CN102604099A - Method for effectively processing industrial waste n-propyl trifunctional silane - Google Patents
Method for effectively processing industrial waste n-propyl trifunctional silane Download PDFInfo
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Abstract
The invention discloses a method for effectively processing industrial waste n-propyl trifunctional silane, which is used for processing the n-propyl trifunctional silane into di-n-propyl bifunctional silane and derivatives thereof by the Grignard reaction. By preparing the di-n-propyl bifunctional silane and the derivatives thereof, the use value of the industrial waste is promoted. Prepared propyl-containing silicon resin, silicon oil and silicone rubber and secondary products thereof have outstanding properties and wide application ranges. The method disclosed by the invention has stable process, is simple, convenient and reliable and has high yield and low cost. The problem of waste processing, which urgently needs to be solved in the current silane coupling agent industry, can be solved. When the environmental pollution is reduced, the wastes are changed into valuables.
Description
Technical field
The present invention relates to a kind of method of effective processing industrial waste n-propyl trifunctional base silane, particularly relate to n-propyl trifunctional base silane is processed into dipropyl two functional group's silane and further prepares six propyl group cyclotrisiloxane, contains the ZGK 5 of dipropyl silica chain link and the process method of Zylox.
Background technology
N-propyl trifunctional base silane (comprising n-propyl Trimethoxy silane, n-propyl triethoxyl silane and n-propyltrichlorosilan) is that the by product of producing in the silane coupling agent process is gone up in industry; Account for 5% of product mixtures; Generation is very big, can serious environment pollution after discarding.But these by products do not obtain good use at present.Main methods on the market is that it is prepared thermal silica through high-temperature calcination.This technology power consumption is big, and value-added content of product is little, can not embody the characteristic property of this material, has caused great waste.Owing to can not such by product be discharged as sewage; Do not having under the background of processing mode and treatment process preferably; Now domestic how tame silane coupling agent manufacturer is all with such by product long-term storage; Occupy very big storage workshop, even badly influenced the normal operation of factory.The producer that has then abandons the separation to such by product, and direct marketing has had a strong impact on the product competitive power on the market at home and abroad without the silane coupling agent of purifying on market.A thereby major issue that solves for the present urgent need of effectively being processed into of such by product.
The utilizability of n-propyl trifunctional base silane is not high, mainly is wherein to exist three functional groups, very easily hydrolysis, and the performance of hydrolysate can not finely be controlled.If want to improve its utility value, relatively facilitated method is exactly that its three functional groups that have are converted into two functional groups.Employed method has a variety of, and one of them method is through grignard reaction (Grignard Reaction) one of them functional group to be converted into inactive group, such as alkyl.When the inactive group after transforming was n-propyl, prepared silane was di two functional group's silane, abbreviates dipropyl two functional group's silane as.
Research for from n-propyl trifunctional base silane preparation dipropyl two functional group's silane does not appear in the newspapers both at home and abroad as yet.At present, have only from the research of haloalkane and tetraalkoxysilane prepared in reaction dialkyl dialkoxy silicane and can use for reference, be divided into two kinds of single stage method and two-step approachs.What introduce among the patent EP460590 is two-step approach, promptly by chlorocyclopentane and magnesium chips prepared in reaction Grignard reagent in tetrahydrofuran solvent, and then with gained grignard reagent and the reaction of equimolar tetramethoxy-silicane, synthetic dicyclopentyl dimethoxyl silane.Because adopt two-step approach synthetic, nature can bring operational loaded down with trivial details, the problem that technical process is long, conversion unit is many, and also content of by-products is higher in synthetic liquid, and reaction yield is low.
In US4958041 and CN1183143 patent; Introduced the method for the synthetic dialkyl dialkoxy silicane of single stage method; Its method is to use alkyl chloride and magnesium chips in methyl-tertbutyl ether solvent, to prepare a spot of Grignard reagent as initiator earlier; And then dripping the mixing solutions of forming by alkyl chloride, tetraalkoxysilane and methyl-tertbutyl ether, dialkyl dialkoxy silicane is synthesized in reaction.Though the one-step synthesis process that patent is introduced is convenient,, still have several problems to need to solve if will be applied to research contents involved in the present invention.At first be that this one-step preparation process needs a small amount of Grignard reagent to make initiator, the industrializing implementation difficulty is big; Secondly,, have a large amount of unreacted Grignard reagents in the reaction and residue in the synthetic liquid, bring difficulty to post-processed by the method that patent is introduced; Once more, the mol ratio of alkyl chloride and tetraalkoxysilane is excessive, can strengthen production cost; Because in the research of the processing n-propyl trifunctional base silane that the present invention relates to, n-propyl trifunctional base silane is an industrial waste, cost is very low; And the alkyl chloride price is higher; The ratio that accounts for raw materials cost is big, calculates by alkyl chloride, and the reaction efficiency of this building-up process is very low.
In order to improve product yield, CN1183143 has also introduced a kind of method of handling filter cake, and the filter cake after being about to filter is handled with Hydrogen chloride, reclaims product and solvent.Because organo-siloxane is to moisture, especially acidic aqueous solution is very responsive, is easy to hydrolysis, and therefore, product in the filter cake and unreacted raw material can be destroyed, and also can in product, bring moisture into simultaneously.
