CN110981901A - Purification method of amino-terminated siloxane - Google Patents
Purification method of amino-terminated siloxane Download PDFInfo
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- CN110981901A CN110981901A CN201911359262.6A CN201911359262A CN110981901A CN 110981901 A CN110981901 A CN 110981901A CN 201911359262 A CN201911359262 A CN 201911359262A CN 110981901 A CN110981901 A CN 110981901A
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- diamine
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- disiloxane
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000000746 purification Methods 0.000 title claims description 31
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 38
- -1 aminosiloxane Chemical class 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- MVODTGURFNTEKX-UHFFFAOYSA-N 2-bromo-n-(2-bromoethyl)-n-(thiophen-2-ylmethyl)ethanamine;hydrobromide Chemical compound Br.BrCCN(CCBr)CC1=CC=CS1 MVODTGURFNTEKX-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 238000010494 dissociation reaction Methods 0.000 claims 1
- 230000005593 dissociations Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 238000010907 mechanical stirring Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 8
- YONLFQNRGZXBBF-KBPBESRZSA-N (2s,3s)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@H](C(=O)O)[C@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-KBPBESRZSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 5
- 229960001270 d- tartaric acid Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- YONLFQNRGZXBBF-ZIAGYGMSSA-N (2r,3r)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@@H](C(=O)O)[C@@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-ZIAGYGMSSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229940116298 l- malic acid Drugs 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- MIOPJNTWMNEORI-MHPPCMCBSA-N [(4r)-7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl]methanesulfonic acid Chemical compound C1C[C@]2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-MHPPCMCBSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229960001367 tartaric acid Drugs 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001348 alkyl chlorides Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for purifying double-end aminosiloxane, which belongs to the technical field of organic chemistry.A commercially available raw material, namely monomer 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane diamine 1 containing β isomer, is added with organic acid to form salt and then dissociate, and a high-purity diamine monomer is obtained on the premise of low loss.
Description
Technical Field
The invention relates to a purification method of a functional material additive, in particular to a purification method of amino-terminated siloxane, belonging to the technical field of organic synthesis.
Background
With the further integration of materials science and organic synthesis technology, the performance of the Polyimide (PI) material can be greatly improved after the siloxane chain is introduced into the PI material. Siloxane-containing diamines are typical examples, are important intermediates in the polymer material industry, and have wide application value.
The patent document reports that 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane is early, and researches on a wide range of siloxane diamine-containing monomers are carried out, and silicon-oxygen-containing groups are introduced into a rigid polyimide main chain to form silicon-containing polyimide, so that the silicon-containing polyimide has excellent solubility, impact resistance, processability, adhesiveness, high and low temperature resistance, lower moisture absorption rate and dielectric constant. Chinese patent No. 103484008 discloses that the addition of 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane monomer to polyimide can significantly improve the performance of the coating. With respect to the synthesis of this monomer, the following are reported in the present disclosure:
chinese patent CN201610794132 discloses that target monomers are obtained in high yield in an autoclave under absolute anhydrous and anaerobic conditions under catalysis of a self-made Karstedt reagent by using allyl amine and a dihydro double-end socket. The method needs to be carried out under absolute anhydrous and anaerobic conditions, has certain difficulty in large-scale production, adopts high-temperature and high-pressure reaction equipment, has strict requirements on production quality and process conditions, and has the following reaction equation:
in addition, the synthesis process and application of organosilicon products, page P270, describes the hydrosilylation reaction under Karstedt catalysis, β isomer cannot be avoided, and the method is not suitable for large-scale production, and the isomer structural formula is as follows:
JP-11021289 reports that the hydrosilylation reaction with a dihydrodicapped head and a protected allylamine followed by deprotection gives products which also do not avoid containing the β isomer, WO2008115190 describes the monomer which is currently available on a large scale on the market with a proportion of isomers between 15 and 18%.
β isomer belongs to a branched structure, when added into Polyimide (PI) material, the composite material formed by the isomer has unstable corresponding performance compared with the straight-chain diamine monomer, and is easy to decompose by heat, therefore, from the practical point of view of application, the lower the content of β isomer, the better.
Commercially available 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane monomer contains 5-15% of unequal β isomer by analysis, the commercially available monomer mixed with β isomer is relatively inexpensive, but the method for effectively removing β isomer is not reported sufficiently and cannot effectively meet the market demand for high-quality diamine monomer.
Disclosure of Invention
In order to overcome the technical problems, the invention discloses a purification method of amino-terminated siloxane, which comprises the steps of utilizing a commercially available raw material, namely monomer 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane 1 containing β isomer, adding organic acid to salify, and then dissociating to obtain a high-purity diamine monomer on the premise of low loss, wherein the content of the isomer is controlled below 1% after purification by the method, and the recovery rate is 80-90%.
