CN102604099B - 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 and n-propyl trifunctional base silane is processed into dipropyl two functional group's silane and further prepares six propyl group cyclotrisiloxane, contain the polysiloxane of dipropyl silica chain link and the processing method of silicon rubber.
Background technology
N-propyl trifunctional base silane (comprising n-propyl Trimethoxy silane, n-propyl triethoxyl silane and n-propyltrichlorosilan) is the by product in industrial production silane coupling agent process, account for 5% of product mixtures, generation is very large, can serious environment pollution after discarding.But these by products are not well utilized at present.Main methods on market is that it is prepared thermal silica by high-temperature calcination.This technique power consumption is large, and value-added content of product is little, can not embody the characteristic property of this material, has caused great waste.Owing to such by product can not being discharged as sewage, do not having under the background of processing mode and treatment process preferably, now domestic many silane coupling agent manufacturers are all with such by product long-term storage, occupy very large storage workshop, even badly influenced the normal operation of factory.Some producers abandon the separation to such by product, and direct marketing without the silane coupling agent of purifying, has had a strong impact on the product competitive power on market at home and abroad 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.The method of using has a variety of, and one of them method is by 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 diη-propyl two functional group's silane, referred to as dipropyl two functional group's silane.
Research for from n-propyl trifunctional base silane preparation dipropyl two functional group's silane there is not yet report both at home and abroad.At present, only have from the research of haloalkane and tetraalkoxysilane reaction preparation dialkyl dialkoxy silicane and can use for reference, be divided into two kinds of single stage method and two-step approachs.What introduce in patent EP460590 is two-step approach, namely reacts the preparation Grignard reagent by chlorocyclopentane and magnesium chips in tetrahydrofuran solvent, and then with gained grignard reagent and the reaction of equimolar tetramethoxy-silicane, synthetic dicyclopentyl dimethoxyl silane.Owing to adopting two step synthesis, nature can bring operational loaded down with trivial details, the problem that technical process is long, conversion unit is many, and also the content of by product 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 first will prepare a small amount of Grignard reagent as initiator in methyl-tertbutyl ether solvent with alkyl chloride and magnesium chips, and then dripping the mixing solutions that is formed by alkyl chloride, tetraalkoxysilane and methyl-tertbutyl ether, dialkyl dialkoxy silicane is synthesized in reaction.Although the one-step synthesis process that patent is introduced is convenient, if will be applied to research contents involved in the present invention, still have several problems to need to solve.At first be that this one-step preparation process needs a small amount of Grignard reagent to make initiator, the industrializing implementation difficulty is large; Secondly, the method for pressing patent Introduction has a large amount of unreacted Grignard reagents and residues in synthetic liquid in reaction, bring difficulty to post-processed; Again, 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 industrial waste, cost is very low, and the alkyl chloride price is higher, the ratio that accounts for raw materials cost is large, 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 processing filter cake, and the filter cake after being about to filter is processed with dilute hydrochloric acid, reclaims product and solvent.To moisture, especially acidic aqueous solution is very responsive due to organo-siloxane, is easy to hydrolysis, and therefore, the product in filter cake and unreacted raw material can be destroyed, also can bring moisture in product simultaneously.
Day, Unexamined Patent 6-345781 provided a kind of laboratory preparation method of dialkyl dialkoxy silicane, and this reaction working medium cost is expensive, is not suitable for industrial production.The aftertreatment of this method is the aqueous solution that first adds inorganic salt, then acid adding processing reaction material, makes in reaction mass solid materials dissolve into inorganic salt and enters water, and the purpose product in reaction mass stays in organic phase, and the organic phase desolvation makes product.This method has been exempted the operations such as filtration and corresponding washing leaching 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 techniques: make solvent with the reactant tetraalkoxysilane, under catalyzer exists, first cause grignard reaction with a small amount of haloalkane and metal magnesium powder, then drip the haloalkane with hydro carbons or ether solvent dilution, through Grignard reagent and tetraalkoxysilane reaction, one-step synthesis dialkyl dialkoxy silicane.But in the technique that this patent is introduced, after reaction finishes and lowers the temperature, directly filter.Because Grignard reagent in chemical reaction related in this technique is excessive, when reaction proceeds to a certain degree, target product obtains, but excess reactant exists, in the process of filtering, Grignard reagent can with the heat release that reacts of airborne oxygen, steam, liberated heat can further impel again excessive Grignard reagent and target product to continue reaction, generates a series of by product.In the process of this process implementing, observed the rising of filtration unit temperature.Owing in system being a large amount of organic reagents, the temperature rising can cause potential danger, so the cancellation process is necessary.
