EP2643379A1 - Procédé de fabrication de mousses souples de polyuréthane - Google Patents

Procédé de fabrication de mousses souples de polyuréthane

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Publication number
EP2643379A1
EP2643379A1 EP11784513.1A EP11784513A EP2643379A1 EP 2643379 A1 EP2643379 A1 EP 2643379A1 EP 11784513 A EP11784513 A EP 11784513A EP 2643379 A1 EP2643379 A1 EP 2643379A1
Authority
EP
European Patent Office
Prior art keywords
component
weight
hydroxyl
glycol
parts
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11784513.1A
Other languages
German (de)
English (en)
Inventor
Norbert Hahn
Sven Meyer-Ahrens
Gundolf Jacobs
Bernd Dohmen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Intellectual Property GmbH
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 Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Priority to EP11784513.1A priority Critical patent/EP2643379A1/fr
Publication of EP2643379A1 publication Critical patent/EP2643379A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8051—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/36
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

Definitions

  • the present invention relates to a process for producing flexible polyurethane foams, wherein the starting material used is an isocyanate component (component B) which contains hydroxyl-containing fatty acid derivatives.
  • the novel flexible polyurethane foams have a density according to DIN EN ISO 3386-1-98 in the range of> 10 kg / m 3 to ⁇ 150 kg / m 3 , preferably from> 20 kg / m 3 to ⁇ 70 kg / m 3 and in In general, their compressive strength according to DIN EN ISO 3386-1-98 is in the range of> 0.5 kPa to ⁇ 20 kPa (at 40% deformation and 4th cycle).
  • a reaction mixture of organic polyisocyanates and solutions of chain extenders of the molecular weight range from 62 to 400 in higher molecular weight polyhydroxyl compounds of the molecular weight range from 1800 to 12000 with the cooperation of catalysts, internal mold release agents and optionally other auxiliaries and additives implemented.
  • Internal mold release agents discussed herein are ester group-containing condensation products having a molecular weight range of 900-4500, an acid value of less than 5 mg KOH / g and a hydroxyl number of 12.5 to 125 mg KOH / g of 3 to 15 moles of ricinoleic acid and one mole of a or polyhydric alcohol in the molecular weight range of 32 to 400 or a total of one mole of a mixture of a plurality of such alcohols.
  • the flexible polyurethane foam should have a good tear strength ("green strength") immediately after production.
  • Containing component A polyol formulation
  • A2 0.5 to 25 parts by weight, preferably 2 to 5 parts by weight (based on 100 parts by weight of the
  • Component AI water and / or physical blowing agents
  • Component AI auxiliaries and additives such
  • A4 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight (based on 100 parts by weight of component A I) of isocyanate-reactive hydrogen atoms having compounds having a molecular weight of 62-399,
  • component B comprising one or more polyisocyanates (B l) and one or more hydroxyl-containing fatty acid derivatives (B2),
  • Component A (Polyol Formulation)
  • the process according to the invention is distinguished by the fact that the polyol formulation is free of hydroxyl-containing fatty acid derivatives.
  • the individual components A I to A4 of the polyol formulation are explained below.
  • Starting components according to component AI are conventional polyether polyols.
  • Conventional polyether polyols in the context of the invention are compounds which comprise alkylene oxide addition products of starter compounds having Zerewitinoff-active hydrogen atoms, ie polyether polyols having a hydroxyl number according to DIN 53240 of> 15 mg KOH / g to ⁇ 80 mg KOH / g, preferably of> 20 mg KOH / g to ⁇ 60 mg KOH / g.
  • starter compounds having Zerewitinoff-active hydrogen atoms usually have functionalities of 2 to 6, preferably of 3, and preferably the starter compounds are hydroxy-functional.
  • hydroxyfidictionelle Starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-l, 5-pentanediol, 1, 12-decanediol, Glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, catechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, methylol-containing condensates of formaldehyde and phenol or melamine or urea
  • Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide and styrene oxide.
