DE2060604A1 - Process for the production of linear polyesters - Google Patents

Description

Description of the patent application

SNIA VISCOSA SOCIETA 'NAZIOHALE INDUSTBIA APPLICAZIONI VISCOSA S.p.A., Milan, Italy

concerning:

• Process for the production of linear polyesters "

The invention relates to the production of linear polyesters which are suitable for fibers or other articles of daily use such as films, compacts, castings and the like.

In particular, the invention relates to the production of linear Mlschpolyeet * r _s that have a high affinity for basic dyes, as well as the objects obtained from these mixed polyesters »

It is known that linear polyesters _f which are in particular in the form of fibers and Garnen- of great in the textile field and egg üle

-Z-

BATH ORIGINAL

have the property of being colorable with basic dyes, produced by reacting an aromatic bicarboxylic acid or an ester-forming derivative thereof with aliphatic glycols in the presence of special compounds with an affinity for the basic dyes, which compounds give the polymer obtained the aforementioned properties.

The said compounds, which are incorporated into the polymer chains of the polyester due to the presence of special functional groups, do not, however, give the resulting polyester excellent properties of being able to be processed with basic dyes, which were especially desirable in the case of the fibers, which are very brilliant and should be heavily colored, like this? is currently provided for the latest technologies «

Mach the invention wised ©. In mixed polymer produced by as starting materials an aromatic carboxylic acid or a

... iur pus formation gea ignites Berivat dersalb ^ n ^ an aliphatic «, Glycol and small amounts of f ^ s ^ taisfioffen used the for eil © invention characterizes and »

w-srclan aIä humg & isgm & tof ' ffc TweptatalsSure or ai * d «rsaolckJlJSrCV r ^ uHky! ester ii'-ri-'iE» ©! ^ · - »!» (especially h ', - uIiBt;, »owla & In Glykole dl © FoiymethTlenoimsl ί";:. f {C> :. ") _0H" where ε »». Ire quite © Zr 1 * 1 smi-

109824/2278

give the polyester the mentioned dyeing properties, are compounds that use one or two to produce Ester bonds suitable functional groups and one or more "carboxylated © metallic" groups with special Affinity for basic dyes contain · These additives added at the beginning or during the esterification reactions react with the other monomers and consequently go into the polymethylene terephthalic chains, in particular into the polyethylene terephthalate chains of the polyester produced a.

The additives mentioned, which thus act as monomers, are metal salts of carboxylic acids which have one or two functional parts suitable for the production of ester bonds Contain groups and which have electroaffine elements or atomic groups that are capable of the AciditSt to increase the said carboxyl group and give it an improved and greater affinity for the basic dyes granted*

It has been found in accordance with the present invention that the characteristic Additives of the outlet reaction race (or the Reaction mass during the following esterification phases) in an amount of at least 0.5 moles and not more than 10 moles per 100 moles of terephthalic radicals present in the reaction, preferably in an amount of 1-5 mol per 100 mol of said terephthalic radicals must be added, about the final polymer produced and that obtained from it To give fibers the most favorable dyeing properties "

-3-

109 82A./22
BATH

The characterizing additives of the present invention include a family of compounds having the following general formula:

R-Z- COO Me

wherein R is a hydrocarbon radical with one or two functional groups suitable for the production of ester bonds are formed from a (optionally esterified) Radical -COOH or -OH or from an aliphatic chain with a number of carbon atoms of at most 3, which with an (optionally esterified) radical -COOH or * -HO ends are formed; Z absent or equal:

j-l-

may be {where Y is absent or from (CH _n ) (where m is a

is 2 m

whole number between 1 and f) formed or consist of oxygen or sulfur and in which the carbon atom - to one or two electroaffine elements or atomic groups

pen, consisting of halogens, NO, -OCH, phenyl, bonded

2 3

den)} -COO Me is a carboxyl salified with an alkali or alkaline earth metal (Me)} with the proviso that in the case the absence of Z R is an aromatic radical which, in addition to the one or two functional groups mentioned, also has at least two electroaffine elements or atomic groups of the type defined above in the ortho-position with respect to the salinated carboxyIs.

