Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/42—Singly bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • 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
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/675—Low-molecular-weight compounds
  • C08G18/6765—Low-molecular-weight compounds containing the unsaturation at least partially in a cyclic ring having at least one oxygen atom in the ring
• • 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
  • C08G2115/00—Oligomerisation
  • C08G2115/02—Oligomerisation to isocyanurate groups

Definitions

• the present invention essentially relates to new furan polyols, the use of these as polyols in the formation of polyurethanes, polyurethanes thus obtained, and their process of preparation.
• the document FR-A-2 536 750 describes new furan compounds with terminal hydroxy groups, capable of forming active components of rigid compositions of urethane and isocyanurate with reduced inflammability.
• the use of 2,5-bis- (hydroxymethyl) furan (BHMF) is described, the chain extension of which is obtained by propoxylation (page 4, lines 6-12, examples 1, 2).
• BHMF homopolymers is recommended (page 4, line 13 to page 9, line 30; example 3, BHMFP table III, example 5, example 6, claims).
• BHMF has a low reactivity, which has greatly limited the use of it.
• the present invention therefore aims to solve the new technical problem of providing a solution for providing new polyols of the furan type capable of significantly improving the temperature resistance of polyurethanes, their dimensional stability to heat wet.
• new furan polyols are provided, characterized in that they are the reaction product: a) of a strain chosen from the group consisting of a polyalcohol, a monoamine or a polyamine, said polyol or said amine optionally containing at least one furan ring; and their mixtures; and b) a chain extender, optionally containing at least one furan ring, consisting of an organic epoxide, provided that this organic epoxide is a furan oxirane when said strain does not contain a furan ring; excluding 2,5bis- (hydroxymethyl) furan as sole strain, when the chain extender does not contain a furan ring.
• this aminoamine or polyamine is a primary or secondary amine.
• this amine can contain one or more hydroxy functions (groups).
• this amine contains at least one hydroxyl function, preferably at least two hydroxyl functions, this hydroxylated amine can be a tertiary amine.
• This hydroxylated amine simultaneously constitutes a polyalcohol according to the invention which is then aminated.
• the above-mentioned polyalcohol corresponds to the following chemical formula (I):
• the aforementioned polyalcohol is a furanic polyalcohol corresponding to the following formula:
• the starting polyalcohol is an aliphatic C 1 -C 4 polyalcohol, preferably chosen from ethylene glycol, propylene glycol, glycerin , trimethylolpropane, pentaerythritol, sorbitol.
• a (mono- or poly-) amine can contain one or more hydroxyl functions by constituting thus an amino polyalcohol, which can advantageously be obtained by reaction of a primary or secondary (mono- or poly-) amine with a chain extender agent consisting of the organic epoxide defined in the description, which can be a furanic epoxide.
• a chain extender agent consisting of the organic epoxide defined in the description, which can be a furanic epoxide.
• amine according to the starting invention NH 3 , methylamine, methylenediamine, ethylamine, ethylenediamine, propylamine, 1,3-propyldiamine, EDTA, as well as the corresponding hydroxylated mono- or polyamines.
• the abovementioned organic epoxide consists of propylene oxide.
• the abovementioned organic epoxide consists of the furan oxirane of formula (II)
• (X) represents either a carbon-carbon single bond, or an organic radical, preferably an aliphatic radical, advantageously having from 1 to 10 carbon atoms.
• this also covers the use of the aforementioned furan polyols to constitute part or all of the polyols used in the formation of polyurethanes including polyisocyanurates by reaction in particular with isocyanates.
• the present invention also covers polyurethanes, including polyisocyanurates, characterized in that they have been obtained by reaction of isocyanates with polyols at least part of which consists of furan polyols, as defined above.
• the invention also covers the process for the preparation of these furan polyols as defined in the claims.
• the new furan polyols according to the invention make it possible to improve, in a completely unexpected manner, the temperature resistance of the polyurethanes, their dimensional stability in humid heat.
• the improvement of the properties depends on the level of these furan polyols according to the invention in the mixture used for the preparation of the polyurethanes. It is preferred that the furan polyols according to the invention constitute the only polyols used in the reaction, although it is possible to use them in combination with other polyols.
• the proportion of the incorporation of the polyols according to the invention can be varied within wide limits. However, it is preferred to respect a number of NCO / OH number greater than or equal to 1 so as to have an NCO number in excess relative to the number of OH, in particular for forming polyisocyanurates.
• NCO / OH number greater than or equal to 1
• NCO number in excess relative to the number of OH, in particular for forming polyisocyanurates.
• the polyalcohol used is acetyl-3- (D-arabino-tetroxybutyl) 5-methyl 2-furan of the following formula
• a furan polyol is thus obtained having a hydroxyl number equal to 610, determined by the conventional method, and indicating the number of OH functions / kg of polyol expressed by weight of KOH.
• This furanic polyol is 4 and its viscosity expressed in centipoises at 20 ° C is equal to approximately 50,000.
• This furanic polyol is used for the preparation of polyurethane foams, bearing the reference F 1 , according to the following formulation, after have neutralized KOH with tartaric acid.
