• 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:

    公开号:SE1500286A1
    申请号:SE1500286
    申请日:2015-06-23
    公开日:2016-11-01
    发明作者:Wernersson Mikael；Mong Ngo Linh
    申请人:Perstorp Ab；
    IPC主号:
    专利说明:

    It has now quit unexpectedly, especially in view of the disclosure of EP 1598357, has been found that the amount of spiroglycol seed particles can be substantially reduced resulting in further increased particle size of yielded spiroglycol product. The present invention accordingly refers to a process for production of a spiroglycol by subjecting pentaerythritol to reaction in water with hydroxypivaldehyde in the presence of a catalytically active amount of at least one acid catalyst and in the presence of a substantially reduced amount of spiroglycol seed particles.
    Pentaerythritol, water, at least one acid catalyst and said spiroglycol seed particles are, in the process of the present invention, charged to a reaction vessel, equipped with heating / cooling and agitation, and under stirring heated to a predeterrnined reaction temperature followed by progressive addition of hydroxypivaldehyde. Said spiroglycol seed particles are preferably particles of at least one 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-dial 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol ( pentaerythritol spiroglycol), and are present in an amount of 0.5-1.0% by weight, calculated on pentaerythritol, water, acid catalyst and hydroxypivaldehyde. Said hydroxypivaldehyde is charged at a rate determined over time by monitoring, for instance occularly and / or spectrometrically, the growth and / or formation of yielded spiroglycol particles. The reaction temperature is, in preferred embodiments, suitably but not limited to 60-100 ° C and said hydroxypivaldehyde is, in likewise preferred embodiments, charged in an amount of 2-3, such as 2.1-2.5 moles / 1 mole of pentaerythritol.
    The hydroxypivaldehyde can, for instance, be initially charged at a low rate which progressively, in one or more steps increases. A typical reaction time is 2-8 hours during which time hydroxypivaldehyde is charged followed by a 1-4 hour (s) post charging reaction time.
    Charged spiroglycol seed particles may, during the hydroxypivaldehyde charging, initially disappear but will reappear after approx. a couple of minutes to half an hour. The process of the present invention typically yields spiroglycol particles, especially 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol (pentaerythritol spiroglycol) having an average particle size of at least 100, such as 100-150 or even more than 150, pm.
    The acid catalyst is in preferred embodiments, but not limited thereto, methane sulphonic acid, p-toluene sulphonic acid, sulfuric acid and / or hydrochloric acid and is in these embodiments suitably present at a molar ratio acid catalyst to pentaerythritol of 0.04-0.08: 1.
    There is no particular preference when it comes to the particle size of said spiroglycol seed particles. Seed particles having an average particle size of at least 20 um is, however, preferred.
    Yielded spiroglycol is finally preferably and suitably recovered by sedimentation, andltration and / or centrifugation and obtained mother liquid, remain after recovery of spiroglycol, can be processed or unprocessed be re-circulated to a process as herein disclosed or to any other process for production of a spiroglycol.
    Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiment is, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following, Example l refers to an embodiment of the present invention and Example 2 to a comparative process evidencing, as given in Graphs 1 and 2, that a higher amount of seed particles does not increase the average particle size and distribution of yielded spiroglycol and / or substantially in fl uences the amount of formed by-products as given in Table l.
    Example 1 (embodiment) 46.8 parts by weight of pentaerythritol (purity 99%) and 232.1 parts by weight of water were charged to a reaction vessel equipped with a heating / cooling device and agitation. The mixture was under stirring heated to 77 ° C and 2.0 parts by weight of HCl (37% aq.) Was, when all pentaerythritol was dissolved, added to the mixture which was subsequently heated to 90 ° C. 2.7 parts by weight of pentaerythritol spiroglycol seed particles (0.75% by weight calculated on pentaerythritol, water, HCl and hydroxypivaldehyde), having an average particle size of 25-35 um, were now added and admixed for approx. 5 minutes. 81.1 parts by weight of hydroxypivaldehyde (purity 90%) were now progressively charged during 4 hours at a rate of 8-10 parts by weight / hour during the first 2 hours of reaction and 24-26 parts by weight / hour during the last 2 hours. The reaction was, when all hydroxypivaldehyde was charged, allowed to continue for a further 2.5 hours.
    Obtained reaction mixture was finally cooled to ambient temperature and yielded pentaerythritol spiroglycol was recovered by filtration, washed with water and dried, thus yielding 92.3 parts by weight of purified pentaerythritol spiroglycol having an average particle size of l00-300um peaking at approx. 150 um and a particle size distribution as given in attached Graph l.
    GC analysis of obtained product is in attached Table 1 given for the desired product and the main by-products.
    Example 2 (comparative) Example 1 was repeated with the difference that 2.0% by weight seed particles (calculated on pentaerythritol, water, HCl and hydroxypivaldehyde) was used instead of 0.75% by weight. 94.3 parts by Weight of pure pentaerythritol spiroglycol having an average particle size of 50-200 um peaking at approx. 100 um and a particle size distribution as given in attached Graph 2 was yielded.
    GC analysis of obtained product is in attached Table 1 for the desired product and the main by-products.
