CN112661965A - Preparation method of organic silicon auxiliary agent - Google Patents
Preparation method of organic silicon auxiliary agent Download PDFInfo
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- CN112661965A CN112661965A CN202011526746.8A CN202011526746A CN112661965A CN 112661965 A CN112661965 A CN 112661965A CN 202011526746 A CN202011526746 A CN 202011526746A CN 112661965 A CN112661965 A CN 112661965A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229920002545 silicone oil Polymers 0.000 claims abstract description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- 230000014759 maintenance of location Effects 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229940069096 dodecene Drugs 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000000654 additive Substances 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 229920001558 organosilicon polymer Polymers 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FSUXYWPILZJGCC-NSCUHMNNSA-N (e)-pent-3-en-1-ol Chemical compound C\C=C\CCO FSUXYWPILZJGCC-NSCUHMNNSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- FSUXYWPILZJGCC-UHFFFAOYSA-N pent-4-en-1-ol Natural products CC=CCCO FSUXYWPILZJGCC-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a preparation method of an organic silicon assistant, which comprises the step of respectively introducing a mixture of hydrogen-containing silicone oil and a catalyst and one or more of double bond-containing aliphatic hydrocarbon, ether and alcohol into a tubular continuous flow reactor to carry out hydrosilylation reaction to obtain the organic silicon assistant, wherein the catalyst is a transition metal salt, the temperature in the tubular continuous flow reactor is controlled to be 50-300 ℃, and the retention time of materials in the tubular continuous flow reactor is 1-600 s. The preparation method can realize continuous production of different types of organic silicon polymer additives, and greatly simplifies the production flow of different types of products; the conversion rate of the raw materials can reach more than 90 percent in a short time, and the conversion rate of the raw materials is stable; the preparation method of the invention can effectively ensure the product quality, improve the production efficiency and reduce the production cost.
Description
Technical Field
The invention particularly relates to a preparation method of an organic silicon auxiliary agent.
Background
The organic silicon material has become an indispensable key material in the fields of aviation, high and new technology, national defense and military industry and national economy, and is listed as one of the major encouragement development industries of the country. At present, the development of downstream high value-added products of the organosilicon is one of the key points of the development of the organosilicon industry. The polymer organic silicon defoaming agent, the leveling agent and the dispersing agent are typical representatives of organic silicon high-added-value products, the production of the series of organic silicon auxiliaries is carried out by adopting an intermittent kettle at present, the reaction time is about 2-5 hours, and in addition, the whole production process can be as long as 6-8 hours in consideration of the time for feeding, titrating and kettle washing. In a factory producing various organosilicon addition agents, the yield of each product is not large, if a special kettle is used for producing each product, huge resource waste is caused, and if different organosilicon addition agents are produced by using the same kettle, huge solvent waste and pollution are caused in the kettle washing process. In addition, the traditional kettle type reactor has small heat exchange area, and has larger potential safety hazard in the reaction at high temperature. The leakage of the materials and the error of the operation of the personnel in the production process of the batch still can cause adverse effects on the stability of the product quality and the human health. Finally, the problem that the product quality cannot be well controlled is caused due to the complex heat and mass transfer conditions of the reaction kettle, and many products which are easy to realize good performance under the small-scale test condition are difficult to realize or have poor performance in the industrial process.
Disclosure of Invention
The invention aims to provide a preparation method of an organic silicon auxiliary agent with short reaction time and high conversion efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of an organic silicon assistant, which comprises the step of respectively introducing a mixture of hydrogen-containing silicone oil and a catalyst and one or more of double bond-containing aliphatic hydrocarbon, ether and alcohol into a tubular continuous flow reactor to carry out hydrosilylation reaction to obtain the organic silicon assistant, wherein the catalyst is a transition metal salt, the temperature in the tubular continuous flow reactor is controlled to be 50-300 ℃, and the retention time of materials in the tubular continuous flow reactor is 1-600 s.
