FI58785C - FORMSTYCKEN BESTAOENDE AV LINEAERA FOSFORHALTIGA POLYESTRAR - Google Patents

Description

ANNOUNCEMENT CQ7RC

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Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 23 ^ 6707.0 (71) Hoechst Aktiengesellschaft, 6230 Frankfurt / Main 80, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (72) Hans-Jerg Kleiner, Bad Soden / Taunus, Manfred Fink Fischbach / Taunus, Ulrich Bollert, Diedenbergen / Taunus, Walter Hervig, Neuenhain / Taunus, Federal Republic of Germany-Föbundsrepubliken Germany (7) (5for) Oy Kolster Ab (5¾) 62) Divided by application 2685 / 7¾ (publication 5878¾) -Avdelad fr & n ansökan 2685 / 7¾ (utläggningsskrift 5878¾)

The invention relates to shaped articles consisting of non-flammable synthetic linear polyesters modified with carboxyphosphinic acids.

Preparations, such as yarns and fibers, formed from linear polyesters containing phosphorus-containing compounds in a polymer molecule are known. Various phosphoric acids and their derivatives, including phosphonic and phosphinic acids, have been used as the phosphorus-containing modifying compounds. German Offenlegungsschrift No. 1,243,819 describes yarns and fibers made from polyesters modified with phosphonic acid esters, the yarns and fibers being highly colorable with basic and dispersible dyes and, in addition, being low-reflective.

Phosphonic and phosphinic acids or their esters are added to the processes described in German Publication No. 1,520,079 and 1,595,598 to 2,58785 for the preparation of a fiber-forming linear polyester and for bonding to polymer chains. The purpose of this modification is also in this first and foremost to improve the dyeability of the corresponding yarns and fibers.

Nothing else means polyester modification with bis- (p-carboxy-phenyl) -phosphinic acid in the process described in German Offenlegungsschrift 1,232,348.

However, it is also known that polyesters containing phosphorus-containing compounds may have flame retardant properties. Thus, mixed polyesters with phosphonic acid moieties which are refractory and heat-resistant are known from French patent FR-PS 1 196 971. These mixed polyester products can be used as fire retardants and impregnants, adhesives, varnishes and impregnants for paper and textiles, and as an intermediate. Instead, spinning into yarns and fibers is not possible because the phosphorus content leads to embrittlement of the products.

It has further been proposed that refractory polyesters be prepared by condensing alkylene, arylene or aralkylene diphosphinic acids which may still contain other heteroatoms such as F, Cl, Br, O and S into the polyester molecule, these polyesters being processable into yarns and fibers and shaped articles (German Public Revenue Publications 22 36 037, 23 28 343, 22 36 038 and 22 36 039). However, according to phosphinic acids, condensation is not quite simple in this case, due in part to their considerable volatility at condensing temperatures. Therefore, non-volatile oligomers of diphosphinic acids with diols are usually used for this condensation, for which, of course, these oligomers have to be prepared.

Finally, refractory polyesters have also been prepared by incorporating polyester-phosphorus compounds that are not incorporated into polymer chains. According to both JA-Publication publications 7 142 230 and 7 142 231, certain phosphoric acid esters of halogen-containing aromatic dihydroxy compounds and polyphosphonates and poly (phosphonate phosphates) according to BE-PS 769 229 have been used as such additives. Although the addition of these additives results in good but not permanent fire protection properties, a few disadvantages cannot be ignored. These depend above all on the considerable transferability of the additives 3,58785 in the polymers. On the one hand, this results in a certain toxicity of the corresponding polymer products, but on the other hand also a relatively easy washability of the additives. For example, in the chemical cleaning of similar fiber products. By washing away the additives, the polymer products then naturally lose their fire-retardant effect.

