WO2006025738A1 - Polyester prepare a partir de l'acide phosphorique ou ses oligomeres - Google Patents

Polyester prepare a partir de l'acide phosphorique ou ses oligomeres Download PDF

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Publication number
WO2006025738A1
WO2006025738A1 PCT/NL2005/000632 NL2005000632W WO2006025738A1 WO 2006025738 A1 WO2006025738 A1 WO 2006025738A1 NL 2005000632 W NL2005000632 W NL 2005000632W WO 2006025738 A1 WO2006025738 A1 WO 2006025738A1
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Prior art keywords
polyester
phosphoric acid
oligomers
polyol
anyone
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PCT/NL2005/000632
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English (en)
Inventor
Stanislaw Penczek
Jacobus Antonius Loontjens
Krzysztof Kaluzynski
Julia Pretula
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Dsm Ip Assets B.V.
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Publication of WO2006025738A1 publication Critical patent/WO2006025738A1/fr

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    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon

Definitions

  • the invention relates to substantially linear polyesters prepared from phosphoric acid and/or its oligomers, a method for their preparation and their use.
  • Polyesters containing phosphorus in the backbone or side chains are known for example from biology in nucleic and teichoic acids.
  • these nucleic and teichoic acids are not substantially linear, are not prepared from phosphoric acid and/or its oligomers, are much more complex and comprise within their structure nitrogen-containing bases and sugars. Their technical application on a larger scale is not possible.
  • Polyesters containing phosphorus in the backbone or side chains are described for example in Macromolecules 1993, 26, 2228-2233. However the phosphorus- containing polyester described there is highly branched and not substantially linear and is not prepared starting from the three-functional phosphoric acid. Phosphorus- containing polymers are also described in Makromol. Chem. 178, 2943-2947 (1977). However the polymers described here contain a phosphorus- hydrogen bond. The presence of the P-H bond makes the adjacent ester bonds very susceptible to hydrolysis. Additionally this polymer is prepared starting from a cyclic phosphor-compound and not from phosphoric acid.
  • substantially linear polyesters without nitrogen in its structure and prepared from a) phosphoric acid and/or its oligomers and b) at least one polyol are not yet known.
  • the substantially linear polyesters prepared from phosphoric acid and/or its oligomers according to the invention can advantageously be represented by the following overall formula (I):
  • R is independently of each other the group -(CR 1 R 2 ) n -O m -(CR 1 R 2 ) q - or
  • R 1 is independently of each other: -H, -OH 1 -OROH, -OROP(O)Q 2, or an alkyl group with 1-5 carbon atoms
  • R 2 is independently of each other: -H 1 -OH, -OROH, -OROP(O)Q 2 , or an alkyl group with 1-5 carbon atoms
  • n is a natural number 1-12 m is O or 1 q is a natural number 1-12 x represents the number of linear fragments and is a natural number 0-50 y represents the number of branched fragments and is a natural number 0-49
  • Q is independently of each other -OH or -OROH Z is independently of each other -OROH or -OROP(O)Q 2 .
  • R 1 R 1 and R 2 are the groups and atoms derived from the polyol that is used to prepare the polyester according to the invention.
  • polyol is meant here and hereinafter an alcohol with two or three hydroxyl-groups.
  • R 1 and R 2 are independently of each other: -H, -OH, or an alkyl group with 1-5 carbon atoms, more preferably -H, or an alkyl group with 1-5 carbon atoms.
  • the linear and branched fragments are randomly distributed along the polyester backbone. When reference is made to linear or branched, the distribution around the phosphorus atom is considered.
  • substantially linear polyester is here and hereinafter meant that the number of linear fragments exceeds the number of branched fragments, thus x being larger than y (x > y).
  • the number of linear fragments exceeds the number of branched fragments with a factor of at least 2 (x ⁇ 2y), more preferably the number of linear fragments exceeds the number of branched fragments with a factor of at least 5 (x ⁇ 5y), even more preferably the number of linear fragments exceeds the number of branched fragments with a factor of at least 10 (x ⁇ 1Oy).
  • Most preferably the number of branched fragments is O.
  • the number of linear and branched fragments can be determined by 31 P-NMR.
  • repeating linear units (x) and repeating branched units (y) can vary between within wide ranges.
  • the numbers for linear and branched units are independent from each other.
  • x will vary between O and 50.
  • x is between 1 -40, more preferably between 2- 30.
  • y will vary between 0 and 49.
  • y is between 1-39, more preferably between 2-29.