The invention can solve the problems of complicated steps, low efficiency, high cost, large pollution, large danger and the like in the traditional preparation method by using the tubular continuous flow reactor to prepare the organic silicon assistant.
Preferably, the feeding molar ratio of the active hydrogen of the hydrogen-containing silicone oil to the double bonds of one or more of the double bond-containing aliphatic hydrocarbon, ether and alcohol is 1: 1-1: 2, and more preferably 1: 1-1: 1.2.
In the invention, the hydrogen-containing silicone oil can be low hydrogen-containing silicone oil or high hydrogen-containing silicone oil.
Preferably, the weight average molecular weight of the hydrogen-containing silicone oil is 100-500000, and the active hydrogen content is 0.01-1.7 wt%.
Further preferably, the weight average molecular weight of the hydrogen-containing silicone oil is 100-5000, and the active hydrogen content is 0.01-0.5 wt%.
According to some embodiments, the catalyst is a salt of a transition metal such as Pt, Rh, Ir, Ru, Fe, etc., wherein the Pt-based catalyst has a higher activity. Preferably, the catalyst comprises one or more of chloroplatinic acid hydrate and a platinum catalyst of Karster platinum, and the catalyst has high catalytic efficiency and needs to form a complex with alcohol or ether or ketone or isopropanol before use.
Preferably, the mass of the catalyst is 0.01-25% of the total mass of the mixture of the hydrogen-containing silicone oil and the catalyst.
Further preferably, the mass of the catalyst is 0.01-0.5% of the total mass of the mixture of the hydrogen-containing silicone oil and the catalyst.
Preferably, the double bond-containing aliphatic hydrocarbon is R-R', wherein R is a hydrocarbon containing one or more double bonds, and is further preferably allyl or vinyl; r 'is alkyl with 5-15 carbon atoms, and R' is straight-chain alkyl or alkyl containing a branched chain.
According to some embodiments, the aliphatic hydrocarbon containing a double bond is one or more of 1-octene, 1-dodecene, 1-octadecene.
Preferably, the double bond-containing ether is R- (R')n-OR ", wherein R is a hydrocarbon containing one OR more double bonds, further preferably allyl OR vinyl; r' is oxygen-containing or non-oxygen-containing alkylene, and is further preferably non-oxygen-containing alkylene, ethoxy subunit and propoxy subunit; n is a natural number; r' is hydrogen, alkyl or alkylene alcohol, more preferably one of ethyl, propyl, butyl, isopropyl, pentylene alcohol and hexylene alcohol.
According to some embodiments, the double bond containing ether is one or more of allyl monoethyl glycol ether, allyl polyethylene glycol 400 monomethyl ether, and allyl polypropylene glycol 500 monomethyl ether.
Preferably, the double bond containing alcohol is R-R', wherein R is a hydrocarbon containing one or more double bonds; r 'is C1-10 alkylene alcohol, and R' is linear alkylene alcohol or branched alkylene alcohol.
The double bond-containing alcohol is a monohydric alcohol or a polyhydric alcohol, and is preferably a monohydric alcohol. According to some embodiments, the double bond containing alcohol is one or more of 3-buten-1-ol, 3-penten-1-ol, 5-hexen-3-ethyl-1-ol.
Preferably, the flow rate of the mixture of the hydrogen-containing silicone oil and the catalyst in the tubular continuous flow reactor is 0.01-1000 mL/min, and the flow rate of one or more of the double bond-containing aliphatic hydrocarbon, ether and alcohol in the tubular continuous flow reactor is 0.01-1000 mL/min. In the present invention, the flow rate is adjusted according to the specification of the tubular continuous flow reactor and the time required for the reaction.
Preferably, the inner diameter of the tubular continuous flow reactor is 1/16-8 mm, and the tubular continuous flow reactor with the proper inner diameter is selected, so that the materials are uniformly heated and fully reacted, and the product conversion rate is improved. The length of the tubular continuous flow reactor may be selected as desired.
