CN110981901B - Purification method of amino-terminated siloxane - Google Patents
Purification method of amino-terminated siloxane Download PDFInfo
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- CN110981901B CN110981901B CN201911359262.6A CN201911359262A CN110981901B CN 110981901 B CN110981901 B CN 110981901B CN 201911359262 A CN201911359262 A CN 201911359262A CN 110981901 B CN110981901 B CN 110981901B
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- 238000000746 purification Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 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 42
- 239000000178 monomer Substances 0.000 claims abstract description 37
- -1 amino siloxane Chemical group 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 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
- 239000000243 solution Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 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
- 238000011084 recovery Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 22
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000010907 mechanical stirring Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 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
- 238000004817 gas chromatography Methods 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
- 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
- 238000002386 leaching Methods 0.000 description 6
- 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 5
- 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- 229960001270 d- tartaric acid Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 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
- 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
- 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
- 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 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
- 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
- 239000012141 concentrate Substances 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012071 phase Substances 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 purification method of double-terminal amino siloxane, belonging to the technical field of organic chemistry. The method comprises the steps of adding organic acid into a commercially available raw material, namely 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane diamine 1 containing beta isomer, for salifying and then dissociating, and obtaining the high-purity diamine monomer on the premise of low loss. The content of the isomer is controlled below 1 percent after the method is adopted for purification, the recovery rate is 80-90 percent, and the market demand for the diamine monomer 1 with high purity is met.
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, describe the hydrosilylation reaction under Karstedt catalysis, beta-isomer cannot be avoided, and the method is not suitable for large-scale production. The isomeric structural formulae are as follows:
japanese patent JP-11021289 reports that the product obtained by hydrosilylation reaction using a dihydrodouble head and a protected allylamine followed by deprotection does not inevitably contain the beta isomer. WO2008115190 describes the monomer, which is currently available on the market in large quantities, with isomer ratios between 15 and 18%.
The beta isomer belongs to a branched chain structure, and when the beta isomer is added into a Polyimide (PI) material, the composite material formed by the beta isomer is unstable in corresponding performance and easy to decompose under heat compared with a linear diamine monomer, so that the lower the content of the beta isomer is, the better the application practice is.
Commercially available 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane monomer was analyzed to contain 5-15% of unequal beta isomers. Commercially available monomers mixed with the beta isomer are relatively inexpensive, however, methods for effectively removing the beta isomer have not been reported sufficiently and are not effective in meeting the market demand for high quality diamine monomers.
Disclosure of Invention
In order to overcome the technical problem, the invention discloses a purification method of amino-terminated siloxane. Commercially available raw materials, namely 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane 1 containing beta isomer, are added with organic acid to form salt, and then dissociated to obtain the high-purity diamine monomer on the premise of low loss. The content of 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 above 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, etc. 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 salt to an aqueous alkali solution or an aqueous acid solution and then separating the resulting 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 beta isomer content can be controlled below 1% by resolving chiral D-dibenzoyltartaric acid from a commercially available cheap beta isomer-containing 1, 3-bis (gamma-aminopropyl) -1,1,3, 3-tetramethyldisiloxane monomer, 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. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with 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 commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] is dropwise added under stirring, white solid is generated after the addition, the stirring reaction is continued for 2 hours at room temperature, filtering is carried out, a filter cake is obtained, and a little methanol is used for leaching to obtain the solid. Dissolving with 20% NaOH aqueous solution, extracting with ethyl acetate, concentrating to dryness to obtain 220g of crude product, and performing GC analysis: 4.5% of beta isomer, and the reduction is not obvious.
Example 2 monomer purification [ S-Camphorsulfonic acid ]
In a 10 liter three-necked flask, equipped with mechanical stirring, 232g [ 1.0mol ] S-camphorsulfonic acid was added, dissolved in 2.0 liters of methanol, 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] was added dropwise thereto under stirring, after the addition, white solid was produced, stirring at room temperature was continued for 2 hours, filtration was carried out to obtain a filter cake, which was rinsed with a little methanol to obtain a solid, dissolved with 20% NaOH aqueous solution, extracted with ethyl acetate, concentrated to dryness to obtain 220g of crude product, GC analysis: 4.6% of beta isomer, 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 commercially available (95% diamine 1+ 5% diamine 2) mixture [ 1.0mol ] is added dropwise while 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 extraction is carried out, concentration is carried out till dryness, 200g of crude product is obtained, and GC analysis: 4.0% of beta isomer, and the reduction is not obvious.
