CN104140532A - Solvent-free process method for continuously producing methyl hydrogen silicone oil - Google Patents

Abstract

The invention discloses a solvent-free process method for continuously producing methyl hydrogen silicone oil. The process method is a production method which uses an organosilicone monomer production by-products-methyldichlorosilane and chlorotrimethylsilane as raw materials and sequentially comprises the steps of hydrolysis, layering, washing extraction, telomerization and oiling so as to prepare methyl hydrogen silicone oil finished products. By means of the solvent-free process method, the defect that an existing traditional intermittent method enables the product efficiency to be low and the quality to be unstable during production and introduces an organic solvent in the traditional production and the like is changed, and the purposes of saving energy and reducing consumption can be achieved. The solvent-free process method has characteristics of environmental pollution reduction and the like, further has the advantages of reducing the production cost, shortening a production period, improving the product quality, increasing finished product yield, being high in industrial operation safety and the like and has good industrial operability.

Description

A kind of processing method of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid

Technical field

The present invention relates to the production technical field of Methyl Hydrogen Polysiloxane Fluid, specifically, is a kind of processing method of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid.

Background technology

Methyl Hydrogen Polysiloxane Fluid is one of extremely important product in silicone oil product, contains ripple group hydrogen alive in its siloxane main chain, and activity is higher, and can with various active radical reaction, its distinguishing feature is good water-proof effect.In actual use, Methyl Hydrogen Polysiloxane Fluid can crosslinked at low temperature film forming, and forms waterproof layer on the surface of material, as antifouling, grease proofing, the waterproof finishing agent of pottery; Can synthesize various modified silicon oils, silicon rubber important intermediate; Can be used as water-resisting agent and the softening agent of natural and synthetic fabrics, silk, leather; The waterproof softening agent of the waterproof of paper, release agent or glass fibre etc.; Certainly, increase day by day along with the demand of liquid silastic, Methyl Hydrogen Polysiloxane Fluid is owing to containing the more active Si-H key of some amount in molecule, easily there is crosslinking reaction, therefore, under the catalysis of Pt catalyst, also can be used as the linking agent of moulding liquid silastic and anti-yellowing dose of high-temperature mixing glue etc., purposes is very extensive.

The production technique of traditional Methyl Hydrogen Polysiloxane Fluid comprises: in reactor, add quantitative solvent and water, drip quantitative dimethyl dichlorosilane (DMCS) and trimethylchlorosilane monomer, after hydrolysis, separated oil reservoir washing three times, add the vitriol oil to telomerize, after reaction finishes, oil-reservoir water is washed till neutrality, desolventizing and low-boiling-point substance, decolorization filtering gets product.But, also there is following defect in the condition of production from present domestic Methyl Hydrogen Polysiloxane Fluid in the production process of Methyl Hydrogen Polysiloxane Fluid:

(1) what existing most production process adopted is all the production technique of " autoclave " rhythmic reaction formula, easily causes the problems such as products production efficiency is low;

(2) in hydrolysis reaction, adopt toluene, sherwood oil equal solvent as primary solvent, be hydrolyzed complete, separated oil reservoir washing three times, adds the vitriol oil to telomerize, after reaction finishes, oil-reservoir water is washed till neutrality, after desolventizing, low-boiling-point substance and decolorization filtering, get product, complex operation step, simultaneously, adopt toluene, sherwood oil etc. as solvent, in product, have unavoidably peculiar smell, also limited the purposes of product;

(3) in subsequent production process, general introducing basic solution enters in production system, and then cause the product produced on colourity, smell lower than quality products, limited the purposes to product, in this technique, the hydrogen in product runs off also very large simultaneously, product quality is very unstable, and the consumption of producing is much larger than external production level, this has just produced great limitation to productivity effect.

Existing situation is, the method of containing hydrogen silicone oil is produced in patent documentation CN102516545B(serialization, 2013.08.07), CN103554502A(no-solvent type containing hydrogen silicone oil and preparation method thereof, 2014.02.05), CN102030905B(prepares the method for the high containing hydrogen silicone oil of no-solvent type, 2012.10.31), CN102643428A(prepares the method for Methyl Hydrogen Polysiloxane Fluid, 2012.08.22), the production technique that high containing hydrogen silicone oil is produced in CN103788377A(serialization, 2014.05.14) on the basis of existing traditional technology, improve, first, from production process, improve, disclose a kind of compared with the higher continuous production method of traditional batch formula production technique efficiency, especially patent documentation CN102516545B and CN102030905B, the conversion unit that has also disclosed especially this serialization production dependence is reactor, simultaneously, in hydrolysis reaction, also avoided toluene, adding of the organic solvents such as sherwood oil, effectively raise the quality product of Methyl Hydrogen Polysiloxane Fluid, on this basis, patent documentation CN103788377A has proposed the production method that a kind of hydrogen content is the high containing hydrogen silicone oil of 1.56～1.60wt%, but from its preparation technology, has equally the defects such as product quality is unstable, productivity effect is low, therefore, the present invention arises at the historic moment.

Summary of the invention

The object of the present invention is to provide a kind of processing method of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid, this processing method is to take organosilane monomer to produce that by product---dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are raw material, successively through hydrolysis, layering, washing extraction, telomerize, after de-low step, make the production method of Methyl Hydrogen Polysiloxane Fluid finished product, this production method can realize continuous suitability for industrialized production, and each step all has the strict residence time to control, while having changed traditional batch method production in the past, product efficiency is low, the defects such as quality is unstable, simultaneously, also avoided the introducing of organic solvent in traditional mode of production, reached energy-saving and cost-reducing object, to reducing environmental pollution, improve product quality and broadened application field and all there is good promoter action.

