WO2021129359A1 - Procédé de purification d'aminosiloxane à double extrémité - Google Patents

Procédé de purification d'aminosiloxane à double extrémité Download PDF

Info

Publication number
WO2021129359A1
WO2021129359A1 PCT/CN2020/134115 CN2020134115W WO2021129359A1 WO 2021129359 A1 WO2021129359 A1 WO 2021129359A1 CN 2020134115 W CN2020134115 W CN 2020134115W WO 2021129359 A1 WO2021129359 A1 WO 2021129359A1
Authority
WO
WIPO (PCT)
Prior art keywords
diamine
monomer
acid
organic
purification method
Prior art date
Application number
PCT/CN2020/134115
Other languages
English (en)
Chinese (zh)
Inventor
黄焱伟
吴伟锋
匡正霞
叶太金
王东
王猛
王方道
Original Assignee
上海彩迩文生化科技有限公司
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 上海彩迩文生化科技有限公司 filed Critical 上海彩迩文生化科技有限公司
Publication of WO2021129359A1 publication Critical patent/WO2021129359A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/20—Purification, separation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a method for purifying functional material additives, in particular to a method for purifying double-terminal amino siloxane, and belongs to the technical field of organic synthesis.
  • siloxane-containing diamine is an important intermediate in the polymer material industry and has a wide range of application values.
  • 1,3-bis( ⁇ -aminopropyl)-1,1,3,3-tetramethyldisiloxane has been reported earlier in the literature, and it is also a more widely studied monomer containing siloxane diamine, which will contain Siloxy groups are introduced into the rigid polyimide main chain to form silicon-containing polyimide, which has excellent solubility, impact resistance, processability, adhesion, resistance to high and low temperatures, and lower moisture absorption and dielectric constant.
  • Chinese patent CN103484008 discloses that adding 1,3-bis( ⁇ -aminopropyl)-1,1,3,3-tetramethyldisiloxane monomer to polyimide can significantly improve the performance of coatings.
  • Current published reports include the following:
  • Chinese patent CN201610794132 discloses the use of allylamine and dihydro double heads, catalyzed by a self-made Karstedt reagent, under absolutely anhydrous and oxygen-free conditions, to obtain the target monomer in a high yield in an autoclave. This method needs to be carried out under absolutely anhydrous and oxygen-free conditions, and there are certain difficulties in large-scale production. At the same time, high-temperature and high-pressure reaction equipment is used, which requires harsh production qualifications and process conditions.
  • the reaction equation is as follows:
  • the ⁇ isomer belongs to the branched structure.
  • the composite material formed by it compared with the linear diamine monomer, its corresponding performance is not stable, and it is easily decomposed by heat. In terms of practical application, the lower the content of ⁇ isomer, the better.
  • 1,3-bis( ⁇ -aminopropyl)-1,1,3,3-tetramethyldisiloxane monomers contain 5-15% beta isomers after analysis.
  • Commercially available monomers mixed with ⁇ isomers are relatively inexpensive. However, there are insufficient reports on effective methods for removing ⁇ isomers and cannot effectively meet the market's demand for high-quality diamine monomers.
  • the present invention discloses a method for purifying two-terminal amino siloxane.
  • Using commercially available raw materials namely the monomer 1,3-bis( ⁇ -aminopropyl)-1,1,3,3-tetramethyldisiloxane 1, which contains ⁇ isomers, is added organic acid to form a salt, Then it dissociates to obtain high-purity diamine monomer under the premise of low loss.
  • the isomer content after purification by this method is controlled below 1%, and the recovery rate is 80-90%.
  • the method for purifying a double-terminal amino siloxane monomer of the present invention includes the following steps:
  • a mixture of disiloxane diamine 1 monomer and disiloxane diamine 2 monomer is added to an organic acid to form a salt in an organic solvent, and high-purity disiloxane diamine 1 monomer is obtained after being freed.
