• 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:
    Non-fluorinated epoxy resins of known type are crosslinked by means of polyfunctional perfluoropolyethers containing groups which are reactive with the epoxy groups and/or with the hydroxy groups present in the starting re­sin. The thus-obtained crosslinked products having a fluori­ne content of not more than 20% by weight, preferably from 5% to 15%, are endowed with a set of properties typical of the corresponding fluorinated resins with a much higher fluorine content, in particular, water- and oil-repellence, resistance to hydrolysis and to solvents, minimum water absorption.
    公开号:SU1660584A3
    申请号:SU874202604
    申请日:1987-05-13
    公开日:1991-06-30
    发明作者:Ре Альберто；Донати Джанни
    申请人:Аусимонт С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing hardened fluorine-containing products based on epoxy resins cured by a simple perfluoropolyether, which have improved water resistance, hydrolysis resistance and organic solvents, a reduced coefficient of friction and can be used as adhesives, construction materials, coatings, sealants and etc.
    The purpose of the invention is to obtain solid products with a low fluorine content based on epoxy resins.
    Example 1.100 g of a liquid epoxy-aia resin with an average equivalent weight of epoxide 190 is mixed at 25 ° C under a nitrogen atmosphere with 81.1 g of a compound of the formula
    H2NXO / 0-CH20 (C2F40); r7 (CF20) f7-fH20-O) -NH2
    0.5 1 (O
    where, 8; , 6,
    average mol. mass 624 (this compound was obtained by reaction of the diol HOCH2 (C2F40) m (CF2O) nCH20H with parafluoronitrobenzene and subsequent reaction with LI AIH / i) The molar ratio of the equivalent of NH2 - epoxy groups is 0.25. 0.5 cm3 of a 0.2 M solution of diethylenediaminobiicycloheptane in acetone is introduced into this mixture. After degassing in vacuum, crosslinking is carried out at 70 ° C for 2 hours and then at 150 ° C for 4 hours.
    The resulting resin contains 16.5% by weight of fluorine, the contact angle of wetting with water is 88 °, the dielectric constant is 3.2 and the volume specific electrical resistance is 8 x 15 Ohm-cm (), the water absorption is 0.1% .% (after 96 h at 70 ° C and a relative humidity of 100%).
    PRI me R 1 a (comparative). Epoxy resin is prepared using diaminodiphenylmethane instead of compound (I), the equivalent ratio of epoxy groups - NH2 is 0.5.
    The following characteristics were obtained: contact angle of wetting with water 45 °; dielectric constant 4.0; volume resistivity of 6.5 to 1015 ohm-cm (25 ° C); water absorption 0.35 wt.%.
    Example 2 100 g of an epoxide resin with an average equivalent weight of epoxide 2000 are mixed at 35 ° C under nitrogen with 57.5 g of a compound of the formula
    CH3-0-HNCO- (c2F,) m (CF2OVCONHXO CH5 DYNCO
    00
    where, 7;
    ,five,
    with an average mol. mass 2300 (this compound was obtained by chemical reaction at 120 ° С of toluene diisocyanate with a perfluoropolyether dibasic acid). 0.5 cm3 of a 0.2 M solution of dibutyl tin diacetate in acetone is introduced into the mixture. The molar ratio of epoxy groups and -NCO-groups is 1. The mixture is stirred for 5 minutes, de-aerated and cross-linked at 50 ° C for 20 hours, and then at 80 ° C for 2 hours.
    A pure resin with a fluorine content of 19.5 wt.%, A contact wetting angle of 90 °, a friction coefficient of 0.15 is obtained.
    Example 2a (comparative). The process is carried out according to example 2, but instead of compound (II) methylenediphenyldiisocyanate is used at the indicated molar ratio of epoxy groups and -NCO-rpynn.
    A crosslinked resin is obtained with the following characteristics: 40 ° contact wetting angle; friction coefficient 0,35.
    Example 3. 100 g of a liquid epoxydiamine resin with an equivalent weight of 190 are mixed under nitrogen at 30 ° C with 73 g of fluorinated dianhydride of the formula; .
    ("24-oV 5o (| P
    where, 8;
    „P 12 3 8
    It is obtained from a pertopropylether diol with CHzOH-terminal groups CP3ZOZR and (C2Hb) 3M. The product with terminal, CHaOSOaCFs groups reacts
    ° ML-Ј GSO S
    SOGSN-)
    then hydrolysis and dehydration is carried out with acetic anhydride with a mole of 694. The ratio of anhydride to epoxy groups is –0.4.
    After deaeration under vacuum, the mixture is cured at 150 ° C for 10 hours and at 180 ° C for 2 hours,
    The resulting resin contains 13t9 wt.% Fluorine, glass transition temperature 150 ° C; dielectric constant 3.4; water absorption 0.3 wt.% after 96 hours immersion at 100 ° C.
