DE1520978A1 - Process for the production of polyesters - Google Patents

Description

DR. E. WIIOAND

MONKS

DIPL.-ING. W. NIEMANN

HAMBURG PATINTANWXLTI

MÖNCHEN 15, “Feoraar 1% 2.

NUSSBAUMSTRASSE 10 TELEPHONE: 555476

V /. 10ϋί; ΐ / 62 7 / liei

Toy ο Rayon Kr.bushiki Kaisha Tokyo (Japan)

Process for the production of polyesters.

The invention relates to a process for the preparation of polyesters j in particular relates to a method for producing polyethylene terephthalate or polyesters containing more than 85 Polyäthylentereph terephthalate containing from lerephthalsäure and Xthylenglykol or terephthalic acid, and a Ithylenglykol

909881/1501

BATH

^ orirfoii IIei \ £: t '' .rittor Kcr-pcne-ir-t-; '. »

Ir, a se int-n bssEie.ht. -I di ^ ^ ri'inuiuv; on ^ in Vc-rf ^ Lren: ^j , ur Ilerjtellui., / from χolyesters, - "at the: uiai bei der ISereit-JTg from Icly ^ thylonterephthr.l-it or from jrolyocit - rn Tiiit öir.ora salary * . or. more r.lo C5 '; a Polyäthylentbrhohalat; vur- Terevhthali-'V.uro and Xtliylenglykol. or mus aüure, ^ .thyler ^ - ^ yIwOl ur: c · eil. .r rerii ..;: en He :.,;O

™ Components L! Ero ^ htli ^ l.: Ilure ur.d Ethylene glycol in one ■ iiolarer. Ratio in excess About 1: 1.3 nil; each other Yer: .. iaolit, anaohließena · εο r ^ oh vie recently a =. a in excess - Schu £ su-egebene Xthylen ^ Lykol distilled off until daa molar Ratio is not more than 1: 1.9, this Uiscfcfcung then esterified at atmospheric pressure or under pressure and thereafter this esterification product polymerizes.

Many suggestions have been made in the past whose purpose is the production of polyethylene terephthalate

^ lat aua is terephthalic acid and ethylene glycol · So is a Process for the production of polyesters from terephthalic acid and ethylene glycol in continuous working processes in the British Patent 776 282 indicated in which Bis (2-hydroethyl) terephthalate produced semi-continuously is obtained by bringing about the presence of bis (2-hydroxyethyl) terephthalate; this procedure is different However, I fully adhere to the method according to Er ~

9 09 881/1 501 _eAD original

Furthermore -sir.v. U; i j.or. '. ork '/ i ^ li -.::- · ^ Teri ".ro :. . Sckvierij-kplv: ¹¹ "toi: ji - ■: _-: .- ΐ ... ucr: ο ■ · I'.i: itili. J;; .J _': V :: uu u ■.

;: - tj; .vlon _t -l "'-: oI"-'i-.t ^ ii. . "i I- V: 1.9 i .-: t, ui: c cei der ilui'irunt; üer .111. ο ': ιύ: ν -Ij.:; ··! trct - .. i". Lt-tr - ^ - jIitliciie tecl: r, i-; che 3oL \ - i ^ ri _; -r-.c-ite ·,; -r.i_% Ve: .r. c -uoh : .. \ _- licL v: ar, Pclyäth ^ lontureyhth-ilr't i.iL a - :: · Iioho: v ür · oichun ^ puriirt zn '-riialteii, ve bi ί.π; }; .. on i ''"rlI.:;> .. ^; " .rri.iir.u :! erlio'.r IIci '. ^ clliu.; - from rol ^ - ^: Lil:; "I ■ ι.v: \ ro ^ *. thru; \"U;"ech:. *. .och - .. ie Schvicrijhoiten, the u \ i £ i \ QT Liii ^v "'} .2-un,:" ... er ^ ero ::. T;:; alnäure in ilir-or. Powdery state in eic lu.ter pressure stenei .ee- Zone De rest _β Hen- gcvAi'.il ΐ :: .. ιι :: - cie hev .: ' :: r; 2.iel: e Arceitt: v; ei ^ e not considered a satisfactory process v: earth «

If, on the other hand, with a view to avoiding such difficulties, the reaction should be brought about under conditions in which excess ether; ^r lengljrlcol \ ^r erwenäet v; ith, d _a h _o in a ratio of terephthalic acid nolaren su ^ thrlengljfkol above 1: 1.3, for example from about 1: 2 to 1: 15, as occurred during the Yeresterungsreaktioi) and Seitenrealitioneii. made the production of polyethylene terephthalate with a high pouring point ■■ impossible «

