048483A1
(en)
*
1980-09-22
1982-03-31
Toray Industries, Inc.
Flame retarding polyester composition
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Assignee
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DE2905253C3
(en)
*
1979-02-12
1986-01-09
Chemische Fabrik Kalk GmbH, 5000 Köln
Fire protection components for thermoplastics
US4338243A
(en)
*
1980-05-07
1982-07-06
E. I. Du Pont De Nemours And Company
Polyethylene terephthalate blends
JPS5798553A
(en)
*
1980-12-11
1982-06-18
Toray Ind Inc
Flame-retardant polyethylene terephthalate composition
US4755573A
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1985-11-15
1988-07-05
General Electric Company
Cationic polymerization of bromoalkenyl aromatic compounds with aromatic chain transfer agent, and products
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1988-04-05
1991-09-10
Phillips Petroleum Company
Polyethylene terephthalate molding resin blends
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1991-07-09
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Rapidly crystallizing polyethylene terephthalate blends
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1989-06-06
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Ferro Corporation
High impact polystyrene containing low molecular weight brominated polystyrene
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Ferro Corporation
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1990-06-20
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Great Lakes Chemical Corporation
Flame retardant brominated styrene-based polymers
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Hoechst Ag
Fully oriented polyester yarn and process for its production.
US6518368B2
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Albemarle Corporation
Brominated polystyrene having improved thermal stability and color and process for the preparation thereof
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Ferro Corporation
Process for the preparation of brominated polystyrene having improved color characteristics
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Brominated polysytrene having improved thermal stability and color and process for the preparation thereof
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Process for brominating polystyrenic resins
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METHOD FOR BROWNING STYRENE POLYMERS
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Brominated polystyrenic resins
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*
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2001-05-22
Albemarle Corporation
Polymer compositions containing brominated polystyrenic resins
US6232408B1
(en)
1996-09-26
2001-05-15
Albemarle Corporation
Brominated polstyrenic resins
US6232393B1
(en)
1996-09-26
2001-05-15
Albemarle Corporation
Polymers flame retarded with brominated polystyrenic resins
US5686538A
(en)
*
1996-09-26
1997-11-11
Albemarle Corporation
Process for brominating polystyrenic resins
US7666944B2
(en)
*
2004-01-21
2010-02-23
Albemarle Corporation
Flame retarded fibers and filaments and process of production therefor
US20050159552A1
(en)
*
2004-01-21
2005-07-21
Reed Jon S.
Flame retarded fibers and filaments and process of production therefor
MX2009013178A
(en)
2007-06-07
2010-02-17
Albemarle Corp
Adducts, adducts and oligomers, or adducts, oligomers and low molecular weight polymers, and their preparation.
US8993684B2
(en)
*
2008-06-06
2015-03-31
Albemarle Corporation
Low molecular weight brominated polymers, processes for their manufacture and their use in thermoplastic formulations
JO3423B1
(en)
*
2008-12-02
2019-10-20
Albemarle Corp
Brominated Flame Retardants And Precursors Therefor
WO2010065462A2
(en)
*
2008-12-02
2010-06-10
Albemarle Corporation
Toluene and styrene derived telomer distributions and brominated flame retardants produced therefrom
EP2479210A1
(en)
*
2008-12-02
2012-07-25
Albemarle Corporation
Branched and star-branched styrene polymers, telomers, and adducts, their synthesis, their bromination, and their uses
KR20110103942A
(en)
*
2008-12-02
2011-09-21
알베마를 코포레이션
Bromination of telomer mixtures derived from toluene and styrene
US20100136334A1
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2008-12-02
2010-06-03
Israeli Processing Co., Ltd.
Fire Retardant Thread and Method of Manufacture
KR20120088535A
(en)
2009-05-01
2012-08-08
알베마를 코포레이션
Pelletized low molecular weight brominated aromatic polymer compositions
JO3059B1
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2009-05-01
2017-03-15
Albemarle Corp
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Assignee
Title
NL128916C
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*
1965-02-18
1900-01-01
CH584731A5
(en)
*
1973-12-17
1977-02-15
Ciba Geigy Ag
1976
1976-10-09
DE
DE2645711A
patent/DE2645711C3/en
not_active
Expired
1977
1977-08-31
IT
IT27121/77A
patent/IT1086069B/en
active
1977-09-14
US
US05/833,062
patent/US4151223A/en
not_active
Expired – Lifetime
1977-09-15
CA
CA286,782A
patent/CA1111165A/en
not_active
Expired
1977-10-06
BE
BE181527A
patent/BE859463A/en
unknown
1977-10-06
CH
CH1224377A
patent/CH629854A5/en
not_active
IP Right Cessation
1977-10-07
GB
GB41784/77A
patent/GB1588642A/en
not_active
Expired
1977-10-07
NL
NL7711055A
patent/NL7711055A/en
not_active
Application Discontinuation
1977-10-07
AT
AT716877A
patent/AT351143B/en
not_active
IP Right Cessation
1977-10-07
FR
FR7730293A
patent/FR2367126A1/en
active
Granted
1977-10-08
JP
JP12053977A
patent/JPS5349124A/en
active
Pending
Cited By (1)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
EP0048483A1
(en)
*
1980-09-22
1982-03-31
Toray Industries, Inc.
Flame retarding polyester composition
Also Published As
Publication number
Publication date
BE859463A
(en)
1978-04-06
JPS5349124A
(en)
1978-05-04
DE2645711A1
(en)
1978-04-13
FR2367126B3
(en)
1980-06-06
CA1111165A
(en)
1981-10-20
DE2645711C3
(en)
1979-06-07
NL7711055A
(en)
1978-04-11
DE2645711B2
(en)
1978-10-05
FR2367126A1
(en)
1978-05-05
IT1086069B
(en)
1985-05-28
AT351143B
(en)
1979-07-10
CH629854A5
(en)
1982-05-14
ATA716877A
(en)
1978-12-15
US4151223A
(en)
1979-04-24
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1976-07-13
Substantially non-inflammable acrylonitrile copolymers containing antimony
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(en)
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Soil release polyester composition having improved washing durability and fiber thereof
Legal Events
Date
Code
Title
Description
1981-07-15
PS
Patent sealed [section 19, patents act 1949]
1984-06-13
PCNP
Patent ceased through non-payment of renewal fee
