CN116284101A - Preparation method of hydrocarbyl chlorosilane - Google Patents
Preparation method of hydrocarbyl chlorosilane Download PDFInfo
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- CN116284101A CN116284101A CN202211095318.3A CN202211095318A CN116284101A CN 116284101 A CN116284101 A CN 116284101A CN 202211095318 A CN202211095318 A CN 202211095318A CN 116284101 A CN116284101 A CN 116284101A
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- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 42
- -1 hydrocarbyl chlorosilane Chemical compound 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000007086 side reaction Methods 0.000 description 13
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- ZUKYLGDWMRLIKI-UHFFFAOYSA-N chloro-ethyl-methylsilicon Chemical compound CC[Si](C)Cl ZUKYLGDWMRLIKI-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- SOYVLBDERBHIME-UHFFFAOYSA-N chloro(diethyl)silicon Chemical compound CC[Si](Cl)CC SOYVLBDERBHIME-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a preparation method of hydrocarbyl chlorosilane, wherein the preparation method comprises the steps of carrying out hydrosilylation reaction on 1-olefin and chlorosilane under the catalysis of a platinum catalyst to obtain the hydrocarbyl chlorosilane; wherein the 1-olefin is C 3 ～C 20 Olefin and chlorosilane are hydrogen-containing chlorosilane; the hydrosilylation temperature is 10-40 ℃ and the pressure is normal pressure. The preparation method of the alkyl chlorosilane can effectively simplify the preparation process of the alkyl chlorosilane and improve the safety and the product quality.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of hydrocarbyl chlorosilane.
Background
Chlorosilane and its derivative are important organic synthesis intermediates, and have very wide application in the fields of conductive high polymer materials, new energy sources, coatings and the like. Specifically, the hydroxyl in the organic silicon can be effectively protected in the process of synthesizing the organic silicon, and simultaneously when long-chain alkyl chlorosilane is connected with the hydroxyl on the branched chain of the high polymer material, the flexibility and the hydrophobicity of the high polymer material and the solubility of the high polymer material in an organic solvent can be effectively improved.
Hydrocarbyl chlorosilanes are a derivative of chlorosilanes, the most predominant method of synthesis of which is hydrosilylation of an olefin with a hydrogen-containing chlorosilane. In general, the hydrosilylation reaction is carried out under the catalysis of high-activity chloroplatinic acid, and the reaction is intense and a large amount of heat is emitted, so even if a high-pressure container is adopted in the reaction, obvious hot stamping phenomenon can occur, and high potential safety hazard exists in the production process. In order to solve the above problems, a certain amount of a solvent is added to a system of hydrosilylation reaction to prevent a rapid increase in reaction temperature (the solvent absorbs a certain amount of heat). However, the use of the solvent not only reduces the production efficiency and increases the production cost, but also requires large-scale post-treatment of the used solvent, which is a burden to both economy and environment. In order to solve the problems of hot stamping and hot stamping, researchers have tried to adjust the addition sequence or addition speed of reactants, which can suppress the rapid temperature rise to a certain extent and suppress the poisoning phenomenon of the catalyst; however, the controllability of the kind and amount of by-products in the process is reduced.
In addition, in the existing hydrosilylation reaction, the catalyst is usually required to be pretreated, and the temperature and the pressure in the process are strictly controlled, so that the defects of complex operation, complex preparation method and the like are overcome; most importantly, the yield and purity of the resulting product are low.
In conclusion, the existing preparation method of the alkyl chlorosilane has the defects of poor safety, complex operation, poor product quality and the like.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method of the alkyl chlorosilane, which can effectively simplify the preparation process of the alkyl chlorosilane and improve the safety and the product quality.
