EP0582602A1

EP0582602A1 - New water-soluble, biologically decomposable carbonic acid polyesters and their use as preparing and slip additives of synthetic fibres

Info

Publication number: EP0582602A1
Application number: EP92909074A
Authority: EP
Inventors: Bernhard Goossens; Reinmar PEPPMÖLLER; Karl Winck
Original assignee: Chemische Fabrik Stockhausen GmbH
Current assignee: Stockhausen GmbH and Co KG
Priority date: 1991-04-27
Filing date: 1992-04-23
Publication date: 1994-02-16
Also published as: US5569408A; JPH06509593A; CN1068812A; UA39928C2; DE4113889C2; ES2061417T1; DE59209726D1; JP2651510B2; ES2136607T3; TW374778B; CN1041837C; GR940300019T1; WO1992019664A1; EP0511589A1; DK0511589T3; DE4113889A1; GR3031566T3; ATE182343T1; EP0511589B1

Abstract

Water-soluble, biodegradable carbonic acid polyesters of the formula <IMAGE> in which: R1 is a linear or branched, saturated or monounsaturated alkyl radical having 6 to 22 carbon atoms, R2 is hydrogen or a methyl group, R3 is hydrogen or <IMAGE> , n is an integer from 0 to 10, m is an integer from 5 to 16, z is an integer from 1 to 3, and the use thereof as finishing agents and lubricants for synthetic fibres.

Description

New water-soluble biodegradable carbonic acid polyesters and their use as preparation and lubricants for synthetic yarns

The invention relates to new water-soluble and biodegradable carbonic acid polyesters (polycarbonates) and their use as preparation and lubricants for synthetic yarns.

In order to be able to machine synthetic fibers and yarns made of polyester, polyamide, polypropylene, polyacrylonitrile and also cellulose regenerate at high speed without wear and breakage, antistatic, friction-reducing oils with low volatility and high flash point are used. For these "spin finishes" generally low-viscosity, water-insoluble mineral oils, ester oils or polyethers are used as basic components (e.g. US Pat. No. 3,338,830), which are adjusted to water miscibility with the aid of emulsifiers in accordance with the application requirements.

With the increasing speed of mechanical processing of synthetic fibers, particularly when used under the harsh conditions of the friction texture, the mechanical and thermal stability of fiber preparations became more important. Undesired cracking residues or tar-like deposits on the heating rail surfaces often mean costly disruptions in the production process for products containing mineral oil. A certain type of polyalkylene glycol ether carbonate has been proposed as a way out (JP-PS 195437/83 and EP-PS

0146234). According to structure and synthesis, however, only water-insoluble or water-emulsifiable products could be obtained be. The use of ethylene (propylene) oxide adducts of the fatty alcohols which were self-emulsifying in water and which could be present as block or random adducts (with random sequences) proved to be advantageous. However, due to their structure, they lacked both the network effect and the biodegradability.

The object of the invention was therefore to provide low-viscosity, water-soluble and biodegradable products with high wetting action and high thermal stability, which can be used as spin finishes, i.e. are suitable as preparation and lubricants for synthetic yarns.

This problem is solved by new carbonic acid polyesters of the general formula

with the following meanings:

R ₁ : linear or branched, saturated or monounsaturated alkyl radical with 6 to 22 C atoms,

R ₂ : hydrogen or methyl group

R ₃ : hydrogen or

n: integer from 0 to 10,

m: integer from 5 to 16,

z: integer from 1 to 3.

The new, oligomeric, low-viscosity carbonic acid esters of polyalkylene glycols have a lower content than the products produced by conventional processes Freezing point, a more favorable consistency at room temperature, better hydrophilicity, show wetting effects and are biodegradable.

The invention is based on the surprising finding that the introduction of ester groups in the form of carbonic acid ester groups leads to the condensation of water-insoluble primary alcohols and to a limited extent water-soluble ones

Alkyl-poly-ethylene glycol ethers of such alcohols can be operated with polyalkylene glycol in such a way that there is no enhancement of the hydrophobic properties, as is customary for ester formations, and instead water-soluble compounds are formed. As usual with polycondensates, the monofunctional, primary alcohol limits the molecular weight of the entire molecule. This results in the following structures for the new fiber preparation: a) complete condensation:

b) incomplete condensation:

with the following meanings:

R ₁ : linear or branched, saturated or simple

unsaturated alkyl radical with 5 to 22 carbon atoms,

R ₂ : hydrogen or methyl group n: integer from 0 to 10,

m: integer from 5 to 16,

z: integer from 1 to 3.

The substituent R ₂ contained in the polyalkylene glycol ether block can, if present several times, in each case be the same or different. In the latter case, there are adducts of ethylene and propylene oxide with block or random sequences.