  • propylene oxide and ethylene oxide are fed to the reaction mixture individually, in a mixture or in succession. If the alkylene oxides are metered in succession, the products produced contain polyether chains with block structures. Products having ethylene oxide endblocks are characterized, for example, by increased levels of primary end groups, which impart advantageous isocyanate reactivity to the systems.
  • Component A2 Component A2
  • component A2 water and / or physical blowing agents are used.
  • physical blowing agents for example, carbon dioxide and / or volatile organic substances are used as blowing agents.
  • auxiliaries and additives are used as component A3.
  • surfactants such as emulsifiers and foam stabilizers in particular those with low emission such as products of the Tegostab ® LF series
  • additives such as reaction retarders (eg acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or Fatty alcohols or dimethylpolysiloxanes), pigments, dyes, flame retardants (such as tricresyl phosphate), stabilizers against aging and weathering, plasticizers, fungistatic and bacterio-static substances, fillers (such as barium sulfate, diatomaceous earth, carbon black and whiting) and release agents.
  • reaction retarders eg acidic substances such as hydrochloric acid or organic acid halides
  • cell regulators such as paraffins or Fatty alcohols or dimethylpolysiloxanes
  • pigments such as paraffins or Fatty alcohols or dimethylpolysiloxanes
  • pigments such as paraffins or Fatty alcohols
  • auxiliaries and additives are described, for example, in EP-A 0 000 389, pages 18 to 21. Further examples of auxiliaries and additives optionally to be used according to the invention as well as details on the use and mode of action of these auxiliaries and additives can be found in the Plastics Handbook, Volume VII, edited by G. Oertel, Carl Hanser Verlag, Kunststoff, 3rd edition, 1993, for example, on pages 104-127.
  • the catalysts used are preferably aliphatic tertiary amines (for example trimethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (for example 1,4-diaza (2,2,2) bicyclooctane), aliphatic aminoethers (for example dimethylaminoethyl ether and N, N, N-trimethyl-N- hydroxyethyl bisaminoethyl ether), cycloaliphatic amino ethers (for example N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as, for example, aminoalkyl ureas, see, for example, EP-A 0 1 76 013, in particular (3-dimethylaminopropylamine) urea) and tin catalysts (such as dibutyltin oxide, dibutyltin dilaurate, tin
  • ß) amines and amino ethers which each contain a functional group which reacts chemically with the isocyanate.
  • the functional group is a hydroxyl group, a primary or secondary amino group.
  • These particularly preferred catalysts have the advantage that they have a greatly reduced migration and emission behavior. Examples of particularly preferred catalysts are: (3-dimethylaminopropylamine) - H fur, 2- (2-dimethylaminoethoxy) ethanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N, N, N-trimethyl N-hydroxyethyl bisaminoethyl ether and 3-
  • component A4 compounds containing at least two isocyanate-reactive hydrogen atoms and a molecular weight of from 32 to 399 are used as component A4. These are to be understood as meaning hydroxyl-containing and / or amino-containing and / or thiol-containing and / or carboxyl-containing compounds, preferably hydroxyl-containing and / or amino-containing compounds which serve as chain extenders or crosslinkers. These compounds generally have from 2 to 8, preferably from 2 to 4, isocyanate-reactive hydrogen atoms. For example, ethanolamine, diethanolamine, triethanolamine, sorbitol and / or glycerol can be used as component A4. Further examples of compounds according to component A4 are described in EP-A 0 007 502, pages 16-17.
  • Component B in the sense of the invention is an NCO-terminated urethane-containing prepolymer obtainable by reacting one or more polyisocyanates (B1) with one or more hydroxyl-containing fatty acid derivatives (B2).
  • the urethane-group-containing prepolymer according to component B preferably has an NCO content of from 5 to 31% by weight, more preferably from 12 to 30% by weight, most preferably from 15 to 29% by weight.
  • Component B 1 and B2 are preferably reacted by the methods known per se to those skilled in the art.
  • the components B 1 and B2 may be mixed at a temperature of 20 to 80 ° C to form the urethane group-containing prepolymer.
  • reaction of component Bl and B2 is completed after 30 minutes to 24 hours to form the NCO-terminated urethane group-containing prepolymer.