According to an embodiment of the first aspect of the present invention, a preparation method of hydrocarbyl chlorosilane is provided, the preparation method includes performing a hydrosilylation reaction between a compound shown in formula I and a compound shown in formula II under the catalysis of a platinum catalyst to obtain hydrocarbyl chlorosilane shown in formula III;
wherein:
in the formula I, R 1 Is C 4 ～C 18 An alkyl group;
in formula II, R 2 And R is 3 Independently selected from C 1 ～C 3 An alkyl group;
the ratio of the amount of the compound shown in the formula I to the amount of the compound shown in the formula II is 1:3.5-4;
the hydrosilylation conditions are room temperature and normal pressure; the room temperature is 10-40 ℃.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
(1) In the conventional art, it is considered that in the hydrosilylation reaction, the side reaction is promoted at high temperature or low temperature and the main reaction is suppressed, so in the conventional preparation method, the temperature of the hydrosilylation reaction is generally controlled to be 50-180 ℃ to improve the yield of the product.
The traditional technology also proves that the bound water in the platinum catalyst can cause serious side reaction at 50-180 ℃, so that the platinum catalyst must be purified and activated in the hydrosilylation reaction process;
also, because the compound of formula II (chlorosilane) generally has a relatively low boiling point, if heated, the hydrosilylation reaction is performed, or a high pressure resistant, sealed reaction vessel is required; or can result in the escape of chlorosilanes into the environment, which can be a safety hazard.
According to the invention, by limiting the temperature of the hydrosilylation reaction, chlorosilane cannot be evaporated violently in the reaction process, so that even if sealing and pressurizing are not performed, serious pollution to air cannot be caused, the preparation process is simplified finally, and the safety is improved; on the other hand, due to the reduction of the hydrosilylation reaction temperature and the limitation of the types and the dosage of the preparation raw materials, the side reaction which can be caused by water in the platinum catalyst is also greatly reduced, so that the pretreatment flow of the platinum catalyst can be omitted, and the limitation of the preparation method on the conditions is reduced, so that the method is more suitable for industrial application; most importantly, the invention also proves that the yield of the product can reach almost 100% under the condition of room temperature.
(2) In the conventional technology, in order to provide a liquid-phase reaction environment and also to suppress a drastic temperature rise in the hydrosilylation reaction, it is generally necessary to add a solvent to the reaction system.
The invention ensures that the chlorosilane shown in the formula II is in a liquid state at normal temperature by limiting the selection of the substituent groups in the compound shown in the formula II, so that the chlorosilane has the function of a solvent, therefore, the preparation method omits the use of the solvent, saves the cost and also saves the subsequent process of solvent recovery and treatment.
(3) In the system obtained by the hydrosilylation reaction, besides the alkyl chlorosilane shown in the formula III, unreacted complete reactants and catalyst are also included, and impurities are removed by adopting a recrystallization or distillation method; however, the compound shown in the formula I has a higher boiling point and is close to the boiling point of a product, so that the compound is difficult to remove by a distillation method; on the other hand, the product has strong water sensitivity, and the recrystallization process is inevitably contacted with air, which can affect the yield and purity, so that the purification effect of the recrystallization is not ideal.
According to the invention, the compound shown in the formula I fully reacts by regulating the ratio of the amount of the compound shown in the formula I to the amount of the compound shown in the formula II, so that the compound shown in the formula I is hardly contained in a system obtained by hydrosilylation reaction, and the impurity can be removed by a simple distillation method because the difference of boiling points of the compound shown in the formula II and the product is large.
That is, the invention simplifies the impurity removal process of the product by selecting the types and proportions of the preparation raw materials.
(4) In conclusion, the invention not only simplifies the preparation method and reduces the potential safety hazard by limiting the types and the dosage of the preparation raw materials; and the prejudice in the prior art is overcome, and the yield of the product (the hydrocarbyl chlorosilane shown in the formula III) which is more than or equal to 99 percent and the purity of the product which is more than or equal to 97 percent are obtained under the condition of room temperature (namely 10-40 ℃), so that unexpected technical effects are achieved.
According to some embodiments of the invention, R in formula I 1 And R in formula II 2 、R 3 The three materials may be the same, two by two, or all the three materials may be different.
According to some embodiments of the invention, in formula I, R 1 Is C 15 ～C 16 An alkyl group.