Based on above present Research, if by Grignard reagent, n-propyl trifunctional base silane is processed, prepare its derivative, 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 be processed industrial waste, improve its use value, turn waste into wealth.
For character and the applied research of dipropyl two functional group's silane, there is not yet at present report both at home and abroad.The category that belongs to dialkyl group two functional group's silane due to dipropyl two functional group's silane, thereby it has the general aspects of dialkyl group two functional group's silane, such as the antistructurizing agent that can be used as the organosilicon rubber unvulcanizate, polypropylene produce in the synthetic agent etc. of three-dimensional properties-correcting agent, room temperature vulcanized silicone rubber chainextender and organosilicon vinyl closure agent of catalyzer, particularly as the basic material of silicone oil and silicon rubber, market demand is very high.Than methyl group chain length, sterically hindered large, dipropyl two functional group's silane are different from common dimethyl two functional group's silane, have had special character due to propyl group, and the application space is more wide.
Dipropyl two functional group's silane can be condensed into homopolymer or multipolymer by 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 was understood further carrying out of facilitation of hydrolysis.
Formula 1:(Pr)
a(R ')
bSiO
(4-a-b)/2(wherein Pr is 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 formula 1 add and less than 1.9 the time, the polysiloxane that obtains has the character of resin.When a and b add and when being 1.98～2.01.The polysiloxane viscosity that obtains is close to rubber.When a and b add and greater than 2.1 the time, last product is the polysiloxane of three organic group end-blockings.The polysiloxane of prepared resin, the liquid of rubber like and end-blocking is as the organosilicon material that traditional group and propyl group are arranged simultaneously, has identical application with polysiloxane with traditional organic group.These materials have special value aspect high-low temperature resistant in addition.Due to 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 polysiloxane that contains dipropyl silica chain link, if be all the dipropyl chain link, is called poly-dipropyl siloxanes; If dipropyl chain link and other chain link (such as dimethyl) copolymerization are called dimethyl dipropyl copolymerization polysiloxane; More than can be referred to as propyl group silicone oil (all adopting this abbreviation below this paper).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 made the second products such as silicone grease, silicon cream, defoamer, 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 larger.Methyl-silicone oil just can obtain by the mode of dimethyl two functional group's silane hydrolyzates.The method of employing cyclosiloxane ring-opening polymerization can obtain the dimethyl silicone oil of high molecular.But synthesizing of diethyl silicone oil is more difficult.This is that the condition of the polysiloxane of synthetic different side chains is therefore not identical yet because the open loop of different side links siloxanes is active different.Although the study on the synthesis of propyl group silicone oil there is not yet report, but still can determine, its synthesis condition is fully different from the synthesis condition of methyl-silicone oil and ethyl silicon oil.
The propyl group silicone oil of preparation high molecular can be by the method for cyclosiloxane ring-opening polymerization.At first the method need to 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, is generally to prepare by three-step approach, and the first step is the hydrolysis of dimethyldichlorosilane(DMCS), is Pintsch process under the highly basic effect subsequently, then goes out hexamethyl cyclotrisiloxane by rectifying separation.But in this process, primary product is 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 hexaetcycletrisiloxane, is also to be prepared by 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 large, sterically hindered large than the volume of methyl and ethyl, three's physicals is different, thereby can be by changing the mode of reaction process, and a step obtains six propyl group cyclotrisiloxane.
From the poly-dipropyl silicone oil of six propyl group cyclotrisiloxane preparations and (or) during dimethyl dipropyl copolymerization polysiloxane, as previously mentioned, preparation technology's difference of preparation technology and methyl-silicone oil and ethyl silicon oil is larger, and this is that impact due to propyl group causes.Must use strong catalyzer just can make six propyl group cyclotrisiloxane open loops, use simultaneously promotor to promote reaction, add at last chain termination agent to make reaction terminating, prevent from that end group from returning to sting to cause the phenomenon appearance that molecular weight reduces and molecular weight distribution is wider.