The present invention is achieved through the following technical solutions: a kind of processing method of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid, this processing method is to take organosilane monomer to produce the preparation method that by product is produced Methyl Hydrogen Polysiloxane Fluid finished product as raw material, while having changed traditional batch method production in the past, product efficiency is low, the defects such as introducing of organic solvent in the unstable and traditional mode of production of quality, not only reach energy-saving and cost-reducing object, also reduced the pollution to environment, make the quality of product simultaneously, Application Areas improves greatly, in the present invention, described organosilane monomer is produced by product and is comprised dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane, in the present invention, the parameter index of described Methyl Hydrogen Polysiloxane Fluid finished product comprises:

Hydrogen content: 1.50～1.66%; Viscosity: 10～50(25 ℃, mm ²/ s);

Density: 0.950～1.015(25 ℃, g/cm ³); Fugitive constituent: < 3%(150 ℃, 3h);

Refractive index: 1.390～1.410(25 ℃); Acid number: 0.001～0.01(mgKOH/g).

Further, described processing method comprises the following steps:

(a) hydrolysis: by dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane by weight (10～60): 1 ratio is added to and in mixing kettle, is mixed and made into monomer mixture, by this monomer mixture, water, low-boiling-point substance is by weight 1:(1～5): the ratio of (0～0.5) continues to be added to the reaction in loop of being hydrolyzed in tubular reactor, obtain acidic hydrolysis material, temperature of reaction is 5～30 ℃, the mean residence time in controlled hydrolysis loop is 30～90min, be optimized for 30～60min, for guaranteeing the cleaning of product and high-quality, water is preferably deionized water as reaction solution,

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, obtain the thick silicone oil in upper strata and lower floor's hydrochloric acid, the acid content of described thick silicone oil is 1000～3000mg/L, and controlling the residence time of acidic hydrolysis material in quantizer is 40～90min;

(c) washing extraction: the thick silicone oil that step (b) is obtained is sent into extracting system, after washing extraction, layering, obtaining acid content is the silicone oil hydrolyzate of 150～500mg/L successively, the residence time is controlled at 50～100min;

(d) telomerize: the silicone oil hydrolyzate that step (c) is made send into dehydration tower dry after, the silicone oil that acquisition moisture content is 15～50mg/L, and send into and telomerizing of catalyzer adjust silicone oil molecular-weight average in device is housed to balance, the residence time is 30～120min.

(e) de-low: the silicone oil that above-mentioned steps (d) is obtained is sent in preheater and heated, temperature is heated to after 60～100 ℃, again silicone oil is sent in de-low device, under 120～180 ℃ of temperature, vacuum-60～-99.5Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, in actual production process, the Methyl Hydrogen Polysiloxane Fluid finished product making is sent into products pot conventionally after cooling, refills case and stores.

Described processing method also comprises: the silicone oil that step (d) is obtained carries out acid number balance adjustment, described acid number balance adjustment comprises that employing balance reagent carries out acid base equilibrium adjusting to the silicone oil telomerizing after balance, the adjustment time is 30～120min, after the pH value of silicone oil is adjusted to 6.8～7.2, send into again the operation of completing steps in preheater (e), from above-mentioned situation, the present invention has also increased this operation steps of acid number balance adjustment, that is: the silicone oil that step (d) obtains need be admitted in preheater and heat again after acid number balance adjustment, it is advantageous that: the stability that improves de-low rear Methyl Hydrogen Polysiloxane Fluid finished product, quality product and product hydrogen content etc., practical effect is good.

In the present invention, carry out the selecting first of balance reagent of acid-alkali accommodation and should consider weakly alkaline reagent, to avoid alkalescence to cause too by force the fracture of silicone oil Si-H key and produce, be cross-linked, for this reason, described balance reagent is that pH value is 7.5～8.5 weakly alkaline solution.

Preferably, described weakly alkaline solution is calcium carbonate soln or sodium hydrogen carbonate solution.

For better realizing hydrolysing step, in described tubular reactor, be loaded with concentration and be 10～30% hydrochloric acid soln, by weight, described monomer mixture and the ratio of hydrochloric acid soln are (1～5): 1, in actual production process, hydrochloric acid soln adds without continuing, conventionally before reaction occurs, splendid attire is in tubular reactor, after reaction raw materials to be added in advance, a certain proportion of hydrochloric acid soln is hydrolysis loop suitable sour environment is provided, thereby improves the reaction process in hydrolysis loop.

In the present invention, the general reaction in hydrolysis loop shows as strong exothermal reaction, for avoiding the decomposition of Si-H under excess Temperature and acidic conditions, in described step (a), temperature of reaction in hydrolysis loop is controlled by special-purpose water cooler by refrigeration system, optimize, temperature of reaction span of control is 5～25 ℃.

The present invention is reasonable in design, and in described step (b), the lower floor's hydrochloric acid obtaining after layering is admitted to that hydrochloric acid tank is standby or sell, and the concentration of described hydrochloric acid is 10～30%, and further, the concentration of hydrochloric acid is 12～30%.

Described extracting system is mainly comprised of extraction stirring tank, water-and-oil separator, and described step (c) comprising:

(c.1) choose inorganic salt solution or water as extraction liquid, the thick silicone oil that step (b) is obtained is sent in extraction stirring tank and is washed extraction, and washing temperature is 25～60 ℃, preferably 35～45 ℃, obtains oil-water mixture;

(c.2) oil-water mixture is sent into water-and-oil separator, remove after the moisture in oil-water mixture, the silicone oil hydrolyzate that acquisition acid content is 150～500mg/L.

In the present invention, extraction liquid can carry out the washing of rapid cleaning to acid residual in thick silicone oil, meanwhile, and in cleaning process, for avoiding Methyl Hydrogen Polysiloxane Fluid crosslinked rapidly under alkaline condition, inorganic salt solution of the present invention is neutrality or weakly alkaline inorganic salt solution.