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, equipped 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 thereto under stirring, and after completion of addition, no solid was produced, and the reaction was continued with stirring at room temperature for 2 hours, 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-dibenzoyltartaric acid (1.0 mol) is added, the L-dibenzoyltartaric acid is dissolved in 3.0L of dichloromethane, 248g of a commercially available (95% diamine 1+ 5% diamine 2) mixture (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, a filter cake is obtained, a little dichloromethane is used for leaching, solid salt is obtained, the solid salt is dissolved by 20% NaOH aqueous solution, dichloromethane is extracted and concentrated to dryness, 230g of the product is obtained, and GC analysis: beta isomer 1.1%.
EXAMPLE 8 purification of monomers [ D-Dibenzoyltartaric acid ]
Mechanical stirring is carried out in a 10 liter three-necked bottle, 376g of [ 1.0mol ] D-dibenzoyltartaric acid is added and dissolved in 3.0 liter 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 1.0 liter 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, GC analysis: beta isomer 0.80%.
EXAMPLE 9 purification of monomers [ D-Dibenzoyltartaric acid ]
Mechanical stirring is carried out in a 10 liter three-necked flask, 376g of [ 1.0mol ] D-dibenzoyltartaric acid is added and dissolved in 3.0 liter 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 produced, stirring 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 1.0 liter 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, GC analysis: beta isomer 0.82%.
EXAMPLE 10 purification of monomers [ D-p-Methylbenzoyltartaric acid ]
In a 10 l three-necked flask, equipped with mechanical stirring, 400g of [ 1.0mol ] D-p-methylbenzyltartaric 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 at room temperature for 2 hours, filtration was carried out to obtain a cake, the cake was rinsed with a little chloroform to obtain a solid, the solid was then slurried with 1.0 l of chloroform/methanol [ volume ratio 95/5 ] for 1 hour, filtration was carried out, the cake was dissolved with 20% aqueous NaOH, chloroform was extracted, and the concentrate was concentrated to dryness to obtain 221g of product, GC analysis: beta isomer 0.91%.
EXAMPLE 11 purification of monomers [ D-p-Methylbenzoyltartaric acid ]
In a 10L three-necked flask, mechanically stirring, adding 400g of (1.0 mol) D-p-methyl dibenzoyl tartaric acid, dissolving in 4.0L of 1, 2-dichloroethane, dropwise adding 248g of a commercially available (89% diamine 1+ 11% diamine 2) mixture (1.0 mol) while stirring, generating white solid after adding, continuously stirring at room temperature for 2 hours, filtering to obtain a filter cake, leaching with a little 1, 2-dichloroethane to obtain a filter cake, concentrating the filtrate, and recovering 1, 2-dichloroethane. Adding 10% hydrochloric acid into the filter cake, extracting the recovered 1, 2-dichloroethane, washing the organic layer with water to obtain an organic phase containing a resolving agent, and continuously adding commercially available diamine into the organic phase to perform salt formation and purification. Adding 20% NaOH aqueous solution into the water phase to adjust the pH value to 9-10, extracting by 1, 2-dichloroethane, concentrating to dryness to obtain 198 products, and performing GC analysis: beta isomer 1.2%. The product was again rectified to give 192 g purity, beta isomer 0.44%.
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 given by way of illustration 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 such changes and modifications are within the scope of the present invention.
Claims (4)
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:
the organic acid is selected from DBTA or DTTA; the organic solvent is a chlorinated solvent, and the chlorinated solvent is selected from dichloromethane, 1, 2-dichloroethane or chloroform; adding the formed salt into an aqueous alkali solution or an aqueous acid solution, and then layering 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.
2. The purification process according to claim 1, characterized in that: the monomer mixture is a commercially available 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 method 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.
4. The purification process according to claim 3, characterized in that: the molar ratio of the organic acid to the mixture of diamine 1/diamine 2 is 1: 1.
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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 |
| 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 |
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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 |
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