  • activators known to the person skilled in the art can be used for the preparation of the NCO-terminated urethane group-containing prepolymer.
  • Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of the formula (I)
  • n 2 - 4, preferably 2 -3,
  • Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 6 to 13 C atoms, or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, C atoms.
  • polyisocyanates for example 2,4- and 2,6-toluene diisocyanate, and any desired mixtures of these isomers
  • polyphenyl polymethylene polyisocyanates such as are prepared by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates (“modified polyisocyanates”), in particular those modified polyisocyanates derived from 2,4- and / or 2,6-toluene diisocyanate or from 4,4'- and / or 2,4'-diphenylmethane diisocyanate is preferably derived as polyisocyanate, at least one compound selected from the group consisting of 2,4- and 2,6-toluene diisocyanate, 4,4'- and 2,4 ' - and 2,4 - and 2,
  • hydroxyl-containing fatty acid derivatives in the context of the invention are hydroxyl-containing fatty acids, hydroxyl-containing fatty acid esters (such as hydroxyl-containing fatty acid triglycerides or hydroxyl-containing fatty acid diglycerides), and esters of fatty acids with an alcohol component which are monohydric and / or polyhydric alcohols having a molecular weight of> 32 g / mol to ⁇ 400 g / mol, understood.
  • Hydroxyl-containing fatty acids are, for example, castor oil
  • hydroxyl-containing fatty acid triglycerides are, for example, castor oil and lesquerella oil.
  • hydroxyl-group-containing fatty acids it is also possible to use ring-opened epoxidized or oxidized fatty acids as hydroxyl-group-containing fatty acids.
  • hydroxyl-containing fatty acid derivatives and hydroxylated fatty acid compounds based on rapeseed oil soybean oil, rapeseed oil, olive oil and / or sunflower oil and / or those based on oil and / or linoleic acid can be used.
  • at least one polyricinoleic acid ester is used as hydroxyl-containing fatty acid derivative.
  • the polyricinoleic acid esters are obtainable by reaction of ricinoleic acid with an alcohol component comprising mono- and / or polyhydric alcohols having a molecular weight of> 32 g / mol to ⁇ 400 g / mol and wherein the reaction is carried out at least partially in the presence of a catalyst.
  • Polyricinolklareester can be obtained for example by polycondensation of ricinoleic acid and mono- or polyhydric alcohols, the polycondensation is preferably carried out in the presence of a catalyst.
  • the amount of catalyst based on the total mass of ricinoleic acid and the alcohol component, for example in a range of> 10 ppm to ⁇ 100 ppm.
  • the polyricinoleic acid esters used preferably have an acid number of less than 25 mg KOH / g, particularly preferably less than 5 mg KOH / g.
  • the Polyricinolklareester used preferably have a hydroxyl number of> 30 mg KOH / g to ⁇ 80 mg KOH / g.
  • the hydroxyl number can be determined according to DIN 53240 and may also be> 40 mg KOH / g to ⁇ 60 mg KOH / g or> 45 mg KOH / g to ⁇ 50 mg KOH / g.
  • Suitable monohydric or polyhydric alcohols may include, but are not limited to, alkanols, cycloalkanols and / or polyether alcohols. Examples are n-hexanol, n-dodecanol, n-octadecanol, cyclohexanol, 1,4-dihydroxycyclohexane, 1,3-propanediol, 2-methylpropanediol-l, 3, 1,5-pentanediol, 1,6-hexanediol, 1, 8-octanediol, sorbitol, pentaerythritol, glucose, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tripropylene glycol, glycerol and / or trimethylolpropane.
  • the alcohols mentioned have boiling points at which a discharge can be avoided together with water of reaction and tend at the usual reaction temperatures also not to undesirable side reactions.
  • Catalysts or catalyst precursors suitable for the polycondensation can be Lewis or Bronsted acids, for example sulfuric acid, p-toluenesulfonic acid, tin (II) salts or titanium (IV) compounds, such as titanium tetrabutoxide or titanium (IV) alcoholates.
