DD144552A5 - METHOD FOR PRODUCING LIGHT-TABILIZED PHOSPHORUS-ACID POLYESTERS - Google Patents

Abstract

1. Process for the manufacture of delustered linear polyesters by reaction of a) terephthalic acid or the dimethyl ester thereof, b) a glycol, c) a compound forming a phosphorus-containing chain member, which amounts to up to 15 weight %, relative to the finished polyester, and which is selected from the group of phosphonic acid and its ester, phosphinic acid and its ester, ethylene-bis-methylphosphinic acid or 2-carboxyethylmethylphosphinic acid, if the phosphorus atom is to be built into the polymer chain, or from the phosphine oxides if the phosphorus atom is to be built into the side chain, and d) oxygen compounds of phosphorus, characterized in that after the ester interchange or esterification step or during the polycondensation reaction phosphoric acid triesters as oxygen compounds of phosphorus for stabilization to light are added, which contain 1 or 2 alkyl groups having from 1 to 4 carbon atoms and simultaneously 2 or 1 alkylene glycol or polyalkyleneglycol groups, the alkylene groups of which having from 2 to 4 carbon atoms, and delustering the polyester with TiO2 .

Description

AP C 08 G / 213 937 55 414/18

Process for producing matted, linear polyester

"Field of application: the invention .

, The invention relates to a process for preparing inat it animal, linear polyester by reacting

a) terephthalic acid or its dimethyl ester,

b) a glycol,.

c) a compound containing a phosphorus-containing chain member, this chain member constituting not more than 15% by weight, based on the finished polyester, and

d) oxygen compounds of the phosphor.

Characteristic of the known technical solutions

The long-known and industrially produced polyesters generally have good or very good fastness to light for practical use. The synthetic linear polyesters used for the testable range are based on terephthalic acid and glycols, e.g. The polyethyleneterephthalate and the polybutyleneterephthalate, in the form of fibers, threads, and polishes, also have reasonably good lightfastness. These polyesters of terephthalic acid, such as the polyethylene terephthalate, can be chemically modified by incorporation of other dicarboxylic acids or diols In order to obtain, for certain purposes of use, specific changes in the properties of, for example, fibers, filaments or foils, other dicarboxylic acids may contain at least

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two acid functions which are capable of ester formation are chemically incorporated into the polyester oil, e.g. Phosphonic acids and phosphinic acids "If groups with phosphorus atoms are incorporated into the polyester molecule, then from a certain additional quantity it is possible, for example, to obtain polyester threads and fibers which, in addition to an improved dyeblock, are also flame-retardant or self-extinguishing.

In addition to the phosphorus-containing co-components, other polyester-modifier components may be used, for example, those containing sulfonate groups or nitrogen-containing compounds to prepare basic or acid-dyeable polyesters (see H. Büttner, Angew .. Malcromol., Ghem., 40/41, 57 (1974). ). -Pill, easily dyeable polyester fibers and filaments can be of .v / Eiteren by use of small amounts of Permanentvernetzern or iemporärvernetzern produced ·

Frequently, modified polyesters often exhibit somewhat less lightfastness than the unmodified polymers. This makes itself e.g. in a greater change in the textiles properties of fibers produced from the polyesters and. Threads noticeable, i. the tear strengths and the biting dimensions decrease more strongly as a function of the exposure time. The cause may lie in the different condensed structural units of the modifying component, if they are more sensitive to photochemical or photooxidative or hydrolytic influences. / ^ '

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As matting agents, polyesters are generally added to titanium dioxide pigments if no shiny fibers and threads are desired. They can be used as pigments

, - ';^:   - '- ", -I '

both anatase and rutile types are preferred, with fibers and filaments generally of an anatase type being preferred because the harder rutile pigments tend to increase the abrasion of filaments and rolls in the yarn. Spinning and stretching lead. It is known that titanium dioxide pigments promote the photodegradation of many polymers and dyes by catalyzed photooxidation. In the unmodified commercial polyethylene terephthalate prepared via dimethyl terephthalate, the photochemical influence of the titanium dioxide pigments is low, i. H. there are virtually no differences in the light resistance of matted fibers and filaments with the usual in practice up to 2 wt .- / δ TiOp levels compared to unmattierten fibers and filaments «