• Formulation F 1 Furanic polyol above: 100 parts Surfactant (Sr242 ® from Schell): 2 parts Catalyst
• the reaction is carried out in a conventional manner, and a cream time of 13 s and a thread time of 67 s are obtained.
• the characteristics of the foam are as follows: Density (kg / m 3 ): 23 apparent in free expansion ⁇ o (mW / m ° C): 0.023 ⁇ oo "": 0.029
• a furanic polyol is obtained having a hydroxyl number of 570, a functionality of 4, a viscosity in centipoises at 20 ° C. equal to approximately 45,000.
• a polyurethane foam formulation is made from this furanic polyol according to the following formulation referenced F 2 :
• Polyurethane foam is obtained by mixing these components, which has a cream time of 20 s and a yarn time of 80 s.
• the characteristics of this foam are as follows
• the starting polyalcohol is methyl acetate 3- (D-arabino-tetroxybutyl) 5-methyl 2-furan of the following formula:
• a furan polyol is thus obtained having a hydroxyl number equal to 570, a functionality of 4, and a viscosity in centipoises at 20 ° C. equal to approximately 45,000.
• Furanic polyol 100 parts
• the starting polyalcohol is 2,5-furfuryl dialcohol of the following formula:
• furyloxirane as chain extender, the proportion of furyloxirane being 64% by weight relative to the abovementioned furfuryl dialcohol, for 48 h, at room temperature, without catalyst.
• the furan polyol thus obtained has a hydroxyl number of 250, a functionality of 2 and a viscosity in centipoises at 2 ° C. equal to approximately 20,000.
• This formulation has an ultra-fast reaction speed, which does not make it possible to determine its cream time or its thread time.
• the characteristics of the polyurethane foam thus obtained are as follows: Density (kg / m 3 ) apparent in free extension: 27 ⁇ o (mW / m ° C): 21
• the starting polyalcohol of ethylene glycol is used as the aliphatic polyalcohol of formula CH 2 OH-CH 2 OH which is reacts with furyloxirane of the following formula:
• the furan polyol thus obtained has a hydroxide number equal to 500, a functionality of 2 and a viscosity in centipoises at 20 ° C. equal to approximately 20,000.
• the mixture of these components makes it possible to prepare the polyurethane foam which has a cream time of 15 s and a thread time of 20 s.
• the starting polyalcohol is glycerol - (aliphatic polyalcohol of formula CH 2 OH-CHOH-CH 2 OH) which is reacted with furyloxirane of the following formula:
• the furyloxirane preparation being 338% by weight relative to the glycerol, for 6 hours and at room temperature with 0.5% of KOH catalyst.
• the furan polyol thus obtained has a hydroxyl number of 590, a functionality of 3.
• the mixture of these components makes it possible to prepare the poyurethane foam which has a cream time of 24 s and a wire time of 39 s.
• the triethanolamine of the following formula (HOH 2 C-CH 2 ) 3 N which is reacted with furyloxirane as chain extender, according to the ratio of 220% by weight relative to the triol, is used as starting polyalcohol. that is to say three molecules of furyloxirane for one molecule of polyol.
• the reaction takes place without a catalyst and starts around 50 ° C while being quite exothermic.
• the furan polyol thus obtained has a hydroxyl number of 470 for a functionality of 3.
• This polyol is used to manufacture a furan polyurethane foam according to the following formulation F 7 :
• This formulation has a cream time of 35 s and a thread time of 57 s.
• the characteristics of the foam obtained are as follows:
• non-furan amino polyol sold by the company DOW CHEMICAL under the reference RA 505, having a hydroxyl number equal to 505, which is a polyol for the production of rigid polyrethane foams of excellent performance, is used as polyol.
• This polyol is used as it is for the formulation of polyurethane foam under the formulation referenced CF 9 below:
• Pore-forming agent 40 parts
• Pore-forming agent (Freon ® 11): 40 parts
• strain used can comprise one or more furan cycles.
• a hydroxylated amine is used which can in this case be a tertiary amine, as previously indicated.
• a preferred example is triethanolamine.
• the polyol produced by the reaction according to the invention may contain furan rings in the chain or pendant from this same chain depending on the position and / or the number of functional groups on the furan ring.
• furan epoxide in particular a furan oxirane of formula II above, is very advantageous because it is very reactive and avoids the use of a basic catalyst type KOH which must be neutralized thereafter, because the polyols do not have to be basic since basicity reduces the reaction with isocyanates.
• Example 4 demonstrates this, no catalyst being used, it can be observed that, even while carrying out the reaction at room temperature, which is a considerable commercial advantage, the duration of the reaction is completely acceptable, that is to say 48 h. Thus, by working at moderate temperatures, for example around 50 ° C., the reaction time is greatly reduced.
• the starting strain can itself be obtained by reaction of a primary or secondary amine (mono- or polyamine) with a chain extender agent preferably formed by an organic epoxide which can be an organic epoxide as defined above.
• the strain is not a liquid, it can advantageously be pasted with extended polyol before carrying out the oxylation.
• the temperature is regulated to a fixed value adjustable between the ambient and 160 ° C according to the nature of the oxyranne and according to the reactivity of the strain used. Raising the temperature accelerates the reaction rate without adding basic catalyst, such as KOH, from about 0 to 250 ppm as well.
• the durations can thus range from a few hours to more than 1 day, as the examples show.
• polyalcohol obtained by the process described in EP-0 234 065, preferably the polyalcohols obtained in Examples 1 to 3.

