DE1595662A1 - Process for the production of polyesters - Google Patents

Description

FARBENFABRIKEN BAYER AG

29. Ju "

LEVERKUSEN-Baycfwerk PATENT DEPARTMENT FT / KG Process for the production of polyesters

The invention relates to a process for the production of polyesters with different segments.

It is known from German Patent 1 004 307 to mix preformed polyesters containing hydroxyl groups with carboxylic acid anhydrides to implement »This results in polyesters containing carboxyl groups, which are equivalent to one of the original hydroxyl groups Have amount of carboxyl groups.

The invention relates to a process for the production of polyesters, which is characterized in that pre-formed polyester molecules containing hydroxyl or carboxyl groups are made from dicarboxylic acids and dihydric alcohols in the presence of a water-immiscible solvent with a boiling point of below 12O ⁰ C by esterification a dicarboxylic acid or a GlykoT are linked, under the condition that when using a preformed polyester from a dicarboxylic acid and a dihydric alcohol for the further esterification a chemically different glycol or chemically different dicarboxylic acid than for the structure of the preformed polyester is used. ,

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The invention thus enables the production of polyesters with

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different types of segments (blocks) made up of at least 3 components. According to the previously known procedures on the other hand, when at least 3 reaction components are reacted, thermal or aceotropic esterification is obtained in the presence of indifferent solvents polyester, which the three Components included statistically distributed.

The following schematic illustration clarifies these relationships based on the three reaction components

A = glycol (i), B = dicarboxylic acid, C = glycol (2)

Hydroxyl groups, for example, can be obtained using previously known methods obtained containing polyesters which contain the three reaction components in a randomly distributed manner, as indicated below, '. 4 moles of glycol A, 3 moles of glycol G and 6 moles of dicarboxylic acid B are esterified.

A-B-A-B-C-B-C-B-A-B-C-B-A

On the other hand, you can, for example, by the method according to the invention from a preformed polyester B-C-B containing carboxyl end groups consisting of components C and B and the Glycol A obtained following polyester composed of segments. The individual components are in the same ratio in the final polyester as in the polyester outlined above, which contains the components contains statistically distributed, present.

A-BCB-A-BCB-A-BCB-A

The process according to the invention thus allows a type of "block esterification" of at least 3 components, v / above the polyester from repeating, different segments (blocks)

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builds and thereby a targeted synthesis of polyesters with the most diverse properties possible 1st.

On the other hand, however, the structure of polyesters from divider-like segments possible, the segments being randomly distributed in the end polyester film.

The pre-formed hydroxyl or carboxyl group-containing poly

- Esters can be built up from two or more reaction components be «, if the -jsu esterifying pre-formed hydroxyl- or Carboxyl groups containing © polyester from only one dicarboxylic acid and only one glycol together »so must for the" block esterification " A chemically different dicarboxylic acid or a chemically different one Glycol used when it was used to make the preformed polyester »

Instead of the dicarboxylic acids or the glycols, those polyester containing hydroxyl or carboxyl groups can also be used for the esterification with the preformed polyester 1 containing hydroxyl or carboxyl groups, which differ from the preformed polyester I by at least one structural component The following dicarboxylic acids or their anhydrides and glycols are used for the production of the "pre-formed" polyester X : Allphatiache dicarboxylic acids with 4-14 C-

- Atoms: - Examples are called selenium * succinic acid, adipic acid, azelaic acid, .... 'sebacic acid · leoeebacic acid, decanedicarboxylic acid undeeahdicarboxylic acid, " maleic acid, dihydromuconic acid, ■ furioaric acid". Preferably adipic acid, «succinic acid, sebacic acid-

Glycols with 2 to 12 carbon atoms and polyethylene glycols. At--

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Examples include: ethylene glycol, propylene glycol (1,2) ♦ Propylene glycol (1,3), diethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-butanediol, neopentyl glycol, 1,4 butenediol- (2), 1,4- * Butynediol (2), decamethylene glycol, allyl monoglycerol ether, preferably Ethylene glycol, butanediol (1.4), hexanediol (1.6), neopentyl glycol. . ·

The carboxyl or hydroxyl groups to be used according to the invention Polyesters I containing can be composed of 2 or more different structural components, preferably of 2 be. They should have molecular weights of 500-2500, preferably 750-2000.

All dicarboxylic acids or glycols which can be reacted with the polyesters I containing hydroxyl or carboxyl groups are the same dicarboxylic acids or glycols as described above for the preparation of the polyesters I. The following dicarboxylic acids or their anhydrides are preferably bsw. Glycols used: maleic anhydride, sebacic acid, adipic acid or neopentglycol, hexanediol (1 «6), butanediol (1.4), diethylene glycol, triethylene glycol (1.4).

