DE2115072A1 - Production of mixed polyesters based on caprolactone - Google Patents

Description

SCHdRIIiG AG

Patent department

Ax / Bu

Production of high polyesters based on caprolactone

The invention relates to a method of production of mixed polyester !! from caprolactones of the general formula

CH - (CR ₂ ) ₄ -C

R-CH- (CRo), -C = O 0-

wherein R is a hydrogen atom, a methyl or an ethyl radical can be and in which R should be an alkyl radical at most three times, and from dicarboxylic acids and polyols with or without the use of inert solvents, which is characterized in that in the first stage the caprolactones with a aliphatic polyol in the presence of an inorganic catalyst, namely antimony (V) chloride or antimony (V) fluoride, reacted, then optionally mixed with a small amount of water and the hydroxide-containing groups formed Ester compounds are reacted with the dicarboxylic acid in the second stage without isolation, with the equivalent ratio Polyol: Dicarboxylic acid should be 1.

Mixed polyesters made from caprolactone, polyols and dicarboxylic acids and their production have already been described (German disclosure documents 1 940 942 and 1 946 430).

In the German Offenlegungsschrift 1 940 942 the production of liquid polyesters based on ε-caprolactone or 6-hydroxycaproic acid, a dicarboxylic acid or its anhydride, a glycol in an excess of 5 to 20 wt. ~? Ö and a polyol with at least 3 hydroxide groups described in the molecule.

The polymerization of these 4 components v / ird at a temperature of 220 to 24O ⁰ C in the presence of tetraalkyl

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SCHERING AG

Patent department

Ax / Bu -2-

titanate carried out as a catalyst and a solvent and / or an entrainer, the catalyst residues are undesirable for further use of the product and are therefore delayed in catalysis got to.

In the German Offenlegungsschrift 1 946 430 v / erden flüs- ™ Sige hydroxyl-containing polyester described. For their production is ε-caprolactone in the presence of a Ion exchange resin bearing sulfonic acid groups a large excess of water to the 6-hydroxy-eapronic acid hydrolyzed.

Then a dicarboxylic acid and a mixture of two different dialcohols in excess of 5 to 20 wt .- $ are added, ^{the added water is driven off with considerable effort (at 2JO 0} ) and then with the addition of a further catalyst (tetraalkyl titanate) at 250 ° C polymerizing esterification carried out "

For further processing, the reaction mixture has to be dehydrated in another apparatus with heating in vacuo and be degassed.

To obtain a product with the desired properties, a polyalcohol with at least 3 OH groups per molecule must also be used during production.

In relation to the two mentioned disclosure documents, the method according to the invention has several of the following in each case Advantages;

I. The lactone used is not hydrolyzed «,

208841/1105

SCILiSRIHG AG

Patent department

Axen / Bu -3

2. It is sufficient to use a single catalyst (antimony (Y) halide), which by adding a very A small amount of water decomposes to form antimony (V) oxide hydrate and thereby receives new desired catalytic ^ properties for the esterification.

5. The method according to the invention requires lower ones Temperatures than the known methods.

4. When the end product is filtered, the catalyst and its decomposition products are completely removed .

5. It is not necessary to use a dialcohol mixture.

6. No additional polyalcohol is required.

7. No excess of dialcohol is required, which must then be removed and / or during the reaction is lost because the temperature is too high.

8. The inventive method required for his successive reaction stages only one reactor and does not require any cleaning or separation processes in between.

According to a proposal that does not belong to the known state of the art, ε-caprolactone is produced in the presence of an antimony (V) halide as a catalyst by a dialcohol as a ring-opening agent to one bearing OH groups at the chain ends Polyester polymerizes. According to the same proposal, the catalyst is then replaced by a small amount of water / water

209841/1105

AG

Patent department
Ax / Bu -4-

decomposed into antimony (V) oxide hydrate, which in a subsequent Supply of heat, if necessary with supply of a small amount Amount of a mono-, di- or polyalcohol, the esterification catalyzes the still free carboxy-l groups. ITach the same proposal will be the catalyst and its Residues from the usual filtration of the reaction product completely removed. - .- -. -

In the implementation of diols or polyols according to the invention with the lactone the polyalcohols are made less volatile due to the chain extension, which is the case for the following Esterification with dicarboxylic acid. is of particular value. The o; -ei- added after the lactone polymerization through Esterification quickly formed water, then destroys the polymerization catalyst and provides antimony (V) oxide hydrate, which, as an esterification catalyst, clearly catalyzes the further esterification.