According to the present inventionSome preferred embodiments of the invention, in formula I, R 1 Is C 16 An alkyl group.
According to some further preferred embodiments of the present invention, the compound of formula I is selected from 1-octadecene (CAS: 112-88-9).
Therefore, compared with the olefin in the middle position, the terminal olefin can reduce the reaction steric hindrance and finally reduce the difficulty of the hydrosilylation reaction.
According to some embodiments of the invention, in formula II, R 2 And R is 3 Independently selected from C 1 Or C 2 An alkyl group.
According to some embodiments of the invention, the compound of formula II represents at least one of dimethylchlorosilane (CAS: 1066-35-9), diethylchlorosilane (CAS: 1609-19-4), and methylethylchlorosilane (CAS: 6374-21-6).
According to some preferred embodiments of the invention, the compound of formula II represents at least one of dimethylchlorosilane and methylethylchlorosilane.
Thus, the compound of formula II has a lower melting point and can be used as a solvent at room temperature. Meanwhile, the boiling point of the compound shown in the formula II is also lower, so that the chlorosilane compound which does not react completely can be separated from the hydrocarbyl chlorosilane shown in the formula III by simple distillation, and the purification step of the product is simplified.
According to some embodiments of the invention, the ratio of the amount of the compound of formula I to the amount of the compound of formula II is about 1:4.
This ensures that the compounds of formula I are reacted to completion, and the resulting mixture of the hydrosilylation reaction contains little or no compounds of formula I, ultimately simplifying the purification process of the product. Meanwhile, excessive compound shown in formula II and platinum catalyst compete to participate in the reaction with the compound shown in formula I, so that side reaction brought by (water of crystallization in) the platinum catalyst is inhibited.
According to some embodiments of the invention, the platinum catalyst comprises at least one of anhydrous chloroplatinic acid (CAS: 16941-12-1) and aqueous chloroplatinic acid (CAS: 16941-12-1) containing crystallization.
Although the crystallization water in the platinum catalyst reacts with the compound of formula I (side reaction) and also causes side reaction of the product (hydrocarbyl chlorosilane of formula III), the temperature is limited and the side reaction is suppressed, so that whether the platinum catalyst contains crystallization water or not has little influence on the yield of the preparation method and the purity of the product.
According to some embodiments of the invention, the chloroplatinic acid containing water of crystallization comprises chloroplatinic acid hexahydrate.
According to some preferred embodiments of the invention, the platinum catalyst is selected from anhydrous chloroplatinic acid.
According to some embodiments of the invention, the ratio of the amounts of the compounds of formula I and the platinum catalyst is 55000 to 3500000:1.
The above proportions affect to some extent the rate of the hydrosilylation reaction:
when the ratio is equal to 3000000:1, the hydrosilylation reaction can be completed within 24 hours;
when the ratio is more than 3000000:1, the hydrosilylation reaction can still be performed, but the time required is longer, for example, about 32 hours or 30 hours;
when the above ratio is < 3000000:1, the time required for the hydrosilylation reaction is greatly shortened, and may be about 18 hours, for example.
However, the amount of the platinum catalyst added does not affect the yield and purity of the product obtained by the preparation method.
According to some preferred embodiments of the invention, the ratio of the amounts of the compounds of formula I and the platinum catalyst is 3000000 to 30550000:1.
According to some preferred embodiments of the invention, the ratio of the amounts of the compound of formula I and the platinum catalyst is 59000 to 60000:1.
According to some embodiments of the invention, the hydrosilylation reaction temperature is 10-30 ℃.
According to some embodiments of the invention, the hydrosilylation reaction is performed under water bath conditions; the water bath was not temperature controlled.
Therefore, although the temperature of the water bath is the same as the room temperature at the beginning of the hydrosilylation reaction, the water bath can take away the heat generated by the hydrosilylation reaction to a certain extent, so that the temperature of the hydrosilylation reaction is maintained within a relatively constant level, the escape of the compound shown in the formula II is effectively inhibited, and the promotion of side reactions by the flushing temperature is effectively inhibited.
