DE1301560B - Process for the production of elastomeric polyesters - Google Patents

Description

1 301 550

It is known ζ. B. from the Oritic patent 779 054 and US Pat. No. 3,023,192. Elastomeric polyesters by condensation of dibasic aromatic carboxylic acids or their esters with linear glycols. z. B. Ethylene Glycoi. and linear polyether glycols. z. B. Polytetrametnyleneglykolen to produce. It is also known to Production of polyesters to use as condensation component la-cyclohexanedimethanol.

The known method is disadvantageous. that only sticky and therefore technically unusable threads can be produced according to them, or that the elastic properties of the threads leave a lot to be desired. A particular disadvantage of the previously known elastomeric threads is that their so-called critical deformation temperatures are too high. The critical deformation temperature of elastomeric filaments is to be understood as the temperature below which the filament no longer returns to its original state after stretching. H. lose their elastic properties. According to the invention, elastomeric polyesters are obtained. > the elastomeric non-sticky threads with excellent elasticity on the sides. particularly low, critical Ve ^r formungstemnet-nturen. process.

The invention is a method for

ίο Manufacture of elastomeric polyesters through condensation one. «mixture of ainem polyether glycol, 1,4 - Cyciohexanedimethanol. and optionally a polytetramethylene glycol. mn. a dicarboxylic acid, in which the carboxyl residues on a

i; hexacarbocyciischen ring are bound, or a Ester of the acid, which is characterized that as a polyether glvko one is a copolyether lykoi the general fcrmei

H H

H— τ-

HO -j-CH ₂

H H

- ο τ-α

used, in which P. denotes a hydrogen atom or; a methyl group and χ and y integers greater than 0. where the sum of χ and ν is between 14 and 130 and χ is less than ais> ·. and that the concentration of the copolyether glycol. based on the M-cyclohexanedimethanol and, if appropriate, polytetramethylene glycol, below 50 mol percent - Prepare oxabicyclo [4: 3 :()] nonane by known processes. Such copolyether glycols are suitable for carrying out the process of the invention. which are composed of 50 to 95 mol percent of tetrahydrofuran residues and 5 to 50 mol percent of: rans-8-oxabicycio [4: 3. <^ - nonane or 3-methyl-8-oxabicycior4:?: 0] nonane residues.

A preferred catalyst for the preparation of the copolyutner glycols used according to the invention is fluorosulfonic acid; other suitable buyers are z. B. perchloric acid, ferric chloride-acetic anhydride complexes. PhqsphorpentaSluorid and Antimony Pentachlorid.

The copolyether glycols used according to the invention can have the consistency at room temperature from viscous liquids to soft waxes. Copohether glycols have proven to be particularly advantageous proven to be 7 to 15 mole percent au. ·. trans-8-oxabicycio [4: 3: 0] nonane or 3-methyl-8-oxabicyclo [4: 3: 0] nonane radicals exist. The average molecular weight of these copolvethers can be 20 (K) to 6 (XM).

Are used to produce the polyester mixtures of copolyether glycol and polytetramethylene glycol used, the mixtures should be at least molar percent trans-8-oxabicyclo [4: 3: 0] nonane or 3-methyl-8-oxabicyclo [4: 3: 0] nonane residues. For example, to produce such mixtures i Weight of copolyether glycol. manufactured from a mixture of 80 mol percent tetrahydrofuran and 20 mol percent 8-oxabicyeio [4: 3: 0jnonane. with up to 3 parts by weight of polytetramethylene glycol get mixed up.

Preferably, polyesters are made by the process of the invention, ranging from 50 to 93, preferably 75 to 8% by weight of copolyether glycol residues contain.

For the production of polyesters with optimal elastomeric properties for the production of threads and fibers, it has proven to be advantageous if .v plus ν values -.on 30 nis Ή corresponding to average molecular weights of 2200 to 51

nevtzer.

