DE2031288A1 - Process for the production of Polyathy lenterephthalat - Google Patents

Description

PATENTANWÄLTE 8 MÜNCHEN 5, 9 ΓΠ 1? R.

DR.-ING. H. FINCKE Molier.troeeJlappe 22Pg?

DIPL.-ING. H. BOHR
DIPL.-INQ. S. STAEQER M 4 T 774

Fet η τ u fi · 26 <0ίΟ

H 4 T Chemicals Ine, New York, SM * _P V ^

Process for the production of polyethylene terephthalate Priority: 24 * 6.1969 - USA

The invention relates to an improved process calibration but Heretellung "τοη polyethylene terephthalate You shall look in particular to an improved polycondensation catalyst for producing polyethylene terephthalate τοη, In this catalyst is at a sulphurous · Organoantimonverbindung

It is known that polyethylene terephthalate can be produced from a suitable methyl ester of terephthalic acid, which in turn is produced by reacting methyl alcohol with terephthalic acid. "If a methyl ester of terephthalic acid is used as the starting material" then this is mixed with ethylene glycol in the presence converted a üneeterungakatalysators with the help of an ester exchange reaction. If terephthalic acid itself is used as a starting material, then it is converted into a direct teresterification reaction with ethylene glycol using a catalytic additive for the first stage or, in other words, an ether inhibitor. In each method, the product obtained, namely a ü'sfcer "is then pin in the presence Oines Polykofidcfloationskondensatori? Ki) m] _v erwLevb to

009082/21 3 4

BATH ORIGINAL

Prepare polyethylene terephthalate. To 3ieren to-polymerized-Bia (B -.- hydroxyethyl) -terephtbalat in a reasonable time, it is necessary to _see "a catalyst to use =, E3 many Katalysatorea were called for this purpose, but it was found.} That that “They react quickly” also cause a quick “Abbe” of the polymer. Another disadvantage is that “many of the known catalysts produce a polymer with a yellowish color. For the production of Faaerm it is necessary to achieve as white a color as possible. For the production of films a clear polymer is necessary.

The aim of the invention is the production of high molecular weight polymers with a high viscosity number! .. Another goal of the Invention is the manufacture of a white or white tile Polyätbylenterephthalat & oljiiers-,

So is gemäsa OCE Ipfladaag ela ferfalirea aar Herste! "- development of Folyäthylenterephthelat vorgesefelagea ^ in which dimethyl terephthalate or TerepbthalsäoreM.t Ithyleogljrkol is amgesetzt ₉ is an ester of terephthalic acid Äthylanglykol ani herzustellenj, whereupon this Eater la presence of a Folykondensationekatalysators is polycondensed. The process is characterized in that the condensation or polymerization of the ester is carried out in the presence of a catalytic amount of a sulfur-containing organoatim compound.

The sulphurous Organoantiiaonverbinäang de?

Invention contains at least one direct sulfur antinon Bond or at least one sulfur-solute bond.

The sulfur-containing antimony compound has the formula Sb (Ys} _ »where Y for R, - SR, OHSH, OOCRSH> JL SRCOQH ' oäer

η L M OUiI 4

~; YEAR ^? _o nl; i: ht, where R uinl R 'independently of one another Alky'

009882 / 213A

Alkenyl. Represents cycloalkyl, aralkyl, aryl, alkaryl or such an inertly substituted radical andl η represents an integer of 3 or 5. The invention includes trivalent and pentavalent antimony compounds,

Examples of antimony compounds are the following:

R _a Sb (SC-HR ' ₂ ) ₅ . _a

R _fl Sb (SR ⁵ COOR) ^ ₈ R ₀ Sb (OOCRSH), _

where a is an integer of O ₁ 1 or 2 and R and R ^{9 are} hydrocarbons

In these compounds, R and R · are hydrocarbon radicals, and »was preferably alkyl- _e alkenyl-. Cycloalkyl, aralkyl and alkaryl radicals and aryl ₉ such inertly substituted radicals, examples of alkyl are straight chain or branched chain alkyls such as _T on «example, methyl, Itby. \, N-propyl, isopropyl _£, η-butyl, isobutyl, eec-butyl , tert-butyl, n-amyl, neopentyl, Ieoamyl, n-Hexyl, Isoheiyl, Heptyl _r Octyl, Deoyl, Dodeoyl, Tetradeoyl, Octadecyl aenr _c - The preferred alkyls are lower alkyls, that means those with about 8 or less carbon atoms « typical alkenyls are initially example, vinyl, allyl, 1-propenyl, methallyl, buten-1-yl, buten-2-yl _f buten-3-yl, penten-l-yl _t hexenyl, heptenyl "octenyl, decenyl, Dodeoenyl _f tetradecenyl , Octadecenyl etc _? Typical cycloalkyls are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. If R is aralkyl, 63 can typically be: Benayl, S-phenylethyi, / ^ phenylpropyl, β-phenylpropyl, etc. Typical aryls are phenyl, haphthyl, etc. _c Typical alkaryls are tolyl. XyIyI, p-Ethylphecy 1, p-Moiiylphenyl etc _c R and R ^:

009882/2134

can be inertly substituted, the heiaet "they can not wear" reactive substituents * as stm as alkyl ₆ Jiryl, cycloalkyl j Aralkylj, alkaryl, Alkeayl, JLther, halogen "nitro, ester ASW _n! Eypiseh © substituted alkyls are aum Example 3- Chloropropylg 2-ltteoxyäthyl, Carboäthoxyjaethjl etc. Substituted Alkenyl © are asu® example 4-Ohlorobatyl, JfS.Phenylpropenyl, Ohloroallyl new ", Substituted Cycloalkyls Bind Bum Example 4" Methy! Cyclohexyl, ^ Chlorocycloliexyl are for example _s anisyl, biphenyl, etc., substituted aralkyls inert siad for example Chlorobensyl »p-Fhenylbenssyl" p-Methylbensyl etc, inertly substituted alkaryls are mm example 3-.Ghloro-5 "methylphenylc 2cö-Bi-tert-butyl ^ -chlorophenyl etc. _o

Specifically sulfur-containing organoantimony compounds, the geder Invention can be used are i

Antimony-

Antimony · trisisooetyl mercaptoacetate antimony thiobenzoate
Antimony thiophenolate
Antimony triethyl hydrosulphide
Antimony tributyl hydrosulfide
Antimony trioctyl hydrosulfide
Antimony tri Bd odecylhydrosulfide antimony tri-SfS ¹ _? S "-thioacetate antimony-tri-S _$ S * _c S" - »thiopropiona t antimony-tri-S, S ', S ⁿ -thiobutyrate antimony-tri-S, SSS" -thiovalerate antimony-tris-S, S · , S ^M thiotallate antimony tris-S, S ', S ^w -butyl mercaptoacetate antimony tris »S, S ·, S ^M -octyl mercaptopropionate antimony tris-S, S * , 3" -butyl mercaptopropionate bis {dibutyl antimony) sulfide
Bis (diocty! Antimony) sulfide
Bis (diphenylantieon) sulfide
009882/2134

OBlQWAt.

Diohlorophenylantimony didodeoyldithiocarbamate Dicyelohexylantimony hexadeoyldithioearbamate Diootylantimony «phenyldithiocarbaiaate Diphenylantimony-diphenyldithiocarbaiBate Dicyclohexyl antimony cyclohexyl dithlocarbamate Phenylantimony diCdioyclohexyldithlocarbamate) ToIylantimony di (allyl ditoblocarbamate) Cyclohexylantimoii-di (diallyldithiocarbamate) Mphenyl antimony benzyl dithiocarbamate Bibenzyl antimony dibenzyl dithiocarbamate Di (diphenylantimony) »methylenebisdithiocarbamate

Di (ditolylantimoss) -äthylenbi8dithiooarbaiaat

Diidicylohexylantimonyj-propylene bisdithiocarbamate

Phenylantimon-trimethylenbisdithiocarbaroat Tolylantimon-tetramethylenbisdithiocarbamat ButylaDtimon-hexamethylenbisdithiocarbamat Allylantiraon "octamethylenbisdithiocarbamat Benzylantimon-o-phenylenbiadithiocarbamat Phenylantimoa M phenyleiibiedithiooarba & at Bi {diphenylantimon) -p-phenylenbiedithiocarbamat di (ditolylantimon) - <slr tolylenbi8dithiocarbaiDat Chlorophenylantimon ^ zylylenbieditbiocarbamat Bi (diphenylantlmon) * - 4" 4 ^t -biphenylenebi8ditbiooarbamate