In the case of chemically modified polyethylene terephthalate, intensified light degradation often occurs with the use of TiO.sub.p IIattants, that is, the matted fibers and filaments have less resistance to light than the corresponding unattached fibers and filaments. The light resistance is therefore also dependent on the amount of added TiO ^ pigment, d. H. The higher the degree of matting, the stronger the photodegradation of the: modified polyester. A particularly pronounced dependence of light resistance on the LiOg content of the fibers and filaments occurs when heteroatoms enter the polyester chain

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are incorporated, which are sensitive to photo-oxidative influences. This is, for example, the pail in polyesters containing phosphorus-containing chain members. Threads and fibers of linear polyesters containing phosphorus-containing chain members are known. In particular ;' Organic derivatives of various acids of phosphorus are suitable, e.g. Phosphonic acid and its esters (DE-AS 1 243 819, DE-OS 1 595 598) and phosphinic acids and their esters (DE-AS 1 232 348, DE-PS 2 236 037). Phosphine; acids can be randomly bound with phosphorus atom bound in the chain in the ester bond in the form of diphosphinic acids corresponding to DE-PS, 2 236 037 or in the form of carboxyphosphinic acids corresponding to DE-OS 2 346 787 in the polyester chain to be built in. However, the phosphorus atom may also be laterally attached to a polyester chain member, e.g. in the form of a phosphine oxide group according to DE-OS 2,242,002.

t) It has now been found that an addition of low-volatile esters of phosphoric acid can bring about a .light stabilization of the light-sensitive, titanium dioxide-matted copolyesters. As general polyester stabilizers for blocking the transesterification catalyst for the purpose of xhermostabilisierung neutral and acidic esters are described in many patents, for example in DE-AS 1,152,259 and DE-OS 2,154,503. The acidic phosphoric acid esters, which are only partially esterified phosphoric acids, while not volatile, but have significant disadvantages as a polyester additive, as they as. Acids promote the formation of Diethylenglykol aus.dem Ethyienglykol. This is uneven as a by-product, as it wows

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as organic! is also incorporated into the polyester molecule and the polyester properties, e.g. In addition, phosphoric acid and its acid esters cause unwanted deposits, especially in continuous production processes, in the real-time by the rapid formation of poorly soluble phosphates and. lead in an excess application to the agglomeration of liiOp pigment when it is used as a matting agent ,

Although the neutral alkyl esters of phosphoric acid also react with the: · divalent metal ions of the transesterification catalysts as well as the phosphoric acid itself to poorly soluble metal phosphates, but the reaction rate of the reaction with the phosphoric acid esters is significant, d. Less orders of magnitude because this is not a fast ionic reaction -more. Therefore, under the operating conditions used, the neutral esters of the type mentioned are already noticeably volatile, as also stated in DE-OS No. 2 412 216. In the case of a light stabilization of copolyesters, the problem of the propensity of the added stabilizer compound is considerably increased since a it is necessary to add more of a phosphoric acid ester than to heat-stabilize alone. tion of the polyester would be necessary.

Aim of the invention ; '. /

The aim of the invention is to provide a simple economical method for producing matted, linear, in particular light-stabilized phosphorus-containing polyesters · '_; , .._. ' , /:

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Explanation of the essence of invention '...

The invention has for its object to find light stabilizers for polyesters with phosphorus-containing chain links, in particular''die. In addition to blocking the activity of TiOg pigments, they also show very little volatility during the vacuum-forming polycondensation process. they are easy to handle and meter to form any deposits in the reactor, lead to thermally stable and color perfect end products, do not complicate the recovery of the glycol and entrain no process interfering substances in the reaction mixture. '' '' · ..; ... , ; .:. - .. ·; :. :

According to the invention, all the desired advantages for light stabilization of chemically modified polyesters are obtained when, after the transesterification or esterification stage or during the polycondensation reaction for light stabilization, phosphoric acid triesters are added as oxygen compounds of the phosphor, which contain 1 or 2 alkyl groups with 1-4 C atoms and simultaneously 2 or 1 alkylene glycol or polyalkylene glycol groups, wherein the alkylene groups in turn contain 2 to 4 carbon atoms, and when the polyesters are matted with TiO ₂ .

