DE1294666B - Process for the production of linear, saturated polyesters - Google Patents

Description

1 2

It is known that, through conversion of dialkyl esters, methylenecyclohexane is 50 to 100 mol percent, more pre-aromatic Dicarboxylic acids with aliphatic diols preferably 70 to 95 mol percent, based on the high-melting linear polyesters are obtained, sum of the diols.

which are used for the production of fibers, threads and films In contrast to the known polyesters can be. However, these products are 5 seats which are produced by the method according to the invention

often a high glass transition temperature because of their strong tendency to crystallize and the polyester produced

the associated shrinkage effects not for and a very low tendency to crystallization. this

the production of moldings after injection molding must be viewed as surprising, since poly-

casting process suitable. In addition, with the crystalline cyclic, polyhydric alcohols, their hydroxylization and post-crystallization a mostly un-io groups on different rings of a condensed

desired turbidity of the molded body connected. So that ring systems are distributed when they are used as polyester

In the case of polyesters crystallization can occur, the component must be used to influence the

On the one hand the macromolecules are able to have a freezing temperature and the tendency to crystallize

To form crystal lattices, on the other hand, they don't have to show. It must also be surprisingly

Macromolecules will see each other with sufficient speed that objects resulting from the invention

place in the crystal lattice. When polyesters obtained according to polyethylene were prepared, the

terephthalate, these two conditions are met. known and interfering with polyethylene terephthalate

For the production of hard, non-crystallizing, not showing the shrinkage effect. The after the

For non-embrittling, clear moldings, it is polyester produced according to the method according to the invention

desirable to start from plastic compounds, 20 also have good surface hardness

their freezing temperature at temperatures above 100 ° C, an impact strength that is sufficient in practice. the

preferably at temperatures above 120 ^° C. Transparency of the objects made from them

Polyethylene terephthalate has a freezing phe- remains up to high usage temperatures,

temperature, which is between 70 to 8O ⁰ C. The freezing- Also with copolyesters made of ethylene glycol, 2,2-di-

The temperature of this polyester is therefore an as methylol-endomethylene cyclohexane and an aromatic

Temperature, which when using utility matic dicarboxylic acid, z. B. terephthalic acid,

plastic objects is often reached. 2,2-Dimethylol-endomethylenecyclohexane has one effect

The range of freezing temperatures associated with a substantial increase in the freezing temperature. at

the high tendency to crystallize makes the polycondensates a strong

Determine ethylene terephthalate for use to prevent crystallization, they are for

production of thicker injection and extrusion bodies production of molded bodies well suited,

not suitable. For the synthesis of the used according to the invention

It is also already known that unsaturated polyester 2,2-dimethylol-endornethylenecyclohexane is added

by condensation of unsaturated dicarbons according to known processes initially according to acrolein

acids, such as maleic acid or fumaric acid, with more than one diene synthesis of cyclopentadiene. The one on this

hydric alcohols in which the hydroxyl group is obtained endomethylenetetrahydrobenzaldehyde

on different rings of a suitable condensation is catalytically hydrogenated and the corresponding ge

ized ring system are distributed to produce. The so saturated aldehyde then with formaldehyde to 2,2-di-

The unsaturated polyesters obtained can be used as methylol-endomethylene cyclohexane of the formula

Use line weights and result in a 40 jj

drying surface. It is also known that c

one, starting from unsaturated endocyclic ^^ | ^ \ ^ - CH ₂ OH

Aldehydes, which with the help of the Diels-Alder reaction easily H ₂ CC ^

are accessible by reaction with carbon monoxide 'CH ₂ i CH ₂ OH

and hydrogen under increased pressure and increased 45 H ₂ C CH ₂

Temperature in the presence of cobalt catalysts ^^ _r ^

a mixture of different reaction products is obtained, S;
which in addition to unchanged aldehyde the corresponding

the dialdehyde formed by addition of the formyl groups and Hy- [TW Campbell and VS Foldi, Journal dration of the double bond, 50 of Organic Chemistry, 26. 4654 (1961)]. However, it is and under certain circumstances also saturated and impossibly possible for the hydrogenation to contain saturated alcohols and aldehyde alcohols only after the reaction. From the endomethylenetetrahydrobenzaldehyde with formaldehyde, this reaction mixture can be converted into the unsaturated diol by means of hydration of the dialdehydes present in predominant amounts in the mixture
easily win cyclic diols. These diols can be ethylene glycol
can be used as raw materials for polyester. Propanediol (1.3)

It has now been found that linear, saturated butanediol (1,4)

Polyester through polycondensation of aromatic di-neopentyl glycol

carboxylic acids containing one or two benzene rings- 60 dimethylolcyclohexane (1,4)

hold and their carboxyl groups on ring carbon - dimethylolcyclohexane (1,3)

Substance atoms represented by at least 1 carbon atom p-xylylene glycol

are separated, bound or their polyester- m-xylylene glycol or

Can produce forming derivatives with a diol, bis-ß-hydroxyethyl ether of diphenols, such as

if the diol is 2,2-dimethylol-endomethylene-65 4,4'-di- (ß-hydroxyethoxy) -benzene

cyclohexane or its mixture with other diols 2,6-di- (ß-hydroxyethoxy) naphthalene

used. 2 _s 2-di- (4-ß-hydroxy-ethoxy-phenyl) -propane

The 2,2-dimethylol-endo fraction can be used here.

3 4

As an aromatic dicarboxylic acid, the one or two heavy metal oxides, such as antimony trioxide,

Benzene rings contain and their carboxyl groups are effective.