The invention relates to a purification method of a double-end aminosiloxane monomer, which comprises the following steps:
adding organic acid into a mixture of disiloxane diamine 1 monomer and disiloxane diamine 2 monomer, salifying in an organic solvent, and dissociating to obtain the high-purity disiloxane diamine 1 monomer.
The route used is represented by the equation:
further, in the technical scheme, the molar ratio of the disiloxane diamine 1 monomer to the disiloxane diamine 2 monomer is 0.85-0.95: 0.15-0.05.
Further, in the above technical solution, the organic acid is selected from the group consisting of R-camphorsulfonic acid, S-camphorsulfonic acid, L-malic acid, D-tartaric acid, L-tartaric acid, D-tartaric acid, L-dibenzoyltartaric acid (L-DBTA), L-di-p-benzoyltartaric acid (L-DTTA), D-dibenzoyltartaric acid (D-DBTA), L-di-p-benzoyltartaric acid (L-DTTA), and mixtures of the same organic acids in different ratios of the two forms. Preferably, the organic acid is selected from DBTA or DTTA.
In the experimental process, when other common organic acids (such as acetic acid or propionic acid and the like) or inorganic acids (such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and the like) are adopted, no obvious effect is produced in the purification.
Further, in the technical scheme, the molar ratio of the organic acid to the mixture of diamine 1/diamine 2 is 0.95-1.05: 1. Preferably, the molar ratio of the two is 1: 1.
Further, in the above technical solution, the organic solvent is selected from methanol, ethanol, isopropanol, methyl tert-butyl ether, ethyl acetate, dichloromethane, 1, 2-dichloroethane, chloroform, acetonitrile, and the like. The organic solvent is preferably chloroalkane such as dichloromethane, dichloroethane, chloroform, etc.
Further, in the above-mentioned embodiment, the liberation operation is carried out by adding the formed diastereomer salt to an aqueous alkali solution or an aqueous acid solution and then separating the mixture into layers in an organic solvent. Adding an alkaline water solution, putting a diamine product in an organic layer, separating the organic layer, adding an acid water solution into the alkaline water layer, and recycling the organic acid again; after addition of the aqueous acid solution, the diamine product is separated in the aqueous layer, the organic layer containing the organic acids is separated off, and the aqueous alkaline solution is added to the acidic aqueous layer to free the product.
Advantageous effects of the invention
The reagents and raw materials used in the invention are commercially available, and the β isomer content can be controlled below 1% by resolving the commercially available cheap monomer containing β isomer 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane through chiral D-dibenzoyltartaric acid, and the recovery rate is 80-90%.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1 monomer purification [ R-Camphorsulfonic acid ]
In a 10L three-necked bottle, mechanical stirring is carried out, 232g of [ 1.0mol ] R-camphorsulfonic acid is added, the R-camphorsulfonic acid is dissolved in 2.0L of methanol, 248g of a mixture (95% of diamine 1+ 5% of diamine 2) sold in the market is dropwise added under stirring, after the addition, white solid is generated, the stirring reaction is continued for 2 hours at room temperature, filtering is carried out, a filter cake is obtained, a little methanol is used for leaching, a solid is obtained, 20% NaOH aqueous solution is used for dissolving, ethyl acetate is used for extracting, concentration is carried out till dryness, 220g of crude product is obtained, and the GC analysis shows that β isomer is 4.5%, and the reduction is not obvious.
Example 2 monomer purification [ S-Camphorsulfonic acid ]
In a 10L three-necked bottle, mechanical stirring is carried out, 232g of [ 1.0mol ] S-camphorsulfonic acid is added, the S-camphorsulfonic acid is dissolved in 2.0L of methanol, 248g of a mixture (95% of diamine 1+ 5% of diamine 2) sold in the market is dropwise added under stirring, after the addition, white solid is generated, the stirring reaction is continued for 2 hours at room temperature, filtering is carried out, a filter cake is obtained, a little methanol is used for leaching, the solid is obtained, 20% of NaOH aqueous solution is used for dissolving, ethyl acetate is used for extracting, concentration is carried out till dryness, 220g of crude product is obtained, and the GC analysis shows that β isomer is 4.6%, and the reduction is not obvious.
EXAMPLE 3 purification of monomers [ L-malic acid ]
In a 10L three-necked bottle, mechanical stirring is carried out, 268g of [ 2.0mol ] L-malic acid is added, the L-malic acid is dissolved in 2.0L of ethyl acetate, 248g of a mixture (95% of diamine 1+ 5% of diamine 2) sold on the market is dropwise added under stirring, after the addition, white solid is generated, the stirring reaction is continued for 2 hours at room temperature, filtering is carried out, a filter cake is obtained, a little methanol is used for leaching, a solid is obtained, 20% NaOH aqueous solution is used for dissolving, ethyl acetate is used for extracting, concentration is carried out till dryness, 200g of crude product is obtained, and after GC analysis, 4.0% of β isomer is not obviously reduced.
