DE1795502A1 - Novel crystallizable copolymers and processes for their preparation - Google Patents

Description

PATENT LAWYERS

DR.-ING. BY KREISLER DR.-ING. SCHDNWALD DR.-ING. TH. MEYER DR. FUES D1PL.-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLDPSCH

COLOGNE 1, DEICHMANNHAUS

Cologne, 7: '-'■>. Si-pte.riber! 969 Kl / En / Ax

Ili ppoa Rayc.i Co., Led.,

5 LJji-tonou-ihl, Uji-Shl, Kyoto-? U (Japan)

New kriscallisieroare copolymers and processes too

their manufacture

1. Removal from patent _β (patent application -F 15 95

The ErfiuJuum looks at new linear crystallizable Copolymers which are polyetheresters and which are composed of at least 2 * .73.l. V3rsoLiedunen vüederkehrenden unit! the P: .rr: iel

S ^ = ³ ^ 0

I, (nao'-irolgend ai & Äthylcaterephthalateinheit be '^ eiolm uad / -CH ₂ CH ₂ -OC- ^ ^ -0- (0Η ₂ ) ^ - 0- ^ ygO- /

(hereinafter referred to as ethylene-1,4-diphenoxybutane-pjp'-dicarboxylate designated)

host en, as well as an '/ experienced in their manufacture and their Use for the connection of shaped objects, v; ie B'asers and films.

Numerous copolymers including polyesters, polyethers and polyether esters are already known. For the most part it was

109887/1548 ⁸ ^ original

but found that the desired degree of crystallinity with increasing content of the Copclymeren Comonomereirihe.iteri compared the corresponding, homopolymer decreases and that in the. Mittelleren regions of the copolymer composition of diosem Reason no crystallization can be observed.

For example, copolymers made from ethylene glycol, terephthalic acid or a derivative forming their ester and an acid such as isophthalic acid, adipic acid, sebacic acid or hydroxybenzoic acid, or a derivative forming their esters, processed into cold-stretchable fibers, films and the like will. However, there are disadvantages in the production of the moldings from these copolymers. Also wise the products obtained have poor properties, the lack of crystallinity and the very broad softening range and the low softening temperatures of the copolymers in the medium composition range.

These disadvantages are particularly evident in those made from terephthalic acid, Sebacic acid or oxybenzoic acid or their ester-forming derivatives of composite copolymers clearly be-2ο noticeable.

In British patent specification 91J>Aj> 6 , a process for the preparation of copolymers is described in which an acidic component of the general formula

COOR ¹

in which X is an omega-Hydroxyälkylrest with 2 to 8 carbon atoms, R is hydrogen or an iMethoxygruppe and R ^{1 is} hydrogen, a β-hydroxyethyl, a methyl or ethyl radical, with an acidic component of the general ■ formula

_BATH ORIGINAL

109887/1548

R ¹¹ OOC-T V-COCR "

ν :: rin R "can be the same or different and is a hydrogen atom, denotes a methyl radical or a β-hydroxyethyl radical and ethylene glycol in the presence of an esterification catalyst is implemented. Likewise, in the patent mentioned, a copolymeric polyether ester made from terephthalic acid, / \ ethylene glycol and an acid of the general formula

COOH

described, in which X is an omega-hydroxyalkyl radical with 2 to S carbon atoms, R a hydrogen atom or a methoxyl radical mean.

The copolymeric polyether esters that make up the units

-CH ₂ CH ₂ OOC-C ^ -COO-

- (CH ₉ ) O- / \ -CCO-

contain, vic-. at η 2, 4, 3 * 6, 7 or 8 irt, have a ver -. '. i.idcr-c -criptallisable content and one, erv: «: terte ^ - JZrv.'ei-2hungsbereica compared to polyesters of terephthalic acid with Polymethylene! Ycol en «

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It has now been found that certain copolymers, the polyether esters represent over the entire range of the copolymer composition are easy to crystallize and are therefore suitable for further processing into shaped bodies, such as Fibers and films with excellent properties such as high tensile strength and good dimensional stability are suitable.

The invention relates to crystallizable copolymers, which consist of at least two different repeating units, one of which is an ethylene terephthalate unit the formula

/ -CH ₀ -CH ₀ -OC- / Vc-0-7

it \ / η 0 ^{Xss /} 0

and the second an ethylene-1,4-diphenoxybutane-p, ρ'-dicarboxylate unit the formula

is,

In the case of synthetic high-molecular substances, such phenomena have so far only rarely been noticed. Until today are therefore only a few reports on mixed crystal formation in copolymer systems have been published, namely on misoh crystal formation in the case of copolymer polyamides and stereoregular copolymers of styrene and substituted styrenes. The education of solid solution in copolymer polyesters and polyether polyesters has not yet been described in the literature. On the contrary, Edger and Hill have the power possibility of such mixed crystal formation in "Journal of Polymer Science ", page 1, issue 8, August 1952, answered in the negative.