  • Lewis or Bronsted acids for example sulfuric acid, p-toluenesulfonic acid, tin (II) salts or titanium (IV) compounds, such as titanium tetrabutoxide or titanium (IV) alcoholates.
  • sulfuric acid is based on the molecule H2SO4. If the catalyst is a Lewis acid, the catalytically active cationic species is used.
  • the process preferably comprises as catalyst tin (II) salts.
  • catalyst tin (II) salts Particularly preferred here is tin (II) chloride. It has been found that tin (II) salts in a subsequent reaction of the Polyricinolklareesters to urethane group-containing prepolymers do not interfere and are therefore particularly advantageous.
  • the proportion of the catalyst for the polycondensation may, based on the total mass of the ricinoleic acid and the alcohol component, also in a range of> 20 ppm to ⁇ 80 ppm, preferably from> 40 ppm to ⁇ 60 ppm.
  • the polycondensation can be carried out at reduced pressure and elevated temperature while simultaneously distilling off the water formed during the condensation reaction. It can also be carried out by the azeotrope process in the presence of an organic solvent such as toluene as entrainer or by the carrier gas method, ie by expelling the resulting water with an inert gas such as nitrogen or carbon dioxide.
  • the reaction temperature in the polycondensation is preferably> 150 ° C to ⁇ 250 ° C.
  • the temperature may also range from> 180 ° C to ⁇ 230 ° C, and more preferably> 190 ° C to ⁇ 210 ° C. These temperature ranges represent a good balance between the desired reaction rate and possible undesired side reactions such as the elimination of water at the OH group of ricinoleic acid.
  • the reaction is preferably stopped when the acid number of the reaction product obtained is less than 25 mg KOH / g, preferably less than 5 mg KOH / g.
  • This value can be determined according to DIN 53402 and determined during the reaction, for example by sampling.
  • the termination of the reaction can in the simplest case by cooling the reaction mixture, for example, to a temperature ⁇ 50 ° C, take place.
  • the molar ratio of ricinoleic acid and the alcohol component is preferably in a range of> 3: 1 to ⁇ 10: 1.
  • this ratio is> 4: 1 to ⁇ 8: 1 and more preferably> 5: 1 to ⁇ 7: 1
  • ricinoleic acid and the alcohol component are first reacted without a catalyst.
  • the catalyst is then added when the water-forming reaction has stopped. Subsequently, the reaction is catalysed further carried out.
  • the fact that the reaction initially proceeds without catalyst means that no additional external catalyst is used.
  • the invention thus also relates to a process for the preparation of the flexible polyurethane foams according to the invention, wherein the polyricinoleic acid ester is obtainable by polycondensation of the ricinoleic acid and the alcohol component without catalyst at a temperature from> 150 ° C to ⁇ 250 ° C until the water formation reaction has come to a standstill, then adding the catalyst and further polycondensation at a temperature of> 150 ° C to ⁇ 250 ° C and distilling off the water formed until the acid number of the reaction mixture ( Polyricinoleic acid ester) is less than 25 mg KOH / g, preferably less than 5 mg KOH / g.
  • the formation of water is deemed to have come to a standstill if, after optical control of the reaction, no more water distils off or if more than 95% of the theoretical amount of water was removed from the reaction. This can be determined for example by a suitably equipped distillation template, a Dean-Stark apparatus or by weight control of the distillate formed. To determine the end of the formation of water, it is also possible, for example, to spectroscopically monitor the absorption behavior of COOH and / or OH groups in the NIR range. Then the reaction can be completed up to previously determined absorbance values.
  • a catalyst susceptible to hydrolysis for example titanium (IV) alcoholates, can be used only at a late point in time at which at least the majority of the water of reaction has already been separated off.
  • the reaction time is not adversely affected because the esterification reaction in the initial stage by the free COOH groups of Ricinolklareismeen is autocatalyzed and catalyst is introduced only when the reaction mixture begins to deplete of COOH groups.
  • the catalyst content is assumed in the case of Brönstedt acids of the neutral compound.
  • sulfuric acid is based on the molecule H2SO4.
  • the catalyst is a Lewis acid, the catalytically active cationic species is used.