The molecule obtained by the complete condensation can be divided into a central, hydrophilic block and two terminal, hydrophobic residues. This explains the preferred use of polyethylene glycol as a condensation component. Adducts with propylene oxide contain at least 80 mol% of ethylene oxide, since otherwise the hydrophilicity and thus the wetting effect of the polycarbonate are weakened too much.

The carbonic acid polyesters according to the invention can be obtained in a simple manner by transesterification of carbonic acid esters of low-boiling alcohols such as dimethyl carbonate and diethyl carbonate, with polyalkylene glycols and higher molecular weight alcohols or the corresponding alkyl (poly) ethylene glycol ethers with alkali analysis. The low molecular weight alcohol is distilled off via a fractionation column. The reaction can be carried out either with submission of portions or directly with the desired mixture of the hydroxy compounds. It is thus possible first to produce higher molecular weight dialkyl carbonate and then to further implement it with polyalkylene glycol and low molecular weight dialkyl carbonate until equilibrium. After the reaction, the alkaline catalyst must be filtered off since it is not soluble in the product and creates a cloudiness. This is also possible without problems if an alkaline earth metal oxide, such as CaO, is used as the transesterification catalyst.

On the other hand, the high molecular weight dialkyl carbonates or the polycarbonates can be prepared on an industrial scale with a safety device in place by phosgenation of the alcohols and polyalkylene glycols.

For the preparation of polyalkylene glycols with alkylene oxide, a diol is generally used as the starting substance, in the simplest case water or ethylene glycol. However, any other dihydric alcohol such as e.g.

1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-hexylene glycol, diethylene glycol ether or triethylene glycol ether can be used.

Bases such as sodium hydroxide, potassium hydroxide or mixtures thereof, and special metal complexes such as cobalt-hexacyano-cobaltate act as catalysts. The average molar mass of the polyether to be linked is limited to the maximum value of 300 according to the OH number, since higher molecular weight adducts cause the viscosity of the texturing oil to increase undesirably in the case of multiple linking. If polyalkylene glycols made of ethylene and propylene oxide are used as the central block, there are no restrictions with regard to the molecular structure. Both blockais and random adducts can be used, whereby each divalent plank can form the central unit.

To determine the molar mass of the polyesters, synthetic, linear and branched primary alcohols with more than six carbon atoms such as hexanol, octanol, nonanol, decanol, undecanol, Dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol and docosanol as well as the linear alcohols obtained from natural fats capron alcohol, oenanthal alcohol, capryl alcohol, pelargon alcohol, lauryl alcohol, cap alcohol, alcohol alcohol, cap alcohol alcohol Behenyl alcohol as well as the monounsaturated such as oleyl alcohol are suitable. These can be used both in unchanged form and as hydroxyethyl ether

Addition product of ethylene oxide. There can be a maximum of 10 moles of ethylene oxide per mole of alcohol. Amounts exceeding this result in a too high viscosity of the end product.

The water-soluble polycarbonates according to the invention can be used without addition or in admixture with other components as a lubricant and preparation for synthetic fibers, especially for the process step of friction texturing. Common additional components are antistatic agents, anti-corrosion agents, anti-foaming agents, preservatives and possibly solubilizers.

The polycarbonates are applied directly when the fibers are spun after leaving the spinning shaft by means of metering pumps or preparation rollers. The compounds can be applied in bulk or as an aqueous solution. In contrast to the oils previously used, emulsifiers no longer need to be added due to their good water solubility and wetting properties. Since the condensation products are fully biodegradable, there is also no environmental hazard if the preparation according to the invention is rinsed off partially from the fiber material in subsequent washing processes. Wastewater treatment can therefore follow the same standards as happen with the commercial washing and cleaning agents.

The following advantages are achieved with the invention: Because of the more uniform fiber wetting and surface covering, there is an improvement in the sliding effect compared to the oils known to be emulsifiable in water. In addition, the use of a water-soluble and emulsifier-free oil also means a reduction in the formation of tar-like, sticky deposits on all critical machine parts. As a result, the processing of fine and ultra-fine yarns is facilitated and the electrostatic problems at high speeds are further reduced.