In the present invention; will be contrary to the one there expressed view that copolymer polyether esters

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BATH

over the £ esa.hiten Btre loh the Gopolymerenzusa .imensetzig issued 1oh.iet crystal! ηLtat have and that the structure of the Copclymeren viii that of the corresponding Hor.; jpoly ::! eren differs.

The most likely reason for this is the identity of the repetition periods of each individual component in the Gopyrneren and the equality of the number of skeletal atoms that each between the benzene rings.

The invention also relates to a method for production of linearea crystalline Gwpolynieren, which are used as materials for the production of threads, fibers, films as well other molded goods are valuable.

The process according to the invention is characterized in that ethylene glycol is condensed with terephthalic acid and 1,4-diphenoxybutane-p, p ^T -dicarboxylic acid or a derivative forming its ester and the condensation product obtained is polycondensed.

Ethylene glycol and terephthalic acid are used as the starting material or their ester-forming derivatives and ethylene-1,4-diphenoxybutane-p, ρ'-dicarboxylic acid or their ester-forming derivatives are used.

The copolymers of the present invention can be prepared according to the for the production of other linear polyesters or polyether esters known processes. To be favoured they obtained by the esterification method and / or the Esteraustaus chfiiethode, depending on the composition of the copolymer Ethylene glycol with the lower alkyl esters such as the methyl esters of the corresponding acids, preferably in the presence of suitable catalysts, heated and the released

y> if alcohol is distilled off from the reaction mixture,

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whereby the corresponding ethylene glycol esters are formed, which then become the actual by further heating under vacuum Polymers with high molecular weight are polymerized or polycondensed. The copolymers of the invention are in this way from ethylene glycol and the lower alkyl esters such as the methyl ethers of terephthalic acid and 1,4-diphenoxybutane-p, ρ'-dicarboxylic acid or their lower alkyl esters. "Have the linear molecules of the reaction product high average molecular weight and are structured in such a way that the two different building blocks that are repeated, namely ethylene terephthalate and ethylene-1,4-diphenoxybutane-pip'-dicarboxylate units, are randomly distributed along the polymer chain. It is possible through matching Selection of the ratio of the components to control the rate of crystallization and melting points of the copolymers. The copolymers according to the invention can easily be pased and process films with high tensile strengths, good elasticities and high resistance to heat shrinkage and which can easily be stretched cold.

In the preparation of the copolymer, others can also be bifunctional Ie compounds such as dibasic acids, oxyacids, Amino acids, amino alcohols and glycols are used as long as the copolymers produced show crystallizability.

BATH ORIGINAL 109887/1548

example 1

Ι25ί3 B Dimethyl-l _i 4 ~ diphenoxybutane-p, p ¹ dicarboxylate, 58 * 2 g of dimethyl terephthalate and 97 g Ä'thylenglykol v / ground heated for about 1 hour at 220 ⁰ C in the presence of cobalt acetate in a condensation vessel in an oxygen-nitrogen stream until most of the methanol has been removed and the ester interchange is practically complete. The reaction product is then heated to 270 ° to 280 ° C. for 1 hour under normal pressure and then subsequently in vacuo for a further 5 hours. The well-crystallized copolymer obtained has a melting point between 160 and 165 ° C. and an intrinsic viscosity of 0.752.

The mol percentage of ethylene-1,4-phenoxybutane-p, p'-dicarboxylato units is 53 * 8 % »

Filaments formed from the molten mass can also be cold drawn to form ribbons, their X-ray diffraction pattern again shows an orientation of the molecules along the paser axis. The X-ray diffraction record also differs of the copolymer again from that of polyethylene terephthalate and that of polyethylene-l, ^ - diphenoxybutane-p, p'-dicarbo: iylats. Following the procedure of Example 1, a number of different copolymers having different compositions produced, again the times required for the polymerization were determined so that the values of The intrinsic viscosity of the individual copolymers is between 0.70 and 0.8c. Melting point and viscosities of these products are compiled in Table 1.

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Table 1

From units of p-trimethyleneoxybenzoate and ethylene-1,4-diphenoxybutane-p, p'-dicarboxylate composite copolymer

MoI-Ji
Ethylene-1,4-diphenoxy-
butane ~ p, p '-dicarboxylate-
units- Melting point (° C) 0.735 10 250 .0.718 17.6 .217 0.739 33.3 177 0.742 50 161 0.752 53.8 162 0.738 70 484 0.735 90 202

These copolymers also crystallize easily over the whole range Range of copolymer composition. The fibers formed from the copolymers again show a high tensile strength and good elastic properties. The polymers can also be used as film-forming materials.