The same with traditional polysiloxane, formula 1 can be converted into the resin of indissoluble by adding solidifying agent.These resins can carry out the accurate control of performance by adding or do not add filler.The aqueous thing of the polysiloxane of organic group end-blocking can use by adding additive to make lubricant.Full-bodied caoutchoid can be converted into silicone elastomer by adding suitable filler and vulcanizing agent.Aspect this, the suitable filler of indication should easily disperse in matrix, as thermal silica, precipitated silica etc.Other also can be used as filler as titanium dioxide, aluminum oxide and carbon black.Top-priority vulcanizing agent is the vulcanizing agent of benzoyl peroxide and dicumyl peroxide.
Summary of the invention
A kind of method that the purpose of this invention is to provide effective processing industrial waste n-propyl trifunctional base silane by preparation dipropyl two functional group's silane and derivatives thereof, has promoted the use value of industrial waste.Due to 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 present silane coupling agent industry, turn waste into wealth in environmental contamination reduction.
The technical scheme that the n-propyl trifunctional base silane that the present invention relates to is processed is: in same reactor with reactant n-propyl trifunctional base silane as initial reactant, by the method for in situ preparation Grignard reagent, single stage method is synthesized the purpose product.The method takes full advantage of the huge reaction heat that discharges when grignard reaction occurs, and makes the reaction of preparation dialkyl dialkoxy silicane be carried out quickly and smoothly.
Concrete steps are as follows:
(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 the mol ratio of described 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, then drip the remaining chloropropane by solvent cut, synthetic dipropyl two functional group's silane; After synthetic liquid is down to room temperature, carry out cancellation with quencher in ice-water bath, after isolating solid substance, obtain highly purified product dipropyl two functional group's silane by fractionation and rectifying;
Wherein: above-mentioned magnesium is magnesium powder, magnesium chips or magnesium rod; Above-mentioned ethers is ether, tetrahydrofuran (THF), methyl tertiary butyl ether, propyl ether, butyl ether or Isosorbide-5-Nitrae-dioxane; Above-mentioned hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene; The volume ratio that in solvent, ethers mixes with hydro carbons is 0.2～1: 0～1; The mol ratio of the consumption of above-mentioned catalyzer 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) diη-propyl two functional group's silane are dissolved in inert solvent, then slowly join this mixed solution in dilute acid soln, the preparation hydrolyzate, after this hydrolyzate is used saturated sodium carbonate, saturated sodium-chloride and distilled water wash and drying successively, obtain highly purified six propyl group cyclotrisiloxane through vacuum fractionation, resistates after 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 described hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene, and described ethers is ether, tetrahydrofuran (THF), methyl tertiary butyl ether, propyl ether, butyl ether or Isosorbide-5-Nitrae-dioxane; Above-mentioned diluted acid is dilute hydrochloric acid, dilute sulphuric acid or dilute acetic acid; Above-mentioned potash catalyzer is potassium 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 hexamethyldisiloxane under nitrogen protection, make poly-dipropyl siloxanes;
Or
(3) with six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane under the existence of catalyzer and promotor in 80 ℃～150 ℃ reactions, make dimethyl dipropyl copolymerization polysiloxane;
Wherein: described in step (3), catalyzer is lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide or Tetramethylammonium hydroxide, and the mass ratio of its consumption and six propyl group cyclotrisiloxane is 0.001～0.05: 1; Described promotor is dimethyl sulfoxide (DMSO), DMF, hexamethylphosphoramide, tetrahydrofuran (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 described end-capping reagent hexamethyldisiloxane and six propyl group cyclotrisiloxane is 0.001～0.01: 1; The mass ratio of described 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, by 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, Concentrative crosslinking agent, vulcanizing agent and other filler blend, through sulfidation, preparation contains the silicon rubber of propyl group and the blended rubber goods of silicon rubber and other rubber.
The change in the larger context of the reactant ratio of using in the present invention and reaction conditions.The objective of the invention is one of them functional group of industrial waste n-propyl trifunctional base silane is converted to propyl group, thereby need to be reacted by the n-propyl trifunctional base silane of a mole and the Grignard reagent of a mole, the activity of considering Grignard reagent is very high, therefore be easy to occur side reaction, first-selected condition is that the molar weight of Grignard reagent is slightly higher than n-propyl trifunctional base silane in the present invention; Grignard reagent is to be prepared by the chloropropane of a mole and the magnesium of one mole, consider that magnesium easily stops proceeding of reaction in oxidized and Grignard reagent that the generate surface that can cover magnesium when dissolving is in bad order, thereby in the present invention, first-selected condition is that the molar weight of magnesium is slightly higher than chloropropane; In sum, in the present invention, 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, and optimized ratio is n-propyl trifunctional base silane: chloropropane: the part by weight of magnesium is 0.9: 1: 1.2.