  • the polyricinoleic acid esters used as component B2 generally have a catalyst content of> 20 ppm to ⁇ 80 ppm, preferably from> 40 ppm to ⁇ 60 ppm.
  • the urethane-containing prepolymer according to component B has an NCO content of from 5 to 31% by weight, more preferably from 12 to 30% by weight, most preferably from 15 to 29% by weight, and is obtainable by reacting Bl) polyisocyanate consisting of at least one component selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate and Polyphenylpolymethylenpolyisocyanat with
  • the reaction components are reacted according to the known one-step process, often using mechanical equipment, for example those described in EP-A 355 000. Details of processing equipment, which are also according to the invention in question, are described in Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl Hanser Verlag, Kunststoff 1993, for example, on pages 139 to 265 described.
  • the flexible polyurethane foams can be produced as molded or also as block foams.
  • the invention therefore provides a process for the production of flexible polyurethane foams, the flexible polyurethane foams produced by the process, the flexible polyurethane foams or flexible polyurethane foams produced by these processes, the use of the flexible polyurethane foams for the production of molded parts and the molded articles themselves
  • Flexible polyurethane foams are used, for example, for furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges and construction elements.
  • the index gives the percentage ratio of the actual amount of isocyanate used to the stoichiometric, i. for the implementation of OH equivalents calculated amount of isocyanate groups (NCO) amount.
  • Flexible polyurethane foams in the sense of the present invention are polyurethane polymers whose density in accordance with DIN EN ISO 3386-1-98 is in the range of> 10 kg / m 3 to ⁇ 150 kg / m 3 , preferably in the range of> 20 kg / m 3 to ⁇ 70 kg / m 3 and whose compressive strength according to DIN EN ISO 3386-1-98 in the range of> 0.5 kPa to ⁇ 20 kPa (at 40% deformation and 4th cycle).
  • Ricinoleic acid Oleo chemistry.
  • Al-1 polyether polyol having an OH number of about 28 mg KOH / g, prepared by addition of propylene oxide and ethylene oxide in the ratio 85 to 15 using glycerol as a starter with about 85 mol% primary OH groups.
  • Al-2 polyether polyol having an OH number of about 37 mg KOH / g, prepared by addition of propylene oxide and ethylene oxide in a ratio of 27 to 73 using glycerol as a starter with about 83 mol% primary OH groups.
  • Bl-1 mixture containing 57% by weight of 4,4'-diphenylmethane diisocyanate, 25% by weight of 2,4'-diphenylmethane diisocyanate and 18% by weight of polyphenylpolymethylene polyisocyanate
  • Multi-core MDI with an NCO content of 32.5% by weight.
  • NCO content based on the DIN 53185 standard The apparent density was determined in accordance with DIN EN ISO 3386-1-98.
  • the compression hardness was determined according to DIN EN ISO 3386-1-98 (at 40% deformation and 4th cycle).
  • the tensile strength and elongation at break were determined according to DIN EN ISO 1798.
  • the compression set DVR 50% (Ct) and DVR 75% (Ct) were determined according to DIN EN ISO 1856-2001-03 at 50% and 75% deformation, respectively.
  • the dephlegmatist temperature was fixed at 60 ° C.
  • the acid value was monitored in the course of the further reaction: the acid number was 10 mg KOH / g after a reaction time of 24 hours, 5 mg KOH / g after 48 hours, 3.5 mg KOH / g after 72 hours and 3 hours after 84 hours , 0 mg KOH / g.
  • the reactor contents were cooled to 130 ° C. Analysis of the resulting polyricinoleic acid B2-1:
  • Viscosity 850 mPas (25 ° C)
  • component Bl-1 1350.0 g of component Bl-1 were mixed with 133.0 g of component B2-1 for 2 min with a stirrer and then allowed to stand for 24 h at 25 ° C. Subsequently, the resulting product was mixed for 3 minutes and the NCO content was determined.
  • NCO content 29.35% by weight
  • component Bl-1 1350.0 g of component Bl-1 were mixed with 266, 1 g of component B2-1 for 2 min with a stirrer and then allowed to stand for 24 h at 25 ° C. Subsequently, the resulting product was mixed for 3 minutes and the NCO content was determined.
