WO1993023450A1 - Copolyesters en bloc contenant des esters d'acide carboxylique epoxydes decyclises - Google Patents

Copolyesters en bloc contenant des esters d'acide carboxylique epoxydes decyclises Download PDF

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Publication number
WO1993023450A1
WO1993023450A1 PCT/EP1993/001153 EP9301153W WO9323450A1 WO 1993023450 A1 WO1993023450 A1 WO 1993023450A1 EP 9301153 W EP9301153 W EP 9301153W WO 9323450 A1 WO9323450 A1 WO 9323450A1
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WO
WIPO (PCT)
Prior art keywords
esters
carboxylic acids
segment
ring
opened
Prior art date
Application number
PCT/EP1993/001153
Other languages
German (de)
English (en)
Inventor
Ulrich Eicken
Peter Daute
Paul Birnbrich
Raymond Mathis
Norbert Bialas
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993023450A1 publication Critical patent/WO1993023450A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • 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).
  • 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.
  • hydrophilic polyether alcohols such as polyethylene glycol or adducts of C 2 -C 4 alkylene oxides with polyhydric alcohols
  • block copolyesters are suitable as textile lubricants.
  • 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.
  • 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.
  • 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.
  • fatty acid mixtures 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 (
  • 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.
  • 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.
  • 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.
  • an acid catalyst for example a strong mineral acid
  • the progress of the reaction can be determined via the content of unreacted epoxy groups, according to the titration method by RR Jay, Analytician Chemie, 36, 667 (1964).
  • 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.
  • 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.
  • diols can open 2 epoxy groups due to their 2 hydroxyl groups, crosslinking reactions can occur.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • esters of higher or polyhydric alcohols 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.
  • 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.
  • 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.
  • 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
  • amides such as fatty acid mono- and / or diethanolamides can also be added to propylene oxide and ethylene oxide.
  • 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.
  • 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.
  • aqueous dispersions with an active substance content of block copolyesters between 0.2 to 4% by weight.
  • 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.
  • Example A 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.
  • MW average molecular weight
  • Sn-based esterification catalyst Swedcat 5 R , from Fa. Swedstab
  • a block copolyester emulsifiable in water was obtained.
  • a block copolyester emulsifiable in water was obtained.
  • the block copolyester obtained is emulsifiable in water.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des copolyesters en bloc comportant des segments hydrophiles et hydrophobes. Le segment hydrophobe contient des restes acides d'acides carboxyliques insaturés époxydés décyclisés et/ou leurs esters, et le reste hydrophile est un reste polyéthylène-glycol. D'autres objets concernent un procédé de fabrication de copolyesters de ce type et leur utilisation en tant que lubrifiants dans des préparations de filage pour filaments synthétiques.
PCT/EP1993/001153 1992-05-18 1993-05-11 Copolyesters en bloc contenant des esters d'acide carboxylique epoxydes decyclises WO1993023450A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19924216418 DE4216418A1 (de) 1992-05-18 1992-05-18 Blockcopolyester enthaltend ringgeöffnete epoxidierte Carbonsäurereste
DEP4216418.4 1992-05-18

Publications (1)

Publication Number Publication Date
WO1993023450A1 true WO1993023450A1 (fr) 1993-11-25

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PCT/EP1993/001153 WO1993023450A1 (fr) 1992-05-18 1993-05-11 Copolyesters en bloc contenant des esters d'acide carboxylique epoxydes decyclises

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DE (1) DE4216418A1 (fr)
WO (1) WO1993023450A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007741A1 (fr) * 1993-09-15 1995-03-23 Henkel Kommanditgesellschaft Auf Aktien Polymeres sequences contenant des groupes ester, utilises comme agents antimoussants pour des systemes aqueux
WO1996016728A1 (fr) * 1994-12-02 1996-06-06 Henkel Kommanditgesellschaft Auf Aktien Emulsion d'eau dans l'huile

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB989252A (en) * 1961-01-10 1965-04-14 Textron Inc Improvements in or relating to water-dispersible drying oil compositions
EP0303066A2 (fr) * 1987-07-24 1989-02-15 Henkel Kommanditgesellschaft auf Aktien Agent lubrifiant utilisé dans la fabrication de fils ou filaments synthétiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB989252A (en) * 1961-01-10 1965-04-14 Textron Inc Improvements in or relating to water-dispersible drying oil compositions
EP0303066A2 (fr) * 1987-07-24 1989-02-15 Henkel Kommanditgesellschaft auf Aktien Agent lubrifiant utilisé dans la fabrication de fils ou filaments synthétiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 86, no. 12, 21. März 1977, Columbus, Ohio, US; abstract no. 74879r, T.C. RAO; ET AL 'Preparation and surface-active properties of poly(oxyethylene) glycol (600) monoesters of fatty acids' Seite 124 ;Spalte 2 ; *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007741A1 (fr) * 1993-09-15 1995-03-23 Henkel Kommanditgesellschaft Auf Aktien Polymeres sequences contenant des groupes ester, utilises comme agents antimoussants pour des systemes aqueux
WO1996016728A1 (fr) * 1994-12-02 1996-06-06 Henkel Kommanditgesellschaft Auf Aktien Emulsion d'eau dans l'huile
US5863461A (en) * 1994-12-02 1999-01-26 Henkel Kommanditgesellschaft Auf Aktien Water-in-oil emulsions

Also Published As

Publication number Publication date
DE4216418A1 (de) 1993-11-25

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