WO1993023450A1

WO1993023450A1 - Block copolyesters containing open-ringed epoxified carboxylic acid radicals

Info

Publication number: WO1993023450A1
Application number: PCT/EP1993/001153
Authority: WO
Inventors: Ulrich Eicken; Peter Daute; Paul Birnbrich; Raymond Mathis; Norbert Bialas
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-05-18
Filing date: 1993-05-11
Publication date: 1993-11-25
Also published as: DE4216418A1

Abstract

The invention relates to block copolyesters with hydrophilic and hydrophobic segments in which the hydrophobic segment contains acid radicals of open-ringed epoxified unsaturated carboxylic acids and/or their esters and the hydrophilic radical is a polyethylene glycol radical. Other objects concern a process for producing such block copolyesters and their use as lubricants in spinning preparations for synthetic fibres.

Description

"Block copolyesters containing ring-opened epoxidized carboxylic acid esters

The invention relates to block copolyesters with hydrophilic and hydrophobic segments, the hydrophobic segment containing acid residues from ring-opened epoxidized unsaturated carboxylic acids and / or their esters and the hydrophilic residue being a polyethylene glycol residue. Other subjects relate to a process for the production of such block copolyesters and their use as lubricants in spin finishes for synthetic filaments.

Block copolyesters in the context of the invention are polymers which are composed of hydrophobic and hydrophilic segments which are linked to one another by an ester bond. Such hydrophilic / hydrophobic block copolyesters are known, for example, from German Offenlegungsschrift DE-A-24 30 342 and in European Patent EP-B-424. The block copolyesters described therein contain, as a hydrophobic segment, copolyesters which are produced by intermolecular esterification of monohydroxycarboxylic acids such as 12-hydroxystearic and / or 9c-octadecen-12-ol acid (ricinoleic acid). The copolyesters are then esterified with hydrophilic polyether alcohols such as polyethylene glycol or adducts of C ₂ -C ₄ alkylene oxides with polyhydric alcohols to give the hydrophobic / hydrophilic block copolyesters. According to German Offenlegungsschrift DE-A-24 30 342, such block copolyesters are suitable as textile lubricants. When using block copolyesters based on ricinoleic acid or its hydrogenated representatives 12-hydroxystearic acid must however, it must be accepted that the quantities available on the market are subject to strong fluctuations. Missing harvests in the main growing regions of Brazil and India lead to a shortage of the raw material castor oil at more or less frequent intervals. There is therefore a need for an equivalent replacement. Above all, the exchange product should be accessible from a broader, less crisis-prone raw material base and be ecologically and toxicologically safe.

The object of the present invention was therefore to provide new block copolyesters which do not have the disadvantages described above.

The present invention relates to block copolyesters consisting of hydrophobic segments A and hydrophilic segments B, characterized in that

Segment A is the acid residue of a mixture of 50 to 100% by weight of epoxidized unsaturated carboxylic acids and / or carboxylic esters ring-opened with alcohols and 0 to 50% by weight of saturated, aliphatic carboxylic acids and / or carboxylic esters - based on the mixture - and

- Segment B is a polyethylene glycol residue.

Segment A of the block copolyesters according to the invention can be either an acid residue of exclusively ring-opened epoxidized unsaturated carboxylic acids and / or carboxylic acid esters or a residue of a mixture of these with saturated aliphatic carboxylic acids and / or carboxylic acid esters. The term ring-opened epoxidized unsaturated carboxylic acids is to be understood as meaning that unsaturated carboxylic acids are epoxidized and the epoxidized carboxylic acids are ring-opened. For the sake of simplicity, these unsaturated, epoxidized carboxylic acids are also referred to as epoxidized carboxylic acids in the following text. The epoxidation is carried out completely or almost completely by methods known per se, such as according to European patent application EP-A-285 937 or German patent DE-C-1042565, it being necessary for the epoxidation that at least one epoxy group per molecule of unsaturated carboxylic acid in the Molecule is created. Suitable unsaturated carboxylic acids which are epoxidized are all known from the prior art, preference is given to those having 12 to 22 carbon atoms and in particular laurolein, myristole, palmitolein, petroselin, oil, linole, linolaidin and / or erucic acid. Technical mixtures of these ring-opened epoxidized carboxylic acids, such as those obtained from natural fats and / or oils such as fish, sperm, palm, cottonseed, sunflower, soybean, linseed, turnip and tall oil, are very particularly preferred . These natural oils and fats always contain saturated aliphatic carboxylic acids. A further embodiment of the present invention therefore also relates to block copolyesters whose hydrophobic segment A is an acid residue which is derived from a mixture of 50 to 90% by weight of ring-opened epoxidized unsaturated carboxylic acids with 12 to 22 C atoms and 10 to 50% by weight. -% saturated aliphatic carboxylic acids with 6 to 22 carbon atoms. The hydrophobic segment A is very particularly preferably derived from fatty acid mixtures which consist of epoxidized soybean oil (epoxy oxygen content 5.8 to 6.8% by weight), high-oleic and / or low-oleic epoxidized sunflower oils (epoxy acid content 4.4 to 6.6) Wt .-%), epoxidized linseed oil (epoxy oxygen content 8.2 to 8.6 wt .-%) and epoxidized tall oil (epoxy oxygen content 6.3 to 6.7 wt .-%) can be obtained after ring opening.