BATH ORIGINAL

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Example 2

125.3 g of dimethyl ester of 1,4-bisCp-carboxyphenoxy ^ utane, 58.2 g of dimethyl ester of terephthalic acid and 96.0 g of ethylene glycol were mixed. 7 ^ mg of tetran-butyl orthotitanate were added to the mixture as a catalyst. The mixture was heated to carry out the Esteraustauschreaktion with stirring to 190 to 23O ⁰ G under normal pressure. The methanol distilled off at this time was removed from the system. The reaction temperature was then increased to 270 to 280 ° G and the pressure was gradually decreased to 0.5 to 0.1 mm Hg. The polycondensation reaction was carried out for 2 to 3 hours. This gave a copolymerized copolyether ester which had a relative viscosity of 1.36 (measured on a 0.5% strength solution in a 1: 1 mixture of tetrachloroethane and phenol) and a melting point of 163 to 170.degree.

The copolymerized gopolyether ester was processed by melt-spinning at 185 ° to give threads which were stretched 4-, 5-fa-Ch. The filaments obtained had a strength of 5,4 g / ο to, an elongation of 2ψ / and a shrinkage of 0.3 to 0.6? Ό in hot water at 100 ⁰ C.

The copolymerized polyether ester prepared according to this example was subjected to X-ray analysis. The spectra recorded showed that the thread is not oriented prior to stretching, and was not crystalline, while the spectrum of the thread 1 hour in hot water at 100 ⁰ G was maintained, showed a non-oriented crystalline structure.

The X-ray diffraction pattern of this copolymer was different from the X-ray diffraction pattern of the two homopolymers whose monomers were used as starting materials. The crystallized product had sharp main maxima at d = 5.09 S ₁ 3.9 ^ - Å and 3.47 Å.

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- ίο -

Example 3

19.4 g of dimethyl ester of terephthalic acid, 161.1 g of dimethyl ester of 1,4-bis (p-carboxyphenoxy) butane and 82 g of ethylene glycol were mixed. Zinc acetate was added to the mixture as a catalyst. The mixture was heated under normal pressure to carry out the ester interchange reaction. The methanol was distilled off and removed from the system. Subsequently, the copolycondensation was carried out under reduced pressure of 0.5 to 0.1 mm Hg to give a copolymerized polyether was obtained having a melting point from 185 to 189 ° C and in 1% solution in o-chlorophenol at 20 ⁰ C measured specific viscosity of 0.45.

The copolymerized copolyether ester obtained was processed by melt spinning at 205 ° G. The received Filaments were drawn 4.4 times and then had a tenacity of 6.2 g / denier, an elongation of 23% and one

Young modulus of 540 kg / cm.

The X-ray diffraction pattern of the copolymer obtained showed that the copolymer was highly crystallizable. The X-ray diffraction pattern was different from the X-ray diffraction pattern of the two homopolymers whose monomers were used as starting materials. That crystallized The product had sharp main maxima at d = »4.63 ä, 4.17 i and 3.38 Ä.

Example 4

53 »7 g of dimethyl ester of 1,4-bis (p-carboxyphenoxy) butane and 25.2 g of ethylene glycol were mixed. Antimony oxide was added to the mixture as a catalyst. To carry out the Esteraustauschreaktion the mixture to 190 to 220 ⁰ C was heated · Separately, lOO ^ g Ithylenglykol and 135.8 g of the dimethyl ester of terephthalic acid mixed. Cobalt acetate was added to the mixture as a catalyst. The mixture became the ester interchange reaction

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heated to 190 to 23O ⁰ G. The two reaction mixtures were mixed and heated to 270 to 280 ° C. at 0.5 to 0.1 mm Hg to carry out the copolycondensation reaction. ^{This gave a copolymerized polyether ester which had a relative viscosity of 1.4-5, measured at 20 0} G, in a C ^ iger solution in a mixture of tetrachloroethane and phenol (4-0: 60) and a melting point of 226 to 228 ⁰ G .

The copolymerized Gopolyetherester was processed by melt spinning, whereby filaments were obtained which had a strength of 6.3 g / den, an elongation of 27% »a Young's modulus of 560 kg / cm and a shrinkage of 0.5 to 1% in had hot water of 100 ⁰ G.

From a copolymerized one prepared in a similar manner Gopolyether ester was made into a film 60 cm wide and 0.15 nm thick by extrusion molding manufactured. The film was stretched about 3 times in the longitudinal direction at a temperature of 80 to 85 ° G and then stretched about 2.5 times in the transverse direction to obtain a transparent, isotropic film which

ρ a tensile strength of 20 to 23 kg / am and an elongation of 4-5%.