Example 4 purification of monomer TM [ acetic acid ]
In a 10 l three-necked flask, equipped with mechanical stirring, 120g [ 2.0mol ] acetic acid was added, dissolved in 2.0 l ethyl acetate, and 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] was added dropwise with stirring, and after the addition, no solid was produced, and the reaction was continued at room temperature for 2 hours with stirring, and no solid was produced. Under the above conditions, the purification of the diamine with acetic acid is not effective.
Example 5 monomer purification [ sulfuric acid ]
In a 10 l three-necked flask, with mechanical stirring, 98g of [ 1.0mol ] acetic acid was added, dissolved in 2.0 l of acetonitrile, and 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] was added dropwise with stirring, and after the addition, no solid was produced, and the reaction was continued at room temperature for 2 hours with stirring, and no solid was produced. Under the above conditions, the purification of the diamine by sulfuric acid is not effective.
EXAMPLE 6 purification of monomers [ D-tartaric acid ]
In a 10 l three-necked flask, with mechanical stirring, 150g [ 1.0mol ] of D-tartaric acid was added, dissolved in 2.0 l of methanol, and 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] was added dropwise with stirring, and after the addition, no white solid was produced, and the reaction was continued at room temperature for 2 hours with stirring, and no solid was produced. Under the above conditions, the purification of the diamine by D-tartaric acid was not effective.
EXAMPLE 7 purification of monomers [ L-Dibenzoyltartaric acid ]
Mechanical stirring is carried out in a 10L three-necked bottle, 376g of L-dibenzoyl tartaric acid (1.0 mol) is added and dissolved in 3.0L of dichloromethane, 248g of a mixture (95% of diamine 1+ 5% of diamine 2) sold on the market (1.0 mol) is added dropwise under stirring, white solid is generated after the addition, the stirring reaction is continued for 2 hours at room temperature, filtering is carried out to obtain a filter cake, a little dichloromethane is used for leaching to obtain solid salt, the solid salt is dissolved by 20% of NaOH aqueous solution, dichloromethane is used for extraction, and the concentration is carried out to dryness to obtain 230g of a product, and GC analysis shows that β isomer is 1.1%.
EXAMPLE 8 purification of monomers [ D-Dibenzoyltartaric acid ]
Mechanical stirring is carried out in a 10L three-necked bottle, 376g of [ 1.0mol ] D-dibenzoyltartaric acid is added and dissolved in 3.0L of dichloromethane, 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] is added dropwise under stirring, after the addition, white solid is generated, stirring reaction is carried out for 2 hours at room temperature, filtration is carried out to obtain a filter cake, a little dichloromethane is used for leaching to obtain solid, then the solid is continuously pulped for 1 hour by 1.0L of dichloromethane/methanol (the volume ratio is 95/5), filtration is carried out, the filter cake is dissolved by 20% KOH aqueous solution, dichloromethane is used for extraction, concentration is carried out to dryness to obtain 220g of product, and GC analysis is carried out to obtain β isomer 0.80%.
EXAMPLE 9 purification of monomers [ D-Dibenzoyltartaric acid ]
Mechanical stirring is carried out in a 10L three-necked bottle, 376g of [ 1.0mol ] D-dibenzoyltartaric acid is added and dissolved in 3.0L of 1, 2-dichloroethane, 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] is added dropwise under stirring, after addition, white solid is generated, stirring reaction is continued for 2 hours at room temperature, filtration is carried out to obtain a filter cake, a little dichloroethane is used for leaching to obtain solid, then the solid is used for 1.0L of 1, 2-dichloroethane/methanol (volume ratio is 95/5) for further pulping for 1 hour, filtration is carried out, the filter cake is dissolved by 20% KOH aqueous solution, dichloroethane is extracted and concentrated to dryness to obtain 215g of crude product, and GC analysis is 0.82% of β isomer.
EXAMPLE 10 purification of monomers [ D-p-Methylbenzoyltartaric acid ]
In a 10 l three-necked flask, equipped with mechanical stirring, 400g [ 1.0mol ] of D-p-methylbenzoyl tartaric acid was added, dissolved in 3.0 l of chloroform, 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] was added dropwise with stirring, after the addition, a white solid was produced, the reaction was continued for 2 hours at room temperature, filtration was carried out to obtain a filter cake, which was rinsed with a little chloroform to obtain a solid, which was then slurried with 1.0 l of chloroform/methanol [ volume ratio 95/5 ] for 1 hour, filtration was carried out, the filter cake was dissolved with 20% aqueous NaOH solution, chloroform was extracted and concentrated to dryness to obtain 221g of product, which was analyzed by GC to be 0.91% of β isomer.