The catalyst amounts preferably used in the lactone polymerization of 0.03-0.06 wt .- ^ antimony (V) chloride (based on the reaction product of finished polyester) are an effective esterification catalyst after hydrolytic cleavage, which is also used in ε-oxycaproyl-free polyesters is to be used with success. By using antimony (V) chloride in this step-by-step "one-pot esterification process", the esterification process can be significantly shortened, the reaction temperatures can be reduced (not above 200 C), the azeotropic removal of the water with entrainers is superfluous and the 5-20 usually used $ £ igeii excess of glycol (above the calculated amount) can be significantly reduced (preferably to 1 tfo of the calculated amount) or even omitted entirely. The method described here is generally applicable and also provides

209841/1105 ^

BATH ORIGINAL

SCHiCRIITG- AG '2 Ί Ί O U / Z

Patent department

Ax / Bu -5-

set of aromatic dicarboxylic acids (e.g. phthalic acid) in addition to aliphatic dicarboxylic acids (e.g. adipic acid) good results. Those produced by the process of the invention Hydroxide-containing polyesters can because of their low or no content of catalyst residues in / solution converted to polyurethanes v / ground. For the reaction of hydroxide-containing polyesters with isocyanates Cleaning with fuller's earth may be necessary in the melt, i.e. the polyester is mixed with active fuller's earth (approx. 1 - 2 $) treated in the heat for a few hours and then filtered off.

According to the invention to be used lactones are un ^ ubstituted or substituted ε-caprolactones of the general formula

R-CH- (CR ₂ ) ₄ -C = O

Q J

with R = Ii, CJU, CpHc, with at most 3 of the radicals R being an alkyl radical may be.

Examples of such lactones are:

ε-caprolactone,

α-, ß-, γ-, δ- or e-methyl-e-caprolactone, Ethyl-ε-caprolactone,

Dimethyl- or diethyl-ε- caprolact on or -β, β, δ- or ßjöjÖ-trimethyl ^ -caprolactone.

Examples of polyols to be used according to the invention are

a) linear or branched diols with up to 12 carbon atoms, such as ethanediol (l, 2), butanediol (l, 4)> hexanediol (l, 6) or trimethylhexanediol (l, 6) or

209841/1105 ■ -6- ■

SCH-JRIIfG AG

Patent department

Ax / Bu -6-

b) linear or branched polyols have at least 3 OH groups per molecule, such as butanetriol- (1,2,4), trimethylol-propane or Hexanetriol- (1,2,6) or

c) unsubstituted or substituted cycloaliphatic polyols, such as cyclohexanediol or 1,4-bis (hydroxymethyl) cyclohexane.

Examples of dicarboxylic acids to be used according to the invention are. '

a) linear or branched aliphatic ^ dicarboxylic acids with

2 to 12 carbon atoms, such as oxalic acid, succinic acid, adipic acid, Trimethyladipic acid, decanedicarboxylic acid or

b) 1,9- or 1,10-heptadecanedicarboxylic acid or

c) unsubstituted or substituted cycloaliphatic dicarboxylic acids with a total of up to 12 carbon atoms, such as cyclohexane dicarboxylic acid, or

d) aromatic dicarboxylic acids, such as phthalic acid or terephthalic acid.

09841/1105

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SCHdHIHG AG

Patent department

Ax / Bu -7-

example 1

Mixed polyester from E-caprolactone / hexanediol-1,6 / adipic acid

in the molar ratio 8: 5 J 4 Caprolactone content: about $ 47

295 g of 1,6-hexanediol and 456 g of ε-caprolactone are presented and with 0.97 g of antimony pentachloride ($ 0.1 "based on the end product) offset.

The reaction mixture is allowed to react for 4-5 hours at 40-50 ° C. and finally to stand above fold. Are then added to the destruction of the catalyst approximately 0.5 ml of water is added and the product heated for 1/2 hour at 12O ⁰ C in a water jet vacuum. In the 2nd reaction stage become the reaction product

292.2 g of adipic acid and

2.95 g (1 i ° of the main amount) hexanediol (1.6)

given and esterified under nitrogen according to the following scheme (start of esterification approx. 130-150 ^° C.):

1 hour from 150 - 175 ° C Λ 1 hour from 175 - 200 ⁰ C> normal pressure

3 hours at 20O ⁰ CJ

8-10 hours at 200 ° C / 15 Torr (acid number drops to

0.5 - 0.1)

A crystalline polyester is obtained with the following key figures:

ber.

Hydroxyl number 57.8 53.7

Acid number 0 0.3

Mp 38-39 ⁰ C

If necessary, the polyester is treated in the heat with fuller's earth and filtered.