Polyesters with valuable properties can, however, also be achieved with the use of copolyether mixtures are produced, the constituents of which have different molecular weights within a molecular weight range from 1 (X) O to 6 (XX).

v- Dicarboxylic acids suitable for carrying out the process of the invention are those in which the carboxyl groups are bound in the para position to a hexacarbocyclic nucleus and which have a total of 6 to 20 carbon atoms. These

5-dicarboxylic acids can also have condensed rings and, for example, from 1.4- or 1.5- or 2,6- or IJ-naphtha dicarboxylic acid exist. the preferred hexacarbocyciic dicarboxylic acids are those containing a trans -cyclohexane ring

f'o or an aromatic nucleus, softer one or contains two benzene rings.

The preferred dicarboxylic acids are terephthalic acid, 4,4-sulfonyldibenzoic acid, 2,6-naphthalene dicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid c.

^r> 5 4.4'-diphenic acid or mixtures thereof are used.

Through the use of copolyether glycine

are not only polyester with improved critical Preserve deformation properties. Rather, the

30!

Use of copolyether glycols is an advantage, that copolyatherglycols of higher molecular weights can be used than is the case with de? Use of Polytetramethylene Glvkoi which is Fai. When using polytetramethylene glycol "Deformation temperatures" become critical in the case of elastomeric polyesters from above 2v € immei observed when the molecular weight of the polytetramethylene glycols is above 3 (XH). in: In contrast to this, copolyatherglycols with molecular weights can be used in the process of enodization used by 10,000, and still own the elastomeric polyester critical deformation temperatures from below 20 C.

Because it is in the Ertinduna procedure It is possible to use copolyether glycols with high molecular weights, that is achieved larger amounts of the copolyatherglycols in the polymer chains can be installed without the melting points being significantly reduced. In case of Polvtetramethylene Glykoi can be products with Process molecular weights of over 3 (XX) with difficulty, and 80 percent by weight of poly-tetra-methylene glycol is the maximum amount from which the polyester can be built up without the Melting point drops to a value that is no longer acceptable. On the other hand, in the method of the invention Copolyatherglycols with much higher molecular weights can be used because a higher weight percentage of the copolyatherglycols make up the Polyester can be used.

According to the process of the invention, polyesters with crystalline melting points of over 150 ° C. and intrinsic viscosities η of at least 1.0 can be produced. Poly-3-esters with intrinsic viscosities of 1.4 to 4.0 have proven to be particularly advantageous.

The inherent viscosities or so-called logarithmic viscosity numbers η were determined using a conventional capillary viscometer at 25 C according to the equation

In ν

in which , _{lr is} the ratio of the viscosity of a 25 weight percent solution of the polyester to the viscosity of the pure solvent, expressed in seconds, corresponding to the flow time through the viscometer, and C means the concentration of the polyester in the solution, ie = 0.25 .

The threads and films which can be produced from the elastonized polyesters obtained according to the invention have a high elongation as well as a favorable recovery after high elongation as well as especially low critical deformation temperatures compared to corresponding polyesters, which, from 5. · going from polytetramethylene glycol alone, manufactured will.

The advantage of low critical strain temperatures of elastomeric polyesters includes that!.; the products made from the polyesters at f *> low temperatures can be used and therefore, for example, also for manufacturing protective elastic covers, for the production of heat-shrinkable closures for bottles, elastic Coatings for paper, for manufacture <>> adaptable elastic films, flexiblet pipes and hoses, to wire coatings and manufacturing of intermediate layers for safety glass.

The polyesters produced by the process of the invention also have an extraordinary quality favorable hydrolytic stability. As a result, can greater hydrolytic stability. As a result, garments made from thread after the Process of the invention producible polyesters have been produced under extreme washing conditions be subjected.

Threads which can be produced from the polyesters which can be produced by the process of the invention also have a low voltage drop. The tension drop to which threads made of elastomeric polyester are subjected can be determined by stretching a thread of the polyester by 300 " _{n for} a certain time. The force required to stretch the thread is measured. The tension drop during the extension is expressed as a percentage of the original tension necessary to stretch the thread by 300%.

