• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The new furanic polyalcohols are characterized in that they are the reaction product: a) of a stock selected amongst the group comprised of a polyalcohol, a monoamine or a polyamine, said polyol or said amine containing optionally at least one furanic cycle; and mixtures thereof; and b) of a chain extension agent containing optionally at least one furanic cycle comprised of an organic epoxide, with the condition that said organic epoxide is a furanic oxirane when said stock contains no furanic cycle; with the exclusion of 2,5bis-(hydroxymethyl)furane only as a stock, when the chain extension agent contains no furanic cycle. These furanic polyalcohols are used for the preparation of polyurethane foams having improved properties.
    公开号:SU1759233A3
    申请号:SU894614483
    申请日:1989-06-09
    公开日:1992-08-30
    发明作者:Рукс Габриель；Риверо Жанин；Гандини Александро
    申请人:Сантр Сьянтифик Э Текник Дю Батиман (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to furan polyols, which are intermediate products of polyurethane foams.
    Known new furan compounds with terminal hydroxyl groups capable of forming the active components of the solid compositions of isourethane and isocyanurate with low flammability, namely, it is known to use
    2,5-bis- (oxymethyl) -furan (BOMF), to obtain polyurethane foams that are resistant to heat.
    However, BOMF has poor reactivity, which greatly limits its use.
    In addition, the mechanical properties of the polyurethanes obtained on its basis are unsatisfactory.
    The purpose of the invention is to obtain new furan-type polyols capable of improving the temperature resistance of polyurethanes and their dimensional stability to wet heating.
    This goal is achieved by the fact that the substrate formed by the polyol of the formula a-7CH -CH 2 he, 0H / n where A is (d-Cd-hydroxyalkyl, or a group of the formula
    1759233 AZ
    where Ri is Cd-Cd-alkyl, (d-Cd-hydroxyalkyl:
    R 2 is a hydrogen atom. St-Sm-acyl. C1-C4 alkoxycarbonyl:
    From - a hydrogen atom;
    η is an integer equal to 1-3 or A means an amine of the formula
    -Ν (R 4 ) 3 ; where R4 is “C1-C4-alkyl. substituted by hydroxy.
    react with an epoxy compound of the formula
    About where Rs is C1 ~ C4-alkyl or 2-furyl, provided that Rs is 2-furyl, the substrate does not contain a furan ring, except when using as a substrate
    2,5-bis (hydroxymethyl) furyl.
    New furan polyols can improve the resistance of polyurethanes to temperature, their dimensional stability in conditions of humidity and temperature.
    The improvement in properties depends on the content of these furan polyols in the mixture used to make the polyurethanes. It is preferred that furan polyols be used fully as polyols used in the reaction, although they can be used in combination with other known polyols.
    The number of polyols can vary widely. However, it is preferred that the ratio of the number of NCO groups and the number of OH groups is greater than or equal to 1, so that the NCO groups are in excess with respect to the number of OH groups, in particular for the production of polyisocyanurates.
    Using polyols, it is possible to obtain all types of polyurethanes or polyisocinaturates, solid or flexible, foamed or not foamed, in whatever way they are obtained.
    Example 1. As the polyol use 3-acetyl-5- (D-arabinotetroxybuti l) -2-methyl l furan n.
    It is introduced into interaction with propylene oxide, taken as a chain extension agent, with the mass fraction of propylene oxide relative to said polyol being 57%. The reaction is carried out for 6 hours at 150 ° C. using 250 ppm KOH as a catalyst.
    In this way, a furan polyol having a hydroxyl number of 610 determined by the classical method is obtained and indicating the number of OH functions per kg of polyol, expressed in units of KOH weight.
    The functionality of this furan polyol is 4 and its viscosity at 20 ° C. is approximately 50,000 cps.
    This furan polyol is used to obtain polyurethane of new Fi foams based on the following formulation after neutralization of KOH with tartaric acid.
    Wording Fi. h:
    Specified Furan Polyol100
    Surfactant (Sr 242®'de Schell) 2
    Catalyst (DMASNA ^ de BASF) 2
    Water1
    Pore-forming agent (freon40
    Isocyanate MDI170
    First, for 13 s with a creamy consistency of the medium, then for 67 s with a fiber-forming consistency of the medium (Cream time is the time the reaction started from the moment of mixing the components, creamy consistency; The time of the thread corresponds to the beginning of polymer gelation and is determined by the beginning of the formation of the thread when the core in contact with the surface of the foamed polyurethane filament-forming consistency).
    The characteristics of the foam are as follows: apparent bulk density of 23 kg / cm 3 with free expansion; λο (m W / m ° C) 0.023; Aoo (m W / m ° C) 0.029; the temperature of the end of decomposition of urethanes 320 ° C; weight loss 26%; ΔΡ at 400 ° C 39%; Δν / U (after 14 days at 70 ° C and 95% relative humidity) 2.4%.