Preferably, the mixture of the hydrogen-containing silicone oil and the catalyst and one or more of the double bond-containing aliphatic hydrocarbon, ether and alcohol are firstly introduced into a mixer and then introduced into the tubular continuous flow reactor for reaction.
According to some embodiments, the type of the mixer can be changed according to the characteristics of the materials, and the type can be selected from W type, E type, T type, P type, V type, S type, F type and EX type mixers.
Preferably, the preparation method further comprises the steps of adding the mixture of the hydrogen-containing silicone oil and the catalyst into a solvent to prepare a diluent, introducing the diluent into the tubular continuous flow reactor for reaction, and then performing reduced pressure distillation on the discharged material in the tubular continuous flow reactor to remove the solvent to obtain the organosilicon auxiliary agent. When the hydrogen-containing silicone oil has high viscosity and can not be directly injected, the hydrogen-containing silicone oil can be diluted by using a solvent, and the solvent is removed from the corresponding discharged material by reduced pressure distillation.
Further preferably, the solvent is alcohol, and the adding amount of the solvent is 0.01-99%, more preferably 1-5% of the total mass of the hydrogen-containing silicone oil, the catalyst and the solvent. The alcohol includes but is not limited to one or more of butanol, pentanol and hexanol.
In the invention, if other types of products need to be produced, materials in the front pipe of the mixer, the mixer and the rear pipe of the mixer can be recycled according to requirements, and the recycled materials can be used for the next production. Wherein the materials before the mixer can be used as raw materials, samples in the mixer and after the mixer can be judged whether to be directly introduced into the continuous flow reaction for reaction according to the mutual solubility condition of the materials, if the mutual solubility is good, the samples are directly introduced into the continuous flow reactor, and if the mutual solubility is poor, a certain proportion of solvent can be added and mixed, and then the samples are introduced into the continuous flow reactor.
The preparation method of the invention can obtain products with different residence times, and then determine the production conditions of the products with optimal performance by comparing with the products produced by the traditional batch still.
The preparation method of the organic silicon assistant comprises the following specific operation steps: a) hydrogen-containing silicone oil with a certain molecular weight (mixed with a catalyst in advance) and double bond-containing aliphatic hydrocarbon and/or double bond-containing ether and/or double bond-containing alcohol are simultaneously introduced into a tubular continuous flow reactor, or are mixed by a mixer and then are introduced into the tubular continuous flow reactor; b) the reaction temperature is set to be 50-300 ℃, the flow rate is set to be 0.01-1000 mL/min, and two materials pass through the tubular continuous flow reactor and then are discharged to obtain the product.
Compared with the traditional batch reactor production method, the whole reaction process is continuous, and only raw materials and operation parameters need to be replaced when different types of products are produced, so that the production flow of different types of products is greatly simplified, the obtained products have more excellent performance compared with the products produced by using a batch reactor, and the product quality is effectively ensured; the method has the advantages of short reaction time, stable and efficient raw material conversion, effectively improved production efficiency and reduced production cost; the production process of the invention does not cause environmental pollution and avoids resource waste.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the preparation method can realize continuous production of different types of organic silicon polymer additives, and greatly simplifies the production flow of different types of products; the conversion rate of the raw materials can reach more than 90 percent in a short time, and the conversion rate of the raw materials is stable; the preparation method of the invention can effectively ensure the product quality, improve the production efficiency and reduce the production cost.
Drawings
FIG. 1: a schematic of the structure of a continuous flow reactor used in the specific examples;
FIG. 2 is a drawing: the conversion of the continuous flow reactor of example 1 was compared to a conventional batch tank reactor;
FIG. 3: the conversion of the continuous flow reactor of example 2 was compared to a conventional batch tank reactor;
FIG. 4 is a drawing: the conversion of the continuous flow reactor of example 3 was compared to a conventional batch tank reactor;
FIG. 5: the conversion of the continuous flow reactor of example 4 was compared to a conventional batch tank reactor;
FIG. 6: foam suppressing performance and defoaming performance of the products of example 1 and comparative example 1 in 128 epoxy resin;
FIG. 7: foam suppressing performance and defoaming performance of the products of example 1 and comparative example 1 in 601 epoxy resin;
FIG. 8: the products of example 1 and comparative example 1 were tested for foam suppressing and defoaming performance in 1753 hydroxyacrylic resin;
FIG. 9: the products of example 1 and comparative example 1 were tested for foam suppressing and defoaming performance in YK304 low-hydroxyacrylic acid resin,
wherein, in figure 1:1. a feed pump module; 2. a mixer module; 3. and the heat exchange reaction module.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the present invention, the apparatus, raw materials and reagents used are commercially available.