For the production of the polyesters containing carboxyl or hydroxyl end groups which, according to claim 2, can be used with the polyesters I instead of the dicarboxylic acids or glycols, the same carboxylic acids or glycols are embossed as stated in the production of the polyester I. the following dicarboxylic acids or glycols are used : adipic acid, sebacic acid, succinic acid, azelaic acid biw. Ethylene glycol, propylene glycol (1,2), butanediol (1 * 4), hexanediol (1,6), heopentyl glycol. , -

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The molecular weights of the above polyesters should be between 500 and 2500, preferably between 750 and 1500. Whether the polyesters I to be used according to the invention or the polyesters to be used according to claim II or the final polyesters, having terminal hydroxyl or carboxyl groups depends on the proportions of the reaction components used. Polyesters containing terminal hydroxyl groups are formed by using an excess of terminal hydroxyl components Polyesters containing carboxyl groups by using an excess of carboxyl components.

The esterification by the process of the present invention becomes like this carried out that one of the carboxyl or hydroxyl end groups containing polyester (I) at such temperatures with a diacid or a glycol or with a carboxyl or hydroxyl end group containing polyester esterified in the presence of solvents, that a transesterification of the ester groups already present is avoided or suppressed. Thus, the structure of the Polyesters used as starting materials are obtained, thereby producing polyester with various segments is made possible.

If polyesters with more than two different segments are to be built up * i.e. 2 or more different types of carboxyl or hydroxyl end groups containing starting polyester I with one or more different glycols or dicarboxylic acids are implemented, the esterification can be carried out gradually, in such a way that always only one structural component with carboxyl or hydroxyl end groups with a glycol or a Dicarboxylic acid until complete conversion of the in relation to the Hydroxyl or carboxy groups are subordinate to the building blocks used. Le A 10 166 '^ "809884/1715

component esterified.

For example, 2 moles of one of hexanediol and adipic acid, constructed polyester (HA), which has 2 terminal hydroxyl groups with 1 mole of maleic acid (M) to a polyester HA-M-HA be esterified. This polyester (1 mol), which has terminal hydroxyl groups, can then in a further stage with 1/2 Mol of another dicarboxylic acid (X) can be built up into a new polyester HA-M-HA-X-HA-M-HA containing hydroxyl end groups. These reaction steps can be repeated several times until the desired final polyester has been formed.

On the other hand, however, it is also possible to have more than 2 different types To mix starting polyester I with one or more glycols or dicarboxylic acids or polyesters according to claim 2 and link by esterification. In this case, a final polyester is obtained which has the various segments at random contains distributed.

The esterification is preferably carried out with solvents with a low boiling point such as toluene or benzene at temperatures of 80-120 ^° C. It can be carried out in the presence of esterification catalysts such as titanium tetrabutoxide, p-toluenesulfonic acid or mineral acids such as sulfuric acid or phosphoric acid. The amounts of catalyst are 0.1-4% by weight, based on the reaction components.

The polyester obtained according to the invention, the terminal carboxyl or have hydroxyl groups, reach molecular weights from 1,500 to 50,000, preferably from 1,600 to 15,000. Of particular The terminal hydroxyl groups are of interest.

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send polyester. The products according to the invention can be used as plasticizers, Emulsifiers are mainly used as the starting materials for plastics.

A selection of the possibilities resulting from the present process is given by the following examples.

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Example 1; $

820 g (1 mol) of a polyester produced from 1,6-hexanediol and adipic acid by melt condensation (OH number 138 = 4 | 2 % OH, acid number 0) and 94 g of azelaic acid (0.5 mol) are added after 1 liter Toluene and 3 g of p-toluenesulfonic acid * esterified aceotropically. The esterification is over when no more water passes over. 17 g of water were obtained (calc. 18 g). Referring now to neutralize the p-toluenesulfonic acid by the addition of 15 g of anhydrous sodium carbonate, stirring is continued at 100-110 ⁰ C for 15 minutes after, filtered off and evaporated in vacuo. The polyester obtained has an OH number of 64, an acid number of 1.2, a softening point of 45 ^° C. and a molecular weight of 1,750.

Example 2;

1 kg (2 mol) of a polyester obtained by melt condensation from 1.72 kg of hexanediol (1.6) and 1.46 kg of adipic acid (OH number 224-6.8 # OH) and 1 kg (1 mol) of one Polyester obtained by snow condensation from 1.04 kg of neopentyl glycol and 1.77 kg of adipic acid (acid number 112 = 9 # COOH, OH number = 0) are esterified after adding 2 liters of toluene and 3 g of p-toluenesulfonic acid until no water After that, nan neutralized with 15 g of anhydrous sodium carbonate, filtered and evaporated in vacuo, as stated above. The resulting polyester is a soft wax with a molecular weight of 1720, which ^{softens at 34 °} C. and has an OH number of 65 and an acid number of 0.5 owns.