Ri Tekaiping 6-345781 provides a kind of prepared in laboratory method of dialkyl dialkoxy silicane, and this reaction working medium cost is expensive, unsuitable industrial production.The aftertreatment of this method is the aqueous solution that adds earlier inorganic salt, adds the s.t. reaction mass again, makes in the reaction mass solid materials dissolve into inorganic salt and gets into water, and the purpose product in the reaction mass stays in organic phase, and organic phase removes solvent and makes product.This method has been exempted operations such as filtration and corresponding washing filter cake.But because the hydrolysising loss of dialkyl dialkoxy silicane is very serious, the target product yield is very low.
Patent CN101225090A provides a kind of novel method that is different from above several kinds of technologies: make solvent with the reactant tetraalkoxysilane; In the presence of catalyzer; Cause grignard reaction with a small amount of haloalkane and metal magnesium powder earlier; Drip haloalkane then, through Grignard reagent and tetraalkoxysilane reaction, one-step synthesis dialkyl dialkoxy silicane with hydro carbons or ether solvent dilution.But in the technology that this patent is introduced, after reaction finishes and lowers the temperature, directly filter.Owing to Grignard reagent in the chemical reaction related in this technology is excessive; When reaction proceeds to a certain degree, title product obtains, but excess reactant exists; In filtering process; Grignard reagent can with the heat release that reacts of airborne oxygen, steam, liberated heat can further impel excessive Grignard reagent and title product to continue reaction again, generates a series of by product.In the process of this process implementing, observed the rising of filtration unit temperature.Because in the system is a large amount of organic reagents, the temperature rising can cause potential dangerous, so the cancellation process is necessary.
Based on above present Research,, prepare its verivate if n-propyl trifunctional base silane is handled through Grignard reagent; Can not blindly indiscriminately imitate the processing condition of similar research; Need on the basis of using for reference the correlative study content, experiment condition be improved, could really effectively handle industrial waste; Improve its use value, turn waste into wealth.
Character and applied research for dipropyl two functional group's silane do not appear in the newspapers at present both at home and abroad as yet.Because dipropyl two functional group's silane belong to the category of dialkyl group two functional group's silane; Thereby it has the general aspects of dialkyl group two functional group's silane; The synthetic agent of three-dimensional properties-correcting agent, room temperature vulcanized silicone rubber chainextender and the organosilicon vinyl closure agent of catalyzer etc. in producing such as the antistructurizing agent that can be used as the organosilicon rubber unvulcanizate, Vestolen PP 7052; Particularly as the basic material of silicone oil and Zylox, market demand is very high.Because propyl group is than methyl group chain length, sterically hindered big, dipropyl two functional group's silane are different from common dimethyl-two functional group's silane, have had special nature, and the application space is more wide.
Dipropyl two functional group's silane can be condensed into homopolymer or multipolymer through self hydrolytic condensation or with other silane hydrolyzate with 1～3 Si-R ' (R ' be non-hydrolysising group).The hydrolysis of dipropyl two functional group's silane is identical with the hydrolytic process of other water-disintegrable silane.When the hydrolysising group of these silane was halogen, the haloid acid that generates during hydrolysis can promote further carrying out of hydrolysis.
Formula 1: (Pr)
a(R ')
bSiO
(4-a-b)/2(wherein Pr is a propyl group, and R ' is non-hydrolysising group)
The character of condensation product depends on the character of Si-R ' and the ratio of propyl group and R ', when a and b in the formula 1 add and less than 1.9 the time, the ZGK 5 that obtains has the character of resin.When a and b add and when being 1.98～2.01.The ZGK 5 viscosity that obtains approaches rubber.When a and b add and greater than 2.1 the time, last product is the end capped ZGK 5 of three organic groups.Prepared resin, the liquid of rubber like and end capped ZGK 5 have identical application as the organosilicon material that traditional group and propyl group are arranged simultaneously with the ZGK 5 that has traditional organic group.These materials have special value aspect high-low temperature resistant in addition.Because the introducing of propyl group, the character of silicone elastomer and resin has had variation, has therefore had application space more widely.
Being set out by dipropyl two functional group's silane to prepare the ZGK 5 that contains dipropyl silica chain link, if be the dipropyl chain link all, be called and gather the dipropyl siloxanes; If dipropyl chain link and other chain link (such as dimethyl-) copolymerization are called dimethyl-dipropyl copolymerization ZGK 5; More than can abbreviate propyl group silicone oil (all adopting this abbreviation below this paper) as.Such novel silicon oil equally also has the ordinary silicon oil properties, such as water-repellancy, resistance to bond, release property, froth breaking, emulsification, lubricated, low volatility etc.Propyl group silicone oil can also be processed second products such as silicone grease, silicon cream, skimmer, releasing agent, paper separant through secondary processing.
But the building-up process difference of the building-up process of dipropyl silicone oil and common silicone oil is bigger.Methyl-silicone oil just can obtain through the mode of dimethyl-two functional group's silane hydrolyzates.Adopt the method for cyclosiloxane ring-opening polymerization can obtain the high-molecular weight dimethyl silicone oil.But, the synthetic difficulty that then compares of diethyl silicone oil.This is that the condition of the ZGK 5 of synthetic different side chains is therefore also inequality because the open loop of different side links siloxanes is active different.Though the study on the synthesis of propyl group silicone oil does not appear in the newspapers as yet, but still can confirm, its synthesis condition is different fully with the synthesis condition of methyl-silicone oil and ethyl silicon oil.