BiidlphenylantiraonJ ^ -chloro-l ^ -phenylenbisdithiocarbamat

Diphenylantimony dimethylenediocarbamate Phecylantlmon-di (pentame ethylene dithiocarbamate) Cyolohexylantimony ~ di {hexamethylene dithiocarbamate) Tolylantimony-III.IBc-.diethyl-'äthylenbiadithiocarbaaiat Diphenyl antimony dithiocarbamate '

Dibutylantimony-methyldithiooarbaiaat Diphenylantimony-diBethylditbiocarbamate Ditolylantimony-ethyldithiocarbanate ^: Diallylantimony-diethyldithiocarbamate Phenylantimony-di (n «-propyldithiocarbamate) Tolylantimoo-002-9arbamylditharbamate

Butylantitaon -di ^ isopropyldithiocarbamat) Alljrlantimon-diCdi -isopropyldithiocarbamat) Benaylantlmon.-di (batyldithioearbamate) GyclohexjlantimoE-di (dibutyldithiocarbamate) Chlorophenylantimony diioctyldithiocarbamate) Octylantimony-dKdioctyLdithlooarbamat) Dibenzylantimony ^ dodecyldithiocarbamate Butylantimony »di (N-» methyl »äthy lditfcioearbama t)

Ally laat imon "1 ₉ ίί ⁹ " dimethyl-hexaue tl ^ leafeis dithiocarbamate

Dichlorophenyantimony-H- (3-chloro-2-b «tenyl)«

cyclobexylaithiQosrbaiaat

Octylantimony difN ^ cyclohexyl ^ amyldithiosarbamat) antimony-S, S ³ ₉ S ⁿ -tri (octaä ®cjl »thiomaleate j

Aatimon-S _S S ³ ₉ s ^M

Triphenylantimony-S, S ^f -bie (iaooctyImercaptoacetate)

The amount of sulfur-containing Fganoantlmonverlbindungen can vary depending on the wide concentration * It is usual for catalysts, the amounts are relatively small. In general, the amount is within the range from 05.003 "to 3550 96, based on the weight of the used to (S-hyäroxy · - ethyl) terephthalate is to lie, "the area is äeirorzügte O ₉ OO6 bia 3 _S 4O ^ _s based on the weight of the bis (t ^ hyciroxyäthyl) terephthalate; a snfriedenstellende reaction rate and the product! Achieve z \ x ^ with suitable yiskositit uaö

Increase the improvement in the speed of polycondensation the new catalysts according to the invention also make the thermal stability of the resulting polymer strong improved, since compounds that eat the catalysts tem · = hold., remain in the polymer «-The presence of the

009882/2134

Catalysts of the present invention greatly improve downstream processing such as spinning of fibers and the casting of films. " These edits are made with a polymer melt at elevated temperatures

The preparation of esters by an ester exchange reaction is generally carried out with a molar ratio of itbylene glycol to dimethyl terephthalate of about 1: 1 to 15: 1 and preferably about 2il to 3: 1. The transesterification reaction is usually carried out at atmospheric pressure in an inert atmosphere, such as nitrogen, for example * and initially in a temperature range from about 1.25 to 290 ⁰ O, preferably around 150 to 260 ⁰ C, working in the absence or presence of an overmestering catalyst , During the first stage, methyl alcohol is evolved and continuously removed by distillation., If the measures previously used in the art are used, the first exchange reaction or the first stage takes approximately 1 to 4 hours.

Any known suitable esterification catalyst can be used in the first stage. The transesterification catalyst is used in concentrations of approximately 0.01 to 0.2 percent by weight, based on the weight of the dimethyl terephthalate used in the starting reaction mixture. Although the new catalyst according to the invention is not itself an transesterification catalyst, it can, if desired, generally already be present during the transesterification . ^:

The production of esters from terephthalic acid and ethylene glycol by direct esterification is generally carried out with a Molar ratio of ethylene glycol to terephthalic acid from 1: 1 to 15Jl and preferably about 2: 1 to 3: 1 carried out- The direct esterification reaction is carried out at a temperature im

009882/2134

BATH

Range from over 170 to 29O ⁰ G is the absence of an oxygen-containing atmosphere at atmospheric or elevated pressure for about 2 to 3 hours. "The air is carried out, for example, by purging with nitrogen - with another oxygen-free inert gas? The polycondensation stage or the polymerization set of the process according to the invention is carried out in this way? that the anti-maa "the BI8 monverbinäung (2-hydroxyethyl) terephthalate is added and the mixture under reduced pressure in the range of about öjOOl mm to 10 mm Hg below Rtthrea 1 bia 4 hours at a Tsmperatur of about 250 to 300 ⁰ G heated, According to the invention, the new catalyst mixture is generally used in amounts in the range from _$ 001 to 0 _? 2 percent by weight, based on the weight of the to be condensed. Esters, higher or lower amounts of the new catalyst mixture used can also be used in the polycondensation reaction

The polymers produced according to the invention can by customary spinning and casting processes can be converted into molded objects, such as films, ribbons, fibers, Bristles and the like- The polymers can be woven and non-woven in the usual way in the manufacture of icmeni «» ten textiles, papers, leather materials and others. structures are used.