  • the molar ratio of the disiloxane diamine 1 monomer to the disiloxane diamine 2 monomer is 0.85-0.95:0.15-0.05.
  • the organic acid is selected from R-camphorsulfonic acid, S-camphorsulfonic acid, L-malic acid, D-tartaric acid, L-tartaric acid, D-tartaric acid, L-dibenzoyl Tartaric acid (L-DBTA), L-di-p-benzoyl tartaric acid (L-DTTA), D-dibenzoyl tartaric acid (D-DBTA), L-di-p-benzoyl tartaric acid (L-DTTA), and the above A mixture of two configurations of the same organic acid in different proportions.
  • the organic acid is selected from DBTA or DTTA.
  • the molar ratio of the organic acid to the diamine 1/diamine 2 mixture is 0.95-1.05:1. Under preferred conditions, the molar ratio of the two is 1:1.
  • the organic solvent is selected from methanol, ethanol, isopropanol, methyl tert-butyl ether, ethyl acetate, dichloromethane, 1,2-dichloroethane, chloroform, acetonitrile Wait.
  • the organic solvent is a chlorinated alkane such as dichloromethane, dichloroethane, and chloroform.
  • the free operation is to add the formed diastereoisomer salt to the aqueous alkali or acid solution, and then layer the salt in an organic solvent.
  • the alkali aqueous solution is added, the diamine product is in the organic layer.
  • the organic layer is separated, the alkaline aqueous layer is added to the acid aqueous solution, and the organic acid is recycled again; after the acid aqueous solution is added, the diamine product is in the water layer and separated
  • the organic layer contains organic acid, and the acidic water layer is added with alkaline aqueous solution to free the product.
  • the reagents and raw materials used in the present invention are all commercially available, from the commercially available cheap 1,3-bis( ⁇ -aminopropyl)-1,1,3,3-tetramethyldisiloxane mono Through chiral D-dibenzoyl tartaric acid resolution, the content of ⁇ isomer can be controlled below 1% after resolution, and the recovery rate is 80-90%.
  • the filter cake is extracted with 10% hydrochloric acid and the above-mentioned recovered 1,2-dichloroethane, the organic layer is washed with water to obtain an organic phase containing a resolving agent, and a commercially available diamine is continuously added to it for salt-forming purification.
  • GC analysis ⁇ isomer 1.2%.
  • the product was rectified again to obtain 192 grams of product.
  • a chiral acid commonly used for resolution is added to a commercially available mixed diamine product to highly selectively remove undesired isomers and improve the purity of the disiloxane diamine 1 monomer.
  • a chiral acid commonly used for resolution is added to a commercially available mixed diamine product to highly selectively remove undesired isomers and improve the purity of the disiloxane diamine 1 monomer.
  • 1,3-bis( ⁇ -aminopropyl)-1,1,3,3-tetramethyldisiloxane monomer containing a significant amount of ⁇ isomer it is disassembled by D-dibenzoyl tartaric acid After separation, the content of ⁇ isomer is controlled below 1%, and the recovery rate is as high as 80-90%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de purification d'aminosiloxane à double extrémité. Le procédé selon l'invention comprend l'utilisation de matières premières disponibles dans le commerce, c'est-à-dire des monomères contenant des isomères β 1,3-bis (γ-aminopropyl))-1,1,3,3-tétraméthyldisiloxane diamine 1, l'ajout d'acide organique, la réalisation d'une formation de sel, puis la dissociation, et l'obtention d'un monomère de diamine de haute pureté avec une faible perte. Après purification par le procédé, la teneur en isomère est régulée à une valeur inférieure à 1 % et la vitesse de récupération est de 80 à 90 %, satisfaisant les exigences du marché pour le monomère diamine 1 de haute pureté.
PCT/CN2020/134115 2019-12-25 2020-12-05 Procédé de purification d'aminosiloxane à double extrémité WO2021129359A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911359262.6 2019-12-25
CN201911359262.6A CN110981901B (zh) 2019-12-25 2019-12-25 一种双端胺基硅氧烷的纯化方法