The use of can reclaiming and again feed intake after reaction finishes due to the reactant that has neither part nor lot in reaction, thereby the excessive use of the arbitrary component in reactant ratio is all within scope involved in the present invention.Within the specific limits, excessive when two kinds of components is also desirable.For example, in the situation that the amount of magnesium is excessive, the chloropropane of from 0.5 to 1.3 mole reacts the n-propyl trifunctional base silane of 1 mole, all can obtain satisfied result.If consider reaction mass magnesium 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 is also possible.In the situation that magnesium is through overactivation and excessive, preferred 0.9: 1 to 1.2: 1.In reaction process, owing to existing cancellation reaction and excessive Grignard reagent can bring side reaction, thereby greatly excessive meeting causes great waste when chloropropane and magnesium powder, therefore not within the scope that the present invention relates to.
The magnesium of selecting in the technology of the present invention has three kinds of magnesium powder, magnesium chips and magnesium rods, and wherein the granularity due to the magnesium powder is little, the large activity of specific surface area is 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, shade if magnesium rod is surperficial, also needs prior polishing.Magnesium after processing 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.Take the amount of substance of reactant magnesium as the basis, the mol ratio of iodine and magnesium is 0.0001: 1 to 0.1: 1 o'clock, all can react smoothly preferred 0.01: 1.
The influence degree that in the present invention, can the dissolving situation of Grignard reagent carry out smoothly to reaction is very large, thereby the selection 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, as ether, tetrahydrofuran (THF), methyl tertiary butyl ether, propyl ether, butyl ether or 1, the 4-dioxane, preferred tetrahydrofuran (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 ether solvent from causing cancellation to reduce productive rate to reaction.Due to shortcomings such as the water removal operation of ethers are more difficult, expensive, boiling point is low, therefore can select the mixed solution of ethers and varsol to make solvent to reduce the usage quantity of 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 of the present invention was divided into for two steps.As indicated above, part material first drops into reactor, and as " bed material ", all the other raw materials drip reactor 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, has obtained satisfied effect in the suitability for industrialized production of purpose product.Chloropropane accounts for chloropropane 10% to 50% of the gross weight that feeds intake in " bed material ", is preferably 10-20%.Solvent in 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 present invention is heterogeneous reaction, so the stirring of reaction is just become the factor of overriding concern.The comparison effective means that at present the present invention adopts is: under mechanical stirring, after joining reactant and catalyzer in reaction vessel, heating makes reaction mixture refluxed.The solid of lower floor mainly carries out mixing by mechanical stirring, and blend is mainly carried out by liquid return in the upper strata.But can not rapid stirring, otherwise heat can scatter and disappear rapidly, can't continue reaction; Also can not stop mechanical stirring after the generation that refluxes, only rely on and reflux, otherwise can can't scatter due to the local reaction heat release, cause local superheating and then cause punching to expect.
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 higher, and reaction Shaoxing opera is strong, but when excess Temperature, easily produces the punching material dangerous, so need to 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 completed under magnesium exists at n-propyl trifunctional base silane and chloropropane, the reaction product that obtains will adopt the whole bag of tricks to separate from mixture.For example, reaction mixture can first remove by filter solid substance, and filtrate obtains product through fractionation.When adopting this method, often can find due to solids thickness relatively, 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, then filters, and washing leaching cake repeatedly, to improve yield.