As a result of the search for a \ ^r experienced in the production of polyethylene terephthalate - for the polyethylene terephthalate with a high melting point as well as a good one

90 9 881/1501

■ -. ■ 4

Hue are obtained ^k:; might and -lien at ACSS feeding Oer Eiri ^ atzinatori is easy to perform, CIIE uniform 7 ermine huiv · eggs Haterialien and the regulation of ZufuhrUJi - simple and v.'irk'ja ::. too affordable. are, -UTt ^ at the :; d-.r moreover in more satisfactory. White a continuous polymerization ', .urshführung and VorflArbuii :; avoided or Pleckenbiloung of polymers v ercien came :, v / urde ri.r ^/:; LG der Lrfindunr- found that by veriaiwchur _n -: r of terephthalic acid and ethylene glycol in a molar ratio in excess of 1: 1.9 »the following as rough as possible before distilling off the excess ethylene glycol: the molar ratio not more than 1: 1.9, subsequent esterification of this mixture at atmospheric pressure or under pressure and subsequent polymerisation of the esterification product, the technical procedures, as they have been described above, overcome in a satisfactory manner can,

ψ A 2v, -eci: the invention is therefore the creation of a

Process for the production of τοη polyethylene terephthalate the similar mixing of the starting materials and the control /: he supply can be easily carried out, dse about it also carried out continuously with good success can be un-'bei de ·:., the polyethylene terephthalate obtained has a high softening point »

Another aspect of the invention is to provide one Process, which the continuous production of Polyäthylenterephthalat with a high softening point possible

909 881/1501

, BAD ORlG ¹ NAL

η · chi, without fear ei? .- ¹ . Abf - 11ε Λ ■. .- · lirveiohuni ^ pur.ktea and aar über or LiIi ¹ UiO with ein-jr: r.:ol'-ren Verhältni.j der lli.:cl,ur .; the Au3j: .. n:; amatöri-tlien. \: lo it for one. Z uf'lhrunj 'according to the traditional ancestors not possible v /' ir, b-ji.r / iel.-r.'öi.-se ■ 80 parts! Terephthalic acid and 40 ropes of ethylene glycol

Another purpose of Brfiiidun ** is creation of a procedure which the *: on uinuicrliche II creation of Polyäthylentereiilithalat with a high standard calibration point possible makes and in which the. access materials can be easily reached without the need to a sudden during the initial stages of the feeling Increase in the drive force required for the leadership, see below run through, like that in the past 'while mixing of the output materials inevitable \; ar *

Other Cwecke and advantages of the invention will become apparent from the following description ₀

According to the Erfindimr are terephthalic acid at üer producing PoIyäthylenterephtlialat or of polyesters with a 3-ehalt of more than 85 ^ Polyäthj'lenterephthaiat from ^ and ^r Ithylengl3 glycol or terephthalic acid, and a small Äthylenglylcol !! narrow third components first, under Anv / end of ethylene glycol in excess, terephthalic acid and ethylene glycol in a molar ratio in excess

1 ί 1 »9 mixed, with a range of 1 ί 2 Ms Ii 15

■■■■■ - ■. t

it is particularly preferred that the excess athy- lenglykol distilled off until the aforementioned molar ratio is not more than 1: 1.9 ^ where the ! Distillation is effected as quickly as possible =, Bas initial-

909081/1501

before AC'-les-tillicrcii des Ilthylür: gly :: oli; von tor in dia:; or Veine '--leichmlUig uurchnicchtcn lü.-cLur. / ur.'. "i'.nr.c-rn L ^ :. i" cl: .rer. Vcrh ^: lltni - ;: e : ^ -.u "ur.t ^ r a bo, -ti:;: it - Vörh ^ ltr.i;:, jofolyt of an AbceGtiilioi-on öo: -: b. i - ^ r licV.iticn rebil. oto :: "./^ ::; er ::, i: t ώί> ΐ \; ichtio ^ - I-Ierlaiial c" .er Erlinr un:> ALi a 3νββΊ.η ±: ι izt .iie]; · ;!: vinui'.rIi-: Le I-Iercte ^ lui'iC by rf-ly ^ tlirlenbero ^ I.tiL-.lat au .. 2erarhthulji: r.ro unu jlyizoleri, dio in d «r 7er- ;; , n ;; er.hoit t: it many 3UH \; _ieri:>: nits b ^ i: u ;; LiOH -or ZiuEhrung the Torephthi.laüure'in ILR: .i rer.ulvcrten Zustund in an under I / ruoi: uto-A Kenae So.'ie accompanies v / ar, according to the. Procedure £ & r Lrz'inaunä ■ 30 ^ ev.'craen that the esterification and. rolymsri :: atioKsreal: tio- ηen can be very easily carried out, since the pulp can be conveyed by means of a ctruaera or a pump to the zone under increased temperature and pressure, where the excess can be removed immediately. According to the invention, a number of third components can also be found. These include compounds capable of forming three-star compounds, such as benzoic acid, isophthalic acid, adipic acid, sebric acid , JuIfobenzoesäure, Diäthylenglylrol, polyo: cyät2; ylenglyl-: ole and A'thanolanin, the additives such as 2olyl3uliOnsäuren, xitanozyd, Huss (carbon black) phthalocyanine and Shrenpignente (threne pigments) una by the various polyesters polynatf trollable ü ±. 3-ufca.t.