The following examples illustrate the invention. The catalysts measured according to the invention can also be used for catalysis of the polymerization of other terephthalic acid esters, such as, for example, the ethyl * propyl * butyl and phenyl esters Availability preferred, but other glycols can also be used, such as, for example, the opylene glycols _for the butylene glycols and other glycols, for example 1,4-oyelohexanedimethanol, l-phenyldiaiethanol and 2,2-BiapMB-hydroxy ethyl )] -pheny lpropane =,

009882/2134

Unless otherwise stated, * all parts refer to and percentages based on weight *

EXAMPLE 1

This example illustrates a complete two-step process in the production of polyethylene terephthalate from dimethyl terephthalate and ethylene glycol,

2000 parts by weight of dimethyl terephthalate »1400 parts by weight of ethylene glycol and 0.3 parts by weight of zinc acetate were heated at atmospheric pressure in a three-necked flask equipped with a tube and a condenser until the theoretically calculated amount of methanol had distilled off. (836 ml of methanol} .- "The Zinkaoetat esterification catalyst was prepared by adding 1 ₉ 38 parts of tri-nonylphenyl-phosphite, stirring and heating of the Reaktionsgemiaches during fifteen minutes zerstörtο The Bie {S-hydroxyethyl) terephthalate-iprodukt was then isoliertο

35.0 grams of the bis (β-hydroxyethyl) terephthalate monomer and 0.017 grams of antimony thiophenolate were placed in a polyester reactor which had been prebit to 250 ^{0 "".} The temperature of the reactor was set to 280 ^° C., a vacuum of 0.25 mm Hg being applied at the same time. The polymerization was carried out for 4 hours *. The ethylene glycol formed as a result of the polymerization was distilled off and collected. After cooling, the polyethylene terephthalate product had a viscosity number of 0.53 and a melting point of 262 ⁰ Ce

EXAMPLE 2 ^:

The procedure of Example 1 was repeated with the difference that that the charge of the polymerization reactor consists of 35.0 grams of bis (O-hydroxyethyl) -terephthala * and 0.0175 grams Antimony * tris-S, S% S "-thiobenzoate existed, the polymerization« reaction was carried out for 4 hours * After cooling

^009882/2134 BADOR ₁ G ₁ NAL

ίο -

The polyethylene terephthalate prodact showed a Yiaköaitätszahl of 0.53 and a Sehmeispunkt of 265 ⁰ C--

EXAMPLE 3

The procedure of Example 1 was repeated, with the exception that the charge was two. Polysaeriaatioasreaktor from 35 s 0 Graram Bis (ß-hyäpoxyäthyl) «- terephtbaiet aaä 0 ^ 0175 Ctramm Antimony-tpiaisoootylmereaptoacetat beataaia The Polyperisa ·» ticna reaction was 3 hours long procbetha showed «phthalate» in the phthalate? viscosity number voa 0 _? 62 and a melting point ton- 260 ° 0 · ο

EXAMPLE 4

The process of Example 1 toe'll repeated old the difference daas the charge of Polymerisstionsreaktors from 35 O ₉ grams of Bie {B-hydroxyltbjl) -terephtlialat and 0.0175 © yaism Aatimon-trie-I ^ K ^ diathylditbiocartaest teatasi Bie Polymerl " · SationereaktioQ wtypde 4 stand »long aswgefüiirt ,, laca the cooling« »cool beaass the Polyäthyltaterepithalat ^ prcäakt eise? Iako» aityasahl of 0.65 and eggEen dobaelepankt ¥ © a 261 ° 0 "

009882/2134

BATH ORIGINAL

Claims (1)