According to some embodiments of the invention, the normal pressure is about 1 standard atmospheric pressure, i.e., about 0.1MPa. This pressure varies slightly with the implementation of the preparation process, but the above variations do not affect the implementation of the preparation process and the corresponding results.
According to some embodiments of the invention, the hydrosilylation reaction is carried out by sequentially adding the compound of formula II, the platinum catalyst, and the compound of formula I to a reaction vessel.
Therefore, the reaction of the crystallization water in the platinum catalyst and the compound shown in the formula I can be fully avoided, namely, side reactions are effectively avoided, the main reaction is promoted, and finally, the yield of the compound shown in the formula III is improved.
According to some embodiments of the invention, the method further comprises purifying the hydrocarbyl chlorosilane of formula III after the hydrosilylation reaction.
According to some embodiments of the invention, the purifying comprises atmospheric distillation and rotary evaporation performed sequentially.
According to some embodiments of the invention, the atmospheric distillation is at a temperature > the boiling point of the compound of formula II. Whereby the compound of formula II, which is not completely reacted, is removed from the system.
According to some embodiments of the invention, the difference between the temperature of the atmospheric distillation and the boiling point of the compound of formula II is less than or equal to 10 ℃. Thus, the occurrence of side reactions can be suppressed as much as possible during the atmospheric distillation.
According to some embodiments of the invention, the atmospheric distillation is performed under water-tight conditions. Thus, the reaction of the hydrocarbyl chlorosilane of formula III and water to produce byproducts can be avoided.
According to some embodiments of the invention, the atmospheric distillation further comprises collecting the distilled compound of formula II;
further, the yield of the compound represented by formula II is 68% or more, for example, 68.5% or 71.3%. The yield here refers to the ratio of the mass of the recovered material to the mass of the fed material.
According to some embodiments of the invention, the temperature of the rotary evaporation is 10-20 ℃ higher than the boiling point of the compound shown in formula II; thereby, the separation and removal of the compound shown in the formula II can be further realized.
According to some embodiments of the invention, the removing of impurities further comprises solid-liquid separation after the hanging steaming; the obtained solid is the platinum catalyst, and the obtained liquid is the purified hydrocarbyl chlorosilane.
The platinum catalyst obtained by the solid-liquid separation can be repeatedly used for 3-5 times, and the yield of the alkyl chlorosilane is not affected; however, as the number of repeated use is increased, the time required for the hydrosilylation reaction is prolonged; the reason for the above phenomenon is that the proportion of active components in the platinum catalyst gradually decreases (i.e., partial poisoning) as the number of repeated use increases.
According to some embodiments of the invention, the yield of hydrocarbyl chlorosilanes of formula III is greater than or equal to 99%. From this, it is clear that the hydrosilylation reaction is almost a proportional reaction, the compound of formula I is almost complete, and that the purification process is almost free of hydrocarbon chlorosilanes.
According to some embodiments of the invention, the purity of the hydrocarbyl chlorosilane of formula III is greater than or equal to 97%.
It is found that the preparation method does not cause serious side reactions due to the decrease in temperature or the presence of crystal water in the platinum catalyst, and the purification effect is good.
On the other hand, it is also known that: if the purification operation is further optimized, it is expected that the purity of the obtained hydrocarbyl chlorosilane is further improved.
Unless otherwise indicated, "about" in the present invention means that the allowable error is within.+ -. 2%, for example, about 100 means that 100.+ -. 2% X100.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
If not specified, the yield in the invention is the ratio between the actual value and the theoretical value of the corresponding substance; the purity is the ratio of the mass of the target product to the total mass of the system in which the target product is located.
Example 1
The reaction formula of octadecyl dimethyl chlorosilane prepared in this example is as follows:
the specific reaction process is as follows:
s1, under magnetic stirring in a water bath (about 25 ℃ C. At room temperature), dimethyl chlorosilane (378.44 g,4 mol), chloroplatinic acid hexahydrate (0.173 mg,0.00033 mmol) and 1-octadecene (252.49 g,1 mol) were added in this order to a three-necked flask equipped with a condenser, and stirring was continued until the reaction was completed (about 32 hours).