In the manufacture of fibers, additives often require gluing of the fiber on the surface of the polymer fiber during drying due to its migration. In particular, the relatively high viscosity polymer additives known from the Belgian patent BE-PS 769 229, due to their viscosity, are also relatively difficult to mix completely homogeneously with the polyesters and also lead to undesirably high diglycol contents if added during the polyester formation reaction.

Compared to polymers containing P-compounds as part of a chain molecule, polymers with the corresponding additives are also less colorable.

Even red phosphorus has been used as an additive to provide fire retardant and self-extinguishing properties to polyester fibers and yarns (German Publication Publication 21 48 348).

Although such yarns and fibers are then sufficiently refractory or self-melting, the addition of red phosphorus does not give white products - and thus only limited use.

The present invention relates to shaped articles of linear polyesters, such as yarns, fibers and films, which polyesters consist of dicarboxylic acid units, which are preferably terephthalic acid units, and diol components, which are preferably mainly diol units of the formula:

HO (CH 2) n OH

where n = 2-10 or 1,4-cyclohexanedimethanol units, as well as β-pitol chain members. Preferred are phosphorus-containing chain member units of the above formula wherein R is or C 8 H 4 and R 2 is CH 3 or C 6 H 4, i.e.: 588785 - p 0 »0¾ o. o - Ρ - Cit2 - ch2 - <j -, -0 - [- Ο '· ί "k 0, C ,, 3 0

O

t 1 'f \. O - P - CH2 - CH2 - C - 3a - 0 - P - Γ'Γ I. 0 Crlls 0 C6II5 0 6 5

Both residue R and residue can still contain 1 or more heteroatoms. The heteroaters are preferably primarily halogen (F, Cl, Br), oxygen and sulfur atoms and may be located both on the side and in the chain, with location in the chain being preferred. Chain location here means a member of a chain of C atoms; due to the unity of the halogen atoms, these naturally differ from the members in the chain and only the Q and S atoms come into question here in the first place. N-atoms, which are likewise possible in the form of -NH- or -NR'-groups (R * = organic residue) as chain members, are less preferred because N-compounds are known to strongly tend to cause undesired staining during polycondensation.

The S atoms may be present in the chain as sulfide, sulfoxide or sulfone groups, attached to the chain or in the aromatic ring mainly as sulfonate groups.

5,58785

Examples of radicals containing heteroatoms are: C1 Br SO „Na -d- · -O- '-6- ·

br

Cl “<y ^ y>“ ^ ^ - Öne ..

Cl Ci - and containing O and S atoms in its chain: - (CH2 ^ -O- ^^ 2 ^ 3 “> - ^ If2 ^ 2” ^ ~ ^^ 2? 2 ~ '“(CH2) 4-0- (CH2) 4-, ((Cl2) -S- (Cl2-4-> CH2) 4- (CH2) 4-,

Cl - <@> - 0- -C ,, 2O'0O'C1I2 · '% -cir2CH2-o00> -ocH2cH2-, jr \ -s_0> -, • CII2_ <C), "SO'CH2 ·' -CH2O - <^> - 0CI! 2-, 03'SO2O "'

O

"CVV ° 03" O '0CH2C1I2' - ROjjNa -, - <3 ~ ° - <3-Cl? 2 "· -CII2Cl120 - / ^ - Q. ^^ - OCII2Cn2-.

c 58785

If R is a saturated open-chain or cyclic alkylene residue, halogen substitution is possible only if the compounds are not cleaved at all or only to a small extent by hydrogen under the conditions for preparing the polyester. Suitable halogen-substituted alkyl radicals of this type are, for example, the radical:

h2 X

-CH2 -c to CH2- CH2 X (X-F; Cl, Br) or perfluorinated alkylene residues.

The residue R 4 can likewise contain heteroatoms, in which case halogen atoms and a sulfonate group are particularly suitable as substituents. Examples are: CH 2 Cl 2, C 8 H 4 Cl, C 8 H 4 Br, C 8 H 4 SO 3 Na, etc.

