CN117126403B - Synthesis method of methyl MQ silicon resin - Google Patents
Synthesis method of methyl MQ silicon resin Download PDFInfo
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- CN117126403B CN117126403B CN202311395329.8A CN202311395329A CN117126403B CN 117126403 B CN117126403 B CN 117126403B CN 202311395329 A CN202311395329 A CN 202311395329A CN 117126403 B CN117126403 B CN 117126403B
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- -1 imidazole siloxane Chemical class 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920002050 silicone resin Polymers 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 7
- PBEDVTDUVXFSMW-UHFFFAOYSA-N 3-methylimidazole-4-carboxylic acid Chemical compound CN1C=NC=C1C(O)=O PBEDVTDUVXFSMW-UHFFFAOYSA-N 0.000 claims description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a synthesis method of methyl MQ silicon resin, which belongs to the technical field of high polymer materials and comprises the following steps: firstly, preprocessing; secondly, synthesizing a product; thirdly, post-treatment; according to the invention, the modified extraction catalyst is added, meanwhile, in the pretreatment process, water vapor is introduced, the modified extraction catalyst contains imidazole rings, hydrogen sulfate ions and-Si-O-Si bonds, sulfonic acid groups are arranged on side chains of the imidazole rings, and due to the existence of alkyl chains on the side chains, the hydrogen sulfate ions in anions are easier to release protons H and are acidic, the synthesis process of the methyl MQ silicon resin can be catalyzed, the yield of the methyl MQ silicon resin is improved, the-Si-O-Si bonds can have good compatibility with the methyl MQ silicon resin, the contact area between tetraethoxysilane and water molecules is promoted by the existence of the water vapor, the hydrolysis process of tetraethoxysilane is accelerated, and the yield of the methyl MQ silicon resin is further improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for synthesizing methyl MQ silicon resin.
Background
The MQ silicone resin is a silicone resin composed of monofunctional silicone chain units and tetrafunctional silicone chain units, can be widely applied to the fields of synthesis of organosilicon pressure-sensitive adhesives, reinforcement of transparent organosilicon gel and silicone rubber, and the like, and is an important organosilicon raw material.
In the prior art, MQ silicon resin is mainly prepared by a water glass method and an ethyl orthosilicate method, wherein the ethyl orthosilicate method has high yield and controllable average molar mass of a product, but in the industrial production process, the existence of a solvent can influence the subsequent treatment and quality of the product, if solvents such as alcohol, ketone and ether which are miscible with water are singly used, pure products cannot be obtained when the solvents are separated, and if solvents such as toluene, xylene and the like which are not dissolved in water are singly used, the molecular weight of the products can be increased, even gel can be generated, and meanwhile, in the preparation process, inorganic acid is commonly used as a catalyst, so that more inorganic anions remain in the synthesized product, and the performance of the product is influenced to a certain extent.
Therefore, how to provide a preparation method of methyl MQ silicon resin with easy solvent separation and high purity is a technical problem to be solved at present.
Disclosure of Invention
The invention aims to provide a synthesis method of methyl MQ silicon resin, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the synthesis method of the methyl MQ silicon resin comprises the following steps:
first, pretreatment: sequentially adding hexamethyldisiloxane, deionized water, absolute ethyl alcohol and ethyl orthosilicate into a reaction kettle with a condenser and a stirrer, dropwise adding a modified extraction catalyst while stirring, and controlling the dropwise adding within 30min, wherein the temperature is maintained to be 10-18 ℃ in the dropwise adding process, and the temperature is kept for reaction for 1-2h to obtain a crude mixture, wherein the dosage ratio of the hexamethyldisiloxane, the deionized water, the absolute ethyl alcohol, the ethyl orthosilicate and the modified extraction catalyst is 26-32mL:30-35mL:14.6-18mL:80-100mL:1.6-1.8mL;
secondly, synthesizing a product: introducing water vapor, performing heat preservation at 10 ℃ for 1h, maintaining the temperature at 13-15 ℃, continuously performing heat preservation for 1-1.5h, then heating to 60-70 ℃ in a gradient way, and continuously performing heat preservation reaction for 4-6h to obtain a crude product;
thirdly, post-treatment: heating to 75-80 ℃, removing absolute ethyl alcohol by rotary evaporation, adding a modified extraction catalyst, extracting, standing for layering, washing with deionized water to be neutral, removing the modified extraction catalyst by reduced pressure distillation, continuously heating to 103-104 ℃, removing low-boiling substances by reduced pressure distillation, cooling and packaging to obtain the methyl MQ silicon resin.