Publications (1)

Publication Number Publication Date
WO2021129359A1 true WO2021129359A1 (fr) 2021-07-01

Family

ID=70076894

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/134115 WO2021129359A1 (fr) 2019-12-25 2020-12-05 Procédé de purification d'aminosiloxane à double extrémité

Country Status (2)

Country Link
CN (1) CN110981901B (fr)
WO (1) WO2021129359A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023060153A1 (fr) * 2021-10-06 2023-04-13 Dow Global Technologies Llc Préparation de composés d'organosilicium amino-fonctionnels

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110981901B (zh) * 2019-12-25 2022-07-05 上海彩迩文生化科技有限公司 一种双端胺基硅氧烷的纯化方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5861085A (en) * 1995-09-19 1999-01-19 Yuki Gosei Kogyo Co., Ltd. Method of purifying 1,3-bis(3-aminopropyl)-1,1,3,3-tetraorganodisiloxane
JP2002194086A (ja) * 2000-12-25 2002-07-10 Dow Corning Toray Silicone Co Ltd アミノアルキル基含有オルガノポリシロキサンの製造方法
CN101445602A (zh) * 2008-12-26 2009-06-03 上海工程技术大学 一种可溶性含硅聚醚酰亚胺及其制备方法
CN110981901A (zh) * 2019-12-25 2020-04-10 上海彩迩文生化科技有限公司 一种双端胺基硅氧烷的纯化方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101668766A (zh) * 2007-03-21 2010-03-10 莫门蒂夫性能材料股份有限公司 生产双（氨基烷基）聚硅氧烷的改进的方法
CN101024652B (zh) * 2007-03-23 2010-05-19 广州天赐有机硅科技有限公司 3-氨烃基三硅氧烷的制备方法
CN106496261B (zh) * 2016-08-31 2019-04-05 成都正威新材料研发有限公司 一种含硅氧烷二胺的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5861085A (en) * 1995-09-19 1999-01-19 Yuki Gosei Kogyo Co., Ltd. Method of purifying 1,3-bis(3-aminopropyl)-1,1,3,3-tetraorganodisiloxane
JP2002194086A (ja) * 2000-12-25 2002-07-10 Dow Corning Toray Silicone Co Ltd アミノアルキル基含有オルガノポリシロキサンの製造方法
CN101445602A (zh) * 2008-12-26 2009-06-03 上海工程技术大学 一种可溶性含硅聚醚酰亚胺及其制备方法
CN110981901A (zh) * 2019-12-25 2020-04-10 上海彩迩文生化科技有限公司 一种双端胺基硅氧烷的纯化方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023060153A1 (fr) * 2021-10-06 2023-04-13 Dow Global Technologies Llc Préparation de composés d'organosilicium amino-fonctionnels
WO2023060154A1 (fr) * 2021-10-06 2023-04-13 Dow Global Technologies Llc Préparation de composés d'organosilicium à fonction imine et de composés d'organosilicium amino-fonctionnel primaire

Also Published As

Publication number Publication date
CN110981901B (zh) 2022-07-05
CN110981901A (zh) 2020-04-10

Similar Documents

Publication Publication Date Title
WO2021129359A1 (fr) Procédé de purification d'aminosiloxane à double extrémité
JP2005247850A5 (fr)
EP1907396A1 (fr) Procede de preparation de la 4 -amino-4'-demethyl-4-desoxypodophyllotoxine
JP5246516B2 (ja) メチル−４−ホルミルベンゾエートとジメチルテレフタレートの単離方法
CN1491927A (zh) 间苯三酚的制备方法
CN101671292A (zh) 盐酸非索非那定的合成方法
CN108467353B (zh) 一种对映纯叔丁基亚磺酰胺的制备方法
JPH10330330A (ja) α−メチル−３−（トリフルオロメチル）ベンゼンエタンアミンの（Ｒ）または（Ｓ）異性体の製造法
JP2009096740A (ja) ヒドロキシペンタフルオロスルファニルベンゼン化合物の製法
CN110615767B (zh) 一种合成5-氟胞嘧啶的方法
CN101218215B (zh) 3,4-二氯异噻唑羧酸的制备方法
CN108409615B (zh) 一种合成对映纯叔丁基亚磺酰胺的方法
JPH09118646A (ja) 光学活性２−ヒドロキシ−４−アリール酪酸またはそのエステルの製造方法
CN1058488C (zh) １，３，６－三烷基六氢－１，３，６－三氮杂辛因－２－酮及其制备方法
CN1256319C (zh) L－β－天门冬酰胺的合成方法
CN108069866A (zh) 一种异丁加巴的不对称合成方法
JP4314602B2 (ja) 光学活性３−ヒドロキシピロリジン誘導体の製造方法
JPH0662489B2 (ja) バルプロ酸の製造法
CN1266116C (zh) 万拉法新及其盐的制备方法
CN1272325C (zh) 坎地沙坦酯中间体1－（（2′－氰基联苯－4－基）甲基）－2－乙氧基苯并咪唑－7－甲酸乙酯的制备方法
CN118146078A (zh) 一种环戊基甲醛的精制方法
CN1397553A (zh) 尼扎替丁的制备方法
CN101550047B (zh) 一种脱叔烷基胺的方法
EP4251605A1 (fr) Procédé respectueux de l'environnement pour l'acylation sélective d'aminophénol
CN114315698A (zh) C5a阻断剂Avacopan手性杂质及其合成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20907271

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20907271

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 23/05/2023)

122 Ep: pct application non-entry in european phase

Ref document number: 20907271

Country of ref document: EP

Kind code of ref document: A1