CN113214311B - Synthesis method of N, N-dimethyl-3-aminopropyl trimethoxy silane - Google Patents
Synthesis method of N, N-dimethyl-3-aminopropyl trimethoxy silane Download PDFInfo
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- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 19
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000012043 crude product Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BMEQUUBENOHASH-UHFFFAOYSA-N n,n-dimethyl-1-trimethoxysilylpropan-2-amine Chemical compound CO[Si](OC)(OC)CC(C)N(C)C BMEQUUBENOHASH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- -1 o-carboxyphenyl disulfides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WFWLQNSHRPWKFK-UHFFFAOYSA-N Tegafur Chemical compound O=C1NC(=O)C(F)=CN1C1OCCC1 WFWLQNSHRPWKFK-UHFFFAOYSA-N 0.000 description 1
- OMIWQUWXCBDCCB-UHFFFAOYSA-N acetic acid trimethoxysilane Chemical compound CO[SiH](OC)OC.C(C)(=O)O OMIWQUWXCBDCCB-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention belongs to the field of production and manufacturing of silane coupling agents, and particularly discloses a synthesis method of N, N-dimethyl-3-aminopropyl trimethoxy silane. According to the invention, the N, N-dimethyl-3-aminopropyl trimethoxy silane is synthesized by using the dimethyl acrylamide and the trimethoxy hydrosilane as raw materials in the presence of a catalyst and a cocatalyst, so that the synthesis process can not only overcome the unsafe problems of use, storage and transportation of dimethylamine, but also avoid the production reaction under high pressure condition and waste of energy; the invention has mild reaction conditions, no pollution, no generation of hydrochloride, simple whole production and preparation process and easy control; in addition, the invention designs a new synthesis process, so that the yield of the prepared N, N-dimethyl-3-aminopropyl trimethoxy silane product is more than 90%, and the purity of the product reaches 99%, thus having a certain application prospect in the field of silane coupling agent production and manufacturing.
Description
Technical Field
The invention belongs to the field of production and manufacture of silane coupling agents, and particularly relates to a synthesis method of N, N-dimethyl-3-aminopropyl trimethoxy silane.
Background
The silane coupling agent is a silane with organic functional groups, can play a role similar to a bridge between interfaces of different materials, connects two materials with different properties, and is a special organic silicide. The silane coupling agent has the following structure general formula of Y (CH 2)nSiX3, wherein X and Y represent two groups with different properties, X represents a hydrolyzable group and can be compatible with inorganic materials, Y has strong affinity with organic materials, is easier to combine with resin and rubber in organic matters, is critical to the coupling effect of the silane coupling agent, determines the performance of the silane coupling agent, and is often obtained according to the Y group, and the two groups coexist and act in the silane coupling agent to endow the silane coupling agent with the functions of reinforcing the bonding of a filler with a resin base material and a coating with an inorganic underlayer, so that materials with different chemical structures and different affinities can be connected at the interface of the materials: the silane coupling agent can change the structure of the particle surface, so that the particles are dissolved in organic matters to improve the crease resistance and flexibility of the fabric; 2) Used as tackifier and adhesive: the silane coupling agent has the function that based on the structural characteristics, the polar structure and the nonpolar structure exist in the molecule at the same time to determine that the silane coupling agent can bond polar materials and nonpolar materials, so that the bonding strength between interface layers can be greatly improved, and organic materials and inorganic materials with different properties are connected; 3) As rubber processing agent: the silane coupling agent can promote the realization of chemical bonding between the filler and the matrix in rubber processing, so that the physical properties of the filled rubber can be obviously improved; the dispersion performance of the filler in the matrix can be improved, the viscosity of the mixed rubber particles can be reduced, and the processability of the filling rubber is improved; the silane coupling agent is also widely applied to adhesion promoters of various coatings and printing inks, and can be directly used as a raw material to participate in the synthesis of materials.
The organosilane coupling agent is used as a novel material, is widely applied to various industries such as energy, traffic, building materials, paint, electronics and the like, can increase the cohesiveness of a coating in the paint industry, can increase the water resistance of the material in the building material industry, and can be used for adhesives, isolating agents, protective agents and the like in the electronics industry.