EXAMPLE 11 purification of monomers [ D-p-Methylbenzoyltartaric acid ]
In a 10L three-necked flask, mechanical stirring is carried out, 400g of [ 1.0mol ] D-p-methylbenzoyl tartaric acid is added, the D-p-methylbenzoyl tartaric acid is dissolved in 4.0L of 1, 2-dichloroethane, 248g of a commercially available (89% diamine 1+ 11% diamine 2) mixture [ 1.0mol ] is added dropwise under stirring, after addition, white solid is generated, stirring is continued for 2 hours at room temperature, filtering is carried out, a filter cake is obtained, a little 1, 2-dichloroethane is used for leaching, the filter cake is concentrated and recovered 1, 2-dichloroethane is obtained, 10% hydrochloric acid and the recovered 1, 2-dichloroethane are added into the filter cake for extraction, an organic phase containing a resolving agent is obtained by washing with water, salt formation purification is carried out by continuing adding commercially available diamine into the organic phase, 20% NaOH aqueous solution is added into the aqueous phase to adjust the pH to 9-10, 1, 2-dichloroethane is used for extraction, concentration is carried out to dryness, and a product is obtained, and GC analysis is carried out, β isomer 1.2% is carried out rectification again, the purity of the product is obtained, 3544.198, and the purity.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (9)
1. A method of purifying a bis-aminosiloxane monomer, comprising the steps of:
adding organic acid into a mixture of disiloxane diamine 1 monomer and disiloxane diamine 2 monomer, salifying in an organic solvent, and dissociating to obtain high-purity disiloxane diamine 1 monomer; the reaction equation is:
2. the purification process according to claim 1, characterized in that: the monomer mixture is a commercial raw material, wherein the molar ratio of the disiloxane diamine 1 monomer to the disiloxane diamine 2 monomer is 0.85-0.95: 0.15-0.05.
3. The purification process according to claim 1, characterized in that: the organic acid is selected from DBTA or DTTA.
4. The purification process according to claim 1, characterized in that: the molar ratio of the organic acid to the mixture of diamine 1/diamine 2 is 0.95-1.05: 1.
5. The purification method according to claim 4, characterized in that: the molar ratio of the organic acid to the mixture of diamine 1/diamine 2 is 1: 1.
6. The purification process according to claim 1, characterized in that: the organic solvent is a chlorinated solvent.
7. The purification process according to claim 6, characterized in that: the chlorinated solvent is selected from dichloromethane, 1, 2-dichloroethane or chloroform.
8. The purification method according to any one of claims 1 to 7, characterized in that: the dissociation operation is carried out by adding the formed salt to an aqueous alkali solution or an aqueous acid solution and then separating the salts in an organic solvent.
9. The purification process according to claim 8, wherein: adding an alkaline water solution, putting a diamine product in an organic layer, separating the organic layer, adding an acid water solution into the alkaline water layer, and recycling the organic acid again; after addition of the aqueous acid solution, the diamine product is separated in the aqueous layer, the organic layer containing the organic acids is separated off, and the aqueous alkaline solution is added to the acidic aqueous layer to free the product.
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| CN101024652A (en) * | 2007-03-23 | 2007-08-29 | 广州天赐有机硅科技有限公司 | Method for preparing amino-hydrocarbyl-trisiloxane |
| CN101668766A (en) * | 2007-03-21 | 2010-03-10 | 莫门蒂夫性能材料股份有限公司 | Improved process for producing bis-(aminoalkyl)-polysiloxanes |
| CN106496261A (en) * | 2016-08-31 | 2017-03-15 | 成都正威新材料研发有限公司 | A kind of preparation method of silicone-containing diamidogen |
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| JP2002194086A (en) * | 2000-12-25 | 2002-07-10 | Dow Corning Toray Silicone Co Ltd | Production method for organopolysiloxane having aminoalkyl group |
| CN101445602B (en) * | 2008-12-26 | 2010-12-01 | 上海工程技术大学 | Dissoluble polyetherimide containing silicon and preparation method thereof |
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| CN101668766A (en) * | 2007-03-21 | 2010-03-10 | 莫门蒂夫性能材料股份有限公司 | Improved process for producing bis-(aminoalkyl)-polysiloxanes |
| CN101024652A (en) * | 2007-03-23 | 2007-08-29 | 广州天赐有机硅科技有限公司 | Method for preparing amino-hydrocarbyl-trisiloxane |
| CN106496261A (en) * | 2016-08-31 | 2017-03-15 | 成都正威新材料研发有限公司 | A kind of preparation method of silicone-containing diamidogen |
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