Ring carbon atoms, which are replaced by at least one For the production of the polyester one can also use titanium carbon atom are separated, are bound, are acid esters, e.g. B. butyl titanate, use the for example suitable: 5 both in transesterification and in poly-

Tereohthalic acid condensation stage are effective as catalysts.

Tc ™ h + hoio3, "- a You can also use the polyester z. B. from the dicarbon

iSOpnillcUSaUrc ",,. - ·:, ._. - - ₍₍

Diphenyldicarboxylic acid (4,4 ') acid chlorides and the diols

The produced by the inventive method

and dicarboxylic acids of the general formulas polyesters are colorless to pale colored,

clear masses with a relatively high average

HOOC '^ ^ R ^ ^ COOH borrowed molecular weight, which can be used to produce

\ ..__ / ^>< X = - / moldings after injection molding and extrusion

procedures are suitable. The ones made from these polyesters

y— ^ / ^ 15 moldings are characterized by high transparency

\ V— R - \ / off.

I B e i s ρ i e 1 1

COOH _{One mixes} 150 g of dimethyl terephthalate and

ao 108 g of _M 2,2-dimethylol-endomethylene cyclohexane with

in which R represents a divalent radical, such as 76 g of ethylene glycol and adds 34 mg of zinc acetate. That

Mixture is heated with stirring to 16O ⁰ C, wherein

CH ₃ methanol is distilled off on the descending condenser.

I The temperature rises over the course of 3 hours

CH ₂ -, C, -CH ₂ CH ₂ ·, ^a 5 210 ⁰ C increased and the mixture as long at this

'Stirred temperature until no more methanol distills off. It is then cooled to room temperature and 45 mg of antimony trioxide added. The Um-

ο CH esterification product is heated to 250 ⁰ C with stirring

30 heats. In the course of about 3 hours, the temperature

Terephthalic acid is increased with particular advantage temperature from 250 to 280 ⁰ C, at the same time the

turns. Gradually reduced pressure to less than 1 torr

Mixtures of 95 to 50 mole percent terephthalic is. At these pressure and temperature conditions

acid and 5 to 50 mol percent isophthalic acid are stirred and the mixture is stirred for a further 5 hours. The obtained reaction

Particularly suitable, since the 35 tion product according to the invention is a clear, almost colorless mass.

Process with these aromatic dicarboxylic acids The freezing temperature is 142 ° C. The reduced

polyester produced advantageous mechanical intrinsic specific viscosity of the product is 1.1 (ge

own properties. measured at a l ° / _o by weight solution in phenol / tetra-

Are usually chloroethane 60:40 at 2O ⁰ C) in place of the dicarboxylic acids. One can get out of this

their polyester-forming derivatives, such as esters, especially 40 polyester molded articles, which are extraordinarily

Dimethyl ester and acid halides are used. borrowed are resistant to impact stress

The polycondensation is known per se and has a good surface hardness.
Manner carried out e.g. B. by the diesters of aro-. ■ 1 9
matic dicarboxylic acids with the diols in example /
elevated temperatures are implemented. It is expedient to mix 45 150 g of dimethyl terephthalate, 60.3 g of _M 2,2-dimers, from the diol methylol-endomethylene cyclohexane used according to the invention and 96 g of ethylene, first of all a precondensate with the aromatic diglycol. Manufactured as a catalyst for the umcarboxylic acid. Since 2,2-dimethylol endoesterification, 34 mg zinc acetate are added. Ummethylene cyclohexane has a relatively high boiling point and esterification and polycondensation are carried out as described in Beiein excess of this diol in the actual condensation game 1. As a catalyst for sation can be removed with difficulty, the polycondensation is recommended, 45 mg of antimony trioxide are added for the transesterification of the additional use of one. It is two and a half hours at 280 ° C and lower boiling other diols, ζ. B. of ethylene 0.1 torr stirred. A colorless, transglycol is obtained. parentes resin is carried out a glass transition temperature of 123 ⁰ C. The transesterification at about 160 to 21O ⁰ C 55 possesses. The reduced specific viscosity of the corresponding lower while distilling off the product is 0.8 (measured on a l ° / pc alcohol, for example methanol. In this case, feed solution proved in phenol / tetrachloroethane 60:40 at 20 ⁰ C). sets small amounts of catalytically active substances. . ₁
cheap, such as B. zinc acetate or calcium acetate. With examples
then the following is the polycondensation reactor 60 A mixture of 100 g Terephthalsäuredimethyltionsgemisch with stirring at temperatures of ester, 50 g of dimethyl isophthalate, 108 g of 2,2-Dietwa 220 to 28O ⁰ C heated; the pressure of methylol-endomethylene cyclohexane and 76 g of ethylene is continuously reduced. It should expediently be processed in the glycol as described in Example 1. Final phase of the polycondensation less than 1 Torr. The catalysts will be 34 mg of zinc acetate and 45 mg. In this condensation stage the 65 antimony trioxide are used. Compared to the polyester described in case macromolecules and the excess of Example 1, the part obtained has the lower-boiling diol, ζ. B. the ethylene product at about the same freezing temperature a glycol, distilled off. The catalyst here is improved notched impact strength. The reduced special

The viscosity of the product is 1.2 (measured
in a solution of phenol / tetrachloroethane
60:40 at 20 ^° C.).

Claims (1)

Claim: Process for making linear, saturated
Polyester through polycondensation of aromatic
Dicarboxylic acids that have one or two benzene rings contain and their carboxyl groups on ring carbon atoms, which by at least one Carbon atoms are separated, bonded or their polyester-forming derivatives with a diol, characterized in that the diol is 2,2-dimethylol-endomethylene cyclohexane or its mixture with other diols is used.