N, N-dimethyl-3-aminopropyl trimethoxy silane is a special silane coupling agent which has the basic characteristics of aminosilane, so that the N, N-dimethyl-3-aminopropyl trimethoxy silane is widely applied to the aspects of material adhesion, modification and the like. At present, the prior art adopts dimethylamine and 3-chloropropyl trimethoxysilane as raw materials to react to synthesize N, N-dimethyl-3-aminopropyl trimethoxysilane. A foreign document (Lamar,Field,Patton,et al.Organic disulfides and related substances.XXXI.Possible anchimeric involvement of an ortho carboxylate moiety in disproportionation of unsymmetrical o-carboxyphenyl disulfides[J].Journal of Organic Chemistry,1971.) reports a method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxy silane, specifically, 3.5mol of 3-chloropropyl trimethoxy silane and 14mol of dimethylamine are taken, 400ml of petroleum solvent is added at the same time, and then the mixture is placed in an autoclave for reaction for 22 hours at 100 ℃ to obtain 570g of product with the yield of 79 percent. But the process has long reaction time, low yield and low industrial production efficiency. A domestic literature (Lin Zuliang, guo Shixin. Development of N-dimethylaminopropyl trimethoxy silane acetate coupling agent [ J ]. Organosilicon materials and application, 1991 (3): 1-2.) reports a method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxy silane, specifically, chloropropyl trimethoxy silane, dimethylamine and solvent are utilized to react in an autoclave, after the reaction is completed, filter residues are removed by cooling, and the product is obtained by rectification, wherein the yield is 85%, and the purity of the product reaches 99%.
Chinese patent document CN105859766A reports a method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxy silane without solvent, specifically, the method comprises the steps of adding chloropropyl trimethoxy silane (1 mol) and dimethylamine (3-6 mol) into a high-pressure reaction kettle to react for 6-8 hours, ending the reaction, discharging excessive dimethylamine gas, filtering and rectifying to obtain the product. The product yield is 87%, and the product purity reaches 99%.
Although N, N-dimethyl-3-aminopropyl trimethoxy silane can be prepared in the synthesis reaction, the reaction is a high-pressure reaction, excessive dimethylamine is needed, certain tail gas pollution exists, salt slag generated by filtration needs to be recycled by sodium hydroxide, the recycled dimethylamine contains water and cannot be fully utilized, in addition, the hydrochloride is rinsed by adopting a solvent N, N-dimethylformamide, and the treatment difficulty is increased for the subsequent recycling rectification by introducing the solvent. Therefore, a new synthesis process of N, N-dimethyl-3-aminopropyl trimethoxysilane is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxy silane, which is characterized in that dimethylacrylamide and trimethoxy hydrogen silane are selected as raw materials, and N, N-dimethyl-3-aminopropyl trimethoxy silane is synthesized in the presence of a catalyst and a cocatalyst. The synthesis process not only can overcome the unsafe problems of dimethylamine use, storage and transportation, but also can avoid the production reaction under high pressure condition and waste energy sources; the invention has mild reaction condition, no pollution, no generation of hydrochloride, simple whole production and preparation process and easy control.
In order to solve the problems in the prior art, the invention is realized by the following technical scheme:
A synthetic method of N, N-dimethyl-3-aminopropyl trimethoxy silane comprises the following steps:
s1, adding dimethyl acrylamide, a catalyst and a cocatalyst into a reaction container, and heating to a certain temperature after uniformly stirring and mixing; then slowly dripping trimethoxy silane to carry out a mixing reaction;
S2, gradually heating up after the trimethoxy silicon in the step S2 is added dropwise, and reacting for 2-3 h at 80-90 ℃ in a heat preservation way;
S3, after the reaction is finished, carrying out reduced pressure distillation to obtain the refined N, N-dimethyl-3-aminopropyl trimethoxysilane. Further, the molar ratio of the amount of the dimethylacrylamine in the step S1 to the amount of the trimethoxysilane in the step S2 is 1: (1.05-1.15).
Further, in the step S1, the molar ratio of the amounts of the dimethylacrylamine to the trimethoxysilane is 1: (1.05-1.15), heating to 60-70 ℃ after uniformly mixing, and mixing reaction to 70-80 ℃.