In one embodiment of the invention, this compound family comprises the compounds of the following type:

-4-

109824/2276 BAD ORKSfMAl

"" ■ ί'ί'ί I; jit

Vs. -Y-C- COO Me

in which the symbols have the meaning given above with the further provision that Y consists of a methylene and that X and X represent ₉ chlorine or fluorine atoms and R and R are alkyls with 1-5 carbon atoms

called family, can also be compounds of the following kind include:

\\ - C - COO Me R 00C- "" ~ X

where X and X represent fluorine atoms and the other symbols have the same meaning as above «

According to another embodiment of the invention, compounds of the following type are used 1

COO Me

wherein X and X. represent chlorine or fluorine atoms · The Ver-I 2

In this embodiment, bindings can also be as follows Be kind 1

_v CQOCH

109824/2278

206060A

wherein X, X2, and X represent chlorine or fluorine atoms

The first class of characterizing additives according to the invention preferably comprises the following examples of connections:

Difluoro (3 »5" -dicarbomethoxy) benzene sodium acetate

CH 0OC

COOCH or the corresponding acetate of another alkali metal

(Potassium, lithium, etc.)

F - C - F

COONa molecular weight

Dichloro-iSjS-dicarbomethoxy-benzene-sodium propionate

CH OCC

COOCH,

or the corresponding prop / ionate of another alkali metal or another brad alkaline metal (Za, Ba, etc.)

XK) Na molecular weight

Dichloro- (p-carbo «ethoxy) phenoxy sodium acetafc 0OCH _-

Cl-C-Cl

COONa molecular weight 301.

109824/2278

In the second Klaaae of the fiction agemSfi characteristic Additives were found to be the following compounds to be preferred:

Sodium salts of p-carboaethoxy-2,6-di-chlorobenzoic acid

Cl

Molecular weight 271.1 Sodium dimethyl (2,4,6-trichloro) trimeaate

CH _- OOC ^ ^ * - COOCH 3 3

Cl Molecular weight 363.5

Some examples follow for a more detailed explanation of the Invention, by which, however, the latter is in no way linked

EXAMPLE 1

In a verauchapolymeriaationareaktion aua roat-free Steel, the> with agitator and distillation column iat, are brought in t

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109824/2278

Dimethyl terephthalate (DMT) ι 194 parts

Monoethylene glycol (GE): 124 parts

oC, oC'-Difluoro, (3,5-Dicarbomethoxy) benzene, sodium acetate: 6.2 parts (corresponding to 2 mol percent based on DMT) Zn acetate bihydrate: 0.0388 parts (corresponding to 0.02 percent by weight based on DMT)

Antimony trioxide: 0.0776 parts ^ corresponding to 0.04 percent by weight based on DMT).

The reaction mass is gradually ^{brought to 220 °} C. in 5 hours, during which time all of the methyl alcohol formed in the ester exchange reaction between DMT and GE is distilled off from the reaction vessel.

An increasing vacuum is then applied to the reaction system reached in about 90 minutes values of 0.5 mm Hg residual pressure, while the temperature of 22O ° C to 28O ^C C is increased. The polycondensation is terminated by holding the reaction mass at 280 ° C. for 3 hours under a vacuum of 0.5 mm Hg.

The polymer formed is then pressed into cold water under nitrogen pressure.

The polymer converted into granules and dried has an excellent degree of whiteness. Also has it has the following characteristics:

ßnj a 0.663 (basic viscosity measured with a phenol / tetra chlorophthalene mixture 60/40 parts by weight;

-8th-

109824/227 β

^: · ': Ϊ́Ρ'ί · "■■■' Τ ¹¹ "'! Lip

2Q60604

1 g of the polymer in 100 ml of the solution -20 · Cj the viscosity is measured at 20 * C ·).

Melting point; 257 * C (measured according to the DTA system

thermal differential analysis)

Carboxyl end groups (/ COOH / / 10 g of polymer): 31: 3 _v

The glycol ether radicals (DEG): 1.65 (based on 100 Glycol radicals).