In the present invention, the concentration of described inorganic salt solution is 5～20%, comprises a kind of in sodium chloride aqueous solution, calcium chloride or sodium bicarbonate aqueous solution.

For better realizing the separation of oil-water mixture, in the present invention, described water-and-oil separator comprises the second quantizer and the 3rd quantizer, in described step (c.2), oil-water mixture is admitted to successively the second quantizer and the 3rd quantizer carries out after oily water separation, obtains silicone oil hydrolyzate, and the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, as the extraction liquid use in step (c.1) or the solvent of extraction liquid, use, that is: water or inorganic salt solution.

The described process that telomerizes completes under the condition of continuity, and further, described step (d) comprising:

(d.1) silicone oil hydrolyzate step (c) being made is sent in dehydration tower, at the temperature of 25～50 ℃, blasts dry gas and takes away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 15～50mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 40～60 ℃, then sends into telomerize and in device, be adjusted to balance.

Use dry gas dewaters, " poisoning " that can avoid excessive water to cause catalyzer, and described dry gas is dry air or the drying nitrogen that provided by nitrogen system, preferably drying nitrogen.

Further, it is carclazyte or the diatomite of 5～20 mgKOH/g that described catalyzer is selected acidity value, and carclazyte or diatomite are slightly acidic, and the strong acidic condition that can avoid strongly acidic catalyst to form impacts Si-H stability.

To better implement the present invention, in described step (e), preheater and de-low device provide thermal source by heat-conducting oil system; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, standby or send in step (a) as process byproducts, as low-boiling-point substance batching, reclaims and uses.

Further, in described step (e), described de-low device adopts thin-film evaporator, and it is controlled parameter and comprises: 125～160 ℃ of vacuum pressure-90～-99.5Kpa, de-low temperatures.

The present invention compared with prior art, has the following advantages and beneficial effect:

(1) processing method the present invention relates to is to adopt the mixture of a certain proportion of dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane as raw material, react with deionized water, and successively through hydrolysis, oleic acid layering, washing extraction, profit layering, dehydration telomerizes, after de-low step, make the production process of Methyl Hydrogen Polysiloxane Fluid finished product, this technique has substituted tank reactor in the past from different being of traditional technology maximum with the hydrolysis loop of tubular reactor, realized continuous production, and each step all has the strict residence time to control, while having changed traditional batch method production in the past, product efficiency is low, the defects such as quality is unstable, realizing the industrial while of serialization, also have and reduce production costs, production yield is high, good product quality, the feature such as with short production cycle, comprehensive production cost is also reduced greatly.

(2) what the present invention adopted for the preparation of the raw materials for production of Methyl Hydrogen Polysiloxane Fluid is by product---dimethyl dichlorosilane (DMCS) and the trimethylchlorosilane during organosilane monomer is produced, in actual industrial production, using these raw materials for production as Methyl Hydrogen Polysiloxane Fluid, not only can reduce production costs, also make organosilicon industrial chain be continued development, process in time the by product in organosilane monomer production, when avoiding environmental pollution, also create good economic results in society, had promotional value.

(3) be further to improve the industrial production efficiency of this technique, the present invention also adds in tubular reactor certain density hydrochloric acid soln, in actual production process, hydrochloric acid soln adds without continuing, and before reaction occurs, splendid attire is in tubular reactor in advance conventionally, after reaction raw materials to be added, a certain proportion of hydrochloric acid soln is hydrolysis loop suitable sour environment is provided, thereby improves the reaction process in hydrolysis loop, with this, reaches the object that improves this technique industrial production efficiency.

(4) the present invention adopts tubular reactor as the reactor in hydrolysis loop, its advantage is that reaction time is shorter, guaranteed that the time that acidic hydrolysis thing stops in acid shortens greatly, reduced the thermal hydrolysis of Si-H under acidic conditions, productive rate and the quality of product have been guaranteed, greatly shortened the production cycle, simultaneously, also avoided the limitation of the batch production of still reaction, reach quantity-produced object, in actual use, for preventing the corrosion of hydrochloric acid to tubular reactor inwall, the common inwall of tubular reactor is coated with and is covered with preservative coat, the life cycle of raising equipment.

(5) the present invention is compared with traditional processing technology, increased this operation steps of acid number balance adjustment, this step is mainly to send in preheater and heat again after the silicone oil of step (d) acquisition is regulated to acid base equilibrium by balance reagent, can improve stability, quality product and the product hydrogen content etc. of de-low rear Methyl Hydrogen Polysiloxane Fluid finished product, and practical effect is good.

(6) the present invention has avoided the introducing of a large amount of organic solvents in traditional mode of production, adopt inorganic salt solution or water as the extraction liquid in extraction step, avoided being difficult in product the peculiar smell of elimination, improved the marketable value of Methyl Hydrogen Polysiloxane Fluid finished product, simultaneously, because washing extraction process adopts the mode of inorganic salt solution or water, carry out, therefore, also realized quick, the salubrious object being separated to product.

(7) the present invention has removed the introducing of the vitriol oil in traditional technology in telomerizing step, adopt efficient solid catalyst, as: slightly acidic carclazyte or diatomite, not only guaranteed efficiently to telomerize effect, more avoided the drawback of the vitriol oil to equipment deep-etching, effectively reduce the hydrogen of silicone oil product under strong acidic environment and run off, thereby guarantee the production of high-quality containing hydrogen silicone oil and the preservation period that has extended product.

(8) the present invention preparation and Methyl Hydrogen Polysiloxane Fluid final product quality good, because solid catalyst impurity used is few, acidity is less than the vitriol oil, therefore, side reaction is few, good product quality, and purity is high, hydrogen content is at least more than 1.5%, and certainly, this is also that traditional technology cannot meet.