Preparing high-molecular weight propyl group silicone oil can be through the method for cyclosiloxane ring-opening polymerization.This method need at first prepare six propyl group cyclotrisiloxane as starting raw material.The building-up process of six propyl group cyclotrisiloxane does not have report yet.The synthetic of hexamethyl cyclotrisiloxane become industry to know together, generally is that the first step is the hydrolysis of dimethyldichlorosilane(DMCS), is Pintsch process under the highly basic effect subsequently, goes out hexamethyl cyclotrisiloxane through rectifying separation then through the three-step approach preparation.But in this process, primary product is an octamethylcyclotetrasiloxane, and the ratio of hexamethyl cyclotrisiloxane is very low, calculates with original feed ratio, and productive rate is lower than 10%.Patent CN101597303A discloses the preparation process of Hexaethyl cyclotrisiloxane, also is to prepare through three-step approach, is respectively hydrolysis, cracking and rectifying.Above-mentioned two kinds of methods all exist step many, and reaction is complicated, use the shortcoming that raw material is many, energy consumption is high.Because propyl group is big, sterically hindered big than the volume of methyl and ethyl, three's physicals is different, thereby can be through changing the mode of reaction process, and a step obtains six propyl group cyclotrisiloxane.
From six propyl group cyclotrisiloxane preparations gather dipropyl silicone oil with (or) during dimethyl-dipropyl copolymerization ZGK 5, as previously mentioned, preparation technology's difference of preparation technology and methyl-silicone oil and ethyl silicon oil is bigger, this is that influence owing to propyl group causes.Must use strong catalyzer just can make six propyl group cyclotrisiloxane open loops, use promotor to promote reaction simultaneously, add chain termination agent at last and make reaction terminating, prevent that end group from returning to sting to cause molecular weight to reduce the phenomenon appearance with the MWD broad.
The same with traditional ZGK 5, formula 1 can be converted into the resin of indissoluble through the adding solidifying agent.These resins can be through adding or not adding the accurate control that filler carries out performance.The aqueous thing of the end capped ZGK 5 of organic group can be made the lubricant use through adding additive.Full-bodied caoutchoid can be converted into silicone elastomer through adding appropriate filler and vulcanizing agent.Aspect this, the appropriate filler of indication should be a dispersive in matrix easily, like thermal silica, precipitated silica etc.Other also can be used as filler like titanium oxide, aluminum oxide and carbon black.Top-priority vulcanizing agent is the vulcanizing agent of Lucidol and dicumyl peroxide.
Summary of the invention
The method that the purpose of this invention is to provide a kind of effective processing industrial waste n-propyl trifunctional base silane through preparation dipropyl two functional group's silane and verivates thereof, has promoted the use value of industrial waste.Because this process stabilizing, easy reliable, productive rate is high, cost is low, can solve and be badly in need of the waste disposal problem that solves in the present silane coupling agent industry, when reducing environmental pollution, turn waste into wealth.
The n-propyl trifunctional base silane Treatment Technology scheme that the present invention relates to is: in same reactor drum with reactant n-propyl trifunctional base silane as initial reactant, through the method for on-site prepn Grignard reagent, single stage method is synthesized the purpose product.This method has made full use of the huge reaction heat that is discharged when grignard reaction takes place, and makes the reaction of preparation dialkyl dialkoxy silicane be able to carry out quickly and smoothly.
Concrete steps are following:
(1) by n-propyl trifunctional base silane: chloropropane: magnesium is 0.8～1: 1: 1～1.5 molar ratio joins the chloropropane of magnesium, n-propyl trifunctional base silane and 10%～50% charging capacity in the solvent that ethers and hydro carbons be mixed and made into, and the mol ratio of said quantity of solvent and n-propyl trifunctional base silane is 1～10: 1; Use iodine to make catalyzer, be heated to 70 ℃～150 ℃ and cause grignard reaction, drip remaining chloropropane then, synthetic dipropyl two functional group's silane by solvent cut; After synthetic liquid is reduced to room temperature, in ice-water bath, carry out cancellation, after isolating solid substance, obtain highly purified product dipropyl two functional group's silane through fractionation and rectifying with quencher;
Wherein: above-mentioned magnesium is magnesium powder, magnesium chips or magnesium rod; Above-mentioned ethers is ether, THF, MTBE, propyl ether, butyl ether or 1, the 4-dioxane; Above-mentioned hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene; Ethers and hydro carbons blended volume ratio are 0.2～1 in the solvent: 0～1; The mol ratio of above-mentioned catalyst consumption and reactant magnesium is 0.0001～0.1: 1; Above-mentioned quencher is methyl alcohol or ethanol, and the mol ratio of its consumption and n-propyl trifunctional base silane is 1～5: 1;
(2) di two functional group's silane are dissolved in the inert solvent; Slowly join this mixed solution in the dilute acid soln then; The preparation hydrolyzate, this hydrolyzate used saturated sodium carbonate, saturated sodium-chloride and distilled water wash and drying successively after, obtain highly purified six propyl group cyclotrisiloxane through vacuum fractionation; Resistates after the fractionation in 150～350 ℃ of cracking, makes six propyl group cyclotrisiloxane under the potash catalyzer;
Wherein: above-mentioned inert solvent is hydro carbons or ethers, and said hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene, and said ethers is ether, THF, MTBE, propyl ether, butyl ether or 1, the 4-dioxane; Above-mentioned diluted acid is Hydrogen chloride, dilute sulphuric acid or dilute acetic acid; Above-mentioned potash catalyzer is Pottasium Hydroxide, salt of wormwood, potassium ethylate or silanol potassium, and its consumption is: the mass percent of potassium in siloxanes is 0.1%～5%;
(3) six propyl group cyclotrisiloxane and catalyzer, promotor in 80 ℃～150 ℃ reactions, are added the end-capping reagent SWS-F 221 under nitrogen protection, make and gather the dipropyl siloxanes;
Or
(3) with six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane in the presence of catalyzer and promotor in 80 ℃～150 ℃ reactions, make dimethyl-dipropyl copolymerization ZGK 5;
Wherein: catalyzer is Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, cesium hydroxide or TMAH described in the step (3), and the mass ratio of its consumption and six propyl group cyclotrisiloxane is 0.001～0.05: 1; Said promotor is DMSO 99.8MIN., N, dinethylformamide, hexamethylphosphoramide, THF, crown ether, cave ether, polyethers or oil of mirbane, and the mass ratio of its consumption and six propyl group cyclotrisiloxane is 0.01～0.20: 1; The mass ratio of the add-on of said end-capping reagent SWS-F 221 and six propyl group cyclotrisiloxane is 0.001～0.01: 1; The mass ratio of said six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane is 0.05～100: 1.