Alkylene glycols and polyalkylene glycol ethers having 2 to 4 carbon atoms per alkylene group are e.g. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, i, 2-butanediol, 1,4-butanediol and their di-, ollgo and polymeric ether. The preferred Ausführungsforrii uses mixtures of Phosphorsauretriestern mono- except 1 or 2 lower alkyl groups

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Polyethylene glycol groups as ester groups. The mixed phosphoric acid esters used according to the invention are preferably prepared by reacting an acidic mono- or dialkyl phosphate or a mixture thereof with an alkylene oxide having 2 to 4 carbon atoms by known processes without using a solvent or catalyst. The alkylene oxide adds to the free hydroxyl groups of the acidic Alkyl phosphates to form 2-hydroxyalkyl ester groups. The "alkylene oxide." However, addition does not stop with this monoaddition, but as long as the reaction mixture is acidic due to highly free acid groups, the alkylene oxide also adds to the terminal hydroxyl groups of the already added alkylene oxide units (see Houben-Y / eyl, Methods of Organic Chemistry, Stuttgart I964, Vol. XII / 2, p. 307). This produces polyalkylene glycol ethers as ester groups of different chain length. If towards the end of the reaction, the concentration of the acid groups decreases sharply, only mono addition products are formed, which can be detected analytically by saponification and gas chromatographic determination in amounts of a few wt .-%. The alkylene oxide addition is continued until the resulting phosphoric acid ester mixture has an acid number less than 1, ie. .pra-ktisch barely absorbs alkylene oxide. The acid number (SZ) is defined as the amount of potassium hydroxide in mg required to neutralize 1 g of substance (see Römpp, Chemie Lexikon, 6.Auf1., Stuttgart 1966, Vol. II, Sp. 2037/3).

The mixed phosphoric triesters used according to the invention by the preferred preparation process

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Qligo and Polyalkylenglykolathergruppen cause the advantage that the added stabilizer during PoIyester Polykondensationspr'ozesses only a very low volatility and thus the (analytically determinable) phosphorus content in the polyester is only slightly below that calculated on the basis of the amount used.

The mixed phosphoric acid esters used as light stabilizers in the process according to the invention can also be prepared in other ways than those described, which is a preferred embodiment. For example, the mono- or dialkylphosphoric acid chlorides can be reacted with glycols or mixtures of glycols with addition of a tertiary amine as base to phosphoric acid triesters. Subsequently, however, the resulting amine hydrochloride must be quantitatively separated, otherwise disturbances in the polyester production occur and the polyester properties are adversely affected. In a similar manner can be prepared by reaction of phosphorus oxychloride, 'POClq' with glycols, polyglycols or mixtures thereof and the simultaneous presence of alkanols or in a subsequent reaction stage - in the simultaneous presence of a base as hydrogen chloride acceptor the above-described mixed Phosphorsäuretriester invention (see. JA-PS 64 30 154; CA, _62, 11737a). Another possibility for their preparation consists in a transesterification reaction, a lower Trialkyphospliats with .Glykolen. These. Reaction takes place even at higher temperatures without a catalyst hur partially and very slowly. At the same time. · Partial hydrolysis. Pur a useful transesterification reaction

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Therefore, basic catalysts are required (see Houben-Weyl, Methoden der Organischen Chemie, Stuttgart

1964, Vol. XII / 2, p. 371). For use as hergesteliter mixed phosphoric acid triesters as polyester stabilizer _v _.) Reu the basic additive previously from the Reaktiönsmischung must be removed or separated .. ·

In the already above erv / similar DE-AS 1 152 259 is as a polyester stabilizer for stabilization; after the transesterification of dimethyl terephthalate, the "tris- (2-hydroxyethyl) phos-, phat" listed · This compound has in one use

However, since it has three terminal, primary hydroxyl groups, it can react as a trifunctional compound in the polycondensation process and be incorporated into the polyester as a point of crosslinking or crosslinking (see MC St. Cyr · SPE Transactioons 1_, ^v - ^; Ho., 1.47-51 (1961).) This leads, as is known, to modified polyesters having markedly altered properties, eg a higher Scheltsz viscosity, lower strength, depending on the amount of trifunctional compound added , and higher transverse brittleness of the yarns, all properties which are desired only in special cases as polyester properties. The stabilizers used in the process according to the invention are mono- or bifunctionally with respect to the hydroxyl groups and can therefore be incorporated into the linear polyester chain or as an end group, • on the polyester molecule. As a result of the lower stabilizer concentration, virtually no disturbance of the polycondensation reaction by chain termination occurs.

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When producing "iris- (2-hydroxyethyl) -phosphate" by adding ethylene oxide to phosphoric acid, it is not possible to obtain a pure, defined compound for the reasons explained above since polyethylene glycol ether units of different chain length are formed as ester group.