Further, in the step S1, the usage amount of the cocatalyst is 3-5% of the mass of the trimethoxysilane.
Further, in step S1, the catalyst includes a catalyst a and a ligand.
Further, the catalyst A is one of a platinum catalyst or a rhodium catalyst.
Still further, the platinum catalyst is chloroplatinic acid.
Still further, the rhodium catalyst is rhodium chloride.
Still further, the ligand is one of tetrahydrofuran, n-propanol, vinyl silicone oil and isopropanol.
Further, in step S1, the cocatalyst is one of methanol, ethanol and n-butanol, preferably methanol.
The synthesis mechanism of the N, N-dimethyl-3-aminopropyl trimethoxysilane is as follows: selecting dimethylacrylamine and trimethoxy silane as raw materials for reaction, adding a platinum catalyst to perform hydrosilylation reaction, wherein high-valence platinum ions are firstly reduced into low-valence platinum by trimethoxy silane, then the trimethoxy silane and a platinum-olefin complex are subjected to oxidative addition, and simultaneously coordinated olefin is inserted into Pt-Si, and finally N, N-dimethyl-3-aminopropyl trimethoxy silane is obtained through reduction and elimination; in addition, ligand (isopropanol) is added into the platinum catalyst to form a complex, and then the crystallization water is removed, so that the induction period of the reaction is further shortened, the uniformity of the catalyst is enhanced, and the occurrence of side reaction is reduced, thereby improving the yield of the N, N-dimethyl-3-aminopropyl trimethoxysilane.
Compared with the prior art, the invention has the following advantages:
1) The invention selects dimethyl acrylamide and trimethoxy hydrosilane as raw materials, and synthesizes N, N-dimethyl-3-aminopropyl trimethoxy silane in the presence of a catalyst and a cocatalyst. The synthesis process not only can overcome the unsafe problems of dimethylamine use, storage and transportation, but also can avoid the production reaction under high pressure condition and waste energy sources; the invention has mild reaction conditions, no pollution, no generation of hydrochloride, simple whole production and preparation process and easy control;
2) The invention designs a new synthesis process, so that the yield of the prepared N, N-dimethyl-3-aminopropyl trimethoxy silane product is more than 90%, and the purity of the product reaches 99%, thus having a certain application prospect in the field of silane coupling agent production and manufacturing.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic reaction diagram of the preparation process of the present invention.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in connection with specific embodiments. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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 fall within the scope of the invention.
The raw materials and equipment used in the present invention are commercially available unless otherwise specified.
Example 1
The synthesis method of the N, N-dimethyl-3-aminopropyl trimethoxysilane comprises the following steps: a magnetic stirring device, a thermometer and a glass flask with a constant pressure funnel are arranged on a water bath heating device, firstly, after the constant pressure funnel is taken down, 85g of dimethyl acrylamide, 0.2g of a composite catalyst synthesized by chloroplatinic acid and ligand (n-propanol) and 4g of methanol are added into the glass flask, and after stirring and mixing are carried out uniformly, the temperature is raised to 60 ℃; then, a constant pressure funnel is arranged on a glass flask, 128.1g of trimethoxy silane is weighed and added into the constant pressure funnel, then, the switch of the constant pressure funnel is controlled, the trimethoxy silane is gradually added into the glass flask in a dropwise manner, the reaction temperature is controlled to be 70 ℃, after the addition is finished, the temperature is raised to 80 ℃, and the reaction is continued for 2 hours.
Obtaining a crude product after the reaction is finished, wherein the content of N, N-dimethyl-3-aminopropyl trimethoxy silane is 90%, and the content of N, N-dimethyl-2-aminopropyl trimethoxy silane is 8%; further, the crude product was subjected to rectification under reduced pressure to obtain 193g of N, N-dimethyl-3-aminopropyl trimethoxysilane with a content of 99.2% and a yield of 92.5%.