    Example 2. As the polyol, ethyl acetate 3- (0-arabinotetroxybutyl) -5-methyl-2-furan is used, which is reacted with propylene oxide, a chain extension agent, with propylene oxide accounting for 52 wt.% Of the indicated furan polyol, the reaction is carried out in 20 hours at 180 ° C without catalyst.
    A furan polyol having a hydroxyl number of 570, a functionality of 4, and a viscosity at 20 ° C. of about 45,000 cps is obtained.
    Get polyurethane foam from this furan polyol contained in the formulation of F 2 .
    Wording F 2 , h:
    Specified Polyol 100
    Surfactant (Sr 242 ^ Schell) 2
    Catalyst (DM СНА® BASF firms) 2 H 2 O 1 Blowing agent 40 (freon®)MDI Isocyanate , 160
    By mixing these components, a polyurethane foam is obtained, which has a creamy consistency of 20 s and a thread-forming consistency of 80 s.
    The characteristics of this foam are as follows: apparent bulk density of 21 kg / m 3 with free expansion; the temperature of the end of decomposition of urethanes 340 ° C; weight loss 33%; Δ P at 400 ° C 45%: Δ V / V (after 14 days at 70 ° C, 95% relative humidity) 2%.
    Example 3. 3- (D-apa6nnotetroxybutyl) -5-methyl-2-furan methyl acetate is used as the starting polyol, which is reacted with prolene oxide as a chain extension agent, with a proportion of propylene oxide on May 52. %, relative to the specified furan, for 9 hours at 180 ° C without catalyst.
    In this way, a furan polyol having a hydroxyl number of 570, a functionality of 4, and a viscosity at 20 ° C. of about 45,000 cps is obtained.
    Wording F3, h:
    Furan Polyol100
    Surfactant (Sr 242® Schell) 2
    Catalyst (DMSNA®BASF) 2
    H 2 O1
    Foaming Agent (Freon-) 40
    Isocyanate MDI160
    With this formulation, a creamy consistency time of 38 s is obtained, a thread-forming consistency time of 75 s and the resulting polyurethane foam has the following characteristics: apparent bulk density of 22 kg / m 3 ; with free expansion Ao (m W / m ° C) 20; temperature of the end of decomposition of urethanes 320 ° С; weight loss 38%; Δ P at 400 ° C 42.5; Δ V / V (after 14 days at 70 ° C and a relative humidity of 95%) 3%.
    Example 4. As the starting polyol using 2,5-furfuryl alcohol of the following formula
    Н0Н 9 С -VX СН2ОН, L О, which is reacted with furyloxyran as a chain extension agent, with the proportion of furyloxiran being 64 wt.% With respect to the specified furfuryl diatomic alcohol, for 48 h at room temperature without a catalyst.
    Thus, the resulting furan polyol has a hydroxyl number of 250, a functionality of 2, and a viscosity at 20 ° C. of about 20,000 cps.
    Thus, the obtained polyol is used to formulate a polyurethane pen according to the formula F4, h:
    Specified Furan Polyol100
    Surfactant (Sr 242® Schell) 2
    Catalyst (DM СНА 1 ® BASF) 2
    H 2 O1
    Foaming Agent (Freon®) 40
    MDI79 isocyanate
    Inactive Reactive Fluid Agent5
    This formulation has an ultrafast reaction rate, which does not allow to determine either the time of the creamy state / nor the time of thread formation.
    The characteristics of the polyurethane foam thus obtained are as follows: apparent bulk density of 27 kg / m 3 with free expansion; JU (m W / m ° C) 21; the temperature of the end of decomposition of urethanes 330 ° C; weight loss 17%; ΔΡ at 400 ° C 42%; ΔΥ / V (after 14 days at 70 ° C and 95% relative humidity) 2%.
    Example 5. Ethylene glycol is used as the starting polyol as an aliphatic polyol of the formula CH 2 ONCH 2 OH, which is reacted with furyloxyran, the fraction of furyloxiran being 72% by weight with respect to ethylene glycol, for 24 hours at 55 ° C without a catalyst.
    The furan polyol thus obtained has a hydroxyl number of 500, a functionality of 2, and a viscosity at 20 ° C. of about 20,000 cps.
    Thus obtained furan polyol is used to formulate a polyurethane foam of the formula Fs, h:
    The specified furan polyol 100
    Surfactant (Sr 242®Schell) 2 Catalyst (DMSNA®BASF) 2
    H 2 O1
    Foaming Agent (Freon 8 ) 40
    MDI isocyanate 142
    The mixing of these components allows to obtain a polyurethane foam, which has a residence time of 15 s in a creamy state and a fiber formation time of 20 s.