(9) the present invention avoids using strong alkaline substance in whole production technique whole process, such as: balance reagent, catalyzer and inorganic salt solution etc., be weak base, slightly acidic or neutrality, its object is: avoid Methyl Hydrogen Polysiloxane Fluid under alkalescence (acidity) condition rapidly the hydrogen under crosslinked and acidic conditions run off, thereby guarantee the production of high-quality containing hydrogen silicone oil.

(10) the explained hereafter system design the present invention relates to is reasonable, adopt the Optimum Combination of Equipments such as mixing kettle, tubular reactor, dehydration tower to form, not only there is the features such as increasingly automated, serialization, energy-conserving and environment-protective, product quality be high-end, in actual process production process, also there is higher security, meet the standard that modernization industry is produced.

(11) the present invention can realize good environmental benefit, because (acid) water that the sour water producing in whole production technique is less, acidity is low, washing produces while extracting also can be recycled, without discharge, therefore, both saved a large amount of water resourcess, also administered contaminated wastewater, killed two birds with one stone, especially suitablely extensively promoted the use of.

(12) industrial production the present invention relates to has industrial operation easily, and in this explained hereafter, the catalyzer of use is solid, and silicone oil product is liquid, and both are easily separated, when being convenient to production operation, can also effectively reduce labour intensity.

(13) because the explained hereafter the present invention relates to is not introduced organic solvent and strong acid, highly basic, therefore, also reduced the investment of equipment and corrosion, be convenient to corrective maintenance and use, meanwhile, more guaranteed quality and the memory cycle of product, increased transportation radius.

Embodiment

Below goal of the invention of the present invention, technical scheme and beneficial effect are described in further detail.

Should be noted that, it is all exemplary below describing in detail, be intended for the requested to provide further explanation of the invention, except as otherwise noted, all technology used herein and scientific terminology have the identical meanings of conventionally understanding with general technical staff of the technical field of the invention.

The present invention relates to a kind of processing method of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid, the organosilane monomer of particularly take is produced the preparation method that by product is produced Methyl Hydrogen Polysiloxane Fluid finished product as raw material, this preparation method and existing patent documentation CN102516545B, CN103554502A, CN102030905B, CN102643428A, the difference of CN103788377A is, when this preparation method has not only changed traditional batch method production in the past, product efficiency is low, the defects such as introducing of organic solvent in the unstable and traditional mode of production of quality, can reach energy-saving and cost-reducing object, reduce the characteristics such as environmental pollution, also have and reduce production costs, shorten the production cycle, improve the quality of products, increase product yield, the many advantages such as industrial operation high safety, and there is good industrial operation.

Below further describing processing method involved in the present invention:

Selection from raw materials for production, the present invention be take organosilane monomer and is produced by product---and dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are raw materials for production, we know, dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are all the by products in direct synthesis methyl chlorosilane monomer process, in actual industrial production, using these raw materials for production as Methyl Hydrogen Polysiloxane Fluid, not only can reduce production costs, also make organosilicon industrial chain be continued development, process in time the by product in organosilane monomer production, when avoiding environmental pollution, also good economic results in society have been created, has promotional value.

Specifically being summarized as follows of this processing step:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent into after metering respectively and be mixed and made into monomer mixture in mixing kettle, in this monomer mixture, the weight ratio of dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane is (10～60): 1, at the production initial stage, in tubular reactor, conventionally can add that to have concentration be 10～30% hydrochloric acid soln, the weight ratio of monomer mixture and hydrochloric acid soln is (1～5): 1, tubular reactor inwall arranges impregnating material and makes, to prevent the corrosion of hydrochloric acid soln to tubular reactor inwall, the cycle of operation of raising equipment, during production, monomer mixture and water continue respectively to send into the be hydrolyzed reaction in loop of tubular reactor after metering, obtain acidic hydrolysis material, in actual mechanical process, whole reaction is in continuously feeding, under the state of continuous discharge, completes, hydrochloric acid soln adds without continuing, its effect is for hydrolysis loop provides suitable sour environment, thereby improves the reaction process in hydrolysis loop, reaches the object that improves this technique industrial production efficiency.In the present invention, the weight ratio of monomer mixture and water is 1:(1～5), for guaranteeing the cleaning of product and high-quality, the preferred deionized water of water; Along with reaction continue carry out, when (e) step takes off low to silicone oil and obtains after low molecule, this low molecule also can be used as low molecule silicone oil (low-boiling-point substance) and continues to add the reaction in loop of being hydrolyzed in tubular reactor, and with monomer mixture and water in the lump as the reaction raw materials in hydrolysis loop, the weight ratio of monomer mixture and low molecule silicone oil is 1:(0～0.5), when system does not generate the low minute period of the day from 11 p.m. to 1 a.m, the add-on of low molecule silicone oil is 0.In the reaction process in said hydrolyzed loop, should control as far as possible the minimum residence time of acidic hydrolysis thing in acid, to reduce its thermolysis of Si-H key under sour condition, therefore, the mean residence time of answering controlled hydrolysis loop is 30～90min, be optimized for 30～60min, temperature of reaction is 5～30 ℃.In the present invention, owing to being hydrolyzed the general reaction in loop, show as strong exothermal reaction, for avoiding the decomposition of Si-H key under excess Temperature and acidic conditions, the temperature of reaction in this hydrolysis loop is controlled by special-purpose water cooler by refrigeration system, optimize, temperature controlling range is 5～25 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid that the thick silicone oil that acquisition upper strata acid content is 1000～3000mg/L and lower floor's concentration are 10～30%, the emphasis of this step is also the decomposition that will reduce to greatest extent Si-H key, therefore, fast, the salubrious operation that is separated is that we are desirable, when actually operating, the residence time should be controlled at 40 ~ 90min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, extracting system is mainly formed, and is completed following steps successively by extraction stirring tank, water-and-oil separator:

(c.1) choosing concentration is that 5～20% inorganic salt solution or water are as extraction liquid, thick silicone oil is sent in extraction stirring tank and washed extraction, extraction liquid can carry out fast acid residual in thick silicone oil, clean washing, its washing temperature is 25～60 ℃, preferably 35～45 ℃, obtain oil-water mixture, in extracting and washing process, for avoiding Methyl Hydrogen Polysiloxane Fluid crosslinked rapidly under alkaline condition, in this process, inorganic salt solution should be selected neutrality or weakly alkaline inorganic salt solution, for example: sodium chloride aqueous solution, a kind of in calcium chloride water or sodium bicarbonate aqueous solution.