Example 1
(1) The feed pump module 1, the mixer module 2 and the heat exchange reaction module 3 of the continuous flow tubular reactor were connected in this order according to the structure shown in fig. 1, and the inner diameter of the continuous flow reactor in this example was 1 mm. The temperature of a circulating system of the heat exchange reaction module 3 is set to be 240 ℃, and the preheating time is set to be 30min, so that the heat exchange reaction module 3 is in a temperature balance state.
(2) The flow rate of the feed pump is set, the flow rate of the mixture of the hydrogen-containing silicone oil and the catalyst (the molecular weight of the hydrogen-containing silicone oil is about 1200, the active hydrogen content is about 0.17 wt%, the catalyst is chloroplatinic acid hydrate, and the dosage is 0.01% of the total mass of the mixture) is controlled to be 1.1mL/min, and the flow rate of the allyl monoethyl ether is 0.2mL/min, and can be adjusted according to the retention time according to the proportion.
(3) After being mixed by the mixer module 2, the two materials enter the heat exchange reaction module 3 for reaction, the reaction temperature is controlled to be 240 ℃, the materials stay in the heat exchange reaction module 3 for 1-600s, the reaction liquid after the reaction is the product, the products with different reaction times are taken, the conversion rate is higher than 90% through titration analysis, and the comparison result is shown in figure 2 when the conversion rate is compared with the conversion rate of the products in the traditional batch kettle type reactor.
As can be seen from FIG. 2, this example can achieve a very high conversion in a very short time (40.7s), and the efficiency is greatly improved compared to the conventional batch reactor. One of the main reasons for the higher conversion rate in the later stage of the batch reactor is that the raw material volatilizes at high temperature, which results in higher analysis results, but the continuous flow reactor does not have the problem.
Example 2
(1) In the continuous flow reactor used in this example, the temperature of the circulation system of the heat exchange reaction module 3 was set to 230 ℃ and the preheating time was set to 30min, so that the heat exchange reaction module 3 was in a temperature equilibrium state, as in example 1.
(2) The flow rate of the feed pump is set, the flow rate of the mixture of the hydrogen-containing silicone oil and the catalyst (the molecular weight of the hydrogen-containing silicone oil is about 1200, the active hydrogen content is about 0.17 wt%, the catalyst is chloroplatinic acid hydrate, and the dosage is 0.01% of the total mass of the mixture) is controlled to be 2.0mL/min, and the flow rate of the 3-butene-1-ol is 0.3mL/min, and can be adjusted according to the requirement of the retention time according to the proportion.
(3) After being mixed by the mixer module 2, the two materials enter the heat exchange reaction module 3 for reaction, the reaction temperature is controlled to be 230 ℃, the materials stay in the heat exchange reaction module 3 for 1-600s, the reaction liquid after the reaction is the product, the products with different reaction times are taken, the conversion rate is higher than 90% through titration analysis, and the comparison result is shown in figure 3.
As can also be seen from FIG. 3, the efficiency of this example is greatly improved compared to the conventional batch tank reactor. The batch reactor has the problem of raw material volatilization at high temperature, so that the analysis result of the later conversion rate is higher.
Example 3
(1) The continuous flow reactor used in this example was the same as that used in example 1, and the temperature of the circulation system of the heat exchange reaction module 3 was set to 200 ℃ and the preheating time was set to 30min, so that the heat exchange reaction module 3 was in a temperature equilibrium state.