  • component Bl-1 1350.0 g of component Bl-1 were mixed with 399.2 g of component B2-1 for 2 min with a stirrer and then allowed to stand at 25 ° C. for 24 h. Subsequently, the resulting product was mixed for 3 minutes and the NCO content was determined.
  • Parts by weight Parts by weight
  • MV weight ratio of component A to component B at the specified index and based on 100 parts by weight of component A; in the case of Comparative Examples 1 and 2, the component B2-1 (polyricinoleic acid ester) used in the polyol formulation is added to component A and thus also to the sum of the parts by weight of component A;
  • phase separation was observed.
  • a second phase formed within 2 hours, in the case of Comparative Example 2 a second phase formed within 3 hours.
  • no phase separation was observed within an observation period of 24 hours.
  • polyurethane flexible foams of the invention (Examples 3 and 4) in which the Polyricinolklareester was processed in the form of a prepolymer, soft foams with good tear propagation resistance of the moldings could be produced directly during demolding.
  • the polyurethane flexible foams of Comparative Examples 1 and 2 were sensitive to demolding and cracked and showed significant surface disturbances.
  • Parts by weight Parts by weight
  • MV weight ratio of component A to component B at the specified index and based on 100 parts by weight of component A; in the case of Comparative Examples 1 and 2, the component B2-1 (polyricinoleic acid ester) used in the polyol formulation is added to component A and thus also to the sum of the parts by weight of component A;

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de fabrication de mousses souples de polyuréthane, dans lequel comme matière première est utilisé un composant isocyanate (composant B) qui contient des dérivés d'acides gras à teneur en groupe hydroxyle. Les mousses souples de polyuréthane selon l'invention présentent une masse volumique apparente selon DIN EN ISO 3386-1-98 se situant dans la plage de ≥ 10 kg/m3 à ≤ 150 kg/m3, de préférence de ≥ 20 kg/m3 à ≤ 70 kg/m3 et, en général, leur résistance à la compression selon DIN EN ISO 3386-1-98 se situe dans la plage de ≥ 0,5 kPa à ≤ 20 kPa (lors d'une déformation de 40 % et du quatrième cycle). L'invention concerne également un prépolymère à teneur en groupe uréthane terminé par NCO, pouvant être obtenu par réaction d'un ou plusieurs polyisocyanates (B1) avec un ou plusieurs dérivés d'acides gras (B2) à teneur en groupe hydroxyle.
EP11784513.1A 2010-11-22 2011-11-18 Procédé de fabrication de mousses souples de polyuréthane Withdrawn EP2643379A1 (fr)

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EP11784513.1A EP2643379A1 (fr) 2010-11-22 2011-11-18 Procédé de fabrication de mousses souples de polyuréthane

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EP10192093 2010-11-22
EP11784513.1A EP2643379A1 (fr) 2010-11-22 2011-11-18 Procédé de fabrication de mousses souples de polyuréthane
PCT/EP2011/070479 WO2012069385A1 (fr) 2010-11-22 2011-11-18 Procédé de fabrication de mousses souples de polyuréthane

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EP (1) EP2643379A1 (fr)
CN (1) CN103261257A (fr)
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CN104530380A (zh) * 2014-12-28 2015-04-22 甘肃银光聚银化工有限公司 一种慢回弹泡沫
CN104927019A (zh) * 2015-06-25 2015-09-23 淄博德信联邦化学工业有限公司 聚氨酯拖把海绵及其制备方法
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CN110862505B (zh) * 2019-10-10 2022-04-29 佳化化学(上海)有限公司 一种聚异氰脲酸酯泡沫及其制备方法
CN111171268B (zh) * 2020-01-22 2022-03-08 黎明化工研究设计院有限责任公司 一种耐热聚氨酯软质泡沫及其制备方法

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CN103261257A (zh) 2013-08-21
WO2012069385A1 (fr) 2012-05-31
US20130261203A1 (en) 2013-10-03
US9701804B2 (en) 2017-07-11

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