Threads made by the method of the invention producible elastomeric polyesters can be produced have a voltage drop, which is very similar to that of rubber and which is the voltage drop of polyurethane segments built-up polymers, as z. B. in the journal "Dyer and Textile Printer", 1962, p. 904, described is superior. This can be seen from the following table.

% Tension drop of threads,
which were stretched 300% for 2 \ 2 minutes

Voltage drop

Threads from j

Polyurethane segments built up |

Polymers J 37 to 40 " ₍ .

rubber

Polyesters manufactured according to the
invention

! 20 ° ,,

16 to 22 ",,

In the following, the production of the for Implementation of the process of the invention required copolyether glycols are described.

A. A mixture consisting of 274 g (3 1/2 mole. 95 mole percent) dry tetrahydrofuran and 24 g (0.2 mole. 5 mole percent) trans-8-oxabicyclo [4: 3: 0] nonane. was cooled to -10 ° C. with stirring. This mixture then became snow! 9.0 ml of fluorosulfonic acid are given. The mixture was then heated rapidly to 4 (V ¹ C and au 2 hours! "A temperature of 35 to 40 'C held Then, 250 ml hot water was worauT added? H steam was introduced into the mixture, the polymer layer obtained, isolated was in Boiling water was washed 3 parts by weight, 250 ml of toluene and a slurry of 35 g of calcium hydroxide in HX) ml of water were added, the mixture was stirred for 1 hour and then filtered, the aqueous layer was separated and the toluene solution was azeotroped After the toluene solution had been filtered again, the solvent was stripped off in vacuo, resulting in Π2 g of copolyether glycol of a waxy consistency at 25 ° C. The polyether glycol melted

at 30 ^° C. and had an average molecular weight of 4380, as was determined by increasing the boiling point in toluene.

B. The procedure described under A was repeated with the exception that 245 g (3.4 moles, 85 mole percent) Tetrahydrofuran, 75 g (0.6 mol, 15 mol percent) of trans-8-oxabicyclo [4: 3: 0] nonane and 14.5 ml Fluorosulfonic acid were used. There were 158 g a copolyether glycol consisting of a viscous liquid with an average Molecular weight of 1707 obtained.

C. The procedure described under A was repeated with the exception that 216 g (3.0 moles, 75 mole percent) Tetrahydrofuran, 126 g (1.0 mol, 25 mol percent) trans-8-oxabicycIo [4: 3: 0] nonane and 12 ml Fluorosulfonic acid were used. 190 g of a viscous liquid was obtained Copolyether glycol with an average molecular weight of 2350 obtained.

D. The procedure described under A was repeated except that 144 g (2.0 moles, 50 mole percent) Tetrahydrofuran, 252 g (2.0 moles, 50 mole percent) trans-8-oxabicyclo [4: 3: 0] nonane and 12 ml Fluorosulfonic acid were used. There became 182 g of a viscous liquid Copolyether glycol with an average molecular weight of 2730 obtained.

E. The procedure described under A was repeated with the exception that 90 g (1.35 moles, 90 mole percent) Tetrahydrofuran, 21g (0.15MoI, 10 mole percent) 3-methyl-8-oxabicyclo [4: 3: 0] nonane and 3.5 ml fluorosulfonic acid were used. There were 58 g of copolyether glycol obtained, which consists of a viscous liquid with a molecular weight of 3970 existed. As determined by nuclear magnetic resonance spectroscopy, this contained Copolyether glycol about 12 mole percent of ether residues, which are derived from 3-methyl-8-oxabicyclo [4: 3: 0] nonane derived.

The following examples are intended to illustrate the process of the invention.

example 1

A 250 ml flask equipped with a stirrer. Nitrogen inlet tube and distillation head, was charged with 8.56 g (0.0308 mol) of dibutyl terephthalate. 7.5 g (0.0520 mol) of trans-1,4-cyclohexanedimethanol and 33.0 g (0.01 mol) of a copolyether with an average molecular weight of 3300 were charged. The copolyether was prepared from a mixture of 85 mole percent tetrahydrofuran and 15 mole percent trans-8-oxabicyclo [4: 3: 0] nonane, 12 g chlorinated triphenyl, 0.4 g dilauryl thiodipropionate and 0.6 ml of a 21% solution of Mg [HTi (OC ₄ H ₉ ).,], In n-butanol.