    The characteristics of this foam thus obtained are as follows: apparent bulk density of 24 kg / m 3 with free expansion: Lo (m W / m ° C) 20; the temperature of the decomposition of urethanes 300 ° C; weight loss 21%; Δ P at 400 ° C 31%; AV / V (after 14 days at 70 ° C and 95% relative humidity) 3%.
    Example 6. As the starting polyol, glycerol (an aliphatic polyol of the formula CHgOH-CHONHSNgON) is used, which is reacted with furyloxyran. moreover, the preparation of furyloxiran is 338 wt.% with respect to glycerol, for 6 hours and at room temperature with 0.5% KOH catalyst.
    Thus obtained furan polyol has a hydroxyl number of 590, functionality 3. It is used to formulate a polyurethane foam of the formula F6, h:
    Specified Furan Polyol100
    Surfactant (Sr 242® Schell) 2
    Catalyst (DMSNA® BASF) 2
    H 2 O .1
    Foaming Agent (Freon ) 40
    Isocyanate MDI112
    The mixing of these components allows you to prepare a polyurethane foam, which has a residence time in a creamy state of 24 s and a threading time of 39 s.
    The characteristics of the foam are as follows: apparent bulk density of 27.9 kg / m 3 with free expansion: L (m W / m ° C) 21.0; the temperature of the end of decomposition of urethanes 340 ° C; weight loss 24%; ΔΡ at 400 ° С 35%: Δ V / V (when kept for 7 days) 0.4%; at 70 ° C and a relative humidity of 95% for 15 days, 0.8%.
    Example 7 (with amine). As the starting polyol, triethanolamine of the following formula HOH2C-CH2 / 3 N. is used which is reacted with furyloxyran as a chain extender at a content of 220 wt.%, I.e. three furyloxiran molecules per polyol molecule. The reaction is carried out without a catalyst and at a temperature of about 50 ° C becomes exothermic.
    Thus obtained furan polyol has a hydroxyl number of 470 for functionality 3. This polyol is used for the manufacture of polyurethane furan foam according to the formula F7, h:
    Specified Furan Polyol100
    Surfactant (Sr 242® * Schel!) 2
    Catalyst (DMSNA ^ BASF) 0.5
    H 2 O1
    Foaming Agent (Freon®) 40
    MDI134 Isocyanate
    This formulation has a cream residence time of 35 s and a thread formation time of 57 s. ,
    The characteristics of the resulting foam are as follows: apparent bulk density of 28 kg / m 3 with free expansion; La (m W / m ° C) 21.7; the temperature of the end of decomposition of urethanes 320 ° C; weight loss 31%; ΔΡ at 400 ° C 41%; Δν / V at 70 ° C, 95% relative humidity after 28 days 3%.
    Example 8 (comparative). As the polyol, an amine-containing polyol, not furan, RA 505 is used, which has a hydroxyl number of 505 and which is a polyol for producing solid polyurethane foams with excellent performance.
    This comparative polyol is used for the manufacture of polyurethane foams formulations SBV, h:
    Polyol RA 505100
    Surfactant (Sr 242®SchtllL2
    Catalyst DAVCO 33L®3P product5
    NgO2
    Foaming Agent (Freon®) 40
    Isocyanate MDI143
    The reaction between these components allows one to obtain a polyurethane foam having a creamy time of 11 s and a thread formation time of 28 s, and this foam has the following characteristics: apparent bulk density of 27.6 kg / m 3 with free expansion of 27.6: Lo (t W / m ° C) 17.2: the end temperature of the decomposition of urethanes 350 ° C; weight loss 51%: Δ P at 400 ° C 60%; Δ V / V (at 70 ° C and relative humidity 95%) after 14 days 10.1%,
    Example 9 (comparative). Use the classic polyol P 130. which has an average hydroxyl number of 460. and which is considered to give solid polyurethane foams with excellent performance.
    This polyol is used to make the polyurethane foam formulation.
    CFg h:
    Polyol P 130 100
    Surfactant (SR 242 R Schell) 2 Catalyst (DAVCO 33 LV ER product) 5
    Foaming Agent (Freon R ) 40
    Izbtsianat MD14154
    The reaction between these components allows to obtain a polyurethane foam, which has a creamy time of 11 s and a thread formation time of 44 s, and which has the following characteristics: apparent bulk density of 23.1 kg / m 3 with free expansion; I about (t W / rn ° C) 0.021; the temperature of the end of the decomposition of urethanes 330 ° C: weight loss 41%; A P at 400 ° C 52.5%; AV / V (at 70 ° C, 95% relative humidity) after 14 days, 10.8%. after 1 day 4.9%.