(4) dipropyl two functional group's silane and other hydrolyzable silane are carried out cohydrolysis, preparation contains various types of resins, the silicone oil product of propyl group, through adding various properties-correcting agent and filler, further prepares all kinds of goods that contain propyl group.
(5) with propyl group silicone oil and reinforced filling, concentrate linking agent, vulcanizing agent and other filler blend, through sulfidation, preparation contains the Zylox of propyl group and the blended rubber goods of Zylox and other rubber.
Employed reactant ratio and reaction conditions change in the larger context among the present invention.The objective of the invention is to convert one of them functional group of industrial waste n-propyl trifunctional base silane into propyl group; Thereby need react by one mole n-propyl trifunctional base silane and one mole Grignard reagent; The activity of considering Grignard reagent is very high; Be easy to take place side reaction, therefore first-selected in the present invention condition is that the molar weight of Grignard reagent is slightly higher than n-propyl trifunctional base silane; Grignard reagent is to be prepared by one mole chloropropane and one mole magnesium; Consider that magnesium is easily oxidized and generate Grignard reagent can cover magnesium when dissolving is in bad order surface stops proceeding of reaction, thereby first-selected condition is that the molar weight of magnesium is slightly higher than chloropropane among the present invention; In sum; First-selected condition is that the amount of substance of n-propyl trifunctional base silane is slightly less than the amount of substance of chloropropane and then is less than the amount of substance of magnesium among the present invention, and optimized ratio is a n-propyl trifunctional base silane: chloropropane: the part by weight of magnesium is 0.9: 1: 1.2.
The use because the reactant that has neither part nor lot in reaction can reclaim and feed intake again after reaction finishes, thereby the excessive use of the arbitrary component in the reactant ratio is all within scope involved in the present invention.Within the specific limits, excessive two kinds of components the time also is desirable.For example, under the excessive situation of the amount of magnesium, from 0.5 to 1.3 mole chloropropane reacts 1 mole n-propyl trifunctional base silane, all can obtain satisfied result.If consider reaction mass magnesium the pre-treatment situation and the ingredient proportion of (being divided into three kinds of magnesium rods, magnesium powder, magnesium chips), the proportional range of above-mentioned chloropropane and n-propyl trifunctional base silane can also enlarge further, and 0.1: 1 to 10: 1 also is possible.At magnesium under overactivation and excessive situation, preferred 0.9: 1 to 1.2: 1.Owing to exist cancellation reaction and excessive Grignard reagent can bring side reaction, thereby greatly excessive meeting causes great waste chloropropane and magnesium powder the time in the reaction process, so not within the scope that the present invention relates to.
The magnesium of selecting for use in the technology of the present invention has three kinds of magnesium powder, magnesium chips and magnesium rods, wherein because the granularity of magnesium powder is little, specific surface area is big active high, thereby is most preferably; Magnesium chips and magnesium rod all need be used the weak acid immersion treatment before use, to improve activity; Particularly magnesium rod if shade in the magnesium rod surface, also needs polishing in advance.The magnesium after handling and the mol ratio of haloalkane are 1: 1 to 2: 1, preferred 1.1: 1 to 1.3: 1.
The ratio of catalyzer also can change in a big way.Amount of substance with reactant magnesium is the basis, and the mol ratio of iodine and magnesium is 0.0001: 1 to 0.1: 1 o'clock, but equal smooth reaction, preferred 0.01: 1.
The influence degree that can the dissolving situation of Grignard reagent carry out reaction smoothly among the present invention is very big, thereby choice of Solvent is extremely important.The most important condition of selective solvent is certain solubleness to be arranged to Grignard reagent; Thereby first-selected ethers, comprise the conventional any ethers that uses in this area, like ether, THF, MTBE, propyl ether, butyl ether or 1; The 4-dioxane, preferred THF.The ethers that relates in the technology of the present invention needs before using through removing water treatment, and its purpose is to prevent that the moisture in the ether solvent from causing cancellation to reduce productive rate to reaction.Because therefore shortcomings such as the water removal operation of ethers is difficult, cost an arm and a leg, boiling point is low can select the mixed solution of ethers and varsol to do the usage quantity of solvent with the minimizing ethers.The varsol that the present invention relates to is hexane, hexanaphthene, heptane, benzene, toluene etc., preferred toluene.The volume content of ethers in mixed solution is 100% to 20%, preferred 50%.
The mol ratio of mixed solution and reaction raw materials n-propyl trifunctional base silane is 1: 1 to 10: 1, is preferably 5: 1 to 9: 1.