There is a small amount of excessive Grignard reagent residue in gained grignard reaction of the present invention residue solid substance, need to quencher, unreacted Grignard reagent be removed after reaction finishes, in order to avoid oxidized and bring danger in subsequent processes.Quencher has also played the effect of thinner simultaneously.Because along with the carrying out of reaction, in system, solid substance increases gradually, the reaction mass retrogradation, the quencher that adds can disperse solid substance simultaneously effectively, increases the mobility of reaction mass, and what be conducive to react carries out smoothly, also is beneficial to lock out operation subsequently simultaneously.Usually selecting quencher is alcohols, makes Grignard reagent be converted into the alkoxyl group magnesium salts by reaction, then filters out by mistake.When if raw material is the n-propyl Trimethoxy silane, the quencher of selecting is methyl alcohol, if during raw material during the n-propyl triethoxyl silane, the quencher of selecting is 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, its silicon chlorine key easily reacts with quencher, thereby be generally first it to be steamed from system, and then add quencher in the residue solid substance under the ice-water bath condition, this simple process, productive rate are not very high.In order to improve the yield of dipropyl dichlorosilane, can first add the inert solvent phenyl ether that reaction system is diluted in system, then the dipropyl dichlorosilane is steamed from system that (boiling point of phenyl ether is higher than the dipropyl dichlorosilane, when distillation, at first the dipropyl dichlorosilane is distilled out of), and then add quencher in the residue solid substance.In order to improve the processing efficiency of n-propyl trifunctional base silane, obtain more product, can select another kind of effectively terms of settlement is that these chlorine atoms are replaced to oxyethyl group, the oxyethyl group derivative that forms so just can easily not be hydrolyzed, and can carry out filter operation in the system of opening wide.Collection filtrate and steaming desolventize, and then obtain product dipropyl diethoxy silane by vacuum fractionation.This can be by adding triethyl orthoformate to realize when reaction finishes.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 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, tetrahydrofuran (THF), methyl tertiary butyl ether, propyl ether, butyl ether or Isosorbide-5-Nitrae-dioxane; Preferred toluene.Diluted acid is dilute hydrochloric acid, dilute sulphuric acid or dilute acetic acid, preferred dilute hydrochloric acid.Described potash catalyzer comprises a kind of in potassium hydroxide, salt of wormwood, potassium ethylate or silanol potassium, and its consumption is: the mass percent of potassium in siloxanes is 0.1% to 5%, preferred potassium hydroxide.
The hydrolyzate that is related 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 target product content in the hydrolyzate of hexamethyl cyclotrisiloxane and hexaetcycletrisiloxane.
In this technical scheme (2), described scission reaction temperature is 150 to 350 ℃, is preferably 200 to 300 ℃.
Relate in technical scheme (3) in patent of the present invention, catalyzer is lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide or Tetramethylammonium hydroxide, preferred Tetramethylammonium hydroxide; The preferred crown ether of promotor.
Relate in technical scheme (5) in patent of the present invention, reinforced filling comprises thermal silica, precipitated silica, titanium dioxide, aluminum oxide and carbon black etc., preferred thermal silica; Vulcanizing agent comprises the vulcanizing agents such as benzoyl peroxide, dicumyl peroxide, preferred benzoyl peroxide.
Achievement of the present invention can solve the waste disposal problem of being badly in need of solution in 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 silicon rubber etc., thus industry R ﹠ D Level and the technical strength of General Promotion China's silane coupling agent industry and even organosilicon industry.
Embodiment
Embodiment 1
The ratio of 7.2g magnesium powder, 32.8g n-propyl Trimethoxy silane, 3g chloropropane and 50mL tetrahydrofuran (THF) (needing through Non-aqueous processing) is joined each reactant in a reaction vessel, put into 0.025g iodine grain, heat this mixture to 74 ℃, produce liquid return.Produce a large amount of bubbles on liquid level, reaction is initiated.At this moment, slowly drip the 16.62g chloropropane that is dissolved in 50mL tetrahydrofuran (THF) (needing through Non-aqueous processing).Control Heating temperature, make system remain slight boiling condition, temperature floats on 76 ℃ of left and right.With gas-chromatography monitoring reaction thing remaining quantity, greater than 99% the time, reaction finishes (about four hours), stopped reaction, naturally cooling when the transformation efficiency of n-propyl Trimethoxy silane.
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.After being merged, filtrate revolves the steaming desolventizing.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 in embodiment 1 into the n-propyl triethoxyl silane, obtain the dipropyl diethoxy silane.
Embodiment 3
Change the magnesium powder in embodiment 1 into magnesium rod (need before use first to polish and use diluted acid immersion treatment, drying then feed intake), obtain dipropyl dimethoxy silane.
Embodiment 4
Change the magnesium powder in embodiment 1 into magnesium chips (needing before use first with feeding intake after diluted acid immersion treatment, drying), obtain dipropyl dimethoxy silane.
Embodiment 5
7.2g the ratio of magnesium powder, 37.0g n-propyl Trimethoxy silane, 6g chloropropane and 60mL tetrahydrofuran (THF) (needing through Non-aqueous processing) joins each reactant in a reaction vessel, after question response is initiated, slowly drip again the 14.64g chloropropane that is dissolved in 40mL tetrahydrofuran (THF) (needing through Non-aqueous processing), when other condition was constant, the productive rate of product dipropyl dimethoxy silane was 87%.