^ In this way the excess ethylene glycol rapidly & bdistilled and the esterification is effected, '- after the molar ratio of ierephthalic acid to ethylene glycol has been reduced to no more than 1: 1.9. The Ver-. esi; erung.sreakTion occurs either at ■ atmospheric pressure or under pressure b.eviendet, "vorzugaw & ise v.'ircl das '-.' asser bei

909881/1 ^ 01

BATH ORIGINAL

ι -

'wfj :: i; "or -Ig IC Eg / crr alu ^ -stil liort. ' λία Before f v-rur. -ah-tal -'- fjfitor becomes ei;. o YeivinJ. ur. ' eir.ej Al ^ '. Iiuut.-.-. IlOv ^ jraalii-ij-i ::: -.- tallp, Si :, Ca, Pb, 8b, Un, Go, Pe, 2i, Dr o ;; he La related *

Genilß car ^ rfindun .; ; -: - by Γ oil; ^ t} ;; - l'iiitor ^; .: hth-l; it ir. Gufriede :: niellender V / ei; o not only through batchwise Pol-nerisatior, -onüerr, -'uol-i cur.il: continuous polymerization directly -iua der Iinchunj'vcn " . l ^v erepl: thal acid and ethylene glycol .odor the Rait a Jerin ^ on it possible 'to third Konponenten veröetsten LIi see tin £ ⁱ obtained: e.rt; ^r jn..

■ V / eiir. the P.oahticr: chr.e Ac ^ estilliez-en en ^ of überschüösi- _Xthylen; : l; ^r hols. executed v; ird, is a noticeable. Waste dec Srvreiuliunrspunkte c acs Pclynerisats obtained unverneielieli, 'not r.ur vronri the Yeresterungareaktion under lirucl; bev ^ irkt y; ird, 3oni em *: uch. \ -: erz them b. i '^ ti.: o spherical bridge causes virc .. _o Gor.äis ü'e:.: Yerfi-hren.! he invention is vird, if:'. Also an extra liquid is used in the ethylene glycol, PbIyilthylentcrephthalat i.it a high level of calibration point -generated from a rise; ruiv; de: 5: .iolar proportions resulting from the fact that the addition and addition. facilitates v: ill .. If aas nolar.e ratio is kept lower than 1.5, ./erden cB _o if used 80 parts of terephthalic acid and 40 parts of ethylene glycol from the beginning in the example described below, ', then the mixture is no 3rei and The addition of the liquid becomes practically unreasonable. a method can be used in which the 'terephthalic acid and the ethylene glycol are fed into the reaction tank separately and mixed'. In this lall are

909881/1501

BATH

the usual rudder-for-ni: enI'isci.erflügel not satisfactory, it is necessary to use kneader-like blades or blades with similar effects. Furthermore, the drive required for the li is at the beginning β steps, very large, v / chei the power requirement to a lower one. Height decreases once thorough mixing has been achieved,

The maximum value for the required driving force becomes ao greater, the smaller the molar ratio virdj v.-eiir. the nolar ratio is 1.1-1.5, the value "beyonöerfj large in comparison with the force" required after reaching a complete diameter, the accompanying drawing illustrates this behavior, it shows the relation 2V / iGchen den Moleren YerhLltniüson% ^τ οη iithyleneglyirol- to terephthalic acid and the driving force required for the mixing "In the diagram, curve (A) shows the maximum values of driving force, while curve (B) shows the compensation values"

M & nn, on the other hand, the excess ethylene glycol is distilled off according to the method of the invention and the molar ratio is set to the prescribed ratio : urch ci «, - rjer. Syitsenkrafttc- ^ arf. attained verä. In addition, the Yernic 'is achieved in the same way', ei-e« "V / ehn uen ;; enä £ c; ..; ; "Method de_-. Inventive- · '.-_: " Γ-, · <τ _._ _f , t