Feeding intake of raw material was divided into for two steps among the present invention.As indicated above, part material drops into reaction kettle earlier, and as " bed material ", all the other raw materials drip reaction kettle again as " dripping material " after reaction starts.The present invention values the consumption of halogenated alkane in " bed material " for making smooth stable startup of reaction very much, in the suitability for industrialized production of purpose product, has obtained satisfied effect.Chloropropane accounts for chloropropane 10% to 50% of the gross weight that feeds intake in " bed material ", is preferably 10-20%.Solvent in the bed material accounts for solvent 10% to 40% of the gross weight that feeds intake, and is preferably 15-25%.
Because the reaction of studying in the present invention is a heterogeneous reaction, so the stirring of reaction is just become the factor of overriding concern.The comparison effective means that the present invention at present adopts is: under mechanical stirring, join reactant and catalyzer in the reaction vessel after, heat and make reaction mixture refluxed.The solid of lower floor mainly carries out mixing by mechanical stirring, and blend is then mainly carried out by liquid return in the upper strata.But can not stir fast, otherwise heat can be lost rapidly, can't continue reaction; Also can not after reflux producing, stop mechanical stirring, only rely on and reflux, otherwise can cause local superheating and then cause and dash material because the local reaction heat release can't be scattered.
Temperature of reaction is according to the boiling point of selected mixed solution, generally at 0 ℃ to 120 ℃, and preferred 70 ℃ to 150 ℃, most preferably 100 ℃ to 130 ℃.Temperature of reaction is high more, and reaction Shaoxing opera is strong, but when temperature is too high, is easy to generate that to dash material dangerous, so need be according to the difference of selected solvent and the conditioned reaction temperature.Reaction of the present invention is preferably carried out under little reflux temperature after reaction starts always.
After reaction was accomplished in the presence of the magnesium, the reaction product that obtains will adopt the whole bag of tricks from mixture, to separate at n-propyl trifunctional base silane and chloropropane.For example, reaction mixture can remove by filter solid substance earlier, and filtrating obtains product through fractionation.When adopting this method, find because solids thickness relatively through regular meeting, can adsorb a large amount of products and cause productive rate on the low side.A kind of very effective solution is to use inert solvent that product mixtures is diluted, filters then, and washing leaching cake repeatedly, to improve yield.
There is a small amount of excessive Grignard reagent residue in the gained grignard reaction of the present invention residue solid substance, need finishes the back in reaction and unreacted Grignard reagent is removed, in order to avoid oxidized and bring danger in the subsequent processes with quencher.Quencher has also played the effect of thinner simultaneously.Because along with the carrying out of reaction, solid substance increases gradually in the system, the reaction mass retrogradation, the quencher of adding can disperse solid substance simultaneously effectively, increases the flowability of reaction mass, helps successful reaction and carries out, and also is beneficial to lock out operation subsequently simultaneously.Usually selecting quencher for use is alcohols, makes Grignard reagent be converted into the alkoxyl group magnesium salts through reaction, filters out through crossing then.When if raw material is the n-propyl Trimethoxy silane, the quencher of selecting for use is a methyl alcohol, if during raw material during the n-propyl triethoxyl silane, the quencher of selecting for use is an ethanol.The mol ratio of the quantity of solvent of quencher and n-propyl trifunctional base silane is 1: 1 to 5: 1, preferred 1: 1 to 3: 1.
When reaction raw materials is n-propyltrichlorosilan; Because product is the dipropyl dichlorosilane; Easy and the quencher reaction of its silicon chlorine key, thereby generally be earlier it to be steamed from system, and then under the ice-water bath condition, in the residue solid substance, add quencher; This technology is easy, and productive rate is not very high.In order to improve the yield of dipropyl dichlorosilane; Can be earlier adding the inert solvent phenyl ether in the system dilutes reaction system; Then the dipropyl dichlorosilane is steamed from system that (boiling point of phenyl ether is higher than the dipropyl dichlorosilane; When distillation, the dipropyl dichlorosilane is at first steamed), and then in the residue solid substance, add quencher.In order to improve the processing efficiency of n-propyl trifunctional base silane; Obtain more products, can select for use another kind of effective solution to be, these chlorine atoms are replaced to oxyethyl group; Just not hydrolysis easily of the oxyethyl group verivate that forms like this can be carried out filter operation in the system of opening wide.Collecting filtrates and steam desolventizes, and obtains product dipropyl diethoxy silane through vacuum fractionation then.This can realize through when reaction finishes, adding triethyl orthoformate.Triethyl orthoformate has also played the effect of quencher simultaneously to Grignard reagent.The ratio of triethyl orthoformate is 1: 1 to 3: 1 for silicon chlorine key, preferred 2: 1.
Relate in the technical scheme (2) in patent of the present invention, inert solvent comprises hydro carbons and ethers.Hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene; Ethers is ether, THF, MTBE, propyl ether, butyl ether or 1, the 4-dioxane; Preferred toluene.Diluted acid is Hydrogen chloride, dilute sulphuric acid or dilute acetic acid, preferred Hydrogen chloride.Said potash catalyzer comprises a kind of in Pottasium Hydroxide, salt of wormwood, potassium ethylate or the silanol potassium, and its consumption is: the mass percent of potassium in siloxanes is 0.1% to 5%, preferred Pottasium Hydroxide.