The method for judging whether the reaction is complete is as follows: monitoring the mixture of the reaction system in real time by adopting a gas chromatograph-mass spectrometer, and when the 1-octadecene is completely consumed, the reaction is considered to be complete;
s2, purifying: under the drying condition, the mixture obtained in the step S1 is distilled under normal pressure (the temperature is about 40 ℃), redundant dimethylchlorosilane is distilled out, 259.23g of dimethylchlorosilane is recovered (the recovery rate is 68.5 percent, the ratio of the recovery mass to the feeding mass is the same as the calculation method in the following implementation mode), and then the residual liquid is subjected to spin-drying at 50 ℃ by a dry rotary evaporator and then is filtered quickly to obtain the target compound of the liquid, wherein the solid part is solid particles of chloroplatinic acid.
In the step, the standard of spin drying is that the temperature of a suspended steaming system rises suddenly; the equipment used in the step is the same as the equipment used in the step S1, and the flask openings at the two sides are sealed in the rotary steaming process.
Example 2
This example prepared an octadecyl dimethylchlorosilane, the specific process differs from example 1 in that:
in step S1, chloroplatinic acid hexahydrate was used in an amount of 8.63mg,1.67 x 10 -5 mol。
Correspondingly, in the step S1 of the embodiment, the time required for the reaction to be completed is about 18 hours.
In this example, the yield of dimethylchlorosilane was comparable to that of the example.
Example 3
This example prepared an octadecylmethyl ethyl chlorosilane, and the specific process was different from example 1 in that:
in the step S1, dimethyl chlorosilane is replaced by methyl ethyl chlorosilane with the same amount of substances;
correspondingly, in the step S1 of the embodiment, the time required for the reaction to be completed is about 30 hours.
Correspondingly, in the step S2 of the present example, the mass of the recovered methyl ethyl chlorosilane was 309.84g, and the corresponding yield was 71.3%.
Example 4
This example produced an octadecyl dimethylchlorosilane, which differs from example 1 in particular in that:
this example uses the chloroplatinic acid catalyst recovered in example 1;
the results obtained differ from example 1 in that:
when chloroplatinic acid is used for the second time (when recovered chloroplatinic acid is used for the first time), the total reaction time is prolonged to 43 hours;
when chloroplatinic acid is used for the third time, the total reaction time is prolonged to 59 hours;
the total reaction time was extended to 96 hours with the fourth use of chloroplatinic acid.
However, the yield of octadecyl dimethylchlorosilane obtained was the same as in example 1 for each repeated use.
In this example, the method for determining the reaction time period was the same as in example 1.
Comparative example 1
This example prepared an octadecylmethyl ethyl chlorosilane, and the specific process was different from example 1 in that:
in step S1, the amount of dimethylchlorosilane was 3mol.
Comparative example 2
This example prepared an octadecylmethyl ethyl chlorosilane, and the specific process was different from example 1 in that:
in the step S1, the reaction temperature is 50 ℃, and the reaction vessel is a closed pressure-resistant vessel.
Test case
The purity of the products obtained in examples 1 to 4 and comparative examples 1 to 2 was quantitatively measured by a gas chromatograph in the first aspect of the test example, and the measurement results showed that the purity of the product obtained in example 1 was 99%, the purity of the product obtained in example 2 was 98.5%, the purity of the product obtained in example 3 was 98.8%, and the purity of the product was 98.2%, 97.9% and 97.3% in this order when chloroplatinic acid was used 2 to 4 times in example 4. In comparative examples 1 to 2, the purity of the product was 89.1% and 93.6% in this order. Therefore, the preparation method provided by the invention can obtain the hydrocarbyl chlorosilane with higher purity.