The mixture was heated to a temperature of 200 ^{° C. with stirring and under nitrogen.} During the first stage of the reaction, butanol was evolved and separated. After 60 minutes, the reaction temperature was increased to 280 ° C. for 40 minutes. It was then quickly evacuated and the pressure was reduced to less than 0.15 mm Hg column within 5 minutes. The polyester formed was stirred at this temperature and this pressure for 60 minutes, the viscosity of the melt ^{increasing rapidly for 6} seconds and the polyester finally wrapping itself around the stirrer. The polyester obtained was allowed to cool, removed from the flask and examined, had an inherent viscosity of 1.68 and consisted of 82.5 percent by weight of the copolyether glycol. As part of further investigations, the polyester was extracted with ether in a Soxhlet extractor for 6 hours in order to remove the chlorinated triphenyl that was still present.

Samples of the extracted elastomeric polyesters were pressed into films. The slides were at stretched at different temperatures in order to determine the increase in length achieved by the stretching. The following results were obtained:

40 percentages
Increase in length *) ...

Temperature in C 0 10 y 15 y 20 y 25:30

47 40 37 ί30 I 27 I 20

*) Calculated by dividing the obtained by stretching the film Increase in length due to the original length of the film and multiply by HX).

Example 2

A polyester was prepared according to the procedure described in Example 1, with the exception however, this time 37 g (0.01 mol) of a copolyether glycol having an average molecular weight of 3700 were used. The copolyether glycol was made from a mixture of 90 mole percent tetrahydrofuran and 10 mole percent 3-methyl-8-oxabicyclo [4: 3: 0] nonane. Films made from the polyester were in turn determines the increase in length after stretching. The following results were obtained: 35

Percentage
Increase in length.

Temperature in C

10

15th

20th

25 I 30

39 32 2s;:

Example 3

The procedure described in Example I was followed. starting from a mixture of 7.25 g (0.0261 mol) of dibutyl terephthalate. 6.24 g (0.0433 mol) of trans-1,4-cyclohexanedimethanol, 24.0 g (0.0089 mol) of a copolyether glycol with a molecular weight of 2700, prepared from a mixture of 90 mol percent 8-oxabicyclo [4: 3 : 0] nonane, 0.6 g of dilauryl thiodipropionate, 12 g of chlorinated triphenyl and 0.6 ml of a 21 °. _o igen solution of Mg [HTi (OC ₄ H ₉ Ly ₂ in n-butanol, repeated. The polyester obtained had an inherent viscosity of 1.61 and consisted of 80 percent by weight of copolyether glycol residues. A sample of the polyester was extracted with ether for 6 hours, to remove trapped chlorinated triphenyl. Films were made from the polyester. The films were stretched at various temperatures to determine the elongation. The following results were obtained:

Percentage
Increase in length.

Temperature in C

10

15th

30th

20th

23

25th

17th

Example 4

According to the process described in Example 1, an elastomeric polyester, starting from a mixture of 7.25 g (0.0261 MoDdibutylterephthalal. 6.24 g (0.0433 mol) of trans-1A-cyclohexanedimethanol. 17.6 g (0.00765 mol) of polytetramethylcnglycol with a molecular weight of 2300 and 6.4 g ( 0.00168 mol) of a copolyether glycol with a molecular weight of 3800. The copolyether glycol was prepared from a mixture of 75 mol percent tetrahydrofuran and 25 mol percent 8-oxabic \ elo [4: 3: 0] nonane, 0.6 g dilauryl thiodipropionate, 12 g chlorinated triphenyl and 0.6 ml of a 21 ° _o solution of Mg [HTi (OC ₄ Hq) ₁ J ₂ ι »n-butanol.