Further, in the second step, the water vapor is introduced at a rate of 35-45cm 3 /min。
Further, in the second step, the gradient heating rate is 10-20 ℃/min.
Further, in the third step, the volume ratio of the modified extraction catalyst is 0.8-1.2 times of that of the ethyl silicate.
Further, in the third step, the temperature of the reduced pressure distillation is 80-85 ℃.
Further, the preparation method of the modified extraction catalyst comprises the following steps:
under the protection of nitrogen, adding 1-methyl-1H-imidazole-5-formic acid into anhydrous DMF, stirring uniformly, adding N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and 3-aminopropyl triethoxysilane, heating to 65-75 ℃, stirring for reacting for 4-6 hours, and after the reaction is finished, carrying out suction filtration, respectively washing a filter cake with absolute ethyl alcohol and deionized water for 2-4 times, and freeze-drying to obtain an imidazole siloxane derivative, wherein the dosage ratio of 1-methyl-1H-imidazole-5-formic acid, anhydrous DMF, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and 3-aminopropyl triethoxysilane is 3.5-4.5g:40-50mL:6-8mL:4-5g:6.5-8.5mL, in the reaction process, anhydrous DMF is used as a solvent, 4-dimethylaminopyridine is used as a catalyst, N, N-dicyclohexylcarbodiimide is used as a dehydrating agent, and carboxyl on 1-methyl-1H-imidazole-5-formic acid and amino on 3-aminopropyl triethoxysilane are subjected to amidation reaction to obtain the imidazole siloxane derivative, and the structural formula is as follows:
。
step A2, adding an imidazole siloxane derivative into anhydrous DMF, dropwise adding 1, 3-propane sultone under stirring at the temperature of 0-4 ℃ in an ice bath, controlling the dropwise adding rate to be 2-4 drops/second, stirring uniformly, heating to 65-75 ℃, continuing stirring to react for 0.3-0.5h, filtering after the reaction is finished, washing with anhydrous diethyl ether for 2-4 times, and drying in vacuum at 50 ℃ for 4-6h to obtain a sultone imidazole salt, wherein the dosage ratio of the imidazole siloxane derivative, the anhydrous DMF and 1, 3-propane sultone is 3-4g:45-55mL:1.1-1.5g, and in the reaction process, the anhydrous DMF is taken as a solvent, and the active nitrogen atom on the imidazole group on the imidazole siloxane derivative and the sulfonate group on the 1, 3-propane sultone undergo ring-opening reaction to obtain the sultone imidazole salt, and the structural formula of the sultone imidazole salt is shown as follows:
。
step A3, dissolving sultone-based imidazole salt in deionized water, adding concentrated sulfuric acid while stirring, heating to 65-75 ℃, stirring and reacting for 2-3 hours, after the reaction is finished, removing the solvent by rotary evaporation at 60 ℃, and washing with anhydrous diethyl ether for 2-4 times to obtain a modified extraction catalyst, wherein the dosage ratio of the sultone-based imidazole salt, the deionized water and the concentrated sulfuric acid is 2-3g:30-40mL:3-5mL, in the reaction process, the sultone imidazole salt and concentrated sulfuric acid are subjected to addition reaction to obtain a modified extraction catalyst, and the structural formula of the modified extraction catalyst is shown as follows:
。
compared with the prior art, the invention has the following beneficial effects: in order to improve the yield of the prepared methyl MQ silicon resin, and reduce the influence of a solvent on a final product, the invention starts from two aspects, firstly, a modified extraction catalyst is added, the modified extraction catalyst contains imidazole rings, hydrogen sulfate ions and-Si-O-Si bonds, the imidazole ring side chains are provided with sulfonic acid groups, so that a space effect is generated, coulomb force between anion and cation structures is weakened due to the existence of alkyl chains on the side chains, the