If segment A is derived from pure ring-opened epoxidized carboxylic acids, it is preferred that it is derived from ring-opened epoxidized oleic acid, which is also referred to as epoxystearic acid. Segment A of the block copolyesters according to the invention is derived either directly from these carboxylic acids or else from their esters from mono- and / or polyfunctional alcohols, preferably from monofunctional aliphatic alcohols having 1 to 22 carbon atoms and / or from glycerol.

When the ring is opened, the epoxidized carboxylic acids and / or their esters are then ring-opened with alcohols. This ring opening reaction is known from the prior art and can take place either by the so-called dropping method or by the one-pot method. After the dropping process, the alcohols provided for ring opening are introduced together with an acid catalyst, for example a strong mineral acid, and the epoxidized carboxylic acid and / or its esters are added continuously or in portions at a reaction temperature between 60 and 120 ° C. According to the so-called one-pot process, all reactants are reacted in the presence of an acid catalyst at temperatures between 20 and 120 ° C. The progress of the reaction can be determined via the content of unreacted epoxy groups, according to the titration method by RR Jay, Analytische Chemie, 36, 667 (1964). After the ring has been opened, the acidic catalyst can be destroyed by neutralization and, if appropriate, excess alcohol can be removed by distillation or by phase separation. It goes without saying that the catalyst and excess alcohols can also remain in the reaction mixture if this does not affect other applications. In principle, saturated, unsaturated, branched, unbranched, cyclic, aromatic monofunctional alcohols or else diols can be used to open the ring. Aliphatic diols with 2 to 22 carbon atoms are particularly suitable as diols. Since diols can open 2 epoxy groups due to their 2 hydroxyl groups, crosslinking reactions can occur. For this reason, monofunctional aliphatic alcohols are preferred, in particular those with 1 to 22 carbon atoms. Alcohols with up to 4 carbon atoms, such as methanol, ethanol, propanol and / or butanol, are very particularly preferred. One can but as monohydric primary alcohols it is also possible to use diols, one hydroxyl group of which has been etherified or esterified like monoalkyl ethylene glycols.

The ring opening of the epoxidized carboxylic acids and / or their esters can take place completely and / or partially. If a complete or practically almost complete ring opening is desired, it is advisable to use the epoxidized carboxylic acids and / or their esters in quantities of 1: 1 to 1:10, preferably 1: 1 to 1: 3 - calculated as mol% of epoxy and based to mol% alcohols - to react with the alcohols mentioned. An at least almost complete ring opening can be included if the reaction is carried out at these quantitative ratios for up to 5 hours until an absolute residual epoxide oxygen content of less than 0.3% by weight occurs. If the reaction is terminated earlier or if conversion ratios are chosen which are below those for a complete ring opening, only a partial ring opening is obtained, but this should at least have progressed to such an extent that the partially ring-opened epoxidized carboxylic acids or their esters per molecule have at least one wear hydroxyl group obtained by ring opening.

When the epoxidized carboxylic acids or their esters are opened with alcohols, compounds are formed which carry at least one free hydroxyl group and, in the adjacent position, an alkoxy group and also a carboxylic acid group or an ester residue. If they carry a hydroxyl group and a carboxylic acid group, they are hydroxymonocarboxylic acids which are able to esterify intermolecularly analogously to the ricinoleic acid described in European Patent EP-B-424. This intermolecular esterification produces oligomeric copolyesters, the molecular weight of which is determined by the degree of polymerization. The degree of polymerization itself again depends on whether chain-terminating monocarboxylic acids which have no hydroxyl group are present are available. The oligomerization of the hydroxymonocarboxylic acids can thus be determined via the amount of chain-terminating monocarboxylic acids. The degree of oligomerization is expediently in the range from 1.5 to 10. For this reason, the hydrophobic segment A present in the block copolyesters according to the invention can be both a monomeric and an oligomeric acid residue which is derived from epoxidized carboxylic acids or carboxylic acid esters ring-opened with alcohol.