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by this stabilizer over the mixed esters' the additional iTaehteil a significantly lower phosphorus content in the molecule, so that a corresponding amount of stabilizer would have to be added to the polyester if a certain phosphorus Konzehtration in polyester is required to achieve the desired stabilizing effect. As a result, the above-mentioned disadvantages of the trifunctional compound can then increasingly occur,. , ; ; '.- ;.

The acid alkyl alkyl phosphates used to prepare the phosphoric triesters are preferably methyl phosphate. d. h, monomethyl phosphate, dimethyl phosphate or mixtures of both. However, it is also possible to use ethyl, propyl or butyl phosphates. These acid Älkylpliosphate can be obtained, for example, by reacting a Polyphosphorsäure with certain PpO ^ content with a certain calculated amount of an alkanol having 1 to 4 carbon atoms, preferably with methanol. Oxidation of dialkyl phosphites to give dialkyl phosphates also gives starting compounds for the mixed phosphoric acid triesters. [.-:: ':' .-.

The acids used for addition to the acidic alkyl phosphates. , Alkylene oxides can be ethylene oxide ,. Be propylene oxide or butylene oxide. Preferably 'ethylene oxide is used.

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The amount of stabilizer according to the invention exposed to light-stabilize the phosphorus-containing copolyesters depends, on the one hand, on the nature and quantity of the modifying component used and, on the other hand, on the degree of coating of the polyester, i. How much TiOp pigment is incorporated in the polyester is as follows from the crystal form of the titanium dioxide and its method of preparation. In chemical modifications of polyoxyester polyesters, up to about 15% by weight of a co-component, based on the finished polyester, in the Practice can be used to get enough high-melting polyester.

Fatty matting agents are used in polyester fibers and filaments in amounts of about 0.04 to about 2.0 weight percent. Both naturally require a similar variation in the amount of stabilizer added. The stabilizing effect is mainly determined by the added amount of pentavalent phosphorus. Therefore, the phosphorus content of the stabilizer compound should also be taken into account. The higher the content of alkyl groups, especially of methyl groups, the higher the phosphorus content of the mixed esters and the less stabilizer needed in the polyester The stabilizer used will be Therefore, based on the phosphorus content, which is thereby added to the polyester. This may be in the range from 10 ppm to 800 ppm of phosphorus, preferably 20-800 ppm of phosphorus, but especially for most practical Anv / endungszwecken between 30 and 300 ppm phosphorus · Here are the 'phosphorus contents, that of the phosphorus-containing chain links in the polyester, not included ·

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Can be used as glycols polymethylene glycols having 2 to 10 ^ C atoms used, but also cyclic glycols such as 1,4 cyclohexanedimethanol and similar compounds. Preference is given to ethylene glycol and butylene glycol ( = 1,4-butanediol) »'^; ,

The advantages of the invention will be apparent from the following Tables 1 and 2. Here, the light resistance of polyethylene terephthalate yarns is compared, namely unmodified polyethylene terephthalate (PET) and polyethylene terephthalate modified with various phosphorus-containing co-components without and with light stabilizers.

. ' .Table. 1 . ,. , . ';. Exposure test in a Xenotest device

Polyoeter pilgrim yarns Modifla ieruyi. ffakompo- ett.te

of the siter dtex 56 f Auaft values 1 gOO Y / lgit «(4)

Go. Zipper- RR]? Weight % , stretch, %

cll / tex %

2,., PET

3. .PET Modif.

2-Gar "boxyethylmethylphosphin

4. PET-Mo.dif ·

5. PST Modif., - +0.15% by weight phosphorous

(7)

phosphoric acid ester .

; with 11y1 wt% P

acid

I fl

5 5 0.36 0.3.6

41.0 39.3

31.2 29.8

36.8 74.6.

6. PET Modif ·

2-Carboxyethylmethylphosphin- (9)

acid

7. PET Modif.,.

+0.08 wt -% phosphoric acid esters ^{^.} wt ^7.2: .-% P · '

0? / 0

52.9 21.6 79.8 74.5 0.38 53.4 19.4 76.2 76.8

35.9; 34.1 78.0 60.2

45.5 67.3

0.04 41.5 26.8 72.8 60.1

0.04 37.5 29.5 75.7 68.2

b Exposure test in a Xenotest device ·

Polyester filament yarn modes fficer TiOg (3) Au s gangsv / he ^te. 1JpOO

from liter., dt ex 56 f 24 -''-substance. Weight% ^ Tear-

, '. , Gevi. -% fixed. stretchable.