The invention is illustrated by the following examples:

A) Preparation of the carbonic acid polyester according to the invention

Example 1:

In a glass flask equipped with a stirrer, reflux condenser and thermometer, 240 g of decyl alcohol (Alfol 10 from Condea AG) with 150 g of dimethyl carbonate and 8 g of calcium oxide were heated under reflux for 2 hours. The condenser was then replaced by a rectification column and the mixture was slowly heated to 100 ° C with stirring. The methanol liberated from the transesterification reaction was accompanied by accompanying dimethyl carbonate at the top of the

Column caught. Then 600 g of polyethylene glycol with a molecular weight of 400 and another 100 g of dimethyl carbonate were added. The mixture was again under 2 hours

Heated to reflux and then the temperature up to 120 ° C. increased, with further amounts of a methanol / dimethyl carbonate mixture distilling over. Finally, vacuum was applied briefly. After cooling to room temperature, the reaction product was filtered. It turned out to be a clear, colorless and thin oil.

Example 2:

In a glass apparatus according to Example 1, 365 g of ethoxylated decanol (2 moles of ethylene oxide attached to Alfol 10 from Condea AG) with 150 g of dimethyl carbonate and 8 g of calcium oxide were slowly heated, first under reflux and then to 100 ° C., liberating methanol together distilled off with dimethyl carbonate. Then 600 g of polyethylene glycol (molecular weight 400) and 100 g of dimethyl carbonate were added and the mixture was treated as in Example 1. After filtering off the catalyst, a clear, thin and colorless oil resulted.

Example 3 and following:

The reaction conditions and the molar ratios of the reactants to one another corresponded to the above information. The components condensed with dimethyl carbonate are shown in Table 1 below.

Table 1;

Reactant 1 Reactant 2

Example 3 PEG 400 4 EO-ALFOL 10 Example 4 PEG 600 n-dodecyl alcohol Example 5 PEG / PPG 600 2 EO-ALFOL 10

(80/20, random)

Comparison of some product data with standard:

Table 2:

Standard fiber preparation * 1 2 3 4 5

viscosity

(Brookfield, mPa * s) 180 150 150 160 170 170

Surface tension

(mN / m, 10%) 29 30 29 29 29 30

solubility in water

(10%) - - - - - - - - - - - - -clear- - - - - - - - - - - - - - - - -

Cracking residue

(220 ° C, 24h,%) 1 1 1 1 1 1

Standard * = Puropol FT 509 (Stockhausen GmbH). Since the product itself is not surface or surface active, 2% of a nonionic wetting agent (oxyethylated fatty alcohol, Intrasol FA 1218/10) was added.

3) Use as a spin finish: a) Measurement of the coefficient of friction: PES filaments (terephthalate, 167 dtex 32 f) were prepared with polycarbonate according to Examples 1 to 5 from an aqueous solution in such a way that an oil coating of 0.5% resulted.

After air conditioning for 24 hours at 20 ° C and 65% relative humidity, the coefficient of sliding friction was determined using an F-meter (from Rothschild), the friction body consisting of chromed and polished steel.

Friction coefficient with a preload of 17cN:

Row 1: fiber / metal (50 m / min); Wrap angle

180 °.

Row 2: fiber / fiber (20 m / min); Wrap angle

6 × 180 °. Standard 1 2 3 4 5

1) 0.41 0.40 0.40 0.41 0.41 0.41

2) 0.31 0.31 0.30 0.30 0.31 0.31 b) Production of polyester POY (titer: 290 dtex 32 f):

The preparation was applied immediately after the molten polymer emerged from the spinneret in the spinning shaft by metering a 10% strength aqueous solution using metering pumps.

The winding speed was 3200 m / min. The preparation overlay on the POY material was 0.4%. c) Friction texturing (final titre 167 dtex 32 f):

The texturing was carried out under the following conditions leads;

Heater length: 2.0 m

Heater temperature: 210ºC

Cooling plate: 1.5 m

Friction unit: 8 ceramic discs

Take-off speed: 700 m / min

D / Y ratio: 2.2

Stretch ratio: 1.608

The following measured values were then obtained:

Standard Examples 1 to 5

1 2 3 4 5

strength

(cN / dtex): 3.63 3.65 3.66 3.64 3.66 3.64

Elongation (%): 25.0 25.0 25.1 25.1 25.2 25.1

Boiling shrink

(%): 8.5 8.7 8.7 8.6 8.7 8.6

Crimp E (%) 41.2 41.1 41.2 41.2 41.2 41.1

K (%) 24.7 24.9 24.9 24.8 24.7 24.8

After 10 days of continuous operation under the test conditions, there were no deposits in the heater. d) Biodegradability:

To test the biodegradability, the standard product and the polycarbonates according to Examples 1 to 5 were subjected to the simulation test ("Confirmatory Test" according to OECD). The following results were obtained after 23 days: Standard Examples 1 to 5 biological. Degradation (%) 20 80

Examples 6 to 10

6) In a glass apparatus according to Example 1, 366 g of n-hexanol (6 moles of ethylene oxide added) were heated with 150 g of dimethyl carbonate and 8 g of calcium oxide. After 2 hours, 600 g of polyethylene glycol (M = 400) and another 220 g of dimethyl carbonate were added. The mixture was again heated under reflux for 2 hours and then the azeotrope of methanol and dimethyl carbonate was distilled off. Finally, vacuum was applied briefly. After cooling, the reaction product was filtered. It turned out to be a clear, light, water-soluble oil.