(c.2) oil-water mixture is sent into water-and-oil separator, water-and-oil separator comprises the second quantizer and the 3rd quantizer, this oil-water mixture is admitted to successively the second quantizer and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 150～500mg/L, the residence time is controlled at 50～100min, the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, as the extraction liquid in step (c.1), uses.

(d) telomerize: this step selects acid clay or diatomaceous earth as catalyzer, comprises the following steps:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 150～500mg/L is sent in dehydration tower, at the temperature of 25～50 ℃, blast dry gas and take away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 15～50mg/L, the drying nitrogen that dry gas can be selected dry air or be provided by nitrogen system, its object is: remove " poisoning " of excessive moisture to avoid excessive water to cause catalyzer, preferred, dry gas is preferably drying nitrogen.

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 40～60 ℃, and send into and telomerizing of catalyzer adjust silicone oil molecular-weight average in device is housed to balance, the residence time is 30～120min, preferred 60～120min, the preferred acidity value of catalyzer is 5 ~ 20(mgKOH/g) carclazyte or diatomite, carclazyte or diatomite are slightly acidic, can avoid the impact on Si-H key of strong acidic condition that strongly acidic catalyst forms, when reality is used, because catalyzer is solid, for existing catalyzer or other impurity to cause the pollution of finished product in the silicone oil after avoiding telomerizing, the present invention is also designed with filtration unit.

(e) de-low: the silicone oil that above-mentioned steps is obtained is sent in preheater and heated, temperature is heated to after 60～100 ℃, again silicone oil is sent in de-low device, under 120～180 ℃ of temperature, vacuum-60～-99.5Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, in actual production process, the Methyl Hydrogen Polysiloxane Fluid finished product making is sent into products pot conventionally after cooling, refills case and stores.In above-mentioned steps, preheater and de-low device provide thermal source by heat-conducting oil system; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, standby or send in step (a) as process byproducts, as reaction raw materials (low-boiling-point substance), uses.De-low device can adopt thin-film evaporator, and its Optimization about control parameter is selected further to comprise: 125～160 ℃ of vacuum pressure-90～-99.5Kpa, de-low temperatures.

From above-mentioned situation, in the hydrolysis loop the present invention relates to, parallel feeding is successional, and the ratio of mixture of dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane row are what can adjust according to the product quality specification demands in market, by different blending ratios, adjust, can obtain different hydrogen contents, different viscosity product silicone oil, therefore, in the present invention, the parameter index of Methyl Hydrogen Polysiloxane Fluid finished product comprises:

For obtaining high-quality Methyl Hydrogen Polysiloxane Fluid finished product, the processing method the present invention relates to also comprises: the silicone oil that step (d) is obtained carries out acid number balance adjustment, comprise and adopt balance reagent to carry out acid base equilibrium adjusting to telomerizing the silicone oil of balance, the adjustment time is 30～120min, after the pH value of silicone oil is adjusted to 6.8～7.2, then send into the operation of completing steps in preheater (e).It is advantageous that: improve stability, quality product and the product hydrogen content etc. of de-low rear Methyl Hydrogen Polysiloxane Fluid finished product, practical effect is good.Certainly, in this process, for avoiding alkalescence to cause too by force the fracture of silicone oil Si-H key and produce, be cross-linked, first balance reagent should consider to select weakly alkaline solution, that is: the weakly alkaline solution that flat pH value is 7.5～8.5, for example: calcium carbonate soln or sodium hydrogen carbonate solution.

After acid number balance adjustment, the hydrogen content of Methyl Hydrogen Polysiloxane Fluid finished product can further be optimized to 1.55～1.66%.

With several exemplary embodiments, enumerate explanation the specific embodiment of the present invention below, certainly, protection scope of the present invention is not limited to following examples.

Embodiment 1:

The present embodiment select weight ratio be the dimethyl dichlorosilane (DMCS) of 10:1 and tri-methyl-chlorosilane as raw material, initial reaction stage, adds in tubular reactor that to have concentration be 10% hydrochloric acid soln, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent in proportion and be mixed and made into monomer mixture in mixing kettle, again this monomer mixture, water are continued to be added to by weight the ratio of 1:1 the reaction in loop of being hydrolyzed in tubular reactor, and obtain acidic hydrolysis thing, wherein, the weight ratio of hydrochloric acid soln and monomer mixture is 1:1, along with reaction continue carry out, the weight ratio of the monomer mixture adding and low molecule silicone oil is 1:0.1, the mean residence time in controlled hydrolysis loop is 30min, and temperature of reaction is 5 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid that the thick silicone oil that acquisition upper strata acid content is 1000mg/L and lower floor's concentration are 10%, the residence time should be controlled at 40min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 5% sodium chloride aqueous solution as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 25 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 150mg/L, the residence time is controlled at 50min, the aqueous solution after the second quantizer and the 3rd quantizer layering divides the extraction liquid system that is all admitted to, and recycles.

(d) telomerize: this step select acidity value be the acidic white earth of 5mgKOH/g as catalyzer, step is as follows:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 150mg/L is sent in dehydration tower, at the temperature of 50 ℃, the drying nitrogen being provided is provided takes away the moisture in silicone oil hydrolyzate by nitrogen system, and obtain the silicone oil that moisture content is 15mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 40 ℃, sends into telomerizing in device of catalyzer is housed is adjusted to balance, and the residence time is 30min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance.