hydrogen sulfate ions in anions are easier to release protons H, the acidity is realized, the synthesis process of the methyl MQ silicon resin can be catalyzed, and the methyl MQ silicon resin synthesized by catalysis does not contain Cl － 、SO 4 － The inorganic ions are added, so that the yield of the methyl MQ silicon resin is improved, and the existence of the-Si-O-Si bond can have good compatibility with the prepared methyl MQ silicon resin, replace the traditional toluene or xylene solvent, and are nontoxic and environment-friendly; secondly, in the pretreatment process, water vapor is continuously introduced, so that the contact area between the tetraethoxysilane and water molecules is promoted, the hydrolysis process of the tetraethoxysilane is accelerated, and the yield of the methyl MQ silicon resin is further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment 1, preferred, this embodiment provides a method for preparing a modified extraction catalyst, comprising the steps of:
under the protection of nitrogen, adding 4g of 1-methyl-1H-imidazole-5-formic acid into 45mL of anhydrous DMF, stirring uniformly, adding 7mL of N, N-dicyclohexylcarbodiimide, 4.5g of 4-dimethylaminopyridine and 7.5mL of 3-aminopropyl triethoxysilane, heating to 70 ℃, stirring and reacting for 5 hours, after the reaction is finished, filtering, washing a filter cake with absolute ethyl alcohol and deionized water for 3 times respectively, and freeze-drying to obtain an imidazole siloxane derivative;
step A2, adding 3.5g of imidazole siloxane derivative into 50mL of anhydrous DMF, dropwise adding 1.3g of 1, 3-propane sultone under stirring at the temperature of 2 ℃ in an ice bath, controlling the dropwise adding rate to be 3 drops/second, uniformly stirring after the dropwise adding, heating to 70 ℃, continuously stirring for reacting for 0.4h, filtering after the reaction is finished, washing 3 times with anhydrous diethyl ether, and drying in vacuum at the temperature of 50 ℃ for 5h to obtain sultone imidazole salt;
and A3, dissolving 2.5g of sultone imidazole salt in 35mL of deionized water, adding 4mL of concentrated sulfuric acid while stirring, heating to 70 ℃, stirring for 2.5h, removing the solvent by rotary evaporation at 60 ℃ after the reaction is finished, and washing 3 times by using anhydrous diethyl ether to obtain the modified extraction catalyst.
Embodiment 2, this embodiment provides a method for synthesizing methyl MQ silicone resin, including the following steps:
first, pretreatment: 26mL of hexamethyldisiloxane, 30mL of deionized water, 14.6mL of absolute ethyl alcohol and 80mL of tetraethoxysilane are sequentially added into a reaction kettle with a condenser and a stirrer, 1.5mL of the modified extraction catalyst prepared in the example 1 is dropwise added while stirring, the dropwise addition is completed within 30min, the temperature is maintained at 10 ℃ in the dropwise addition process, and the reaction is carried out for 1h under heat preservation, so that a crude mixture is obtained;
secondly, synthesizing a product: introducing water vapor, carrying out heat preservation treatment for 1h at 10 ℃, maintaining the temperature at 13 ℃, continuing to carry out heat preservation for 1h, then carrying out gradient heating to 60 ℃ at the heating rate of 10 ℃/min, and continuing to carry out heat preservation reaction for 4h to obtain a crude product;
thirdly, post-treatment: heating to 75 ℃, removing absolute ethyl alcohol by rotary evaporation, adding the modified extraction catalyst prepared in the embodiment 1, extracting, standing for layering, washing with deionized water to neutrality, distilling under reduced pressure at 80 ℃ to remove the modified extraction catalyst, continuously heating to 103 ℃, distilling under reduced pressure to remove low-boiling substances, cooling and packaging to obtain the methyl MQ silicon resin.