Linear polyesters containing said special structural units as chain members are obtained as follows. Conventional starting materials capable of preparing high molecular weight - especially fiber - and film-forming - linear polyesters are reacted in a manner known per se, with the addition of bifunctional carboxyphosphinic acids and possibly further heteroato- or possibly other heteroatoes before, during or immediately after the polycondensation. their esters with a lower alcohol having in particular 1 to 4 carbon atoms or with a diol which also forms the diol component of the polyester. Oligomers of these carboxyphosphinic acid diol esters can also be used. It is also possible to use cyclic anhydrides of phosphinic acids which are easy to form and readily available. The amount of the carboxyphosphinic acid component should be about 3-20 mole% of the total acid component.

The carboxyphosphinic acids used herein have the formula: 7,58785

O

t

HO-P-R-COOH

* 1 where R and R | mean the same as above.

As dicarboxylic acid starting materials, in addition to the preferred terephthalic acids, other dicarboxylic acids are preferably used, either in free form or in esterified form with lower aliphatic alcohols (preferably having 1 to 4 carbon atoms, in particular CH2OH), preferably as mixed components. Examples which may be mentioned are isophthalic acid, 5-sulfoisophthalic acid, 5-sulfopropoxyisophthalic acid, naphthalene-2,6-carbonic acid, diphenyl-ρ, ρ'-dicarboxylic acid, p-phenylenediacetic acid, diphenyloxide, diphenyloxide, p'-dicarboxylic acid hexahydro-terephthalic acid, adipic acid, sebacic acid, 1,2-cyclobutane-dicarboxylic acid, etc.

In addition to ethylene glycol, higher homologues of, for example, propanediol-1,3, butanediol-1,4 and butanediol 1,4, as well as 2,2-dimethylpropanediol-1,3, 1,4-cyclohexanedimethanol, etc., are also suitable as mixed components.

When, in addition to terephthalic acid, other of the aforementioned dicarboxylic acids are used, substantially no more than about 10 mole of the total acid component is preferably used. The procedure is similar for the diol component assembly. When, for example, other diols are added here as mixed components in addition to ethylene glycol, the amount of these is preferably not substantially greater than 10 mol% of the total diol component in a sauna manner.

If starting from free dicarboxylic acids and diols, it is first esterified directly and then to a polycondensate, which is customary for these reaction parties. If starting from dicarboxylic acid esters instead of free dicarboxylic acids - in particular dimethyl esters - then the transesterification is carried out as usual and then polycondensed in the same manner, using the usual catalysts in each case.

8 58785

Of course, in addition to catalysts, conventional additives (wetting agents, opacifiers and stabilizers, nucleating agents, colorants and fillers, etc.) can also be used in the production of polyester.

The bifunctional carboxyphosphinic acids added before, during or just before the polycondensation, which may still contain other heteroatoms, or their esters or cyclic anhydrides can be prepared as follows.

Carboxyphosphinic acids which contain only one C atom between the P atom and the COOH group are obtained, for example, by H.G. According to the reaction described by Henring, J.Prakt Chem. 29, 86 FF (1965), starting from o (rCl or O (rBr-acetic acid alkyl esters and phosphonic acid alkyl esters). It is also possible to obtain carboxymethyl-phenylphosphinic acid by this route.

O

T

HO-P-CH 2 COOH

C6H5

When R is an alkylene group having 2 or more C atoms, the reaction scheme published by V.K. Chajrullin et al. Z. obso. Chim. 37 (1967) no. 3, pp. 710-714, starting from dichlorophosphines and unsaturated carboxylic acids, i.e. for example: 958785 α! m NN- to fr · * »r«. (υ β ρ; π i ο C) - · 'Ö Qj · * \ £ Ο * -ι β t ϋ = ο ^ J2'