  • the substantially linear polyesters according to the invention are itself almost colourless, have an increased hydrolytic stability and are substantially linear.
  • the polyesters according to the invention are advantageously used in various compositions, for example a composition comprising, in addition to the polyester according to the invention, also at least one other polymer that is structurally and/or chemically distinct from the polyester according to the invention, or a composition comprising, in addition to the polyester according to the invention, at least one crosslinker, or a composition comprising, in addition to the polyester according to the invention, at least one crosslinker and at least one additive and optionally one or more pigments and one or more fillers.
  • the substantially linear polyesters according to the invention are advantageously used as a flame retardant or primer or adhesion improver.
  • the invention also relates to a method of preparation of polyesters directly from a) phosphoric acid and/or its oligomers and b) at least one polyol.
  • a readily available source of phosphor is phosphoric acid and/or its oligomers. Starting from this kind of phosphor source an alcohol source would be needed to arrive at the ester stage. However it is generally known to the man skilled in - A -
  • phosphoric acid is tri-functional, that is, it has three acid groups available for reaction, it is expected to lead to excessive gelation under normal esterification conditions.
  • the invention also relates to a process for the preparation of a polyester based on phosphoric acid and/or its oligomers.
  • the process for the preparation of the polyesters uses only these components a) and b).
  • the process for the preparation of a polyester based on a) phosphoric acid and/or its oligomers and b) at least one polyol comprises at least the following steps: a. combining and mixing the phosphoric acid and/or its oligomers with the at least one polyol, b. reacting the phosphoric acid and/or its oligomers with the at least one polyol.
  • polyol It is possible in the preparation process according to the invention to use one kind of polyol, but it is also possible to use a combination of different polyols.
  • different polyols is both meant: two or more alcohols with the same functionality but with a different chemical structure and two or more alcohols with a different functionality.
  • An example of the first combination of "different alcohols” is ethylene glycol with hexane diol (2-functional).
  • An example of the second combination of "different alcohols” is ethylene glycol (2- functional) combined with trimethylolpropane (3-functional).
  • “functionality” in relation to the polyol is meant the number of hydroxyl- groups that is available for reaction. It has been found advantageous to use only 2-functional polyols (so-called “diols”).
  • polyols examples include substituted and unsubstituted aliphatic and cyclo-aliphatic polyols and polyetherpolyols.
  • the polyols advantageously contain between 1-50 carbon atoms.
  • polyols are used with 1-30 carbon atoms, more preferred between 1-20 carbon atoms.
  • polystyrene resin examples include ethylene glycol, propylene glycol, butane diol, heptane diol, cyclohexyldimethylol, 1 ,4- butene diol, diethylene glycol, trimethylolpropane, di(trimethylolpropane), glycerol, hexanetriol, trimethylol ethane and combinations of any of them.
  • ethylene glycol, propylene glycol and/or diethylene glycol are used.
  • Phosphoric acid and/or its oligomers are being used in the process according to the invention.
  • Phosphoric acid is widely known and generally available. It is possible in the process according to the invention to use anhydrous phosphoric acid, however it is also possible to use phosphoric acid that contains a small amount of water. However anhydrous phosphoric acid is preferred as in that case less water needs to be removed from the production process.
  • Suitable oligomers of phosphoric acid are triphosphoric acid and polyphosphoric acid.
  • substantially linear polyesters that can be prepared with the process according to the invention it is advantageous to use only the compounds a) phosphoric acid and/or its oligomers and b) at least one polyol, with the exclusion of other components.
  • the man skilled in the art of polyester synthesis knows how the phosphoric acid and/or its oligomers and the polyol should be combined and can easily find the conditions where under reaction will take place. It has been found advantageous for obtaining higher yields on the di-ester compared to the tri-ester, to add the polyol to the phosphoric acid and/or its oligomers.
  • the process of the invention can advantageously be used for the preparation of substantially linear polyesters.
  • Substantially linear polyesters that can be prepared with the process according to the invention can be described by the following formula: Formu
  • R is independently of each other the group -(CR 1 R 2 ) n -O m -(CR 1 R 2 ) q - or -(CR 1 R 2 HCR 1 R 2 )-
  • R 1 is independently of each other: -H, -OH, -OROH, -OROP(O)Q 2, or an alkyl group with 1-5 carbon atoms
  • R 2 is independently of each other: -H, -OH, -OROH, -OROP(O)Q 2 , or an alkyl group with 1-5 carbon atoms n is a natural number 1-12 m is O or 1 q is a natural number 1-12 x represents the number of linear fragments and is a natural number 0-50 y represents the number of branched fragments and is a natural number 0-49 Q is independently of each other -OH, -OROH
  • Z is independently of each other -OROH or -OROP(O)Q 2 .