7) As in Example 6, 482 g of 2-ethylhexanol (8 moles of ethylene oxide added) were reacted with 300 g of polyethylene glycol (M = 600) and a total of 210 g (150/60) of dimethyl carbonate. After the azeotrope had been distilled and the catalyst had been separated off, a light one was obtained Obtain oil that formed small amounts of a solid sediment when stored.

8) As in Example 6, 620 g of oleyl alcohol (Ocenol 60/65 from Henkel KGaA), reacted with 8 moles of ethylene oxide, were heated with 150 g of dimethyl carbonate and 8 g of calcium oxide. Then 1200 g of polyethylene glycol (M = 600) and another 220 g of dimethyl carbonate were added and the methanol released was distilled off as an azeotrope. After filtration of the product at 60 ° C., a water-soluble wax that was soft at room temperature was obtained. 9) As in Example 6, 422 g of n-decanol (Alfol 10 from Condea AG), reacted with 6 moles of ethylene oxide, were heated with 600 g of polyethylene glycol (M = 200) and 450 g of dimethyl carbonate (150/300). After the azeotrope had been distilled and the catalyst had been separated off, a light, thin, water-soluble oil was obtained.

10) As in Example 6, 756 g of n-behenyl alcohol (10 moles of ethylene oxide added) were reacted with 1200 g of polyethylene glycol (M = 600) and a total of 370 g of dimethyl carbonate. After working up at 60 ° C, a light water-soluble wax was obtained.

Test results for Examples 6 to 10:

Fiber preparation 6 7 8 9 10

Viscosity (Brookf., MPa * s) 180 150 solid 210 solid surface tension (mN / m, 10%) 29 28 29 30 30 solubility in water, 10% - - - - - - - - - - clear - - - - - - - - - - - - Cracking residue (220ºC, 24 h,%) 1 1 1 1 1

Friction coefficient with a preload of 17 cN: 6 7 8 9 10

1) 0.41 0.41 0.39 0.40 0.39 2) 0.31 0.30 0.30 0.31 0.31

Strength: 3.65 3.62 3.66 3.65 3.63 (cN / dtex)

Elongation (%): 25.1 25.3 25.0 25.1 25.2

Cook shrinkage (%): 8.6 8.7 8.5 8.6 8.7

Crimp E (%): 41.2 41.1 41.1 41.2 41.1

K (%): 24.8 24.9 24.8 24.7 24.8

Biol. Degradation (%): - - - - - - - - - - - - -> 80 - - - - - - - - - - - -

Size of the coefficients n, m and z in Examples 1 to 10:

Example 1 2 3 4 5 6 7 8 9 10 n 0 2 4 0 2 6 8 8 6 10 m 9 9 9 14 13.5 9 14 14 5 14 z 2 2 2 2 2 3 1 4 6 4

Claims

PATENT CLAIMS

1. Water-soluble biodegradable carbonic acid polyesters of the general formula:

with the following meanings:

R ₂ : hydrogen or methyl group

R ₃ : hydrogen or - n: integer from 0 to 10,

m: integer from 5 to 16,

z: integer from 1 to 3.

2. carbonic acid polyester according to claim 1, characterized in that the polyalkylene glycol sequence of the formula

the carbonic acid polyester consists of a polyethylene glycol started with water or a diol.

3. carbonic acid polyester according to claim 1, characterized in that the polyalkylene glycol sequence of the formula of the carbonic acid polyester consists of at least 80 mol% of ethylene oxide and at most 20 mol% of propylene oxide units.

4. carbonic acid polyester according to any one of claims 1 to 3, characterized in that its 10% by weight aqueous solution reduce the surface tension of the water to at least 35 mN / m.

5. carbonic acid polyester according to any one of claims 1- 4, obtainable by condensation of primary alcohols or alkyl (poly) ethylene glycol ethers and polyalkylene glycols with low molecular weight dialkyl carbonate, preferably dimethyl or diethyl carbonate or with phosgene.

6. Use of the carbonic acid polyester according to one of claims 1 to 5 as a preparation and lubricant for synthetic fibers.

7. Use of the carbonic acid polyester according to claim 6, characterized in that the spin finish contains, in addition to the carbonic acid polyesters, antistatic agents, anti-corrosion agents, anti-foaming agents, preservatives and / or solubilizers as further components.