    Example 10 (comparative). Use the polyol obtained by oxypropylation of 2,5-bis- (hydroxy) -furan having a hydroxyl number of 515. to formulate the following polyurethane foam CF10, h:
    Polyol2-B100
    Surfactant (Sr 242 R Schell) 2
    Catalyst
    DAVCO 33LV R ER product5
    H 2 O2
    Foaming Agent (Freon R 11) 40
    Isocyanate MDI162
    The reaction between these components allows you to get a polyurethane foam, which has a residence time in a creamy state of 17 s and a threading time of 32 s. and has the following characteristics: apparent bulk density of 25.3 kg / m 3 with free expansion; Ao (m W / m ° C) 23; the temperature of the end of the decomposition of urethanes 330 ° C: weight loss of 37%; Δ P at 400 ° C 46%; AV / V (at 70 ° C. 95% relative humidity) after 13 days 20%; after 20 days - 26.5%.
    Comparative examples 8 and 10 make it possible to demonstrate an improvement in the properties obtained with furan polyols and the percentage weight loss of polyurethane is 21-31%. and when using BOMF - 37%.
    Explanation of abbreviations used: AR - weight loss of the sample subjected to thermal analysis (ie, weight loss depending on temperature): Δ V / V - dimensional changes in the sample subjected to accelerated aging, referred to its original volume; DAVCO Lud R - diazobicyclooctane-based catalyst; Freon R - product C DS 11 (chlorine-fluoro-carbon) used in polyurethane compositions; Surfactant - Sr 242 R Schell is a silicone based surfactant.
    权利要求:
    Claims (2)
    [1]
    Claim
    A method for producing furan polyols, which are intermediate products of polyurethane foams, based on a polyol and an epoxy compound, characterized in that, in order to increase the resistance of polyurethane foams when heated at high humidity, the substrate formed by a polyol of the formula a- / cn-cn 2 he , he / n where A is C1 ~ C <hydroxyalkyl or a group of the general formula where Ri is CadC ^ -alkyl, CgCd-hydroxyalkyl;
    R 2 is hydrogen, C1-C4 acyl, Cr ~ C4 alkoxycarbonyl;
    Of is hydrogen;
    η is an integer equal to 1-3, or A means an amine of the General formula
    N (R4) 3!
    where R4 is C1 ~ C4 alkyl substituted with hydroxy, is reacted with an epoxy compound of the general formula o
    where Rs is C1-C4 alkyl or 2-furyl, provided that Rs is 2-furyl, the substrate does not contain a furan ring, with the exception of. when used as a substrate
    [2]
    2,5-bis (hydroxymethyl) furyl.
    类似技术:
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    同族专利:
    公开号 | 公开日
    JPH02501654A|1990-06-07|
    DK450388A|1988-08-11|
    EP0336932A1|1989-10-18|
    FR2608155B1|1990-09-14|
    AU618244B2|1991-12-19|
    FR2608155A1|1988-06-17|
    FI892872A0|1989-06-12|
    MW2789A1|1989-11-08|
    KR890700123A|1989-03-02|
    FI892872A|1989-06-12|
    WO1988004295A1|1988-06-16|
    CN87108373A|1988-07-13|
    DK450388D0|1988-08-11|
    AU1051288A|1988-06-30|
    IN170508B|1992-04-04|
    HU205097B|1992-03-30|
    OA09455A|1992-11-15|
    US4973715A|1990-11-27|
    BR8707933A|1990-03-01|
    引用文献:
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    US4426460A|1981-08-10|1984-01-17|Quaker Oats Company|Polyurethanes or isocyanurates from alkoxylated hydroxymethylfuran|US5831100A|1995-06-07|1998-11-03|Agouron Pharmaceuticals, Inc.|Syntheses of optically pure compounds useful as GARFT inhibitors and their intermediates|
    US5814011A|1996-04-25|1998-09-29|Medtronic, Inc.|Active intravascular lung|
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    US9290698B2|2010-07-15|2016-03-22|Battelle Memorial Institute|Biobased polyols for potential use as flame retardants in polyurethane and polyester applications|
    CN109111413B|2018-09-29|2020-08-21|南京工业大学|Total biological vegetable oil polyalcohol and preparation method and application thereof|
    CN112939906B|2021-02-07|2022-01-25|南京工业大学|Vegetable oil polyalcohol without suspension chain, preparation method and application thereof in polyurethane material|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8617441A|FR2608155B1|1986-12-12|1986-12-12|NOVEL FURANNIC ALCOHOLS, USE OF THE SAME AS POLYOLS IN THE FORMATION OF POLYURETHANES, POLYURETHANES THUS OBTAINED AND THEIR PREPARATION METHOD|
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