    Example For (comparative). The process is carried out according to Example 3, but instead of using compound (III), methylnadic acid anhydride is used at the indicated ratio anhydride-epoxide. The water absorption of the obtained resin is 1.7% by weight.
    Example 4. UOg of a liquid epoxy-dian resin with an equivalent weight of 190 (0.52 equivalents), 32.4 g of hexahydrophthalic anhydride (0.21 mol), 60.4 g of fluorinated dianhydride of the formula
    0
    five
    (IV /
    PP-oc 24c o) m- (cF2o) n-cHzo- {Qr; 0
    P
    - -oo
    where, 8; 5, 3,
    with mol. mass 2300 (0,026 mol) and 0.2 g diethylenediaminebicycloheptane mixed in 500 ml of anhydrous acetone. After evaporation of the solvent, the mixture is solidified for 1 hour at 100 ° C and then for 8 hours at 150 ° C.
    Example 5 (comparative). 100 g of fluorinated epoxy polymer, obtained by condensation of 0.2 m of biophenol A, 0.2 M of perforated polyetherdiol MM-400 and 1.2 M of epichlorohydrin with epoxy-equivalent, 420 are mixed with 18.3 g (0.119 mol) of hexahydrophthalic anhydride and 0.15 g diethylenediaminebicycloheptane. Curing is carried out under the conditions specified in Example 4.
    Example 6 (comparative). 100 g of fluorinated epoxy polymer according to example 5 with an equivalent weight of 420 (0.238 equivalents) are mixed with 500 ml of acetone with 136 (0.059 mol) of fluorinated dianhydride according to example 4 and 0.2 g of diethylenediaminebicycloheptan. After evaporation of the solvent, the mixture is crosslinked under the conditions of example 4,
    Example 7 (comparative). 100 g of a liquid resin bisphenol A - epichlorohydrin with an equivalent weight of 190 (0.26 mol) is mixed with 40 g (0.52 equivalents) of hexahydrophthalic anhydride and 0.15 g of diethylenediaminobicycloheptane. The mixture is cured under the conditions of example 4.
    Example 8. 100 g of an epoxy resin with an equivalent weight of 190 are mixed in a stream of nitrogen at 30 ° C with 65 g of acetic anhydride and 1.5 g of a perfluoropolyether diacid of the formula
    HOOCCF20-iC2F40) m- (CF20) n-CF2COOH where, 2;
    ,
    with an average mole weight of 2000, and 1 g of N-butylimidazole is added as a catalyst to accelerate the reaction. After evacuation, the mixture is cured at 65 ° C for 1 hour and then at 150 ° C for 40 hours. A resin with a glass transition temperature of 46 ° C, a dielectric constant of 2.3 (25 ° C / 50 Hz), and a dielectric resistance of 28 , 4 kW-mm 1 (25 ° С). bulk resistance of 1015 ohm-cm (25 ° C) / These results with the results of tests of resins obtained without the use of fluorinated diacid. The fluorine content in the resulting resin is 0.45%.
    Example 9. 100 g of an epoxy-dian resin with an equivalent weight of 190 is mixed with 55 g of acetic anhydride, 15 g of fluorinated anhydride


    ten
    20
    CF30 () nCFjCH20-CO
    about
    -
    s °;
    where, 2, mol. mass 870, obtained by reaction of trimethylitic anhydride with the corresponding perfluoropolyether alcohol (final group СНаОН) and 1 g of butylimidazole as a catalyst for acceleration. After removing gaseous products, the mixture is cured at 165 ° C for 1 h and kept at 150 ° C for 40 h
    In the obtained resin with a fluorine content of 9%, the glass transition temperature is 138 ° C, the dielectric constant is 2.3, (at 15–25 ° C / 50 Hz), the dielectric resistance is 26.5 kV-mm 1 (25 ° C) and high impact rochnost.
    In tab. 1 shows the physico-mechanical properties of the cured products in examples 1-9,
    In tab. Table 2 shows the resistance of the products in Examples 1-9 to oil and organic solvents.
    权利要求:
    Claims (1)
    [1]
    The invention of the method for producing hardened fluorine-containing products by mixing epoxy resin and hardener followed by hardening, characterized in that, in order to obtain hardened products with low fluorine content based on epoxy-dianes, the compound
    Formulas Rx -Z -Rf - Z -Rx,
    oh.
    soon
    -1C of .C ° MM ° ° RH ° 2F4 ° lm
    ,eight; , 6-15, or formulas.
    45
    -CFjO-lcFjCFO -Cr O-CF3
    where, 2.
    Table 1
    Absorbance at room temperature after one day.