Example 2
The synthesis method of the N, N-dimethyl-3-aminopropyl trimethoxysilane comprises the following steps: a magnetic stirring device, a thermometer and a glass flask with a constant pressure funnel are arranged on a water bath heating device, firstly, after the constant pressure funnel is taken down, 85g of dimethylacrylamine, 0.3g of a composite catalyst synthesized by chloroplatinic acid and ligand (isopropanol) and 5g of methanol are added into the glass flask, and after stirring and mixing are carried out uniformly, the temperature is raised to 65 ℃; then, a constant pressure funnel is arranged on a glass flask, 134.2g of trimethoxy silane is weighed and added into the constant pressure funnel, then, the switch of the constant pressure funnel is controlled, trimethoxy silane is gradually added into the glass flask in a dropwise manner, the reaction temperature is controlled to be 75 ℃, after the addition is finished, the temperature is raised to be 85 ℃, and the reaction is continued for 2.5 hours.
Obtaining a crude product after the reaction is finished, wherein the content of N, N-dimethyl-3-aminopropyl trimethoxy silane is 90%, and the content of N, N-dimethyl-2-aminopropyl trimethoxy silane is 8%; further, the crude product was subjected to rectification under reduced pressure to obtain 192g of N, N-dimethyl-3-aminopropyl trimethoxysilane with a content of 99.1% and a yield of 92.8%.
Example 3
The synthesis method of the N, N-dimethyl-3-aminopropyl trimethoxysilane comprises the following steps: a magnetic stirring device, a thermometer and a glass flask with a constant pressure funnel are arranged on a water bath heating device, firstly, after the constant pressure funnel is taken down, 85g of dimethyl acrylamide, 0.4g of rhodium chloride and ligand (isopropanol) synthesized composite catalyst and 6g of methanol are added into the glass flask, and after stirring and mixing uniformly, the temperature is raised to 70 ℃; and then installing a constant pressure funnel on a glass flask, weighing 140.3g of trimethoxy silane, adding the trimethoxy silane into the constant pressure funnel, controlling the switch of the constant pressure funnel, gradually dropwise adding the trimethoxy silane into the glass flask, controlling the reaction temperature to 80 ℃, heating to 90 ℃ after the addition is finished, and continuing to perform heat preservation reaction for 3 hours.
Obtaining a crude product after the reaction is finished, wherein the content of N, N-dimethyl-3-aminopropyl trimethoxy silane is 90%, and the content of N, N-dimethyl-2-aminopropyl trimethoxy silane is 8%; further, the crude product was subjected to rectification under reduced pressure to obtain 194g of N, N-dimethyl-3-aminopropyl trimethoxysilane, the content was 99.3%, and the yield was 93.7%.
Comparative example 1
The synthesis of N, N-dimethyl-3-aminopropyl trimethoxysilane was substantially similar to example 1, except that only 0.2g of chloroplatinic acid was added as catalyst.
Obtaining a crude product after the reaction is finished, wherein the content of N, N-dimethyl-3-aminopropyl trimethoxy silane is 84 percent, and the content of N, N-dimethyl-2-aminopropyl trimethoxy silane is 14 percent; further, the crude product was subjected to rectification under reduced pressure to obtain 187g of N, N-dimethyl-3-aminopropyl trimethoxysilane with a content of 99.1% and a yield of 86%.
Comparative example 2
The synthesis of N, N-dimethyl-3-aminopropyl trimethoxysilane was substantially similar to example 1, except that 4g of methanol was not added.
Obtaining a crude product after the reaction is finished, wherein the content of N, N-dimethyl-3-aminopropyl trimethoxy silane is 81 percent, and the content of N, N-dimethyl-2-aminopropyl trimethoxy silane is 11 percent; further, the crude product was subjected to rectification under reduced pressure to obtain 178 g of N, N-dimethyl-3-aminopropyl trimethoxysilane with a content of 86.2% and a yield of 85%.
Comparative example 3
The synthesis of N, N-dimethyl-3-aminopropyl trimethoxysilane was substantially similar to example 2, except that 5g of methanol was replaced with 5g of isobutanol.
Obtaining a crude product after the reaction is finished, wherein the content of N, N-dimethyl-3-aminopropyl trimethoxy silane is 88%, and the content of N, N-dimethyl-2-aminopropyl trimethoxy silane is 10%; further, the crude product was subjected to rectification under reduced pressure to obtain 190g of N, N-dimethyl-3-aminopropyl trimethoxysilane with a content of 99.3% and a yield of 88.4%.