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

Applications Claiming Priority (2)

Publications (1)

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• 1986
  • 1986-12-12 FR FR8617441A patent/FR2608155B1/fr not_active Expired - Fee Related
• 1987
  • 1987-12-07 IN IN1044/DEL/87A patent/IN170508B/en unknown
  • 1987-12-10 AU AU10512/88A patent/AU618244B2/en not_active Ceased
  • 1987-12-10 US US07/229,169 patent/US4973715A/en not_active Expired - Fee Related
  • 1987-12-10 BR BR8707933A patent/BR8707933A/pt not_active Application Discontinuation
  • 1987-12-10 JP JP63500567A patent/JPH02501654A/ja active Pending
  • 1987-12-10 EP EP88900234A patent/EP0336932A1/de not_active Withdrawn
  • 1987-12-10 HU HU88471A patent/HU205097B/hu not_active IP Right Cessation
  • 1987-12-10 KR KR1019880700922A patent/KR890700123A/ko not_active Application Discontinuation
  • 1987-12-10 WO PCT/FR1987/000491 patent/WO1988004295A1/fr not_active Application Discontinuation
  • 1987-12-12 CN CN198787108373A patent/CN87108373A/zh active Pending
• 1988
  • 1988-08-11 DK DK450388A patent/DK450388A/da not_active Application Discontinuation
• 1989
  • 1989-05-17 MW MW27/89A patent/MW2789A1/xx unknown
  • 1989-06-09 SU SU894614483A patent/SU1759233A3/ru active
  • 1989-06-12 OA OA59593A patent/OA09455A/xx unknown
  • 1989-06-12 FI FI892872A patent/FI892872A/fi not_active Application Discontinuation

Non-Patent Citations (1)

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