The polyester obtained was 80% by weight from polytetramethylene glycol and copolyether glycol residues. The polyester had an inherent viscosity from 1.81. An extracted sample was pressed into a sheet of which the degree of Length increase at different temperatures was determined. The following results were obtained:

Percentage
Linen increase.

Temperature in ^C C

10

15th

30th

20th

20th

25th

17th

30th

13th

From these results it can be seen that the critical deformation temperature is around 13 ° C lies.

The polyester was easy to spin into threads with the following properties:

Strength, e D 0.372

Stretching. " ₍ , 620

Secant module
at 100 ° ο elongation, g D 0.038

Recovery from 400 ° ₀ elongation, ° ₀ 95.5

Recovery from 600 ° ₀ elongation, ⁿ “92.1

Permanent increase in length
after 16 hours of stretching around
150 ",, ° ₍ , 17

Bonding temperature. C 104 to 119 ^

Example 5

The process described in Example 1 was repeated, starting from a mixture of 9.12 g (0.0328 mol) of dibutyl terephthalate, 8.05 g (0.0558 mol) of trans-M-cyclohexanedimethanol, 22.1 g (0.0098 mol) of a copolyether glycol from a mixture of 85 mol percent tetrahydrofuran and 15 mol percent 8-oxabicyclo [4: 3: 0] nonane with an average molecular weight of 2300. 12 g of chlorinated triphenyl, 0.6 g of dilauryl thiodipropionate and 0.6 ml of a 21 ° _o solution of

. Mg [HTi (OC ₄ H ₉ ) _{I 2}

in n-butanol.

The polyester obtained consisted of 74.5 percent by weight of copolyether glycol residues and had one Inherent viscosity of 1.74. A sample of the polyester extracted with ether was pressed into a film, whereupon the increase in length was measured at different temperatures. The following results were obtained obtain:

Percentage
Increase in length.

Temperature in 15th 20th C. 10 33 27 25th 40 23

Samples of the films had an elongation at break of 900 ° o and an elastic recovery from a 400 ° _o elongation of 92% -

Comparative example

A polyester was made according to the process described in U.S. Patent 3,023,192 Dimethyl terephthalate and a glycol mixture, which is 60 percent by weight of polytetramethylene glycol and the remainder consisted of ethylene glycol. The molar ratio of polytetramethylene glycol that possessed a molecular weight of 2700 to 3000, to ethylene glycol was 85:15. The obtained polyester had an inherent viscosity of 1.64. The polyester was then melt spun to Spun threads. The filaments had an inherent viscosity of 1.47. But they were so sticky that they do not move away from the roller on which they were wound without being destroyed let.

Accordingly, unfavorable results were obtained when the method was performed using a Glycol mixture consisting of 90 mol percent of ethylene glycol and 10 mol percent of polytetramethylene glycol, corresponding to a weight ratio of 50:50, was repeated. The received Polyester had an inherent viscosity of 1.48, while the inherent viscosity of the spun filaments was 1.29 fraud. In this case, too, the threads were far too sticky to be processed.

Claims (9)

Claim: Process for the production of elastomeric polyesters by condensation of a mixture from a polyether glycol, 1,4-cyclohexanedimethanol, and optionally a polytetramethylene glycol, with a dicarboxylic acid in which the carboxyl groups are attached to a hexacarbocyclic Ring are bound, or an ester of the acid, marked thereby e t that one can use the general formula as a polyether glycol HO T T \ H H \ / R. - O ^H / \ \ H _n / / H CH ₂ /H ^X H -CH ₂ H H Ix 909 5? 4 9 10 used, wherein R is a hydrogen atom or a methyl group and χ and y are integers greater than 0, where the sum of χ and y is between 14 and 130 and χ is less than y, and that the concentration of the copolyether glycol, based on the 1,4-Cyclohexanedimethanol and optionally polytetramethylene glycol, keeps below 50 mol percent.