§> οι-Ρ, -ο '1 I

Ο I o t fi 4 ΚΝ Η ωχ

Cxj W «β Π5 ►fi υ Ή -Ρ H C. .-„ · - <Q) u ° S χ e. ρ /> »I. +> / -, en • H / S (0 N ω S. P o K x X P &

o X υ S

\ ^ X -G

O <- Ρ, - «P J '* H

Ö n> ♦ IP ° h N. β

P \ I g X

0 ^ K1 10

β \ w 22 -H

1 \ υ ί »

T I ^ 'r * S S

1 -H O <- P <- «p -H

of! m (0 CO | O 'Γ *

• V, -H

o p en 0 .k Λ + j

0 o (U

U B «1 5 B Ä S.

* r «: c \ J Γλ» ι) G -I ϋ 2 1 ρ β &

N 'di X

li> * p

o ^ β S

v H Remained β

B

O

CU

a J rt + Ä ad G «3 - ^ i ι 5 V s s · (H P LO to <J (+ J £ O '' - 1 OS E S Λ Ή

2 t-. cg o · ο 5 S

. «S v v V v s ^ s μ I S% *> ~ t 3 S? 7 ^ o 3 64" 10 58785

Carboxyphosphinic acids with an aromatic residue (R = arylene) between P and COOH groups can be prepared from L.D. According to the principle of the method described by Quin et al., J.Org.Chem. 27, 4120 (1962), or in accordance with the method of co-pending patent application P 23 46 657.1 (internal no. HOE 73 / F 288).

In this process, halobenzoic acid esters are reacted with phosphonic acid diesters according to the principle of the Arbusov reaction. The resulting carboxyalkylphosphinic acid esters can be saponified, for example, with strong inorganic acids or bases.

Carboxyphosphinic acids in which R = aralkylene can be prepared in analogy to Belgian patent BE-PS 601 710 from carboxybenzyl halides and phosphonic acid esters and then saponifying the ester groups to the free acids.

Carboxyphosphinic acids or their esters or cyclic anhydrides, in contrast to various diphosphinic acids, are not volatile under the conditions of the polyester formation reaction and are thus completely and well condensable.

The final polyester product then has an organophosphorus moiety statically distributed in the macromolecule. As a result of this static distribution, the carboxyphosphinic acid units may also occasionally be end groups. To ensure the desired fire resistance, at least about 0.5% by weight of phosphorus in polyester is required in the pulps, and at least about 1% by weight in the fibers and yarns. The fire protection properties are further improved when the P-containing chain members in the polyesters as heteroatoms contain halogens.

The pre-condensed polyesters are then spun into yarns and fibers in the usual manner, stretched and post-processed or also extruded into films or molded in a known manner by compression, injection molding or. by extrusion into moldings. Particularly preferred are yarns, fibers, films and moldings which contain mainly terephthalic acid as the dicarboxylic acid component and mainly ethylene glycol as the diol component. All of these molded preparations are likewise the subject of this invention.

Fibers and yarns have very good and durable fire resistance and self-extinguishing properties. Their whiteness is about 58785 and they stain very well with disperse dyes, acid dyes from medium to deep hues. While the P-containing chain members still contain sulfonate groups, staining with basic dyes is also possible. The diglycol content of the polyester is only negligibly elevated, the tensile strength, glass transition point, melting point, etc. of the fibers and yarns roughly correspond to the values that the underlying, unmodified polyesters have.

The fibers and yarns are suitable for use wherever flammable textiles and technical products must not be present, for example in protective fabrics, carpets, window curtains, etc. The yarns can also be used as a single component in two-component yarns together with other polymers.

Films and moldings are also used wherever there is a higher risk of ignition and fire than usual. For example, inorganic fibrous materials such as glass fibers, quartz fibers, asbestos and hydrocarbons may be added to the shaped bodies in ordinary amounts to increase their strength if their transparency is not valued. Examples of shaped bodies are, for example, housings, components for electrical equipment, mechanical transmission parts in vending machines, hollow bodies, components in large-area counting machines and sensitive electronic devices.