Claim 1. Process in which the ethyl terephthalate or terephthalic acid reacted with ethylene glycol to make an eater aua To produce terephthalic acid and ethylene glycol »and in which the resulting ester is polycondensed in the presence of a polycondensation condenser, characterized in that the condensation or polymerization of the eater is carried out in the presence of a catalytic amount carried out a sulfur-containing organoantimony compound ( 2- The method according to claim 1, characterized in that the sulfur-containing orgonoantimony compound at least one has a direct sulfur-antimony bond or at least one direct sulfur-carbon bond, 3} Method according to claim 2, characterized in that the sulfur-containing antimony compound has the formula Sb (Y) _n , where Y is R ₅ SR. ORSH, OOCRSH, SCR, SROOOR 'or -SCNR ^r 2 (where R and R ^{f are} independent of one another Alkyl, alkenyl, cycloalkyl, aralkyl, aryl or alkeryl radicals or such inertly substituted radicals i . mean) and η stands for 3 or 5 4 ^ method according to claim 3 »characterized in that the antimony compound has the formula R Sb (SR'COOR), where a is O, 1 or 2 and R and R 'are Hydrocarbon radicals - 009882/2134 BATH ORIGINAL • ft ' 5-, the method according to claim 4p, characterized «that as an antimony compound, antimony-tria-SgS '^ "- isooctyl mercaptoacetate is used ο 6.- The method according to claim 4 _S, characterized in that the antimony compound antimony »tris-S _r S ^P pS ^w -> thiotallate is used- 7- The method according to claim 4 _5, characterized in that the antimony compound is antimony triads, S ⁹ _? S "-butylmereaptoacetate is used- 8 ^ Method according to claim 4 »characterized in that antimony tri3-S, S% S ⁿ ~ octyl mercaptopropionate is used as the antimony compound ο 9- Method according to claim 4 »characterized in that antimony tris-S, S ^J ₉ S" -butyl mercaptopropionate is used as the antimony compound ο 10- The method of claim 3 »characterized in that the sulfur-containing antimony compound of formula R ₁₁ Sb (SH ^1}» _a where fiir β 0 _£ 1 or 2 and R and ^R; fllr hydrocarbon radical are _P 11. The method according to claim 10, characterized in that antimony thiobenzoate as the sulfur-containing antimony compound is used. Ί2- method according to claim 10, characterized in that antimony thiophenolate is used as the sulfur-containing antimony compound 009882/2134 © AD 13- The method according to claim 10, characterized in that antimony-tri-SeS ⁸ * S ⁿ -thioacetate is used as the sulfur-containing antimony compound, 14 ·. A method according to claim 10, characterized in that _g daaa as sulfur-containing antimony compound antimony tri-S ^ 'S', S ⁿ is used thiopropionate " 15. ·, · Method according to claim 10, characterized in that the » ala sulfur-containing antimony compound antimony ~ tri-S, S ', S "-thiobutyrate is used., ' 16ο method according to claim 10, characterized in that ₉ is used as the sulfur-containing antimony compound antimony tri-S, S ^'7, S ^w ,, thiovalerat 17- The method according to claim 3 »characterized» that the sulfur-containing antimony compound is the formula S R ₈ Sb (SCNR ⁹ 2 ^ a has «where a stands for O _f 1 or_2 and R and R 'stand for hydrocarbon radicals * 18ο Method according to claim 17, characterized in that λ is used as the sulfur-containing antimony compound antimony-tris-N _t N-diethyldithiocarbam »t. 19 «- Method according to claim 17 _f, characterized in that the sulfur-containing antimony compound is diphenylantimondi-. thiocarbamate is used, 20- The method according to claim 17 * characterized in that as a sulfur-containing antimony compound, dibutylantimonoethyldithiocarbaiaate is used, 009882/2134 BATH 21- method according to _spoke 1 ίν äadiaroh characterized. that as a sulfur-containing antimony compound dipheaylantimony «· dimetfayldithioearteraai is used« 22. The method according to claim 17 _f, characterized in that butyl antimony di- »(iBopropyldithiocarijamate) is used as the sulfur-containing antimony compound, Method according to spoke 2 ,. thereby gekena ^ eichiaet _{8 which} bis (dibaty! antimony) sulfide is used as a sch'vefelhaltiges antimony compound " 24- Procedure naoh Aüspraeh 2 ₄ dadörch- gefeenns ei leveled that ala sulfur-containing antimony compound bis (dioetylantimoia) sulfide is used ο 25- The method according to claim 2, fladareh characterized in that As a sulfur-containing antimony compound, bis (dipheny! antimony) sulfide is used, 009 882/21 34 bad original