The hydrolyzate that relates to technical scheme (2) preparation by patent of the present invention; Wherein the content of six propyl group cyclotrisiloxane is very high; Directly underpressure distillation just can obtain higher yields, is different from the low characteristics of title product content in the hydrolyzate of hexamethyl cyclotrisiloxane and Hexaethyl cyclotrisiloxane.
In this technical scheme (2), said scission reaction temperature is 150 to 350 ℃, is preferably 200 to 300 ℃.
Relate in the technical scheme (3) in patent of the present invention, catalyzer is Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, cesium hydroxide or TMAH, preferred TMAH; The preferred crown ether of promotor.
Relate in the technical scheme (5) in patent of the present invention, reinforced filling comprises thermal silica, precipitated silica, titanium oxide, aluminum oxide and carbon black etc., preferred thermal silica; Vulcanizing agent comprises vulcanizing agents such as Lucidol, dicumyl peroxide, preferred Lucidol.
Achievement of the present invention can solve the waste disposal problem of being badly in need of solution in the present silane coupling agent industry; Reduce discharging of waste liquid, save production cost, reduce the industry energy consumption; The various product innovations that contain propyl group of superior performance can also be provided simultaneously; Comprise silicone oil, silicone resin and Zylox etc., thereby promote the industry research and development level and the technical strength of China's silane coupling agent industry and even organosilicon industry comprehensively.
Embodiment
Embodiment 1
The ratio of 7.2g magnesium powder, 32.8g n-propyl Trimethoxy silane, 3g chloropropane and 50mL THF (need through no water treatment) is joined each reactant in the reaction vessel, put into 0.025g iodine grain, heat this mixture to 74 ℃, generation liquid return.Produce great amount of bubbles on the liquid level, reaction is initiated.At this moment, slowly drip the 16.62g chloropropane that is dissolved in the 50mL THF (need) through no water treatment.The control Heating temperature makes system remain slight boiling condition, and temperature floats on about 76 ℃.With gc monitoring reaction thing remaining quantity, when the transformation efficiency of n-propyl Trimethoxy silane greater than 99% the time, reaction finishes (about four hours), stopped reaction, naturally cooling.
Under the ice-water bath condition, add anhydrous methanol 20mL, react cancellation.Filter and washing precipitation.With a small amount of anhydrous methanol washing precipitation.To filtrate to revolve to steam to remove after merging and desolvate.Product mixtures is carried out fractionation.Carry out product with infrared and nuclear-magnetism and confirm product dipropyl dimethoxy silane, calculating productive rate according to the amount of the n-propyl Trimethoxy silane that adds is 90%.
Embodiment 2
Change the n-propyl Trimethoxy silane among the embodiment 1 into the n-propyl triethoxyl silane, obtain the dipropyl diethoxy silane.
Embodiment 3
Change the magnesium powder among the embodiment 1 into magnesium rod (need polishing earlier before using and with feeding intake after diluted acid immersion treatment, the drying), obtain dipropyl dimethoxy silane.
Embodiment 4
Change the magnesium powder among the embodiment 1 into magnesium chips (needing earlier with feeding intake after diluted acid immersion treatment, the drying before using), obtain dipropyl dimethoxy silane.
Embodiment 5
7.2g the ratio of magnesium powder, 37.0g n-propyl Trimethoxy silane, 6g chloropropane and 60mL THF (needing through no water treatment) joins each reactant in the reaction vessel; After question response is initiated; Slowly drip the 14.64g chloropropane that is dissolved in the 40mL THF (need) again through no water treatment; When other condition was constant, the productive rate of product dipropyl dimethoxy silane was 87%.
Embodiment 6
When changing the THF among the embodiment 5 the equal proportion mixed solution of THF and toluene (both all need through no water treatment) into, other condition is constant, and the productive rate of product dipropyl dimethoxy silane is 80%.
Embodiment 7
The ratio of 7.2g magnesium powder, 39.3g n-propyltrichlorosilan, 3g chloropropane and 50mL THF (need through no water treatment) is joined each reactant in the reaction vessel, put into 0.025g iodine grain, heat this mixture to 74 degree centigrade, generation liquid return.Produce great amount of bubbles on the liquid level, reaction is initiated.At this moment, slowly drip the 16.62g chloropropane that is dissolved in the 50mL THF (need) through no water treatment.The control Heating temperature makes system remain slight boiling condition, and temperature floats on 76 deg.c.After four hours, stopped reaction, naturally cooling.
After adding the 50mL phenyl ether, steam low boiling point solvent through common distillation earlier, underpressure distillation then can obtain the dipropyl dichlorosilane, and product yield is more than 50%.
Embodiment 8
Change 50mL phenyl ether among the embodiment 7 into the 100g triethyl orthoformate chlorine silicon key is replaced to oxyethyl group, through filtering, filtrate collection and steaming are desolventized then.Vacuum fractionation can obtain the dipropyl diethoxy silane.Product is confirmed with nuclear-magnetism with infrared, by the amount of the n-propyltrichlorosilan that begins to add, calculates productive rate and surpasses 60%.
Embodiment 9
The dipropyl dichlorosilane of 10mol, the dimethyldichlorosilane(DMCS) of 10mol and the trimethyl silane of 0.1mol are added in the 1L frozen water, and hydrolyzate neutralizes with yellow soda ash.The oil reservoir that obtains is separated from water layer, and this organosilicon liquid substance includes the silica-based unit of dipropyl, the silica-based unit of dimethyl-and trimethyl silicon based unit, can be used as lubricant and heat transfer baffle.