As a further segment, the block copolyesters according to the invention contain the hydrophilic segment B, which represents a polyethylene glycol residue, preferably a polyethylene glycol residue with an average molecular weight of

200 to 20,000, preferably from 400 to 10,000 and in particular from 600 to 3,000.

The block copolyesters according to the invention can contain the segments A and the segments B in different amounts. The block copolyester can thus easily contain 5 to 95% by weight of segment A and 95 to 5% by weight of segment B, based on block copolyester. If the block copolyesters according to the invention are to be used as lubricants, it is advisable to use block copolyesters which contain the hydrophobic segment A in amounts of 40 to 95% by weight and segment B in amounts of 5 to 60% by weight.

The present invention further provides a process for the preparation of the block copolyesters according to the invention which is characterized in that esters of a carboxylic acid mixture of 50 to 100% by weight of epoxidized unsaturated carboxylic acids ring-opened with alcohols and 0 to 50% by weight of saturated aliphatic carboxylic acids are transesterified with polyethylene glycol in the presence of esterification catalysts. Details of the procedure can be found in the text above. This process is opposed to a direct esterification of ring-opened epoxidized carboxylic acids with polyethylene glycols are preferred, since there are practically no side reactions such as ether formation. This process is particularly suitable for production if ring-opened epoxidized carboxylic acid esters of lower alcohols, such as, for example, the methyl esters, are used, since the methanol formed after the transesterification can be distilled off without problems. If esters of higher or polyhydric alcohols are used, such as, for example, the triglycerides of the ring-opened epoxidized fatty acids, the transesterification with polyethylene glycol also produces by-products in addition to the block copolyesters according to the invention, for example only partially transesterified triglycerides. Such reaction mixtures also belong within the scope of the present invention.

The transesterification itself is carried out in a manner known per se, preferably in the presence of customary transesterification catalysts such as tin and titanium compounds, alkali metal alcoholates and lithium hydroxide. The transesterification is preferably carried out at temperatures in the range from 100 to 200.degree. If desired, work can be carried out in the presence of solvents or else solvent-free.

The block copolyesters according to the invention are easily emulsifiable in water and have smoothing properties. For this reason, they can be used very well as biodegradable lubricants in spin finishes for synthetic filaments. The block copolyesters can be used either alone or in a mixture with lubricants known from the prior art. Known lubricants are mineral oils, fatty acid esters of alkanols with 8 to 22 carbon atoms in the fatty acid residue and 1 to 22 carbon atoms in the alcohol residue, for example methyl palmitate, tallow fatty acid 2-ethylhexyl ester, fatty acid esters of polyols with 2 to 6 hydroxyl groups, alkoxylated alcohols, for example addition products of ethylene oxides and propylene oxides on tallow alcohol, polyalkylene glycols such as ethylene oxide-propylene oxide copolymers and / or silicones. If the block copolyesters according to the invention are used in a mixture with known lubricants, it is expedient for the block copolyesters to be present in amounts of 15 to 95% by weight, preferably 50 to 90% by weight, based on the lubricant mixture, in addition to that from the prior art known lubricants can be used. When the block copolyesters are used as lubricants in spin finishes, they are preferably applied from an aqueous dispersion in the form of a suspension or emulsion. To prepare the aqueous dispersion, block copolyesters are generally emulsified in water before application. To improve the emulsifiability, the emulsifiers known from the prior art, such as mono- and / or diglycerides, alkoxylated fats, oils, fatty alcohols having 8 to 24 C atoms and / or C ₈ -C ₁₈ alkylphenols and / or fatty alcohols, can expediently be used If desired, amides such as fatty acid mono- and / or diethanolamides can also be added to propylene oxide and ethylene oxide.

If a pronounced antistatic is required for the spin finishes, commercially available antistatics such as alkali and / or ammonium salts of alkoxylated, optionally end-capped C ₈ -C ₂₂ alkyl and / or C ₈ -C ₂₂ alkylene alcohol sulfonates, reaction products of alcohol with phosphorus pentoxide be added in the form of their alkali, ammonium and / or amine salts.