From the results of examples 1 to 3, it can be seen that the new synthesis process of the invention is adopted, so that the yield of the prepared N, N-dimethyl-3-aminopropyl trimethoxy silane product is over 90%, the purity of the product is up to 99%, and the yield and purity of the prepared product are higher than those of the 3 synthesis processes described in the background art;
comparative example 1 is different from example 1 in that the catalyst added does not contain a ligand (isopropyl alcohol), the content of the produced N, N-dimethyl-3-aminopropyl trimethoxysilane is 99.1%, the yield is 86%, and the yield in example 1 is higher because the ligand (isopropyl alcohol) is added to the catalyst to form a complex, and then the crystallization water is removed, thereby further shortening the induction period of the reaction, enhancing the uniformity of the catalyst, reducing the occurrence of side reaction, and further improving the yield of the N, N-dimethyl-3-aminopropyl trimethoxysilane;
Comparative example 2 is different from example 1 in that no auxiliary agent was added, the produced N, N-dimethyl-3-aminopropyl trimethoxysilane was 86.2% in the yield of 85%, and the purity and yield in example 1 were higher because the reaction rate was greatly accelerated after the auxiliary agent was added, and the reaction was incomplete in comparative example 2 under the same reaction time since no auxiliary agent was added in comparative example 2, and the produced product was lower in yield and purity.
Comparative example 3 was different from example 2 in that 5g of methanol was changed to 5g of isobutanol, and the produced N, N-dimethyl-3-aminopropyl trimethoxysilane was 99.3% in yield of 88.4% and was slightly lowered compared to example 2, further indicating that methanol is an optimal auxiliary agent.
In summary, the invention adopts the dimethyl acrylamide and the trimethoxy hydrosilane as raw materials, and synthesizes the N, N-dimethyl-3-aminopropyl trimethoxy silane under the existence of a catalyst and a cocatalyst. The synthesis process not only can overcome the unsafe problems of dimethylamine use, storage and transportation, but also can avoid the production reaction under high pressure condition and waste energy sources; the invention has mild reaction condition, no pollution, no generation of hydrochloride, simple whole production and preparation process and easy control.
The above examples are only specific embodiments of the present invention for illustrating the technical solution of the present invention, but not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the foregoing examples, it will be understood by those skilled in the art that the present invention is not limited thereto: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention.
Claims (5)
1. The synthesis method of the N, N-dimethyl-3-aminopropyl trimethoxy silane is characterized by comprising the following steps of:
s1, adding dimethyl acrylamide, a catalyst and a cocatalyst into a reaction container, and heating to a certain temperature after uniformly stirring and mixing; then slowly dripping trimethoxy silane to carry out a mixing reaction;
S2, gradually heating up after the trimethoxy silicon in the step S2 is added dropwise, and reacting for 2-3 h at 80-90 ℃ in a heat preservation way;
S3, after the reaction is finished, carrying out reduced pressure distillation to obtain the refined N, N-dimethyl-3-aminopropyl trimethoxysilane;
In step S1:
The molar ratio of the dosage of the dimethyl acrylamide to the dosage of the trimethoxysilane is 1: (1.05-1.15), heating to 60-70 ℃ after uniform mixing, wherein the temperature of the mixing reaction is 70-80 ℃;
the catalyst comprises a catalyst A and a ligand; the catalyst A is one of a platinum catalyst or a rhodium catalyst; the ligand is one of tetrahydrofuran, n-propanol, vinyl silicone oil and isopropanol;
The cocatalyst is one of methanol, ethanol and n-butanol.
2. The method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxysilane according to claim 1, wherein the catalyst is used in an amount of 0.2 to 0.5% by mass of the dimethylacrylamide.
3. The method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxysilane according to claim 1, wherein the amount of the cocatalyst is 3-5% by mass of the trimethoxysilane.
4. The method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxysilane according to claim 1, wherein the platinum catalyst is chloroplatinic acid.
5. The method for synthesizing N, N-dimethyl-3-aminopropyl trimethoxysilane according to claim 1, wherein the rhodium catalyst is rhodium chloride.
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