The crystallizability or crystallinity of the according to Copolymers prepared in this example were determined by X-ray analysis. The X-ray spectrum of this Co ~ polymeric was different from the X-ray spectrum of the two homopolymers, their monomers as starting materials were used. The copolymer was highly crystallizable. The crystallized product showed sharp main maxima at d «5, O9 1, 3.95 p. and 3.4-7 pounds.

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Example 5

116.4 g of dimethyl ester of terephthalic acid, 14.5 g of dimethyl ester of adipic acid, 119 »O g of ethylene glycol and 71.6 g of dimethyl ester of 1,4-bis (p-car" boxyphenoxy) butane were mixed. Antimony acetate was added to the mixture as a catalyst. To carry out the ester interchange reaction the mixture was heated to 190 to 220 C under normal pressure heated. The methanol distilled off at this time was removed from the system. The reaction temperature was then to carry out the copolycondensation reaction is increased to 270 to 280 ° C. under reduced pressure. This gave a copolymerized polyether ester which had a melting point of 167 °> is 169 ° 0. Crystalline filaments were obtained by spinning and drawing the copolyetherester.

Example 6

215.1 g of bis-ß-hydroxyethyl terephthalate and 33.7 g of 1,4-bis (p-carboxyphenoxy) butane were mixed. To the mixture was added tetra-n-butyl orthotitanate (128 mg) as a catalyst. The mixture was heated to carry out the Esteraustauschreaktion with stirring at I90 to 230 ⁰ O at atmospheric pressure. The methanol distilled off at this time was removed from the system. Subsequently, the reaction mixture was heated to carry out the copolycondensation reaction for 2 to 3 hours at 270 to 280 ° C with gradual lowering of the reaction pressure to 0.5 "to 0.1 mm Hg. A copolymerized polyether ester was obtained which had a specific viscosity of 1, 40, measured at 20 ° C. in a 5> ^ iger solution in a 1: 1 mixture of tetrachloroethane and phenol, and had a melting point of 229 to 231 ^° C.

The copolymer obtained was processed by melt spinning at 260 ^° C. into threads which were drawn 4.6 times. The filaments had a tensile strength of - ■ '5 6.7 g / d, an elongation of 22% and a Xoung module

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of 560 kg / cm. The shrinkage in hot water at 100 C. was 0.5 to 0.1 / δ.

It was found by X-ray analysis that the copolymer was highly crystallizable. The X-ray diffraction patterns these Gopolyineren were from the Hontgenbeugungöbildern of the two homopolymers different, their i; ionomers were used as starting materials. The X-ray diffraction pattern of the crystallized product had sharp main maxima at d = 5 »O9 Å, 4.00 Å and 3j4-6 Å.

Example 7

97.0 g of dimethyl terephthalate, 89.5 g of dimethyl ester of 1,4-bis (p-carboxyphenoxy) butane and 112 g of ethylene glycol were mixed. Zinc acetate was added to the mixture as a catalyst. The mixture was heated to 190 to 230 G at normal pressure to carry out the ester interchange reaction. The methanol distilled off at this time was removed from the system. The reaction temperature for carrying out the polycondensation reaction was then increased to 280 ^° C. at a pressure of 0.5 to 0.1 mm Hg. Here, a copolymer! Lized polyetherester was obtained which had a melting point of 175 *> is 177 ° C and a relative viscosity of from 0.4 to 0, measured at 20 ⁰ G in an I ^ solution in o-chlorophenol.

The obtained copolymer was melt-spun at 205 ° G with an extruder-type melt-spinning machine Processed threads that have been stretched 4 or 6 times. the The threads obtained had a tensile strength of 6.2 g / denier and an elongation of 25 $

The X-ray diffraction pattern of the prepared according to this example Copolymers was from the X-ray diffraction patterns of the two homopolymers, using their monomers as starting materials used differently. The X-ray diagram also showed that this copolymer was highly Dimensions was crystallizable and that the crystallized Co-

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polymeric sharp major peaks at d «5» 33 S, 3.90 and 3.54 £ Ϊ had.

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Claims (2)

Godfather η t a η s ρ r ü c h e 1) Crystallizable copolymers of polyether esters, marked by at least two different recurring units of the formulas / -CH ₀ -CH ₀ -OC- - d d n {Ethylene terephthalate) and / -CH ₀ GH ₀ -OC-0 (Ethylene-1,4-diphenoxybutane-p, p ¹ -dicarboxylate) 2)} Process for the production of cepolymers according to claim 1, characterized in that ethylene glycol is polycondensed with terephthalic acid and 1,4-diphenoxybutane-p, ρ ^f -dicarboxylic acid or ester-forming derivatives of these acids, optionally in a mixture; .iit other components. j) Use of copolymers according to Claim 1 for the production of Pasorrij films and formulas. 109887 / 154B BATH ORIGINAL