  • R, R 1 and R 2 are the groups and atoms derived from the polyol that is used to prepare the polyester according to the invention.
  • R 1 and R 2 are independently of each other: -H, -OH, or an alkyl group with 1-5 carbon atoms, more preferably -H, or an alkyl group with 1-5 carbon atoms.
  • the linear and branched fragments are randomly distributed along the polyester backbone.
  • the process will comprise at least the following steps: a. combining and mixing the phosphoric acid and/or its oligomers with the at least one polyol, b. reacting the phosphoric acid and/or its oligomers with the at least one polyol, c. and heating the phosphoric acid and/or its oligomers or heating the at least one polyol or heating both, whereby optional step c) can be performed in any order relative to step a) and b).
  • the best reaction temperature depends on the chemical nature of the polyol. The man skilled in the art can easily determine the best temperature.
  • the reaction according to the invention of ethylene glycol with phosphoric acid can advantageously be performed between 50-200 0 C, preferably at a temperature between 75-140°C, more preferably at a temperature between 90-110°C.
  • the process will comprise at least the following steps: a. combining and mixing the phosphoric acid and/or its oligomers with the at least one polyol, b. reacting the phosphoric acid and/or its oligomers with the at least one polyol, c. heating the phosphoric acid and/or its oligomers or heating the at least one polyol or heating both, whereby optional step c) can be performed in any order relative to step a) and b), d. adding a catalyst, whereby the addition of the catalyst can be performed in any order relative to step a) b) and c).
  • the catalysts that were found to be advantageous were metal salts.
  • metal salt catalysts were used wherein the metal has a configuration of 3d- and 4s- outer electron shells, especially Stannum and the elements with number 21 to 30 in Mendeleyev's table (as presented on the inside cover of the Handbook of Chemistry and Physics, 65 th edition, CRC Press Inc.) preferably the elements with number 21-28.
  • the catalyst can be added to the reaction in its salt-form or it can be added in its metallic-form whereupon a salt is formed in-situ in the reaction mixture. It is possible to use one catalyst, however it is also possible to use a mixture of catalysts.
  • Especially preferred catalysts are derivatives of Sc, Ni, Cr, Co and Sn.
  • the counter ions to the metal ion can be chosen more or less freely.
  • Preferred counter ions are acetate, trifluoromethanesulphonate, chloride, octanoate and 2-ethylhexanoate.
  • the molar ratio between the phosphoric acid and the polyol is not particularly critical and can be chosen between broad ranges, for example between 10:1 and 1 :10.
  • a preferred ratio acid-to-polyol is chosen between 5:1 and 1 :5, more preferably the ratio is chosen between 1 :3 and 2:1 , most preferably the ratio acid-to- polyol is approximately 1 :1.
  • the reaction between phosphoric acid and/or its oligomer and the polyol can be performed in the bulk without any solvent or in a solvent.
  • the reaction is performed in the bulk.
  • a dry, inert gas is applied.
  • the polymerisation is preferably conducted in such a way as to enable continuous removal of water.
  • a purge gas stream can be applied, for example nitrogen, argon or helium.
  • a solvent as reaction medium.
  • a solvent it should be chosen so as to be inert towards the reactants, phosphoric acid and/or its oligomers and the polyols used.
  • solvents inert compounds can be used that form azeotropes with water. In such a case the reaction can be performed at the boiling temperature of the azeotrope.
  • suitable solvents are benzene, toluene, xylene, heptane, cyclohexane, and methyl-cyclohexane and combinations of any of them.
  • a combination of benzene and toluene is used.
  • a preferred ratio between benzene and toluene is 1 ;1 ,5 (on volume basis).
  • the polyesters prepared according to the invention are generally built on chains of poly (di-esters of phosphoric acid).
  • the polyesters prepared may also contain fragments with higher orders of polyester, for example tri-esters of phosphoric acid.
  • the group Z in formula I is -OROP(O)Q 2 .
  • the amount of poly(tri-esters) formed is less than 33 mol% relative to the total of products formed.
  • the amount of poly(tri-esters) formed is less than 17 mol%, even more preferred the amount of poly(tri-esters) formed is less than 9 mol% More preferably the prepared polyesters are only built on chains of poly (di-esters of phosphoric acid), thus the amount of poly(tri-esters) being 0 mol%.