90988 1/150 1 ■ bad ORIGINAL '

v.-ircl, it is not necessary that a heater of excessively large capacity is arranged for the boiler, nor / does the mixer need to be such a one with particular efficiency. Furthermore, to whom: during the fermentation process, catalysts or additives such as etv / a alkali salts or sitane oxide are grounded, the incorporation of which is carried out very uniformly, -./ which leads to a yerbeaaerun. In addition, there is a further effect of the invention in the fact that the container, the rectification column for separating off water and the distillation lines are washed during the distillation of the ethylene glycol. This avoids both clogging of the lines and discoloration or staining of the polymer »

According to the process of the invention, polyethylene terephthalate is made with a high softening point and a good one Preserved shade; the procedure is such that the supply of the starting materials as well as their regulation and their uniform mixing can be achieved easily and effectively; the polymerization reaction can be more satisfactory Be carried out continuously and, in addition, can avoid discoloration of the polymers,

One embodiment of the method of FIG Invention described using an example, the invention

809881/150 1. . '

however, it is not based on di & 3e working method lesqhr: xkt "■ example

CC Ϊοϋ-Ξ -! Terephthalic acid and 130 parts of ethylene glycol v; u; 'den 2U3: .n.: En r.i't a small II en; ge 7üreat '"run-; ri: k \ tH-Xy 5 -tor (ie, 0.05 je \ :, f ₃ Ko bait el. lc rid and 0.05 Oev;. ^ Hatrlumhydror.yd, U" saj3: n -.uf fiio Iprcphthal & l-Iure) .au ο in en Br -.- i ■ mixed and in one. Autoclaves set up »lum

™ vairden ciuroh r '-: -: ohu increase csr l} enper ^- -vtur at Atrßowphäreiiv.ruok 140 parts of ethylene glycol were distilled off ₀ This was then done by increasing the pressure and temperature to 4 kg / om ¹ "■ bz'r' o 240 ⁰ C distilled water formed and the esterification reaction causes · Then, a small amount of Polyaerisationsanregern (d »h ^ 0.05 Gevu antimony and 0.1 i» Xriphenylphosphat based: -., uf the "terephthalic acid) was added and a Polymerization reaction up to a high CJrad in a vacuum of 1 mm Hg "," whereby

fc a polymeric Ilaterial was η-it a good hue, a softening point of 259 ^u O and / 7) J7-value of 0.65, in göEiessen Vein-sr 60/40 phenol / tetrachloroethane-Iöaung obtained.

SJO 9 8-0 J / Π'.Π Ί: ■ "'

BAD ORiGiNAL

Claims (1)

P. -j t ent an s ρ r ü ehe Υο ·· ί '; ΟΐΓθΐ. only manufacturer rl lüii f from lolyesterr. With the preparation of rolyte / ethylene terephthalate or polyesters which contain more than 85% polyethylene terephthalate, from terephthalic acid and irlcyl glycol or from terephthalic acid, ethylene glycol and a small amount of third components, characterized in that terephthalic acid and ethylene glycol are mixed in an excess mixed over 1 ϊ 1.9, then ά · Λΰ irr. Via: -chu3 added ethylene glycol distilled off as quickly as possible until the molar ratio is no more than 1: 1.9%, then the esterification reaction at atmospheric pressure. Pressure or under pressure and d; .. the esterification formed is polymerized prooulrt ", 2o process according to claim 1, characterized in that serephthalic acid and ethylene glycol are mixed with one another in a molar ratio in the range from 1: 2 to 1:15", ■. ... ■ · ... 3o method 4: .aoh claim 1 or 2, characterized in that arai as a third component one ocer several substances from the group Eusetst, which before. ! to the 31 tion vie of esters of compounds capable etva Ijensoeuäure, l & Ophth \ .l; fvure, adipic acid _f-Seb icirr-Lure, bulfcbenr-xecäure, Diäti, l ^ irlyLcl, Polyoxyäthvlenglykol-ii U2.g lithanolaiiin, ■ '. . c.en -uucltivoi, vie etva E ¹ OIyI ^ uIrOiK - "!!: - !, 2itr: no ;; --- d, Ilusc (carbon 11 / -: ..) Phthalac;: me: \ mC S ] ireii :: i ^ ;: onteh (threne pif: in ^ ;; tt;) um cgi; from r> äyv ^ -tn ^ ii.v-rv.: - ^: i ^ G ^ r.ejT ^ ol -r · -.- 0 308 1/1 ΒΠ1 AL Blank page