The present invention will now be further illustrated by the following examples.

Example 1 1000 g of dimethyl terephthalate are transesterified with 730 ml of ethylene glycol in the presence of 230 mg of manganese acetate, 4 .mu.l as a catalyst under a nitrogen atmosphere at a temperature between 170 and 220 ° C. At the end of the methanol separation, 100 g of 2-carboxyethylmethylphosphinic acid (prepared according to V.K. Chajn'lin et al. Z. obsc. Chim. 37 (1967) no. 3, pp. 71Q-714) are added and esterified. After the addition of 35 mg of Sb 2 O 3, the reaction vessel is reheated but at the same time slowly aspirating the gas so that a pressure of 1 torr is reached to 250 ° C at an internal temperature. The polycondensation is carried out at 0.2 torr and 275 ° C until the relative viscosity (1% solution in dichloroacetic acid at 25 ° C) is 1.85. Melting point 244-248 ° C, phosphorus content: 1.85%.

12,58785

The condensate was spun from the melt under normal conditions and then stretched in a ratio of 1: 3/65. The strength of the obtained fibers is 33p / tex with an elongation at break of 35%. They were made into a leotard with color tests as well as a flame test.

Dyeing with acid dyes bearing the trade names Supranol Echta (C.I. no. 24 79Q)

Alphanol Echthlau FGLL (C.I. no. 62 155) and

Lanaperlgelb 3 G (C.I. no. 19 Q25) gave good color tones.

The flame test was performed according to the oxygen index method according to ASTM D 2863-70 test guideline. In this case, the knitwear was placed in a corresponding device in a vertical position and ignited from above. The oxygen content of the artificial oxygen / nitrogen atmosphere at which the sample still burned directly was determined.

The value was 29% by volume of Oj. A similar knitwear from unmodified polyethylene terephthalate already burned at an oxygen content of 20% by volume.

Examples 2-8

The experiment of Example 1 was repeated with other carboxyphosphinic acid or derivatives thereof capable of settling on a polyester molecule. The results obtained are summarized in the following table.

• 13 58785 15¾ • H I δ -μ ft ή αν · η 0) C! -Ρ ft Ο <6 Μ · ρ, 5 ^ ** · * τ * * ** * ο λ · η ω% 3 3 3 3 ο * C? in <D>>> ►>> «Ο W -Ρ Η 0 ο οο m σ> ο κ η η η μ ν η« CÖ • ι-Ι 1 ι ^ CQ · Η ** «« ^ H * * · ^ _ρ β »^ to ν * · <τ ^ η 0 · Η 0) 1 *" · f-ί * Η * Η * «« CO Ρ <3 • HI 2 d co Ö

•B

U l «-> .. Au t> o -p .o

Φ »« o ° ° «%, °»% V

ft. · «V« VTT S V

3-85 2 * 3 2 2 2 2 ä -3-S s s - »* s 5 0 m ft 05, Λ S S X 5 S? 5 • o ω -Γ w „*,; - ft AI <u '' i mp * ft · Η · Η · Η W> CO ft ft> 5 tl H It It II * · * ft $ «a 8 SS 88 S 2 3 ιοβ Vl - M" "> CO Id} ft

• H <3 X

^ g ice o °

s i Ȁ. a 3 H

6 6 $ »s Ia * S

a 5 .5¾ s n. .s • "j, Ni .7 s'" f ^ i §

Ϊ "5B 3 SU -5 Γ S 'S

»S" S * tm «* &” 1 r r: '-a §w r: ss 5k s | e * 2 * E * 2 * S "£

is 7S ΪΡ 7cigfl 'M

s # Ss §. e * es $ s§ ft «c« s §3§ -c, * Sii ~ | > 51> 5 | W fttö> 51> 5iMn t +> I · Η <0 ^ ^ Sh 3 ^ -> r “N s 1 • S f f. B f? -s 11 4; U ^ 5ο, u. , | υ '* ft

ft O o "S

• H ·

see G

12 φ • Soo "* o» - ·

to | CO WWW

14 58785

Example 9

The experiment of Example 1 was repeated by replacing 6 mole% DMT with dimethyl isophthalate in the transesterification. The melting point of the polymer was then 236-238 ° C, the relative viscosity was 1.82. Knitted or crocheted fabrics made from this material have an oxygen index value of 30%.