Embodiment 10
Change the dipropyl dichlorosilane among the embodiment 9 into dipropyl dimethoxy silane or dipropyl diethoxy silane; Do not change dimethyldichlorosilane(DMCS) or change into and be dimethyldimethoxysil,ne or change dimethyldiethoxysilane into, all can be included the silica-based unit of dipropyl, the silica-based unit of dimethyl-and trimethyl silicon based unitary organosilicon liquid simultaneously.
Embodiment 11
In reaction vessel, add the hydrochloric acid of the 6mol/L of 200mL, be dissolved in the 40g dipropyl dimethoxy silane in the 50mL toluene while stir then slowly to add.After dropwising, continue to stir 4 hours.Standing demix, difference water, saturated potassium carbonate, saturated sodium-chloride and distilled water wash oil reservoir, and use anhydrous magnesium sulfate drying, can obtain highly purified dipropyl siloxanes hydrolyzate.
With the hydrolyzate vacuum fractionation, and carry out product with infrared, nuclear-magnetism and mass spectrum and confirm that can obtain six propyl group cyclotrisiloxane, purity is more than 99%.
Embodiment 12
Dipropyl siloxanes hydrolyzate among the embodiment 11 is carried out 250 ℃ of pyrolysis and decompression separation low-boiling-point substance in the presence of Pottasium Hydroxide, can obtain the dipropyl mixture of siloxanes.With this mixture vacuum fractionation, and carry out product with infrared, nuclear-magnetism and mass spectrum and confirm that can obtain six propyl group cyclotrisiloxane, purity is more than 99%.
Embodiment 13
Hydrolyzate with fractionating out among the embodiment 11 behind the six propyl group cyclotrisiloxane carries out 250 ℃ of pyrolysis and decompression separation low-boiling-point substance in the presence of Pottasium Hydroxide, can obtain the dipropyl mixture of siloxanes.With this mixture fractionation, and carry out product with infrared, nuclear-magnetism and mass spectrum and confirm that can obtain six propyl group cyclotrisiloxane, purity is more than 99%.
Embodiment 14
The six propyl group cyclotrisiloxane of 100 parts of (mass parts) purity more than 99% are carried out polyreaction under the catalysis of 1 part of Pottasium Hydroxide, can make and gather the dipropyl siloxanes, claim propyl group silicone oil again.
Embodiment 15
Change the catalyzer among the embodiment 14 into TMAH alkali glue, can make and gather the dipropyl siloxanes.Catalyzer in the product can be removed through intensification.
Embodiment 16
100 parts of (mass parts) purity, six propyl group cyclotrisiloxane, 100 parts of octamethylcyclotetrasiloxanes and 1 part of SWS-F 221 more than 99% carried out polyreaction under the catalysis of 1 part of Pottasium Hydroxide, can obtain the multipolymer of high-molecular weight dimethyl siloxane dipropyl siloxanes.Catalyzer in the product can neutralize with silica-based SULPHOSUCCINIC ACID ESTER.
Embodiment 17
Change the catalyzer among the embodiment 16 into TMAH alkali glue, also can make dimethyl siloxane dipropyl silicone copolymers.Catalyzer in the product can be removed through intensification.
Embodiment 18
100 parts of (mass parts) purity, six propyl group cyclotrisiloxane, 100 parts of octamethylcyclotetrasiloxanes, 10 parts of tetramethyl-tetrem alkenyl siloxane and 1 part of SWS-F 221 more than 99% carried out polyreaction under the catalysis of 1 part of TMAH alkali glue, can obtain the dimethyl siloxane dipropyl silicone copolymers that high-molecular weight has vinyl.Catalyzer in the product can be removed through intensification.
Embodiment 19
With the WHITE CARBON BLACK that adds equivalent in the copolymer 1 00 part (mass parts) behind the catalyzer of removing among the embodiment 18; On mixing roll, carry out blend; Heated 30 minutes down at 160 degrees centigrade then; Add 3 parts of Lucidols then, handled 20 minutes 180 degrees centigrade of following pressurized, heated again, at last again 160 degrees centigrade of following thermal treatments 1 hour.Can obtain the special Zylox of superior performance aspect high-low temperature resistant.
The unit of mass parts described in the foregoing description is gram.