(2) The flow rate of the feed pump was set to control the flow rate of the mixture of hydrogen-containing silicone oil and catalyst (the molecular weight of hydrogen-containing silicone oil was about 1200, the active hydrogen content was about 0.17 wt%; the catalyst was a platinum-platinum catalyst, and the amount used was 0.02% of the total mass of the mixture) to 2.0mL/min, and the flow rate of dodecene to 0.8mL/min, and was adjusted according to the residence time required.
(3) After being mixed by the mixer module 2, the two materials enter the heat exchange reaction module 3 for reaction, the reaction temperature is controlled to be 200 ℃, the materials stay in the heat exchange reaction module 3 for 1-600s, the reaction liquid after the reaction is the product, the products with different reaction times are taken, the conversion rate is higher than 90% through titration analysis, and the comparison result is shown in figure 4.
As can also be seen from FIG. 4, the efficiency of this example is greatly improved compared to the conventional batch tank reactor. The batch reactor has the problem of raw material volatilization at high temperature, so that the analysis result of the later conversion rate is higher.
Example 4
(1) In the continuous flow reactor used in this example, as in example 1, the temperature of the circulation system of the heat exchange reaction module 3 was set to 240 ℃, and the preheating time was set to 30min, so that the heat exchange reaction module 3 was in a temperature equilibrium state.
(2) The flow rate of the feed pump is set, the flow rate of the mixture of the hydrogen-containing silicone oil and the catalyst (the molecular weight of the hydrogen-containing silicone oil is about 1200, the active hydrogen content is about 0.17 wt%, the catalyst is a Kansted platinum catalyst, the dosage is 0.02% of the total mass of the mixture) is controlled to be 2.4mL/min, and the flow rate of the allyl polyethylene glycol 400 monomethyl ether is 2mL/min, and can be adjusted according to the requirement of the retention time according to the proportion.
(3) After being mixed by the mixer module 2, the two materials enter the heat exchange reaction module 3 for reaction, the reaction temperature is controlled to be 240 ℃, the materials stay in the heat exchange reaction module 3 for 1-600s, the reaction liquid after the reaction is the product, the products with different reaction times are taken, the conversion rate is higher than 90% through titration analysis, and the comparison result is shown in figure 5.
As can be seen from FIG. 5, the conversion rate of this example is significantly higher than that of the conventional batch reactor, and this example can achieve a relatively high conversion rate in a very short time (40.7s), and the efficiency is greatly improved compared to the conventional batch reactor. The advantages of this example are evident because the boiling point of the raw materials used in this example is high and there is no problem of volatilization.
Comparative example 1
10.2g of allyl monoethylene glycol ether and 129.6g of a mixture of hydrogen-containing silicone oil and a catalyst (the molecular weight of the hydrogen-containing silicone oil is about 1200, the active hydrogen content is about 0.17 wt%, and the catalyst is chloroplatinic acid hydrate, and the amount of the catalyst is 0.01% of the total mass of the mixture) are added into a 250mL three-neck flask, the mixture is heated to 240 ℃ under stirring, and after a constant-temperature reaction is carried out for 10min, the mixture is taken out and cooled, and then products LQh-1200 of a comparative example 1 are obtained.
Samples with residence times of 276.9s (P4), 138.5s (P7), 60.2s (P12) and 40.7s (P14) in example 1 and products LQh-1200 prepared in comparative example 1 were selected for defoaming and foam suppressing performance tests as follows:
respectively adding 0.2% of different samples, LQh-1200 or blank samples under different resin systems, sealing, vibrating for 10min with a vibrator, and taking out.
Foam inhibition performance: the height of the liquid level before the oscillation is recorded as H0Recording the height H of the liquid level when the height of the bubble is not increased after the oscillation1The liquid level change rate (%) (H)1-H0)/H 0100, dividing the foam suppressing ability according to the liquid level height change rate.