209841/1105

-8th-

SCHERIlTG AG

Patent department

Ax / Bu -8-

Example 2

Mixed polyester from ε-caprolactone / hexanediol-1,6 / adipic acid

in a molar ratio of 8: 7: 6 Caproiactone content: approx. $ 38

The procedure is analogous to Example 1 and a crystalline polyester is obtained with the following characteristics:

Hydroxyl number acid number

ber. found 46.8 44.9 ' 0 0.3 Mp 41-42 ⁰ C

Example 3

Mixed polyester from ε-caprolactone / hexanediol-1,6 / adipic acid

in a molar ratio of 8: 8: 7 Caproiactone content: approx. $ 34.6

The procedure is analogous to Example 1 and a crystalline polyester is obtained with the following characteristics:

here. found

Hydroxyl number 42.7 40.6

Acid number 0 0.3

Mp 41-42 ⁰ C

Example 4

Mixed polyester from ε-caprolactone / hexanediol-1,6 / adipic acid

in a molar ratio of 6: 9: 8 Caproiactone content: approx. 26 fo

The procedure of Example 1 is repeated and a crystalline one is obtained Polyester with the following key figures:

209841/1105

-9-

SGHERIIiG AG

Patent department

Ax / Bu -9-

Hydroxyl number acid number

ber. found 42.7 39.4 , O 0.5 Ip: 43-44 ⁰ C

Example 5

Mixed polyester made from ε-caprolactone / hexanediol-1.6 / adipic acid

in a molar ratio of 2: 9: 8 caprolactone content: approx. 10.5 %

The procedure is analogous to Example 1, but with the modification that instead of 0.1 $ antimony (V) chloride, 0.025 μl antimony (V) chloride are used here, and a crystalline polyester with the following parameters is obtained:

ber.

Hydroxyl number 51.7 47.4

Acid number 0 0.6

Example 6

Mixed polyester from ε-caprolactone / hexanediol-1,6 / succinic acid

in a molar ratio of 8: 6: 5

The procedure is analogous to Example 1 and an initially liquid polyester which later crystallizes very slowly is obtained with the following key figures:

ber.

Hydroxyl number 55.3 52.5

Acid number 0 0.2

-10-209841 / 1105

SCHiiRING AG-

Patent department

Ax / Bu ■ -10-

Example 7 . -

Mixed polyester from ε-caprolactone / hexanediol-1,6 / adipic acid / Phthalic acid · ■ '

in a molar ratio of 8: 5: 2: 2

The procedure is analogous to Example 1 and an initially liquid, later very slowly crystallizing polyester is obtained with the following key figures:

here. ■ found

Hydroxyl number · -56.7 53.7 acid number 0 1.4

Example 8

Mixed polyester made from ω-hydroxypolycaproic acid (SZ 45.2) / 1,6-hexanediol / adipic acid

in the molar ratio 0.5: 9 J 8 The mixture of

1062 g of 1,6-hexanediol
1168.8 g of adipic acid and
620 g ω-hydroxypolycaproic acid (acid 45.2)

is heated to 60 ^° C., 0.05 % antimony (V) chloride is added and the mixture is heated further. The elimination of water begins at 125 C and is continued according to the following scheme:

1 hour 125-175 ° C for 1 hour 175-200 ⁰ C} normal pressure for 4 hours at 200 ⁰ C.

209841 / Ή05

ber. found 45 4-7.9 O 1.0

SCEiärING AG-

Patent department

Axen / Bu -11-

Then allowed to about 10O ⁰ C to cool, is 10.6 g of hexane-1,6 added and allowed for 8 hours at 200 ^O C / react l5 torr. A crystalline polyester is obtained with the following key figures:

Hydroxyl number acid number

Example 9

Mixed polyester from ε-caprolactone / hexanediol-1,6 / adipic acid

in a molar ratio of 6: 9: 8
Caprolactone content: approx. 26 ^

The procedure is analogous to Example 1, but with the modification that instead of 0.1 $ antimony (V) chloride here 0.05 i °
Antimony (V) fluoride (based on the end product) can be used as a catalyst.

ber.

Hydroxyl number 42.7 37. "

Acid number 0 0.2

Example 10

Mixed polyester from dimerized fatty acid (dimer content:
96 5 ^) / hexanediol-1,6 / e-caprolactone in the molar ratio of
2: 3: 6. The procedure is analogous to Example 1 and a liquid polyester is obtained with the following key figures:

ber.

Hydroxyl number 53 51

Acid number 0 0.4

209841/1105

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Claims (1)

G AG
Patent department
Ax / Bu -12- Patent entitlement Process for the production of mixed polyesters from caprolactones the general formula CH - (CR ₂ ) ₄ -C R-CH- (CR ₉ ), -C = O 0 · where R is a hydrogen atom, a methyl or an ethyl radical can be and in which R should be at most three times an alkyl radical, and from dicarboxylic acids and polyols with or without the use of inert solvents, characterized in that in the first stage the caprolactones with an aliphatic Polyol in the presence of an inorganic catalyst, namely antimony (V) chloride or antimony (V) fluoride, reacted, then optionally mixed with a small amount of water and the hydroxide-containing groups formed Ester compounds are reacted with the dicarboxylic acid in the second stage without isolation, with the equivalent ratio Polyol: dicarboxylic acid should be> 1. 209841/1105