Embodiment 3, this embodiment provides a method for synthesizing methyl MQ silicone resin, including the following steps:
first, pretreatment: adding 29mL of hexamethyldisiloxane, 32.5mL of deionized water, 16.3mL of absolute ethyl alcohol and 1.7mL of tetraethoxysilane in a reaction kettle with a condenser and a stirrer in sequence, dropwise adding the modified extraction catalyst prepared in the example 1 while stirring, controlling the dropwise adding within 30min, maintaining the temperature at 14 ℃ in the dropwise adding process, and carrying out heat preservation reaction for 1.5h to obtain a crude mixture;
secondly, synthesizing a product: introducing water vapor, carrying out heat preservation treatment for 1h at 10 ℃, maintaining the temperature at 14 ℃, continuing to carry out heat preservation for 1h, then carrying out gradient heating to 65 ℃ at the heating rate of 15 ℃/min, and continuing to carry out heat preservation reaction for 5h to obtain a crude product;
thirdly, post-treatment: heating to 77 ℃, removing absolute ethyl alcohol by rotary evaporation, adding the modified extraction catalyst prepared in the embodiment 1, extracting, standing for layering, washing with deionized water to be neutral, distilling under reduced pressure at 82.5 ℃ to remove the modified extraction catalyst, continuously heating to 103.5 ℃, distilling under reduced pressure to remove low-boiling substances, cooling and packaging to obtain the methyl MQ silicon resin.
Embodiment 4, this embodiment provides a method for synthesizing methyl MQ silicone resin, comprising the following steps:
first, pretreatment: adding 32mL of hexamethyldisiloxane, 35mL of deionized water, 18mL of absolute ethyl alcohol and 100mL of tetraethoxysilane in sequence into a reaction kettle with a condenser and a stirrer, dropwise adding 1.8mL of the modified extraction catalyst prepared in the example 1 while stirring, controlling the dropwise adding within 30min, maintaining the temperature at 18 ℃ in the dropwise adding process, and carrying out heat preservation reaction for 2h to obtain a crude mixture;
secondly, synthesizing a product: introducing water vapor, carrying out heat preservation treatment for 1h at 10 ℃, maintaining the temperature at 15 ℃, continuing to carry out heat preservation for 1h, then carrying out gradient heating to 70 ℃ at a heating rate of 20 ℃/min, and continuing to carry out heat preservation reaction for 6h to obtain a crude product;
thirdly, post-treatment: heating to 80 ℃, removing absolute ethyl alcohol by rotary evaporation, adding a modified extraction catalyst, extracting, standing for layering, washing with deionized water to be neutral, removing the modified extraction catalyst by reduced pressure distillation at 85 ℃, continuously heating to 104 ℃, removing low-boiling substances by reduced pressure distillation, cooling and packaging to obtain the methyl MQ silicon resin.
Comparative example 1
The 3-aminopropyl triethoxysilane in example 1 was removed, the remaining raw materials and the preparation process were unchanged, and the prepared material was replaced with the modified extraction catalyst in example 3, and the remaining raw materials and the preparation process were unchanged.
Comparative example 2
The modified extraction catalyst in the first step of example 3 was replaced with concentrated sulfuric acid having a concentration of 98%, and the remaining raw materials and preparation process were unchanged.
Comparative example 3
The modified extraction catalyst in the third step of example 3 was replaced with toluene, the remaining materials and preparation process were unchanged.
Performance detection
The yield and purity of the methyl MQ silicone resins prepared in examples 2 to 4 and comparative examples 1 to 3 were examined, respectively, and the specific examination results are shown in table 1:
TABLE 1
。
As can be seen from Table 1, the methyl MQ silicone resins obtained by the synthesis methods provided in examples 2-4 have higher yields than comparative examples 1-3.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A synthesis method of methyl MQ silicon resin is characterized in that: the method comprises the following steps:
first, pretreatment: sequentially adding hexamethyldisiloxane, deionized water, absolute ethyl alcohol and tetraethoxysilane into a reaction kettle with a condenser and a stirrer, dropwise adding a modified extraction catalyst while stirring, controlling the dropwise adding within 30min, maintaining the temperature at 10-18 ℃ in the dropwise adding process, carrying out heat preservation reaction for 1-2h to obtain a crude mixture,
secondly, synthesizing a product: introducing water vapor, performing heat preservation at 10 ℃ for 1h, maintaining the temperature at 13-15 ℃, continuously performing heat preservation for 1-1.5h, then heating to 60-70 ℃ in a gradient way, and continuously performing heat preservation reaction for 4-6h to obtain a crude product;