  • the end groups, Q can be the same or different and are dependent on the reaction conditions and especially on the relative amounts of the components during the preparation. The end groups can therefore be a hydroxyl-group or a group represented by -OROH.
  • both groups at the same P that are represented in formula I by Q are hydroxyl-groups (-OH)
  • the unity at the end of the polyester chain can be regarded as a mono-ester of phosphoric acid
  • 1 Q-group is a hydroxyl- group and the other Q at the same P is represented by -OROH
  • the unity at the end of the polyester chain can be regarded as a di-ester of phosphoric acid
  • both Q- groups at the same P are represented by -OROH
  • the unity at the end of the polyester chain can be regarded as a tri-ester of phosphoric acid.
  • the polyester according to the invention will generally have acid groups available. These acid groups originate from the phosphoric acid or its oligomer.
  • the polyester will also have hydroxyl-groups available. It is preferred to have a polyester with both acid- and hydroxyl- functionality. It is even more preferred to have a polyester with a higher acid value than hydroxyl-value.
  • the final product from the preparation process can contain moieties with the same or with different structures. In the last case, where the structures are different, a mixture of molecules that differ structurally is formed.
  • the final product can have a linear character, however it is also possible with the process according to the invention to obtain branched and/or star-shaped polyesters. Even cyclic structures are possible, for example as represented in Formula II:
  • i and h are natural numbers, independently chosen between 1-10.
  • i and h are chosen so as to form a 5-, 6-, or 7- membered ring structure
  • k is a natural number between 1-99.
  • the value for k can be regulated with the amount of triol that is used in the preparation of the polyester.
  • the polyester according to the invention or the polyester prepared according the process of the invention can be used in industry as such or, for example, in a composition.
  • the invention therefore also relates to the use of the polyesters according to the invention.
  • the polyester according to the invention can for example be used as a flame retardant.
  • the polyester can be used in a process for improving the flame retardancy of a composition that comprises at least a polymer B.
  • polymer B is meant a polymer that is chemically or structurally different from the polyester according to the invention.
  • Polymer B is regarded to be the matrix material and can be chosen from any material that is able to suit the mechanical and/or aesthetical requirements of the part to be produced.
  • the outcome of the process is a composition with improved flame retardancy. This result can be obtained by adding to the composition comprising at least polymer B, a polyester according to the invention.
  • the polyester is described above in more detail.
  • the composition can contain more than one polymer; it can also in addition to the at least one polymer contain usual additives and fillers.
  • the amount of the flame-retardant polyester according to the invention is generally less than 50 % compared to the weight of polymer B.
  • the amount of flame-retardant polyester is related to the total amount of polymers making up polymer B.
  • the amount of flame-retardant polyester according to the invention is less than 35%, more preferably less than 25%, most preferably less than 15%.
  • Polymer B can be chosen from a wide range of polymers. Its choice is more or less determined by the structural or aesthetical properties of the object that is finally obtained from the flame-retardant composition.
  • polystyrene examples include polyethylene, polypropylene, polyisobutene, and ethylene-propylene rubber, as for example EPM and EPDM-rubber. More preferred is polypropylene.
  • Polyamides are for example nylon-6, nylon-6,6, nylon-6,10, nylon-6,12, nylon-11 , and nylon-12.
  • Polyesters are for example polyethylene terephthalate and polybutylene terephthalate.
  • the polyester according to the invention can for example be used as a primer or adhesion improver of a composition on a substrate.
  • the polyester can be used in a process for improving the adhesion of a composition on a substrate.
  • the outcome of the process is a composition with improved adhesion.
  • This result can be obtained by adding to the composition a polyester according to the invention.
  • the polyester according to the invention can for example be used as a dispersion agent.
  • the dispersion agent can improve the dispersion of for example pigments or fillers in a composition, preferably a coating composition.
  • the polyester can be used in a process for improving the dispersion of a component in a composition.
  • the outcome of the process is a composition with improved dispersion of the component.
  • Examples of components that benefit from an improved dispersion are pigments and fillers.
  • the polyester is described above in more detail.
  • the substrate is not particularly critical as it turned out that the polyester according to the invention improves the adhesion of all kinds of compositions on all kinds of substrates both of an organic and inorganic nature. It especially improved the adhesion of coating compositions.
  • substrates are: metal, glass, ceramics, stone, concrete, paper, cardboard, wood, leather, cork and plastic.