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    同族专利:
    公开号 | 公开日
    EP0249048A3|1990-06-20|
    DE3782187T2|1993-05-06|
    US4816545A|1989-03-28|
    ZA873313B|1987-11-02|
    CN87104186A|1988-04-06|
    EP0249048A2|1987-12-16|
    CN1016431B|1992-04-29|
    EP0249048B1|1992-10-14|
    IT1207998B|1989-06-01|
    IT8620434D0|1986-05-14|
    AT81516T|1992-10-15|
    DE3782187D1|1992-11-19|
    JPS6322823A|1988-01-30|
    KR870011164A|1987-12-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4451646A|1967-02-09|1984-05-29|Montedison, S.P.A.|High molecular weight polymeric perfluorinated copolyethers and process for their preparation from tetrafluoroethylene|
    US3458571A|1967-04-06|1969-07-29|Minnesota Mining & Mfg|Fluorocarbon polyamines|
    US3810874A|1969-03-10|1974-05-14|Minnesota Mining & Mfg|Polymers prepared from poly compounds|
    US3720639A|1971-06-24|1973-03-13|Us Navy|Fluorinated polyols|IT1205118B|1987-06-02|1989-03-15|Ausimont Spa|FLUORINATED CROSS-LINKING AGENTS FOR EPOXY RESINS AND RESIN PREPARATION PROCESS|
    JPH073689B2|1987-10-27|1995-01-18|株式会社日立製作所|Magnetic recording medium|
    JPH01146207A|1987-12-02|1989-06-08|Hitachi Ltd|Coated wire rod for ultrasonic junction|
    US5539059A|1988-09-28|1996-07-23|Exfluor Research Corporation|Perfluorinated polyethers|
    US5506309A|1988-09-28|1996-04-09|Exfluor Research Corporation|Perfluorinates polyethers|
    DE3906220C1|1989-02-28|1990-05-17|Th. Goldschmidt Ag, 4300 Essen, De|
    JPH05156002A|1991-06-04|1993-06-22|Natl Starch & Chem Investment Holding Corp|Polyether amine compound and epoxy adhesive|
    IT1254631B|1992-02-20|1995-09-28|Ausimont Spa|PREPOLYMERS CONTAINING A PERFLUOROPOLYETHER CHAIN AND CARBOXYL AND / OR OXYDRYL TERMINAL GROUPS, SUITABLE AS CROSS-LINKING AGENTS FOR EPOXY PRE-POLYMERS.|
    CA2162844A1|1993-05-14|1994-11-24|Robert John Barsotti|Anhydride-epoxy coating composition modified with a fluoropolymer|
    US5827907A|1993-08-30|1998-10-27|Ibm Corporation|Homo-, co- or multicomponent thermoplastic polymer dispersed in a thermoset resin|
    JP3368094B2|1995-04-21|2003-01-20|キヤノン株式会社|Method of manufacturing ink jet recording head|
    FR2798732B1|1999-09-17|2003-07-04|Denso Corp|SEMICONDUCTOR PRESSURE SENSOR DEVICE COMPRISING A SENSOR PLATE COVERED BY A PROTECTIVE ELEMENT|
    JP3718098B2|2000-03-22|2005-11-16|株式会社ニデック|Fundus camera|
    US6558803B1|2000-07-03|2003-05-06|Adhesives Research Inc.|Ambifunctional perfluorinated polyethers|
    JP3784247B2|2000-08-31|2006-06-07|株式会社ニデック|Fundus camera|
    US8322754B2|2006-12-01|2012-12-04|Tenaris Connections Limited|Nanocomposite coatings for threaded connections|
    CN101215367B|2007-12-29|2010-08-11|海洋化工研究院|Epoxy resin containing perfluoroalkyl side chain and its preparing method and application|
    JP4507263B2|2008-01-16|2010-07-21|信越化学工業株式会社|Fluorine-containing curable composition|
    US8563115B2|2008-08-12|2013-10-22|Xerox Corporation|Protective coatings for solid inkjet applications|
    US8191992B2|2008-12-15|2012-06-05|Xerox Corporation|Protective coatings for solid inkjet applications|
    CN105358764A|2013-07-04|2016-02-24|福伊特专利有限公司|Roll cover with low surface energy|
    AR100953A1|2014-02-19|2016-11-16|Tenaris Connections Bv|THREADED PIPE FOR AN OIL WELL PIPING|
    WO2016079053A1|2014-11-19|2016-05-26|Solvay Specialty Polymers Italy S.P.A.|Amino derivatives of perfluoropolyethers|
    CN105968368A|2016-05-25|2016-09-28|湖南晟通纳米新材料有限公司|Perfluoropolyether modified epoxy resin and preparation method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT8620434A|IT1207998B|1986-05-14|1986-05-14|CROSS-LINKING OF EPOXY RESINS BY MULTIPURPOSE PERFLUOROPOLYETERS.|
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