Grading standard of bubble inhibiting capability: 1: 0 to 1 percent; 2: 1 to 5 percent; 3: 5 to 15 percent; 4: 15 to 30 percent; 5: is more than 30 percent; +: better still; -: worse; wherein, a smaller value represents a better foam suppressing effect, a larger value represents a poorer foam suppressing effect, and under the same value, "+" represents a better foam suppressing effect, and "-" represents a poorer foam suppressing effect, for example, in terms of a foam suppressing effect from good to bad: 2>3+ + >3+ >3- >3- - > 4. .
Defoaming performance: standing the vibrated test sample for 1h, observing the bubble condition and grading, wherein the grading standard is as follows: a: no air bubbles at all; b: almost no bubbles; c: the number of bubbles is less, and only the upper half liquid layer has some bubbles; d: the bubbles are numerous and not very tight; e: the bubbles were numerous and no liquid was visible; +: better still; -: the worse.
The results of foam suppressing and defoaming properties are shown in tables 1-4.
The results of comparison of the foam inhibiting and defoaming performances of P4, P7, P12, P14 and P LQh-1200 in 128 resin are shown in Table 1 and FIG. 6, and blank samples, P12, P14, LQh-1200, P4 and P7 are added into 128 resin in sequence from left to right in FIG. 6. Because the defoaming agent has certain incompatibility with the 128 resin, the system is turbid and opaque after bubbles disappear, but the liquid level height is basically not different.
TABLE 1
| Blank space | LQh-1200 | P4 | P7 | P12 | P14 | |
| Foam inhibition | 5-- | 2++ | 2++ | 2++ | 2++ | 2++ |
| Defoaming property | E | C | C | C | C+ | C+ |
The results of comparison of defoaming and foam inhibiting performances of P4, P7, P12, P14 and P LQh-1200 in 601 resin are shown in Table 2 and FIG. 7, and blank samples, P7, P4, LQh-1200, P12 and P14 are added to 601 resin from left to right in FIG. 7. Because the defoaming agent has certain incompatibility with the 601 resin, the system is turbid and opaque after bubbles disappear, but the liquid level height is basically not different.
TABLE 2
| Blank space | LQh-1200 | P4 | P7 | P12 | P14 | |
| Foam inhibition | 4 | 2 | 2 | 2 | 2+ | 2+ |
| DefoamingProperty of (2) | C | C+ | C+ | C+ | C++ | C+ |
The results of comparison of defoaming and foam inhibiting performances of P4, P7, P12, P14 and P LQh-1200 in 1753 resin are shown in Table 3 and FIG. 8, and blank samples, LQh-1200, P12, P7, P14 and P4 are added into 1753 resin from left to right in the sequence of FIG. 8.
TABLE 3
| Blank space | LQh-1200 | P4 | P7 | P12 | P14 | |
| |
3-- | 3+ | 3+ | 3+ | 3+ | 3+ |
| Defoaming property | C | C | C | C | C | C |
The results of comparison of defoaming and foam inhibiting performances of P4, P7, P12, P14 and P LQh-1200 in YK304 resin are shown in Table 4 and FIG. 9, and blank, LQh-1200, P7, P14, P4 and P12 are added to YK304 resin from left to right in FIG. 9.
TABLE 4
| Blank space | LQh-1200 | P4 | P7 | P12 | P14 | |
| Foam inhibition | 3- | 3+ | 3+ | 3+ | 3+ | 3+ |
| Defoaming property | C+ | C | C | C | C | C |
From the above experimental results, it can be seen that the silicone defoamer prepared using a shorter residence time has defoaming and foam suppressing properties equivalent to or even better than LQh-1200, wherein the foam suppressing properties are more superior, and 60.2s (P12) has more excellent defoaming and foam suppressing properties under many test conditions.