  • the invention also relates to a composition
  • a composition comprising at least a. one polyester based on a ⁇ phosphoric acid and/or its oligomers and a 2 ) at least one polyol and b. at least one crosslinker.
  • Polyester a. is the polyester according to the invention and is as described above. By combining polyester a. with at least one crosslinker it is possible to obtain a crosslinked network. Such a crosslinked network is advantageously obtained on the surface of a substrate, thereby forming a coating on the surface.
  • any known crosslinker that is able to react with the functional groups on polyester a. can be used. Examples of suitable crosslinkers are:
  • crosslinkers of the epoxy type for example triglycidyl isocyanurate
  • polyisocyanates for example caprolactam blocked IPDI (isophorone diisocyanate) derivatives, uretidione of IPDI, TDI (toluene diisocyanate) derivatives, TMXDI (tetramethylxylene diisocyanate) derivatives, or trimers thereof
  • IPDI isophorone diisocyanate
  • TDI toluene diisocyanate
  • TMXDI tetramethylxylene diisocyanate
  • polyphenols for example polyphenols of the resol or novolac type
  • amino resins for example alkylated melamine or benzoguanimine resins.
  • alkylated melamine is hexamethoxymethylmelamine (HMMM).
  • hexamethoxymethylmelamine or an epoxy resin crosslinker is used.
  • the amount of crosslinker is not particularly critical, however depending on the nature of the crosslinker and the polyester and the functionality of both, the amount of crosslinker is optimised so that the obtained coating after curing is able to fulfil the chemical, mechanical and other requirements.
  • the crosslinker is present in an amount of at least 0,1 w% relative to the sum of polyester and crosslinker, preferably at least 1 w%, more preferred at least 5 w%, most preferred at least 7 w%.
  • the crosslinker is present in an amount less than 50 w% relative to the sum of polyester and crosslinker.
  • the crosslinker is present in an amount of not more than 30 w%, more preferable not more than 20 w%, most preferable not more than 15 w%.
  • the composition can optionally contain other polymers that take part in the formation of a network.
  • other polymer is meant a polymer that is structurally and/or chemically different from the polyester according to the invention.
  • suitable optional other polymers are polyolefin, polyamide, polystyrene, saturated or unsaturated polyester, polycarbonate, polyurethane, polyepoxy, acrylic resin, phenol resin, polyphenylene.
  • suitable functional groups that are reactive to the crosslinker used need to be present in or on the polymer.
  • the optional polymer is a polyester.
  • a coating composition generally comprises next to the binder of the composition according to the invention, one or more customary additives, optionally one or more fillers and optionally one or more pigments.
  • the invention also relates to such a coating composition.
  • additive is generally meant a substance that is added in a small quantity and which has a particular chemical or technological effect.
  • additives are: degassing agents, dispersing agents, flow control agents, flow- promoting agents, rheology-influencing agents, anti- or de-foaming agents, (light)stabilizers, thickeners, wetting agents, anti-skinning agents, anti-sedimentation agents, anti-flocculation agents, adhesion promoters, structural additives, gloss- enhancing additives, catalysts, and flatting agents.
  • stabilizers are: primary and/or secondary antioxidants, UV stabilizers for example quinones, (sterically hindered) phenolic compounds, phosphonites, phosphites, thioethers and HALS compounds (hindered amine light stabilizers).
  • degassing agents are benzoin and cyclohexane dimethanol bisbenzoate.
  • flow agents include polyalkylacrylat.es, fluorohydrocarbons and silicone fluids.
  • suitable additives are for example additives for improving tribocharging, for example sterically hindered tertiary amines that are described in EP-B-0.371.528.
  • filler is generally meant a compound that gives the coating material a greater volume (body).
  • fillers are: chalk, talcum, metal oxides, silicates, carbonates and sulphates.
  • pigment is generally meant a finely divided colouring compound.
  • the pigment can be of an organic or inorganic nature. Examples are titanium dioxide, carbon black, pearlescent pigments, zinc phosphate, zinc sulphide, iron oxide and chromium oxide.
  • a suitable example of an organic compound is the group of azo compounds.
  • a difference is made between a pigment and a dye, whereby the dye is regarded as a colouring compound that dissolves in the composition.
  • dyes are incorporated within the term pigments.
  • the coating composition according to the invention can next to the binder and the at least one additive and optional filler and pigments, contain one or more solvents and/or dispersants.