Example 10

Example 1 was repeated with the difference that 75 g of its cyclic anhydride 2-methyl-2,5-dioxo-1-oxa-2-phospholane was used instead of the 100 g of 2-carboxyethylmethylphosphinic acid used therein.

0 r CH.-P-CH,

1 I

O OH-

V

M

O

and 300 mg GeHPO 3 instead of 350 mg SB 2 O 2.

The pure white polyester containing 1.5% phosphorus was cold crushed. The reduced intrinsic viscosity of the granules was 1.08 (measured in phenol / tetrachloroethane = 3: 2 at 25 ° C). Solids condensation in a rotating vessel at 230 ° C and 0.2 torr gave a grain viscosity of 1.36 with a condensation time of 8 hours.

The granules were sprayed into sheets on an injection molding machine, the cylinder temperature was 260/270/260 ° C, the mold temperature was 20 ° C. Plates measuring 6Q x 60 x 6 were transparent and completely colorless, with a reduced intrinsic viscosity of 1.25. The impact toughness of the plates was examined by a drop test. In this case, the plates were subjected to impact stress by dropping a drop piece (drop hammer) vertically against the plates stretched on the frame from different heights. The tip of the drop hammer was formed by a hemisphere with a radius of 10 mm; weight was 1 g. For each height, 10 plates were tested. At a given drop height, for example, 15Q cm, the impact energy was sufficient to break 50% of the plates. The impact toughness of the example plates was 200 cm.

is 58785

Plates obtained under the same conditions - but without the phosphorus modifying compound and with a reduced intrinsic viscosity of 1.32 - gave an impact strength of 190 cm when shocked under the same conditions.

For the flame resistance test, the granules were compressed at a temperature of 230-250 ° C at a pressure of 8Q atm into 1.3 mm thick plates. From these, test rods measuring 127 x 12.7 mm were cut.

The fire test according to ASTM D 635-68 was rated "non-flammable" by Underwrites Laboratories (ULJ Subject 94 with the fire test "SE O").

Example 11

Example 10 was repeated with the difference that instead of 75 g, only 35 g of this compound was used in 2-methyl-2,5-dioxo-1-oxa-2-phospholane. The phosphorus content was then 0.7%. The fire test according to ASTM D 635-68 was rated "self-extinguishing".

Claims (5)

1. Molds, such as trees, fibers and foils, consisting of linear polyesters, which polyesters are dicarboxylic acid units, which are preferably units of terephthalic acid, and diol components, which are preferably mainly units of diols of the formula: HO (CH ) OH = n = 2-10, or units of 1,4-cyclohexanedimethanol, saint of P-containing chain links, characterized in that the P-containing chain links are evenly distributed in the macromolecule and are structural units of the formula: r -OPRC- I in O where R is a saturated acyclic or cyclic alkylene group, arylene or aralkylene group having 1-15, preferably 2-10 carbon atoms and is an alkyl group having no more than 6 carbon atoms, aryl or aralkyl group, and is 3-20 mole% of the polyester acid components. Moldings according to Claim 1, characterized in that in the P-containing structural units R is -CH2-CH2- or -CgH4- and R1CH3 or C3Hg. 3. Moldings according to claim 1, characterized in that in the P-containing structural units the groups R and / or R 2 contain one or more heteroatoms, such as F, Cl, Br, O and S. Moldings according to claim 3, characterized in that the heteroatoms are atoms 0 or S and are in a position in the chain.