Other common auxiliaries for spin finishes are thread closing agents, pH regulators, bactericides and / or anti-corrosion agents. The block copolyesters are preferably used in the form of their aqueous dispersion. The aqueous dispersion of the block copolyesters have a water content of 99.8 to 60% by weight and an active substance content of block copolyesters of between 0.2 to 40% by weight. For laboratory tests, especially on preparation-free filaments, aqueous dispersions with an active substance content of block copolyesters between 0.2 to 4% by weight. For practical use, the active substance content is preferably 3 to 40 and in particular 5 to 30% by weight. If further smoothing agents or further additives known from the prior art are to be used, the active substance content of block copolyesters should be reduced accordingly.

For example

A) Preparation of ring-opened epoxidized esters

Example A 1 Methyl epoxystearate with methanol

To a boiling solution of 5.9 g of concentrated sulfuric acid in 340 g, corresponding to 10.6 mol, of methanol, 1359 g of epoxystearic acid methyl ester with an epoxide oxygen content of 4.71% by weight, corresponding to 4 mol, based on epoxide oxygen, were added dropwise. After the epoxide had practically completely reacted, the reaction mixture was neutralized with 22 g of 30% strength by weight methanolic sodium methylate solution. The methanol was distilled off.

A clear yellow liquid was obtained with the following characteristics: hydroxyl number (OHZ) according to DIN 53240 = 138; Saponification number (VZ) according to DIN 53401 = 170; Iodine number (JZ) according to DGF CV, 11b = 9.3; Acid number (SZ) according to DIN 53402 = 0.2.

Example A 2 Methyl epoxystearate with ethylene glycol

100 kg of epoxystearic acid methyl ester with an epoxy oxygen content of 4.95% by weight, corresponding to 309 moles based on the epoxy content, and 38.3 kg of ethylene glycol, corresponding to 617 moles, were heated to 90 ° C. in the presence of 34 g of concentrated sulfuric acid. After the reaction was virtually complete (about 1.5 hours; residual epoxy oxygen content: 0.03% by weight), the reaction mixture was neutralized with 160 g of 30% by weight methanoic sodium methoxide solution, and the methanol was distilled off. A clear, yellow liquid was obtained with the characteristic data: 0HZ = 234.6; VZ = 162.06; JZ = 6.9; SZ = 0.7. Example A3

Analogously to Example 1, 2360 g of epoxidized soybean oil with an epoxy oxygen content of 6.78% by weight, corresponding to 10 moles based on epoxy oxygen, were added dropwise to a boiling solution of 9 g of concentrated sulfuric acid in 960 g, corresponding to 30 mol, methanol. After the reaction was virtually complete, the reaction mixture was neutralized with 18 g of diethylethanolamine and excess methanol was distilled off. A clear, yellow liquid was obtained with the characteristic data 0HZ = 185; VZ = 163; JZ = 19.4; SZ = 1.6.

Example A 4 Partial ring opening of epoxidized soybean oil

5820 g of epoxidized soybean oil with an epoxy oxygen content of 6.88, corresponding to .... moles based on epoxy oxygen, were heated to 50 ° C. with 1600 g methanol, corresponding to 50 moles. After adding 27.5 g of concentrated sulfuric acid, the temperature was raised to 65 ° C. When the residual epoxide oxygen content was 2.7%, the reaction was stopped, neutralized with diethylethanolamine and methanol was distilled off.

Example A 5 Partial ring opening of epoxidized soybean oil

The reaction was carried out analogously to Example A 4, but the

Reaction stopped at a residual epoxide oxygen content of 5.3%.

B) Production of block copolyester

Example B 1

350 g of ring-opened epoxystearic acid methyl ester according to Example A 1, 150 g of polyethylene glycol with an average molecular weight (MW) of 1000 and 1.0 g of Sn-based esterification catalyst (Swedcat 5 ^R , from Fa. Swedstab) heated to 200 - 220 ° C. The methanol formed was separated off by distillation (16 ml). The block copolyester obtained is emulsifiable in water.

Example B 2

Analogously to Example B 1, 187 g of ring-opened epoxystearic acid methyl ester according to Example A 1 were transesterified with 80 g of polyethylene glycol (mean MW = 1000) in the presence of 0.8 g of 30% strength by weight sodium methoxide solution at 100 to 120 ° C. for 5 hours. The resulting methanol (10 ml) was removed by distillation.

A block copolyester emulsifiable in water was obtained.

Example B 3

Analogously to Example B 1, 145 g of ring-opened soy polyol according to Example A 3 were transesterified with 195 g of polyethylene glycol (mean MW = 1000) and 0.4 g of Swedcat5 ^R at 195 ° C. for 30 to 45 minutes.