Example 3:

1 kg (1 mol) of a melt condensation of 900 g butane

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diol (1.4) and 1.75 kg of adipic acid (acid number 112 = 9 # COOH, OH number 0) and 1 kg (2 mol) of a f from 1.72 kg of hexanediol (11.6) and 1.46 kg of polyester produced adipic acid (OH number 224 = 6.8 i » OH, acid number 0) are esterified as indicated above after adding 2 liters of toluene and 3 g of p-toluenesulfonic acid. It is neutralized with 15 g of anhydrous sodium carbonate, filtered and evaporated in vacuo. The polyester has an OH number of 68, an acid number of 0.8, a softening point of 37 ^° C. and a molecular weight of 1650.

Example 4:

820 g (1 mole) of a ^T iexandiol- (1.6) and adipic acid produced by melt condensation polyester (OH number = 138 4,25ε OH, acid number = 0) and 49 g of maleic anhydride (0.5 moles) after addition esterified azeotropically by 1 liter of toluene and 3 g of p-toluenesulfonic acid. The procedure is as indicated in Example 1, and a waxy polyester with an OH number of 58, an acid number of 0.5, a softening point of 43 ^° C. and a molecular weight of 1930 is obtained.

Example 5:

820 g (1 mol) of a polyester produced from hexanediol (1.6) and adipic acid by melt condensation (OH number 138 = 4.2? Ί OH, acid number 0) and 101 g of sebacic acid (0.5 mol) are added after addition operates on 1 liter of toluene and 3 g of p-toluenesulfonic acid azeotropically verestert.Man, as indicated in example 1, and receives a waxy polyester of OH number 70, acid number 0.8, softening point 45 -. 46 ⁰ C.

Example 6;

If, in example 5, the sebacic acid is replaced by isosebacic acid, Le A 10 166 - -9 "909884/1715

a polyester with an OH number of 7-1, an acid number of 1.8 and a softening point is obtained while maintaining the other conditions from 38 C.

Example 7;

700 parts of an adipic acid-ethylene glycol polyester (polyester A), (acid number 0.5, OH number 56, molecular weight 2,000) are mixed with 300 parts of an adipic acid-diethylene glycol polyester (polyester B), acid number 0.7, OH Number 46, molecular weight 2,440), and mixed with 55 parts of adipic acid and subjected to an azeotrope esterification with circulating toluene. The esterification temperature is maintained at 120 ⁰ C. After an acid number of about 10 the mixture is 0.05 percent by weight of 3 g of p-toluenesulfonic acid was added and continued at 120 ⁰ C. The esterification is interrupted after 36 hours and the toluene is finally distilled off in a vacuum of 12 mm Hg. The result is a higher molecular weight polyester built up from polyesters A and B, acid number 0.8, OH number 10.7, molecular weight 10,500 with a gauze-like consistency at room temperature in contrast to polyester A, which is solid and polyester B, which is liquid.

Example 8;

850 parts of an adipic acid-ethylene glycol polyester, acid number 0.5, OH number 56, molecular weight 2000, with 150 parts of an adipic acid-1,6-hexanediol-2,2-dimethyl-propanediol-1,3 mixed polyester, Acid number 1.2, OH number 64, molar weight 1750, and mixed with 61 parts of adipic acid and an azeotropic reaction with circulating toluene at an esterification temperature

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door τοπ 120 ⁰ C subject. After an acid number of about 10 to the mixture is added 3 ig p-Toluolsulfonaäure and weitervereetert at 120 ⁰ C. After a transesterification time of 38 hours, the toluene is distilled off, finally in a vacuum of 1 mm Hg, and the polyester is poured onto a drying tray. The result is a higher molecular weight polyester which is solid at room temperature and has an acid number of 1.2 and an OH number of 10.5 and a molecular weight of 10,700.

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Claims (5)

_ia 159R662 Claims; JY 1V) Process for the production of polyesters, characterized in that pre-formed polyester molecules (I) containing hydroxyl or carboxyl groups are made from dicarboxylic acids and dihydric alcohols in the presence of a water-immiscible solvent with a boiling point of below 120 ^° C Esterification with dicarboxylic acids or glycols are linked, with the condition that when using a preformed polyester from only one dicarboxylic acid and only one; bivalent glycol for the further esterification a chemically different glycol or chemically different dicarboxylic acid than for the structure of the preformed polyester (I) is used. 2.) Process according to claim 1, characterized in that instead of the dicarboxylic acid or the glycols, a carboxyl or polyester containing hydroxyl groups is used, which is distinguished by at least one structural component from the hydroxyl or preformed polyester (I) containing carboxyl groups. 3.) Processor according to claim 1 and 2, characterized in that the esterification is carried out in the presence of esterification catalysts. 4.) Process according to claims 1-3, characterized in that toluene or benzene are used as the inert solvent. BATH ORIGINAL Le A 10 166 -12- 909884/17 15 1E95R62 5.) Method according to claims 1-4, characterized in that as Components for the production of the carboxyl or hydroxyl group-containing polyester (l), hexanediol (1,6) and Adipic acid can be used. Le A 10 166 909884/171 5