    权利要求:
    Claims (1)
    [1]
    The method according to any one of claims 1-5, characterized in that the obtained spiroglycol has an average particle size of at least 100 μm. The process according to any one of claims 1 to 6, characterized in that the spiroglycol obtained is 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol. that said spiroglycol germ particles are 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol particles. The process according to any one of claims 1 to 7 characterized in that the spiroglycol obtained is recovered by sedimentation, filtration and / or centrifugation. The method according to any one of claims 1-8, characterized in that said spiroglycol seed particles have an average particle size of at least 20 μm.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR20200014365A|2020-02-10|Process for preparing methane sulfonic acid
    AU2014206958B2|2017-08-10|Method for preparing a pyripyropene compound
    JP2013537536A5|2014-09-18|
    SE1500286A1|2016-11-01|Process for production of a spiroglycol
    US2927943A|1960-03-08|Preparation of p-nitrodiphenylamine
    JP2005330207A|2005-12-02|Method for producing highly pure spiroglycol having improved particle diameter
    JP2005187425A|2005-07-14|Method for producing spiroglycol
    WO2011107843A3|2012-03-01|Process for the preparation of atazanavir sulfate substantially free of diastereomers
    JP6275596B2|2018-02-07|Method for producing ammonium salt of telmisartan
    WO2016128999A1|2016-08-18|Process of preparation of compounds having chf 2c| group
    MY165642A|2018-04-18|Process for preparation of methacrylic acid and methacrylic acid ester
    JP6605311B2|2019-11-13|Process for producing 4-hydroxybenzoic acid long chain ester
    JP2016222551A|2016-12-28|Purification method of 4-hydroxy benzoic acid long chain ester
    US10239814B2|2019-03-26|Process for the purification of levulinic acid
    WO2015193911A1|2015-12-23|Process for the preparation of 2-| benzamide
    WO2016105106A3|2016-09-15|Continuous production method for anhydrous sugar alcohol
    RU2412155C1|2011-02-20|1-nitroxyadamantane synthesis method
    JP2007291029A|2007-11-08|Method for producing 1,2,3-propanetricarboxylic acid plate crystal
    CN112399968A|2021-02-23|Catalytic ethynylation
    KR20110061590A|2011-06-09|Method of crystallizing carnosol
    WO2017208253A3|2018-01-04|An improved process for the synthesis of ivacaftor
    JP2016210700A|2016-12-15|Method for purifying 4-hydroxy benzoic acid long chain ester
    KR20160080775A|2016-07-08|Preparation method for high purity antimony triglycolate
    WO2015118561A1|2015-08-13|Processes for producing 1,1,1,5,5,5 hexafluoroacetyl acetone
    BR102013006781A2|2013-10-29|Ammonia Sulfate Production Process Food Grade From Methyl Methacrylate Production By-Product
    同族专利:
    公开号 | 公开日
    JP6496428B2|2019-04-03|
    EP3313848A1|2018-05-02|
    SE538723C2|2016-11-01|
    WO2016209140A1|2016-12-29|
    CN107709331B|2020-12-08|
    TWI601729B|2017-10-11|
    KR20180019128A|2018-02-23|
    CN107709331A|2018-02-16|
    JP2018521048A|2018-08-02|
    US20180186809A1|2018-07-05|
    EP3313848A4|2018-11-21|
    TW201710266A|2017-03-16|
    US10077275B2|2018-09-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3092640A|1961-02-01|1963-06-04|Spencer Chem Co|Processes for preparing bis|
    JP2796130B2|1989-06-26|1998-09-10|広栄化学工業株式会社|Method for producing β, β, β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol|
    JP3652713B2|1994-02-03|2005-05-25|住友化学株式会社|Process for producing spiroglycol with improved particle size|
    JP2000044569A|1998-07-27|2000-02-15|Mitsubishi Gas Chem Co Inc|Production of spiroglycol|
    JP4576667B2|1999-06-10|2010-11-10|住友化学株式会社|Method for producing 3,9-bis -2,4,8,10-tetraoxaspiro [5.5] undecane|
    JP2001302674A|2000-04-25|2001-10-31|Mitsubishi Gas Chem Co Inc|Method for producing high-purity spiroglycol|
    JP2004224749A|2003-01-24|2004-08-12|Sumitomo Chem Co Ltd|Method for producing diester of hydroxyphenylpropionic acid|
    JP4604562B2|2003-06-18|2011-01-05|三菱瓦斯化学株式会社|Method for producing spiroglycol|
    JP4645032B2|2003-12-26|2011-03-09|三菱瓦斯化学株式会社|Method for producing spiroglycol|
    JP4604549B2|2004-05-19|2011-01-05|三菱瓦斯化学株式会社|Method for producing high purity spiroglycol with improved particle size|
    JP5151071B2|2006-05-30|2013-02-27|三菱瓦斯化学株式会社|Method for producing dioxane glycol|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1500286A|SE538723C2|2015-06-23|2015-06-23|Process for production of a spiroglycol|SE1500286A| SE538723C2|2015-06-23|2015-06-23|Process for production of a spiroglycol|
    PCT/SE2016/000033| WO2016209140A1|2015-06-23|2016-06-09|Process for production of a spiroglycol|
    EP16814803.9A| EP3313848A4|2015-06-23|2016-06-09|Process for production of a spiroglycol|
    CN201680036652.8A| CN107709331B|2015-06-23|2016-06-09|Process for producing spiroglycol|
    US15/738,363| US10077275B2|2015-06-23|2016-06-09|Process for production of a spiroglycol|
    JP2017567111A| JP6496428B2|2015-06-23|2016-06-09|Method for producing spiroglycol|
    KR1020177037901A| KR20180019128A|2015-06-23|2016-06-09|Spiroglycol production method|
    TW105119417A| TWI601729B|2015-06-23|2016-06-21|Process for production of a spiroglycol|
    [返回顶部]