This polymer is made into a roving with 31 elementary threads and one Total titre converted from 150 den "which one." tubular knitted fabric is produced

A goods oyster is 1 hour while boiling with a # 3 aqueous LBsung (due to the weight of dry fiber) basic dye dam Basacryl red GL BASF in the presence of 2% üniperol AN, dispersant the BASF, as well as from 1 ml / lt 35 ^ -ig ·· CH COOH treated.

The goods are dyed with a medium red tint and have good wash resistance.

For comparison, a sample of poly (ethylene terephthalate) is prepared by observing all of the process conditions described above , except that no further monomer is added to the DMT. A polymer is obtained which has the following properties:

Melting point 260 ^° C

(COOH) / 1O ί 30.1

DEG s 1.58 Molproflsent »

• ■ Q «·

109 8 2 4/227

BATH ORIGINAL

This polymer becomes a yarn and a tubular Knitted fabric obtained, which is dyed under the same conditions as the modified polyester. This comparative yarn only absorbs traces of the dye, which are easily removed during washing.

EXAMPLE 2

Under the same process conditions as in example 1 a mixed polyester sample is prepared, but using the following as an additional monomer:

, ß- (3i5-dicarbo »ethoxy) benzene potassium propionate in an amount of 9.83 parts (corresponding to 2.5 moles per 100 moles of DMT). The polymer obtained has the following properties:

ClJ - °> ⁶ 55
Melting point: 255 ° C (DTA)

(CQmJ / ΙΟ ⁶ ι 35.5

BEG i 1,8Smöl £.

This polymer is spun and, as in Example 1, converted into a knitted fabric. A sample of the goods is treated for 2 hours at 120 ° C. with a 3% aqueous lorning (on the surface of the weight of the dry goods) of blue glass GC (general aniline and film Co.) colored. Man ~ he holds a "good BlautdruÄng with excellent WaschbestXndi £ k * it · The War" from DE® unmodified PolySthylenter "phthalic * t niEsat in Gegeneata hiersu hm ± of their coloring under similar conditions d 'n dye were running in n * un * ni

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109824/2278 ORIGINAL BATHROOM

■■ ■ '' ■■■ ... ■ :: ■■■■,! ■■■■; ■■ ;:.:. ■■■!, ^ "! J ^

/ 11

example

value mass. EXAMPLES 3ί 4 »5 and 6

Mixed polyesters with the following monomers are obtained under the process conditions described in Example 1 manufactured j

Example 3: 6 parts of dichloro (p-carboethoxy) phenoxy Sodium acetate, corresponding to 2 moles per 100 moles

DMT Example 4: 5.42 parts of the sodium salt of the p-carbomethoxy

2,6-chlorobenzoic acid, corresponding to 2 mol

per 100 moles of DMT Example 5: 7.27 parts of sodium dimethyl (2,4,6-trichloro) -

-Trimesat, corresponding to 2 moles per 100 moles of DMT Example 6 s 6.58 parts of sodium salt of 2,6-dichloro-C ^ -

-ResorcylsSurediacetats, corresponding to 2 mol

per 100 moles of DMT.

The properties of the polymers obtained are summarized in the table below.

/ 10

DEG mole percent

Melting point (DTA)

0.633 0.631 0.620 0.615

21 29

30.5 26.5

1.25 1.80 1.88 1.90

254 * C 253 ° C

252.5

Samples of goods that are obtained from these polymers by the usual methods are classified under the conditions described in Example 1

109824/22 7 6

Subject to the specified conditions for smoking.

All samples show a satisfactory dye uptake, with the staining after a number of Waadhi treatments. gene is resistant.