(e) de-low: the silicone oil that above-mentioned steps is obtained is sent in preheater and heated, temperature is heated to after 60 ℃, again silicone oil is sent in thin-film evaporator, under 120 ℃ of temperature, vacuum-99.5Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts is standby, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 1:

Table 1

Embodiment 2:

The present embodiment select weight ratio be the dimethyl dichlorosilane (DMCS) of 60:1 and tri-methyl-chlorosilane as raw material, initial reaction stage, adds in tubular reactor that to have concentration be 30% hydrochloric acid soln, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent in proportion and be mixed and made into monomer mixture in mixing kettle, again this monomer mixture, water are continued to be added to by weight the ratio of 1:5 the reaction in loop of being hydrolyzed in tubular reactor, and obtain acidic hydrolysis thing, wherein, the weight ratio of hydrochloric acid soln and monomer mixture is 1:5, along with reaction continue carry out, the weight ratio of the monomer mixture adding and low molecule silicone oil is 1:0.5, the mean residence time in controlled hydrolysis loop is 90min, and temperature of reaction is 30 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, acquisition upper strata acid content is that thick silicone oil and the lower floor's concentration of 3000 mg/L is the hydrochloric acid of 30 %, the residence time should be controlled at 90min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose water as extraction liquid, thick silicone oil is sent in extraction stirring tank and washed extraction, washing temperature is 60 ℃, obtains oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 500mg/L, the residence time is controlled at 100min, the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acidic white earth of 20mgKOH/g as catalyzer, step is as follows:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 500mg/L is sent in dehydration tower, at the temperature of 50 ℃, the drying nitrogen being provided is provided takes away the moisture in silicone oil hydrolyzate by nitrogen system, and obtain the silicone oil that moisture content is 50mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 60 ℃, sends into telomerizing in device of catalyzer is housed is adjusted to balance, and the residence time is 120min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance.

(e) de-low: the silicone oil that above-mentioned steps is obtained is sent in preheater and heated, temperature is heated to after 100 ℃, again silicone oil is sent in thin-film evaporator, under 180 ℃ of temperature, vacuum-60Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; The low molecule condensation after metering being removed by de-low device is reclaimed, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 2:

Table 2

Embodiment 3:

The present embodiment select weight ratio be the dimethyl dichlorosilane (DMCS) of 35:1 and tri-methyl-chlorosilane as raw material, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent in proportion and be mixed and made into monomer mixture in mixing kettle, again this monomer mixture, water are continued to be added to by weight the ratio of 1:3 the reaction in loop of being hydrolyzed in tubular reactor, and obtain acidic hydrolysis thing, along with reaction continue carry out, the weight ratio of the monomer mixture adding and low molecule silicone oil is 1:0.25, the mean residence time in controlled hydrolysis loop is 65min, and temperature of reaction is 17.5 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid that the thick silicone oil that acquisition upper strata acid content is 1500mg/L and lower floor's concentration are 20%, the residence time should be controlled at 65min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 12.5% calcium chloride water as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 37.5 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 325mg/L, the residence time is controlled at 75min, and the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acidic white earth of 12.5mgKOH/g as catalyzer, step is as follows:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 325mg/L is sent in dehydration tower, at the temperature of 50 ℃, the drying nitrogen being provided by nitrogen system is provided and takes away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 32.5mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 50 ℃, sends into telomerizing in device of catalyzer is housed is adjusted to balance, and the residence time is 75min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance.

(e) de-low: the silicone oil that above-mentioned steps is obtained is sent in preheater and heated, temperature is heated to after 80 ℃, again silicone oil is sent in thin-film evaporator, under 150 ℃ of temperature, vacuum-80Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 3:

Table 3

Embodiment 4:

The present embodiment select weight ratio be the dimethyl dichlorosilane (DMCS) of 35:1 and tri-methyl-chlorosilane as raw material, initial reaction stage, adds in tubular reactor that to have concentration be 20% hydrochloric acid soln, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent in proportion and be mixed and made into monomer mixture in mixing kettle, again this monomer mixture, water are continued to be added to by weight the ratio of 1:2.5 the reaction in loop of being hydrolyzed in tubular reactor, and obtain acidic hydrolysis thing, wherein, the weight ratio of hydrochloric acid soln and monomer mixture is 1:3.5, along with reaction continue carry out, the weight ratio of the monomer mixture adding and low molecule silicone oil is 1:0.15, the mean residence time in controlled hydrolysis loop is 60min, and temperature of reaction is 12.5 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid that the thick silicone oil that acquisition upper strata acid content is 1200mg/L and lower floor's concentration are 21%, the residence time should be controlled at 80min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 15% sodium chloride aqueous solution as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 38.5 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 230mg/L, the residence time is controlled at 70min, and the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acidic white earth of 12mgKOH/g as catalyzer, step is as follows:

(d.1) acid content above-mentioned steps being obtained is that the silicone oil hydrolyzate of 230 mg/L is sent in dehydration tower, at the temperature of 50 ℃, the drying nitrogen being provided by nitrogen system is provided and takes away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 20mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 50 ℃, sends into telomerizing in device of catalyzer is housed is adjusted to balance, and the residence time is 60min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance;

(e) de-low: the calcium carbonate soln that employing pH value is 7.8, as balance reagent, carries out acid base equilibrium adjusting to the silicone oil after filtering, and the adjustment time is 75min, after the pH value of silicone oil is adjusted to 6.8, then sends in preheater; Use preheater to heat silicone oil, temperature is heated to after 80 ℃, again silicone oil is sent in thin-film evaporator, under 147.5 ℃ of temperature, vacuum-95Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 4:

Table 4

Embodiment 5:

The present embodiment select weight ratio be the dimethyl dichlorosilane (DMCS) of 30:1 and tri-methyl-chlorosilane as raw material, initial reaction stage, adds in tubular reactor that to have concentration be 20% hydrochloric acid soln, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent in proportion and be mixed and made into monomer mixture in mixing kettle, again this monomer mixture, water are continued to be added to by weight the ratio of 1:2 the reaction in loop of being hydrolyzed in tubular reactor, and obtain acidic hydrolysis thing, wherein, the weight ratio of hydrochloric acid soln and monomer mixture is 1:2.5, along with reaction continue carry out, the weight ratio of the monomer mixture adding and low molecule silicone oil is 1:0.1, the mean residence time in controlled hydrolysis loop is 45min, and temperature of reaction is 25 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid that the thick silicone oil that acquisition upper strata acid content is 1200mg/L and lower floor's concentration are 20%, the residence time should be controlled at 50min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 15% sodium bicarbonate aqueous solution as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 35 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 210mg/L, the residence time is controlled at 50min, and the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acidic white earth of 15mgKOH/g as catalyzer, step is as follows:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 210mg/L is sent in dehydration tower, at the temperature of 50 ℃, the drying nitrogen being provided is provided takes away the moisture in silicone oil hydrolyzate by nitrogen system, and obtain the silicone oil that moisture content is 20mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 40 ℃, sends into telomerizing in device of catalyzer is housed is adjusted to balance, and the residence time is 90min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance.

(e) de-low: the calcium carbonate soln that employing pH value is 7.5 is as balance reagent, silicone oil after filtering is carried out to acid base equilibrium adjusting, the adjustment time is 40min, after the pH value of silicone oil is adjusted to 7.0, sending into preheater heats again, temperature is heated to after 60 ℃, again silicone oil is sent in thin-film evaporator, under 135 ℃ of temperature, vacuum-95Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 5:

Table 5

Embodiment 6:

The present embodiment select weight ratio be the dimethyl dichlorosilane (DMCS) of 60:1 and tri-methyl-chlorosilane as raw material, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent in proportion and be mixed and made into monomer mixture in mixing kettle, again this monomer mixture, water are continued to be added to by weight the ratio of 1:5 the reaction in loop of being hydrolyzed in tubular reactor, and obtain acidic hydrolysis thing, along with reaction continue carry out, the low molecule silicone oil adding and the weight ratio of monomer mixture are 1:0.5, the mean residence time in controlled hydrolysis loop is 90min, and temperature of reaction is 15 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid that the thick silicone oil that acquisition upper strata acid content is 2500mg/L and lower floor's concentration are 15%, the residence time should be controlled at 120min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 20% calcium chloride water as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 55 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate that acquisition acid content is 280mg/L, the residence time is controlled at 90min, and the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: it is 18mgKOH/g that this step is selected acidity value) acidic white earth as catalyzer, step is as follows:

(d.1) acid content above-mentioned steps being obtained is that the silicone oil hydrolyzate of 280 mg/L is sent in dehydration tower, at the temperature of 90 ℃, the drying nitrogen being provided by nitrogen system is provided and takes away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 20mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 60 ℃, sends into telomerizing in device of catalyzer is housed is adjusted to balance, and the residence time is 110min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance.

(e) de-low: the calcium carbonate soln that employing pH value is 8.5 is as balance reagent, silicone oil after filtering is carried out to acid base equilibrium adjusting, the adjustment time is 120min, after the pH value of silicone oil is adjusted to 7.2, sending into preheater heats again, temperature is heated to after 100 ℃, again silicone oil is sent in thin-film evaporator, under 160 ℃ of temperature, vacuum-90Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 6:

Table 6

Embodiment 7:

The present embodiment selects 3800kg dimethyl dichlorosilane (DMCS) and 125kg tri-methyl-chlorosilane as raw material, and it is 15m that dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are stored in respectively capacity ³hydrogeneous single storage tank and capacity be 5m ³in front three single storage tank, initial reaction stage, adds in tubular reactor that to have concentration be 20% hydrochloric acid soln, and concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent into and are mixed and made into monomer mixture in mixing kettle by above-mentioned metering, again this monomer mixture, water are continued to be added to by the metering of 300kg/h and 700kg/h the reaction in loop of being hydrolyzed in tubular reactor, and obtain approximately 1150 kg acidic hydrolysis things, wherein, the add-on of hydrochloric acid soln is 150kg, along with reaction continue carry out, the low molecule silicone oil adding for 15kg/h, the mean residence time in controlled hydrolysis loop is 50min, and temperature of reaction is 10 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid 980kg that the thick silicone oil 170kg that acquisition upper strata acid content is 1250mg/L and lower floor's concentration are 23%, the residence time should be controlled at 100min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose water as extraction liquid, thick silicone oil is sent in extraction stirring tank and washed extraction, washing temperature is 45 ℃, obtains oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate 170kg that acquisition acid content is 200mg/L, the residence time is controlled at 75min, the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acidic white earth of 13mgKOH/g as catalyzer, step is as follows:

(d.1) acid content above-mentioned steps being obtained is that the silicone oil hydrolyzate of 200 mg/L is sent in dehydration tower, at the temperature of 35 ℃, blasts dry air and takes away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 25mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 45 ℃, send into and telomerizing of catalyzer is housed in device, is adjusted to balance, the residence time is 50min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance, obtains the silicone oil of 170kg.