Embodiment 6
When changing the tetrahydrofuran (THF) in embodiment 5 the equal proportion mixed solution of tetrahydrofuran (THF) and toluene (both all need through Non-aqueous processing) 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 tetrahydrofuran (THF) (needing through Non-aqueous processing) is joined each reactant in a reaction vessel, put into 0.025g iodine grain, heat this mixture to 74 degree centigrade, produce liquid return.Produce a large amount of bubbles on liquid level, reaction is initiated.At this moment, slowly drip the 16.62g chloropropane that is dissolved in 50mL tetrahydrofuran (THF) (needing through Non-aqueous processing).Control Heating temperature, make system remain slight boiling condition, temperature floats on 76 degrees centigrade of left and right.After four hours, stopped reaction, naturally cooling.
After adding the 50mL phenyl ether, first steam low boiling point solvent by common distillation, then underpressure distillation can obtain the dipropyl dichlorosilane, and product yield is more than 50%.
Embodiment 8
Change 50mL phenyl ether in embodiment 7 into the 100g triethyl orthoformate chlorine silicon key is replaced to oxyethyl group, then after filtration, filtrate collection and steaming are desolventized.Vacuum fractionation can obtain the dipropyl diethoxy silane.Product is confirmed with infrared and nuclear-magnetism, 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 sodium carbonate.The oil reservoir that obtains is separated from water layer, and this organosilicon liquid substance includes dipropyl silica-based unit, the silica-based unit of dimethyl and trimethyl silicon based unit, can be used as lubricant and Heat Conduction fluid.
Embodiment 10
Change the dipropyl dichlorosilane in 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 obtain including simultaneously the organosilicon liquid of dipropyl silica-based unit, the silica-based unit of dimethyl and trimethyl silicon based unit.
Embodiment 11
In reaction vessel, add the hydrochloric acid of the 6mol/L of 200mL, slowly add while then stir the 40g dipropyl dimethoxy silane that is dissolved in 50mL toluene.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, can obtain six propyl group cyclotrisiloxane, purity is more than 99%.
Embodiment 12
Dipropyl siloxanes hydrolyzate in embodiment 11 is carried out 250 ℃ of pyrolysis and decompression separation low-boiling-point substance under potassium hydroxide exists, 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, can obtain six propyl group cyclotrisiloxane, purity is more than 99%.
Embodiment 13
With the hydrolyzate that fractionates out in embodiment 11 after six propyl group cyclotrisiloxane, under existing, potassium hydroxide carries out 250 ℃ of pyrolysis and decompression separation low-boiling-point substance, can obtain the dipropyl mixture of siloxanes.With this mixture fractionation, and carry out product with infrared, nuclear-magnetism and mass spectrum and confirm, 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 potassium hydroxide, can make poly-dipropyl siloxanes, claim again propyl group silicone oil.
Embodiment 15
Change the catalyzer in embodiment 14 into Tetramethylammonium hydroxide alkali glue, can make poly-dipropyl siloxanes.Catalyzer in product can be removed by intensification.
Embodiment 16
Six propyl group cyclotrisiloxane with 100 parts of (mass parts) purity more than 99%, 100 parts of octamethylcyclotetrasiloxanes and 1 part of hexamethyldisiloxane are carried out polyreaction under the catalysis of 1 part of potassium hydroxide, can obtain the multipolymer of the dimethyl siloxane dipropyl siloxanes of high molecular.Catalyzer in product can neutralize with silica-based phosphoric acid ester.
Embodiment 17
Change the catalyzer in embodiment 16 into Tetramethylammonium hydroxide alkali glue, also can make dimethyl siloxane dipropyl silicone copolymers.Catalyzer in product can be removed by intensification.
Embodiment 18
Six propyl group cyclotrisiloxane with 100 parts of (mass parts) purity more than 99%, 100 parts of octamethylcyclotetrasiloxanes, 10 parts of tetramethyl-tetrem alkenyl siloxane and 1 part of hexamethyldisiloxane are carried out polyreaction under the catalysis of 1 part of Tetramethylammonium hydroxide alkali glue, can obtain the dimethyl siloxane dipropyl silicone copolymers with vinyl of high molecular.Catalyzer in product can be removed by intensification.