CN / tex %

.8th. vPET-Modif.

2-C ar boxy ethyl

methylphosphine · (9). , '

... sour

9

+0.14 wt -.% Phosphorus

(S)

phosphoric ester ^ '

, at 7.7. Wt.% P 10. * "PEiD Modif ..

11, PST-iodif.,:

+0.28% by weight of PhOQ

, phosphoric acid ester. - , With; 7 * 7% by weight P

0.38

0.38

42.3 33.0, 44.3

44.5

Il .. 3, 1 3 35, 4 34 6 21 5 η 3 .1 3 41 2 21 9 63 9th

34.8 32.7 78.7 72.4

11.0 60.3

12th PET-Modif,. , Ethylene-bis-methylphosphine 3 , , ; -. 33 , 9 31 's 71, 3 54 6          '. 13 ·   ΡΞΤ-Modif ·    . ' » 3 0.38 31 , 0 26 32 4 ; 8th, VTi te. r \ i H. PET-Modif., +0.25%, -S5 phosphoric acid ester ^ ' '' with 11.1% by weight P Il 3 0.38 35 , 6 22 68 7 59, 2 ^:; ! 2.10.1979 lP C 08 G / 2 'Ϊ5 414/18 "υ U) VO U) - <!

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Explanations to the table in detail.

It means: ',

(1) The exposure test was carried out in a device Xenotest- at 65% relative humidity and a · _Samples: room temperature of 30 to 35 ° C. The temperature of the samples themselves, ie the black panel temperature, was about 40 ^° C.

(2)% by weight of the modifying component is based on the content in the finished polyester *

(3) The anatase type TiOp pigment incorporated in the polyesters during the manufacturing process is the "Kronos AD". The weight % , refer to the content in the finished polyester. _: . , ,

(4) Coiling Hours: The exposure took place in a helical run (day-yacht rhythm), so that the pure exposure time was only 50 % of the sample transit time.

(5) RRP means the residual tensile strength, RRD the residual tensile strength, expressed as a percentage of the initial tear strength and the initial ultimate elongation.

(6) All polyethylene terephthalate (PET) polyesters were prepared by the dimethylterephthalate transesterification process with ethylene glycol, optionally with the phosphorus-containing llodification component added after the transesterification step: i) esterification catalyst: i _: in (II) acetate;

Polycondensation catalyst: Sb ₉ O _n ;

2+ thermal stabilizer to block the Mn. :. hopo

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(only in the case of the polyesters prepared without the addition of a phosphoric acid ester), the "phosphoric acid esters (7) and (8) were added after the esterification stage.

(7) The phosphoric acid ester used was a product

, from a mixture of mono- and Dime thylphosphat by reaction with ethylene oxide to an acid number. X 0.5 was obtained and had a phosphorus content of 11.1 wt .-%,. v. : · V:. ν

(8) As the phosphoric acid ester, products were used, which consisted of monomethyl phosphate, CH ^ O-P (= 0) (OH) ρ, by. .

Reaction with ethylene oxide up to an acid number X 0.5 were obtained and a phosphorus content of 7 »2. bzy /. 7.7% by weight had

(9) 0

HO - P - CH ₉ - CH ₀ - COOH . to DE-OS 2 346 787 ^0H 3; : ..: ^; ν;

(10) HO - P - CH ₀ - CH ^ -P - OH according to DE-PS 2 236 037

ι ^ - '.-- έ [t - .' .-. . ·

^0H 3:

Claims (2)

Process for the preparation of matted, linear polyester. Implementation of. a) / terephthalic acid or its dimethyl ester, b) a glycol c) a compound containing a phosphorus-containing chain member, this chain member constituting up to 15% by weight, based on the finished polyester, and d) oxygen compounds of the phosphor, characterized in that after the transesterification or esterification stage or during the polycondensation reaction for light stabilization as phosphorus phosphoric acid triesters are added which contain 1 or 2 alkyl groups having 1-4 C atoms and simultaneously 2 or 1 alkylene glycol or polyalkylene glycol groups, wherein the alkylene groups in turn contain 2 to 4 carbon atoms, and that the polyesters are matted with TiOp. 2 »method according to item 1, characterized in that the amount of phosphoric acid triester added to a phosphorus content used by 10 to 800 iag / kg, based on the finished polyester corresponds.