A block copolyester emulsifiable in water was obtained.

Example 4

Analogously to Example B 1, 145 g of partially ring-opened soy polyol according to Example A 4 were transesterified for 1 hour at 215 to 220 ° C. with 62 g of polyethylene glycol (mean MW = 1000) and 0.4 g of Swedcat5 ^R. A block copolyester emulsifiable in water was obtained.

Example 5

Analogously to Example B 1, 145 g of partially ring-opened soy polyol according to Example A 5 were transesterified with 62 g of polyethylene glycol (average MW = 1000) and 0.4 g of Swedcat5 ^R at about 220 ° C. for 10 minutes. The block copolyester obtained is emulsifiable in water. C) Use as a lubricant for synthetic filaments

A 0.4 and 0.8% strength by weight aqueous emulsion of the block copolyesters according to Examples 1 and 4 were placed on polyester filaments (yarn type: pre-oriented yarn-Pes; fineness: 147 dtex, number of filaments: 430; spinning speed: 1300 m / min) 3 applied. The active substance content of the product layer was 0.2 and 0.4% by weight.

In order to test the properties of the block copolyesters according to the invention as lubricants, the following parameters were determined:

- dynamic friction quotient against ceramic at a speed of 2 to 200 m / min, measured on the Rothschild F-Meter (climate 23 ° C, 60% relative humidity)

- Electrostatic charging on ceramics at a speed of 2 to 200 m / min, measured on the Eltex inductive voltmeter (climate 23 ° C, 60% relative humidity).

Table I summarizes the dynamic friction ratios and Table II summarizes the electrostatic charge which was observed in the aqueous emulsions with a product coating of 0.2 and 0.4% by weight.

Claims

Patent exams

1. Block copolyester consisting of hydrophobic segments A and hydrophilic segments B, characterized in that

- Segment A, the acid residue of a mixture of 50 to 100% by weight of epoxidized unsaturated carboxylic acids and / or carboxylic esters ring-opened with alcohols and 0 to 50% by weight of saturated, aliphatic carboxylic acids and / or carboxylic esters - based on the mixture - and

- Segment B is a polyethylene glycol residue.

2. Block copolyester according to claim 1, characterized in that the acid residue of segment A is derived from ring-opened epoxidized carboxylic acids having 12 to 22 carbon atoms and / or their esters, preferably from laurolein, myristole, palmitolein, petroselin, oil -, Linoleic, linolaidic, erucic acid and / or their esters.

3. Block copolyester according to claim 1, characterized in that the acid residue of segment A is derived from a mixture of 50 to 90 wt .-% ring-opened epoxidized carboxylic acids with 12 to 22 carbon atoms or their esters and 10 to 50 wt .-% saturated aliphatic carboxylic acids with 6 to 22 carbon atoms and / or their esters.

4. Block copolyester according to claim 1, characterized in that segment A is the acid residue of esters of mono- and / or polyfunctional alcohols, preferably of monofunctional, aliphatic alcohols having 1 to 22 carbon atoms and / or of glycerol.

5. Block copolyester according to claim 1, characterized in that segment A is the acid residue of with monofunctional, aliphatic alcohols having 1 to 22 carbon atoms and / or of epoxidized carboxylic acids and / or carboxylic acid derivatives ring-opened with aliphatic diols having 2 to 22 carbon atoms .

6. Block copolyester according to claim 5, characterized in that segment A is the acid residue of completely and / or partially ring-opened epoxidized carboxylic acids and / or esters, the partially ring-opened epoxidized carboxylic acids or carboxylic esters per molecule carrying at least one hydroxyl group obtained by ring opening.

7. Block copolyester according to claim 1, characterized in that B is a polyethylene glycol residue with an average molecular weight of 200 to 20,000, preferably 400 to 10,000 and in particular 600 to 3,000.

8. Block copolyester according to claim 1, characterized in that the block copolyester consists of 5 to 95 wt .-% of segment A and 95 to 5 wt .-% of segment B - based on block copolyester.

9. A process for the preparation of block copolyesters with hydrophobic segments A and hydrophilic segments B, characterized in that esters of a carboxylic acid mixture of 50 to 100 wt .-% epoxidized unsaturated carboxylic acids ring-opened with alcohols and 0 to 50 wt .-% saturated aliphatic carboxylic acids with polyethylene glycol are transesterified in the presence of esterification catalysts.

10. Use of block copolyesters according to claim 1 as a lubricant in spin finishes for synthetic filaments.