thirdly, post-treatment: heating to 75-80 ℃, removing absolute ethyl alcohol by rotary evaporation, adding a modified extraction catalyst, extracting, standing for layering, washing with deionized water to be neutral, removing the modified extraction catalyst by reduced pressure distillation, continuously heating to 103-104 ℃, removing low-boiling substances by reduced pressure distillation, cooling and packaging to obtain methyl MQ silicon resin;
the modified extraction catalyst is prepared by carrying out amidation reaction on 1-methyl-1H-imidazole-5-formic acid and 3-aminopropyl triethoxysilane to obtain an imidazole siloxane derivative, then carrying out ring-opening addition reaction on the imidazole siloxane derivative and 1, 3-propane sultone to obtain sultone imidazole salt, and finally carrying out substitution reaction on the sultone imidazole salt and concentrated sulfuric acid, and the preparation method of the modified extraction catalyst specifically comprises the following steps:
under the protection of nitrogen, adding 1-methyl-1H-imidazole-5-formic acid into anhydrous DMF, uniformly stirring, adding N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and 3-aminopropyl triethoxysilane, heating to 65-75 ℃, stirring for reacting for 4-6 hours, after the reaction is finished, performing suction filtration, respectively washing a filter cake with absolute ethyl alcohol and deionized water for 2-4 times, and freeze-drying to obtain an imidazole siloxane derivative;
step A2, adding an imidazole siloxane derivative into anhydrous DMF, dropwise adding 1, 3-propane sultone under stirring at the temperature of 0-4 ℃ in an ice bath, controlling the dropwise adding rate to be 2-4 drops/second, uniformly stirring, heating to 65-75 ℃ in a gradient way, continuously stirring for reacting for 0.3-0.5h, filtering after the reaction is finished, washing for 2-4 times with anhydrous diethyl ether, and drying in vacuum at the temperature of 50 ℃ for 4-6h to obtain sultone imidazole salt;
and A3, dissolving sultone imidazole salt in deionized water, adding concentrated sulfuric acid while stirring, heating to 65-75 ℃, stirring for 2-3h, removing the solvent by rotary evaporation at 60 ℃ after the reaction is finished, and washing with anhydrous diethyl ether for 2-4 times to obtain the modified extraction catalyst.
2. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the step A1, the dosage ratio of the 1-methyl-1H-imidazole-5-formic acid, anhydrous DMF, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and 3-aminopropyl triethoxysilane is 3.5-4.5g:40-50mL:6-8mL:4-5g:6.5-8.5mL.
3. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the step A2, the dosage ratio of the imidazole siloxane derivative, the anhydrous DMF and the 1, 3-propane sultone is 3-4g:45-55mL:1.1-1.5g.
4. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the step A3, the dosage ratio of the sultone imidazole salt, deionized water and concentrated sulfuric acid is 2-3g:30-40mL:3-5mL.
5. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the first step, the dosage ratio of the hexamethyldisiloxane, the deionized water, the absolute ethyl alcohol, the ethyl orthosilicate and the modified extraction catalyst is 26-32mL:30-35mL:14.6-18mL:80-100mL:1.6-1.8mL.
6. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the second step, the water vapor is introduced at a rate of 35-45cm 3 /min。
7. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the second step, the gradient heating rate is 10-20 ℃/min.
8. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the third step, the volume of the modified extraction catalyst is 0.8-1.2 times of that of the ethyl orthosilicate.
9. The method for synthesizing methyl MQ silicone resin according to claim 1, wherein the method comprises the following steps: in the third step, the temperature of reduced pressure distillation is 80-85 ℃.
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| US8728345B2 (en) * | 2011-12-19 | 2014-05-20 | Momentive Performance Materials Inc. | Epoxy-containing polysiloxane oligomer compositions, process for making same and uses thereof |
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| JP2001139990A (en) * | 1999-08-31 | 2001-05-22 | Lion Corp | Method for producing emulsion composition containing silicone and water-swellable clay mineral and detergent composition containing the emulsion composition |
| CN102796274A (en) * | 2012-05-25 | 2012-11-28 | 常州大学 | Composite proton exchange membrane for high temperature-resistant fuel cell and preparation method for composite proton exchange membrane |
| CN104892519A (en) * | 2015-04-23 | 2015-09-09 | 河南师范大学 | Imidazolyl bionic ionic liquid preparation method |
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