Pa t en t an s ρ τη oho

1Q.9 # .24 / 2276

Claims (1)

DH. ING. F. WtTESTHOFI1 I) IVL. IMC. O. VU: 'Ά BBvS? IäJi? Zi «*" 20606QA MÜNOH3N90 IA-3 8 March 3, 1971 • 4 PATE NTA NSPRUCHE 1. Process for the production of linear polyesters, which have a good affinity for basic dyes have, characterized in that the typical substances used to form the polyester (aromatic carboxylic acid or a derivative thereof suitable for ester formation and aliphatic glycol) are copolymerized with an additive consisting of metallic salts of Carboxylic acids, which have one or two functional groups suitable for the formation of ester bonds, and electroaffins Contain elements or atomic groups which are suitable, the affinity of the salified carboxyl group the basic To increase dyes compared to. 2 · The method according to claim 1, characterized in that the monomeric additive is a compound of the general formula R-Z- COO Me is used in which: R is a hydrocarbon radical with one or two to form is functional groups suitable for formation, those from a (optionally esterified) radical —COOH or —OH or from an aliphatic chain with a number of Carbon atoms of 3 or less, marked with a · «(if applicable esterified) radical -COOH or -OH ends, formed are} Z absent or equal to s I.
YC- 1 09824/2276 «13- BAD ORIG) NAL can be, where Y can be absent or from (CH) 2 m (where m is an integer between 1 and 5) or can consist of oxygen or sulfur and wherein the carbon atom - C - - on one or two electroaffine elements or atomic groups, consisting of halogens, NO, -OCH, phenyl, is bonded; -COO Me is a carboxyl which is salified with an alkali or alkaline earth metal (Me), with the condition that, in the absence of Z, R is an aromatic radical which, in addition to the functional groups mentioned, also has at least two electroaffine elements or atomic groups of the type defined above in the ortho position in relation on the salted carboxyl 3 · Process according to claims 1 or 2, characterized in that said monomeric additives terephthalic radicals present in an amount of 0.5-10 moles per 100 moles in the other starting materials of the reaction be used" 4. Process according to Claims 1-3 , characterized in that the said monomeric additives are used in amounts of 1-5 mol per 100 mol of terephthalic radicals present in the other starting materials of the reaction. 5. The method according to claims X and 2, characterized in that a compound of the following type is used becomes 2 -H- 103824/2278 BATH ORIGINAL WT * r "M .ϊρ !!! *», ■■ ■ .ί-Ρ.ϊΙΙ / ηϋΙΊΙΒΙΙΙΙιρί! ;; ...)!; ::!: - :. ■ ■■ ,, .. ,, ",;. ,,, .., ..,:,; ",. ,, gn ,,,",;;,. , - Y - C - COO Me wherein Y consists of a methylene, X and X chlorine or FluoratoBie are and R and R are alkyls with 1-5 carbon atoms « 6. The method according to claims 1 and 2, characterized in that a compound of the following type is used will : wherein X and X are fluorine atoms and R and R are alkyls with 12 12 Are 1 to 5 carbon atoms. 7. The method according to claims 1 and 2, characterized in that a compound of the following type used M ^Wirdi COO Me CO OOCH where X and X consist of chlorine and fluorine atoms. 1 2 8. The method according to claims 1 and 2, characterized in that a compound of the following type is used -15- 109 824/2276 becomes,; ■■ CH OOC OO Me OOCH wherein X, X and X consist of chlorine or fluorine atoms. 12 3 9 · Polyester product old high affinity basic Compared to dyes, characterized in that it has units in its mixed polymer structure which are composed of the mixed polymerization of terephthalic and glycol radicals with an additive, which consists of metallic salts of carboxylic acids, one or two functional groups and electroaffine elements or atomic groups suitable for the formation of ester bonds in one have such a position that the affinity of the with an alkali or alkaline earth metal salted carboxyl * is enlarged compared to the basic dyes · 10. Polyester according to claim 9, characterized in that it has electroaffine elements in its mixed polymer structure or contains atomic groups which consist of halogens, NO, -OCH, phenyl. 11. Polyester according to claims 9 and 10, characterized in that it corresponds to said additive Mixed polymer units in an amount of 0.5-10 moles each 100 mol of the terephthalic radicals contained in the polyester contains -16-109824 / 22 76 206 06 OA 12. Polyester according to claims 9-11, characterized in that it corresponds to the said additive Mixed polymer units in amounts of 1-5 moles per 100 moles the terephthalic radicals contained in the polyester " -17- 1.09 * .24 / 22? G