Embodiment 19
With the white carbon black that adds equivalent in copolymer 1 00 part (mass parts) after catalyzer of removing in embodiment 18, carry out blend on mixing roll, then heated 30 minutes under 160 degrees centigrade, then add 3 parts of benzoyl peroxides, processed 20 minutes 180 degrees centigrade of lower pressurized, heated again, at last again 160 degrees centigrade of lower thermal treatments 1 hour.Can obtain the special silicon rubber of superior performance aspect high-low temperature resistant.
The unit of mass parts described in above-described embodiment is gram.
Claims (10)
1. a method of processing industrial waste n-propyl trifunctional base silane, be by grignard reaction, n-propyl trifunctional base silane to be treated as diη-propyl two functional group's silane and derivatives thereof, it is characterized in that, described treatment process is:
(1) by n-propyl trifunctional base silane: chloropropane: magnesium is that the molar ratio of 0.8～1:1:1～1.5 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 the mol ratio of described 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, then drip the remaining chloropropane by solvent cut, synthetic dipropyl two functional group's silane; After synthetic liquid is down to room temperature, carry out cancellation with quencher in ice-water bath, after isolating solid substance, obtain highly purified product dipropyl two functional group's silane by fractionation and rectifying;
Wherein: above-mentioned magnesium is magnesium powder, magnesium chips or magnesium rod; Above-mentioned ethers is ether, tetrahydrofuran (THF), methyl tertiary butyl ether, propyl ether, butyl ether or Isosorbide-5-Nitrae-dioxane; Above-mentioned hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene; The volume ratio that in solvent, ethers mixes with hydro carbons is 0.2～1:0～1; The mol ratio of the consumption of above-mentioned catalyzer 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) diη-propyl two functional group's silane are dissolved in inert solvent, then slowly join this mixed solution in dilute acid soln, the preparation hydrolyzate, after this hydrolyzate is used saturated sodium carbonate, saturated sodium-chloride and distilled water wash and drying successively, obtain highly purified six propyl group cyclotrisiloxane through vacuum fractionation, resistates after 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 described hydro carbons is hexane, hexanaphthene, heptane, benzene or toluene, and described ethers is ether, tetrahydrofuran (THF), methyl tertiary butyl ether, propyl ether, butyl ether or Isosorbide-5-Nitrae-dioxane; Above-mentioned diluted acid is dilute hydrochloric acid, dilute sulphuric acid or dilute acetic acid; Above-mentioned potash catalyzer is potassium 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 hexamethyldisiloxane under nitrogen protection, make poly-dipropyl siloxanes;
Or
(3) with six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane under the existence of catalyzer and promotor in 80 ℃～150 ℃ reactions, make dimethyl dipropyl copolymerization polysiloxane;
Wherein: described in step (3), catalyzer is lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide or Tetramethylammonium hydroxide, and the mass ratio of its consumption and six propyl group cyclotrisiloxane is 0.001～0.05:1; Described promotor is dimethyl sulfoxide (DMSO), DMF, hexamethylphosphoramide, tetrahydrofuran (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 described end-capping reagent hexamethyldisiloxane and six propyl group cyclotrisiloxane is 0.001～0.01:1; The mass ratio of described six propyl group cyclotrisiloxane and octamethylcyclotetrasiloxane is 0.05～100:1.
2. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described n-propyl trifunctional of step (1) base silane: chloropropane: the part by weight of magnesium is 0.9:1:1.2; The consumption of catalyzer and the mol ratio of magnesium are 0.01:1.
3. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: in the described solvent of step (1), ethers selects tetrahydrofuran (THF), and hydro carbons selects toluene, and the volume ratio that in solvent, ethers mixes with hydro carbons is 1:1.
4. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described quencher of step (1) selects methyl alcohol, and the mol ratio of its consumption and n-propyl trifunctional base silane is 3:1.
5. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described inert solvent of step (2) selects toluene; Described diluted acid selects dilute hydrochloric acid.
6. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described potash catalyzer of step (2) selects potassium hydroxide, and its consumption is: the mass percent of potassium in siloxanes is 0.1%.
7. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described cracking temperature of step (2) is 200～300 ℃.
8. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described catalyzer of step (3) selects Tetramethylammonium hydroxide.
9. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described promotor of step (3) is selected crown ether.
10. process according to claim 1 the method for industrial waste n-propyl trifunctional base silane, it is characterized in that: the described temperature of reaction of step (3) is 100 ℃～130 ℃.
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