The present invention is described in detail in order to make those skilled in the art understand the content and practice the present invention, and the present invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (11)
1. The preparation method of the organic silicon assistant is characterized in that a mixture of hydrogen-containing silicone oil and a catalyst and one or more of double bond-containing aliphatic hydrocarbon, ether and alcohol are respectively introduced into a tubular continuous flow reactor to carry out hydrosilylation reaction to prepare the organic silicon assistant, wherein the catalyst is a salt of a transition metal, the temperature in the tubular continuous flow reactor is controlled to be 50-300 ℃, and the retention time of materials in the tubular continuous flow reactor is 1-600 s.
2. The preparation method according to claim 1, wherein the charging molar ratio of the active hydrogen of the hydrogen-containing silicone oil to the double bond of one or more of the double bond-containing aliphatic hydrocarbon, ether and alcohol is 1:1 to 1: 2.
3. The preparation method according to claim 1, wherein the hydrogen-containing silicone oil has a weight average molecular weight of 100 to 500000 and an active hydrogen content of 0.01 to 1.7 wt%.
4. The preparation method according to claim 1, wherein the aliphatic hydrocarbon containing double bonds is R-R ', wherein R is a hydrocarbon containing one or more double bonds, and R' is an alkyl group having 5 to 15 carbon atoms; the double-bond-containing ether is R- (R ') n-OR', wherein R is a hydrocarbon containing one OR more double bonds, R 'is an oxygen-containing OR non-oxygen-containing alkylene group, n is a natural number, and R' is hydrogen, alkyl OR alkylene alcohol; the double-bond-containing alcohol is R-R', wherein R is a hydrocarbon containing one or more double bonds; r' is an alkylene alcohol having 1 to 10 carbon atoms.
5. The method according to claim 1 or 4, wherein the double bond-containing aliphatic hydrocarbon, ether or alcohol is one or more of dodecene, allyl monoethyl glycol ether, allyl polyethylene glycol 400 monomethyl ether and 3-buten-1-ol.
6. The preparation method according to claim 1, wherein the mass of the catalyst is 0.01-25% of the total mass of the mixture of the hydrogen-containing silicone oil and the catalyst.
7. The preparation method according to claim 1, wherein the flow rate of the mixture of hydrogen-containing silicone oil and catalyst in the tubular continuous flow reactor is 0.01-1000 mL/min, and the flow rate of one or more of the double bond-containing aliphatic hydrocarbon, ether and alcohol in the tubular continuous flow reactor is 0.01-1000 mL/min.
8. The preparation method according to claim 1, wherein the inner diameter of the tubular continuous flow reactor is 1/16-8 mm.
9. The preparation method according to claim 1, wherein the mixture of hydrogen-containing silicone oil and catalyst and one or more of double bond-containing aliphatic hydrocarbon, ether and alcohol are introduced into a mixer and then introduced into the tubular continuous flow reactor for reaction.
10. The preparation method according to claim 1, further comprising adding the mixture of hydrogen-containing silicone oil and catalyst into a solvent to prepare a diluent, introducing the diluent into the tubular continuous flow reactor for reaction, and then performing reduced pressure distillation on the discharged material from the tubular continuous flow reactor to remove the solvent to obtain the organosilicon assistant.
11. The preparation method according to claim 9, wherein the solvent is an alcohol, and the amount of the solvent added is 0.01 to 99% of the total mass of the hydrogen-containing silicone oil, the catalyst and the solvent.
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| WO2022135443A1 (en) * | 2020-12-22 | 2022-06-30 | 埃夫科纳聚合物股份有限公司 | Preparation method for organosilicon auxiliary agent |
| CN114957666A (en) * | 2022-06-28 | 2022-08-30 | 埃夫科纳聚合物股份有限公司 | Preparation method of hydrogen-containing silicone oil |
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| CN115895440A (en) * | 2022-10-28 | 2023-04-04 | 上谷新材料(苏州)有限公司 | Easy-reworking rubber surface treating agent and preparation method thereof |
| CN115717335A (en) * | 2022-11-28 | 2023-02-28 | 浙江理工大学桐乡研究院有限公司 | Moisture-absorbing and sweat-releasing finishing agent for cotton and preparation method thereof |
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