The second aspect of the test example calculates the yields of the products obtained in examples 1 to 4 and comparative examples 1 to 2 by (mass of the target product x purity of the product)/theoretical mass of the target product. Wherein the mass of the target product theoretically represents the mass of the target product which can be obtained by carrying out the reaction according to the proportion of the chemical reaction formula. The results showed that the yields of the products in examples 1 to 4 were almost 100%, i.e., the reaction was quantitative (yield after purification, sum of the mass of the three-necked flask after purification and the mass of the content, the mass of the three-necked flask was subtracted, and the ratio of the mass of the target product to the mass theoretically producible was the yield). This demonstrates that the preparation process of the present invention significantly suppresses the occurrence of side reactions, whereas in comparative example 1, the yield of the product is only about 95% because the compound of formula I is not completely reacted, and in comparative example 2, the yield of the product is only about 93% because the increased temperature promotes the formation of complicated side reactions to some extent.
In the third aspect of the test example, the nuclear magnetic results of the products obtained in examples 1 to 3 were tested, and the results showed no impurity peak in the nuclear magnetic results, which further demonstrates that the purity of the products prepared by the present invention is higher. Specific:
the nuclear magnetic resonance of the product obtained in example 1 was:
13 C NMR(CDCl 3 )δ：33.05，32.00，29.78，29.76，29.74，29.60，29.44，29.32，23.07，22.74，22.07，22.74，19.03，14.13，1.72。
1 H NMR(CDCl 3 )δ：0.39(s,6H),0.79-0,81(t,2H),0.86-0.88(m,3H),1.24-1.41(m,32H)。
the nuclear magnetic resonance results of the products obtained in examples 2 and 4 were almost the same as those obtained in example 1.
The nuclear magnetic resonance of the product obtained in example 3 was:
1 H NMR(CDCl 3 )δ：0.41(s,3H),0.60-0.81(t,7H),0.86-0.94(m,5H),1.24-1.41(m,32H)。
13 C NMR(CDCl 3 )δ：33.15，32.07，29.78，29.76，29.73，29.64，29.44，29.35，23.12，22.55，22.10，22.77，19.04，13.40，14.12，2.05,1.85。
in conclusion, the preparation method provided by the invention can indeed improve the yield and purity of the target product on the basis of simplifying the preparation process and improving the preparation safety.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The preparation method is characterized by comprising the steps of carrying out hydrosilylation reaction on a compound shown in a formula I and a compound shown in a formula II under the catalysis of a platinum catalyst to obtain the hydrocarbyl chlorosilane shown in a formula III;
wherein:
in the formula I, R 1 Is C 4 ～C 18 An alkyl group;
in formula II, R 2 And R is 3 Independently selected from C 1 ～C 3 An alkyl group;
the ratio of the amount of the compound shown in the formula I to the amount of the compound shown in the formula II is 1:3.5-4;
the hydrosilylation conditions are room temperature and normal pressure; the room temperature is 10-40 ℃.
2. The production method according to claim 1, wherein the platinum catalyst comprises at least one of anhydrous chloroplatinic acid and chloroplatinic acid containing crystal water.
3. The process of claim 1, wherein R in formula I 1 Is C 15 ～C 16 An alkyl group.
4. The process of claim 1, wherein in formula II, R 2 And R is 3 Independently selected from C 1 Or C 2 An alkyl group.
5. The process according to any one of claims 1 to 4, wherein the ratio of the amounts of the compound represented by formula I and the platinum catalyst is 55000 to 3500000:1.
6. The process according to any one of claims 1 to 4, wherein the amount of the compound of formula I and the compound of formula II is about 1:4.
7. The process according to any one of claims 1 to 4, wherein the yield of the hydrocarbyl chlorosilane of formula III is not less than 99%.
8. The process according to any one of claims 1 to 4, wherein the purity of the hydrocarbyl chlorosilane of formula III is not less than 97%.
9. The process according to any one of claims 1 to 4, further comprising purifying the hydrocarbyl chlorosilane of formula III after the hydrosilylation reaction.
10. The method of claim 9, wherein the purifying comprises atmospheric distillation and rotary evaporation performed sequentially.
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