Claims (10)
1. a method of effectively handling industrial waste n-propyl trifunctional base silane is through grignard reaction n-propyl trifunctional base silane to be treated as di two functional group's silane and verivates thereof, it is characterized in that said treatment process is:
(1) by n-propyl trifunctional base silane: chloropropane: magnesium is 0.8～1: 1: 1～1.5 molar ratio joins the chloropropane of magnesium, n-propyl trifunctional base silane and 10%～50% charging capacity in the solvent that ethers and hydro carbons be mixed and made into, and the mol ratio of said quantity of solvent and n-propyl trifunctional base silane is 1～10: 1; Use iodine to make catalyzer, be heated to 70 ℃～150 ℃ and cause grignard reaction, drip remaining chloropropane then, synthetic dipropyl two functional group's silane by solvent cut; After synthetic liquid is reduced to room temperature, in ice-water bath, carry out cancellation, after isolating solid substance, obtain highly purified product dipropyl two functional group's silane through fractionation and rectifying with quencher;
Wherein: above-mentioned magnesium is magnesium powder, magnesium chips or magnesium rod; Above-mentioned ethers is ether, THF, MTBE, propyl ether, butyl ether or 1, the 4-dioxane; Above-mentioned hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene; Ethers and hydro carbons blended volume ratio are 0.2～1 in the solvent: 0～1; The mol ratio of above-mentioned catalyst consumption and reactant magnesium is 0.0001～0.1: 1; Above-mentioned quencher is methyl alcohol or ethanol, and the mol ratio of its consumption and n-propyl trifunctional base silane is 1～5: 1;
(2) di two functional group's silane are dissolved in the inert solvent; Slowly join this mixed solution in the dilute acid soln then; The preparation hydrolyzate, this hydrolyzate used saturated sodium carbonate, saturated sodium-chloride and distilled water wash and drying successively after, obtain highly purified six propyl group cyclotrisiloxane through vacuum fractionation; Resistates after the fractionation in 150～350 ℃ of cracking, makes six propyl group cyclotrisiloxane under the potash catalyzer;
Wherein: above-mentioned inert solvent is hydro carbons or ethers, and said hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene, and said ethers is ether, THF, MTBE, propyl ether, butyl ether or 1, the 4-dioxane; Above-mentioned diluted acid is Hydrogen chloride, dilute sulphuric acid or dilute acetic acid; Above-mentioned potash catalyzer is Pottasium Hydroxide, salt of wormwood, potassium ethylate or silanol potassium, and its consumption is: the mass percent of potassium in siloxanes is 0.1%～5%;
(3) six propyl group cyclotrisiloxane and catalyzer, promotor in 80 ℃～150 ℃ reactions, are added the end-capping reagent SWS-F 221 under nitrogen protection, make and gather the dipropyl siloxanes;
Or
(3) with six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane in the presence of catalyzer and promotor in 80 ℃～150 ℃ reactions, make dimethyl-dipropyl copolymerization ZGK 5;
Wherein: catalyzer is Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, cesium hydroxide or TMAH described in the step (3), and the mass ratio of its consumption and six propyl group cyclotrisiloxane is 0.001～0.05: 1; Said promotor is DMSO 99.8MIN., N, dinethylformamide, hexamethylphosphoramide, THF, crown ether, cave ether, polyethers or oil of mirbane, and the mass ratio of its consumption and six propyl group cyclotrisiloxane is 0.01～0.20: 1; The mass ratio of the add-on of said end-capping reagent SWS-F 221 and six propyl group cyclotrisiloxane is 0.001～0.01: 1; The mass ratio of said six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane is 0.05～100: 1.
2. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said n-propyl trifunctional of step (1) base silane: chloropropane: the part by weight of magnesium is 0.9: 1: 1.2; The mol ratio of catalyst consumption and magnesium is 0.01: 1.
3. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: ethers selects THF in the said solvent of step (1), and hydro carbons selects toluene, and ethers and hydro carbons blended volume ratio are 1: 1 in the solvent.
4. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said quencher of step (1) selects methyl alcohol, and the mol ratio of its consumption and n-propyl trifunctional base silane is 3: 1.
5. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said inert solvent of step (2) selects toluene; Said diluted acid selects Hydrogen chloride.
6. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said potash catalyzer of step (2) selects Pottasium Hydroxide, and its consumption is: the mass percent of potassium in siloxanes is 0.1%.
7. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said cracking temperature of step (2) is 200～300 ℃.
8. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said catalyzer of step (3) selects TMAH.
9. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said promotor of step (3) is selected crown ether.
10. according to the method for the said processing industrial waste of claim 1 n-propyl trifunctional base silane, it is characterized in that: the said temperature of reaction of step (3) is 100 ℃～130 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102964373A (en) * | 2012-12-22 | 2013-03-13 | 威海新元化工有限公司 | Preparation method of trimethyl tri-n-propyl cyclotrisiloxane |
| CN114751930A (en) * | 2022-05-17 | 2022-07-15 | 山东博苑医药化学股份有限公司 | Method for recovering hexamethyldisiloxane from waste solvent containing trimethylsilylether and hexamethyldisiloxane |
| CN112300207B (en) * | 2020-11-19 | 2024-01-30 | 南京曙光新材料有限公司 | Method for removing polysulfide silane coupling agent in byproduct brine |
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| US4958041A (en) * | 1988-06-25 | 1990-09-18 | Schering Aktiengesellschaft | Methods for producing diorganodialkoxysilanes |
| CN101225090A (en) * | 2007-01-15 | 2008-07-23 | 临邑县鲁晶化工有限公司 | Method for directly synthesizing dialkyl dialkoxy silicane by one-step process |
| CN101597303A (en) * | 2009-07-09 | 2009-12-09 | 武汉市化学工业研究所有限责任公司 | The preparation method of Hexaethyl cyclotrisiloxane or triethyl trimethyl cyclotrisiloxane |
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| US4958041A (en) * | 1988-06-25 | 1990-09-18 | Schering Aktiengesellschaft | Methods for producing diorganodialkoxysilanes |
| CN101225090A (en) * | 2007-01-15 | 2008-07-23 | 临邑县鲁晶化工有限公司 | Method for directly synthesizing dialkyl dialkoxy silicane by one-step process |
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| CN102964373A (en) * | 2012-12-22 | 2013-03-13 | 威海新元化工有限公司 | Preparation method of trimethyl tri-n-propyl cyclotrisiloxane |
| CN112300207B (en) * | 2020-11-19 | 2024-01-30 | 南京曙光新材料有限公司 | Method for removing polysulfide silane coupling agent in byproduct brine |
| CN114751930A (en) * | 2022-05-17 | 2022-07-15 | 山东博苑医药化学股份有限公司 | Method for recovering hexamethyldisiloxane from waste solvent containing trimethylsilylether and hexamethyldisiloxane |
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