  • solvent is meant a liquid or blend of liquids that is able to dissolve the binder. Examples include butyl acetate, butyl glycol, white spirit and water.
  • Dispersants are liquids that do not dissolve the binder but instead hold them in a dispersion or emulsion. Examples are water and in non-aqueous dispersions hydrocarbons. The invention will be further illustrated in the following, non-limitting, examples.
  • esters, pyrophosphates and unreacted H 3 PO 4 were expected in the reaction mixture.
  • Esters of orthophophoric acid are classified according to the number of ester groups in the phosphate group: mono-ester, di-ester and tri-ester.
  • the 31 P NMR spectra were measured at 24,2 MHz on a JeolFX60 apparatus, with 85 wt% H 3 PO 4 as an external standard.
  • reaction product is a mixture of products of the polymerization degree ⁇ 8, with the following end-groups: either acid at both ends or alcohol at both ends as well as the acid group on one side and the alcohol group on the other side. These products contain both in repeating units and in the end-groups, segments of di- and triethylene glycols. GLC analysis of the hydrolysis products revealed, that these units do not exceed triethylene glycol.
  • the hydrolysis products were obtained by decomposition of the polyesters at elevated temperature, in the presence of an aqueous solution of p-toluenesulfonic acid.
  • Example V A mixture of 5.49 g (0.056 mole) H 3 PO 4 , 5.52g (0.089 mole) ethylene glycol and 0.0126g (2.56-10 "5 mole) scandium trifluoromethanesulfonate (catalyst) was placed in a round bottom flask equipped with a magnetic stirrer, condenser and azeotropic head and refluxed under normal pressure for 140 hours under a separate phase of benzene/toluene (1 :1.5 v/v) mixture boiling at 100 0 C. At the chosen times samples of the reaction mixture were removed and the proportions of mono-, di-, and triesters were determined with 31 P- NMR method.
  • Example Vl 6.97 g (0.071 mole) of H 3 PO 4 and 6.77 g (0.109 mole) of ethylene glycol (EG) (the initial ratio of reagents ([EG] 0 / [H 3 P0 4 ] o 1.54) were put into a two-neck flask equipped with a magnetic stirrer and the mixture was heated for 300 hours at a temperature of 100 0 C on an oil bath in a stream of slowly flowing argon. Samples were taken at certain points in time and their ester- content was determined with the 31 P- NMR method as described above. The following results were obtained: after 50 hours: 15.8% of monoesters and 13.8% of diesters. After 100 hours: 25.4% of monoesters and 29.4% of diesters.
  • EG ethylene glycol
  • the mixture contains compounds of the polymerisation level ⁇ 5.
  • the compounds are bilaterally ended with acid groups, alcohol groups, as well as the acid group at one side and the alcohol group at the other side.
  • EG ethylene glycol

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention a trait à de nouveaux polyesters sensiblement linéaires préparés directement à partir de l'acide phosphorique et/ou de ses oligomères et au moins un polyol. Les nouveaux polyesters peuvent être représentés par la formule générale (1). L'invention a également trait à un procédé pour la préparation de ces nouveaux polyesters sensiblement linéaires. Les nouveaux polyesters sensiblement linéaires peuvent être utilisés dans le liant d'une composition de revêtement; ils peuvent également être utilisés dans d'autres compositions tels qu'un ignifugeant ou une amorce ou un agent d'amélioration d'adhérence.
PCT/NL2005/000632 2004-09-02 2005-09-01 Polyester prepare a partir de l'acide phosphorique ou ses oligomeres WO2006025738A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7638201B2 (en) 2006-05-05 2009-12-29 Rohm And Haas Company Acid functional phosphorus-containing polyester powder compositions and powder coatings made therefrom

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US3275667A (en) * 1959-02-24 1966-09-27 Hoechst Ag Process for the manufacture of phosphate ester derivatives of polyalkylene glycols
EP0000125A1 (fr) * 1977-06-15 1979-01-10 Bayer Ag Esters tensio-actifs de l'acide phosphorique et leur utilisation.
EP0259681A2 (fr) * 1986-09-01 1988-03-16 Vianova Kunstharz Aktiengesellschaft Procédé pour la préparation de liants modifiés par l'acide phosphorique et diluables à l'eau, pour vernir au four
JPH08106139A (ja) * 1994-10-05 1996-04-23 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

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US7638201B2 (en) 2006-05-05 2009-12-29 Rohm And Haas Company Acid functional phosphorus-containing polyester powder compositions and powder coatings made therefrom

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