(e) de-low: the calcium carbonate soln that employing pH value is 8.0 is as balance reagent, silicone oil after filtering is carried out to acid base equilibrium adjusting, the adjustment time is 60min, after the pH value of silicone oil is adjusted to 7.0, sending into preheater heats again, temperature is heated to after 70 ℃, again silicone oil is sent in thin-film evaporator, under 145 ℃ of temperature, vacuum-95Kpa, silicone oil is taken off to reduction process, the Methyl Hydrogen Polysiloxane Fluid finished product of de-low rear acquisition 165kg, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 7:

Table 7

Embodiment 8:

The present embodiment selects 3800kg dimethyl dichlorosilane (DMCS) and 150kg tri-methyl-chlorosilane as raw material, it is in 5m3 front three single storage tank that dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are stored in respectively hydrogeneous single storage tank and the capacity that capacity is 15m3, initial reaction stage, in tubular reactor, add that to have concentration be 15% hydrochloric acid soln, concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent into and are mixed and made into monomer mixture in mixing kettle by above-mentioned metering, again this monomer mixture, deionized water are continued to be added to by the metering of 300kg/h and 600kg/h the reaction in loop of being hydrolyzed in tubular reactor, and obtain 1050 kg acidic hydrolysis things, wherein, the add-on of hydrochloric acid soln is 150kg, along with reaction continue carry out, the amount of the low molecule silicone oil adding is 10kg/h, the mean residence time in controlled hydrolysis loop is 80min, and temperature of reaction is 20 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid 875kg that the thick silicone oil 175kg that acquisition upper strata acid content is 1200mg/L and lower floor's concentration are 20%, the residence time should be controlled at 60min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 10% sodium chloride aqueous solution as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 40 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate 175kg that acquisition acid content is 230mg/L, the residence time is controlled at 50min, the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acid diatomite of 16mgKOH/g as catalyzer, step is as follows:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 230mg/L is sent in dehydration tower, at the temperature of 40 ℃, the drying nitrogen being provided is provided takes away the moisture in silicone oil hydrolyzate by nitrogen system, and obtain the silicone oil that moisture content is 20mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 55 ℃, send into and telomerizing of catalyzer is housed in device, is adjusted to balance, the residence time is 100min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance, obtains the silicone oil of 175 kg.

(e) de-low: the calcium carbonate soln that employing pH value is 8.5 is as balance reagent, silicone oil after filtering is carried out to acid base equilibrium adjusting, the adjustment time is 110min, after the pH value of silicone oil is adjusted to 7.1, sending into preheater heats again, temperature is heated to after 90 ℃, again silicone oil is sent in thin-film evaporator, under 155 ℃ of temperature, vacuum-96Kpa, silicone oil is taken off to reduction process, the Methyl Hydrogen Polysiloxane Fluid finished product of de-low rear acquisition 168kg, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, and as process byproducts, sends in step (a), as low molecule silicone oil, uses.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 8:

Table 8

Embodiment 9:

The present embodiment selects 3800kg dimethyl dichlorosilane (DMCS) and 200kg tri-methyl-chlorosilane as raw material, and it is 15m that dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are stored in respectively capacity ³hydrogeneous single storage tank and capacity be 5m ³in front three single storage tank, initial reaction stage, adds in tubular reactor that to have concentration be 20% hydrochloric acid soln, and concrete steps are as follows:

(a) hydrolysis: dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane are sent into and are mixed and made into monomer mixture in mixing kettle by above-mentioned metering, again this monomer mixture, water are continued to be added to by the metering of 300kg/h and 900kg/h the reaction in loop of being hydrolyzed in tubular reactor, and obtain 1350kg acidic hydrolysis thing, wherein, the add-on of hydrochloric acid soln is 150kg, the mean residence time in controlled hydrolysis loop is 65min, and temperature of reaction is 15 ℃.

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, the hydrochloric acid 1183kg that the thick silicone oil 167kg that acquisition upper strata acid content is 2100mg/L and lower floor's concentration are 15%, the residence time should be controlled at 70min, and it is standby or sell that the lower floor's hydrochloric acid obtaining after layering is admitted to hydrochloric acid tank.

(c) washing extraction: the thick silicone oil obtaining through first layer device is sent into extracting system, and completes following steps successively:

(c.1) choose concentration be 15% calcium chloride water as extraction liquid, thick silicone oil is sent in extraction stirring tank and wash extraction, washing temperature is 25 ℃, acquisition oil-water mixture;

(c.2) oil-water mixture is sent into the second quantizer successively and the 3rd quantizer carries out after oily water separation, the silicone oil hydrolyzate 167kg that acquisition acid content is 200mg/L, the residence time is controlled at 60min, the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, recycle.

(d) telomerize: this step select acidity value be the acidic white earth of 15mgKOH/g as catalyzer, step is as follows:

(d.1) the silicone oil hydrolyzate that acid content above-mentioned steps being obtained is 200mg/L is sent in dehydration tower, at the temperature of 50 ℃, the drying nitrogen being provided is provided takes away the moisture in silicone oil hydrolyzate by nitrogen system, and obtain the silicone oil that moisture content is 20mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 50 ℃, send into and telomerizing of catalyzer is housed in device, is adjusted to balance, the residence time is 90min, sends into filtration unit again and remove by filter impurity after silicone oil is adjusted balance, obtains the silicone oil of 167kg.

(e) de-low: the calcium carbonate soln that employing pH value is 8.2 is as balance reagent, silicone oil after filtering is carried out to acid base equilibrium adjusting, the adjustment time is 75min, after the pH value of silicone oil is adjusted to 7, sending into preheater heats again, temperature is heated to after 80 ℃, again silicone oil is sent in thin-film evaporator, under 125 ℃ of temperature, vacuum-95.5Kpa, silicone oil is taken off to reduction process, the Methyl Hydrogen Polysiloxane Fluid finished product of de-low rear acquisition 158kg, this Methyl Hydrogen Polysiloxane Fluid finished product is water white solvent-free product, after cooling, send into products pot, refill case and store; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, standby as process byproducts.

The Methyl Hydrogen Polysiloxane Fluid finished product that aforesaid operations step is obtained carries out the test of parameter index, obtains data as shown in table 9:

Table 9

The parameter index of the Methyl Hydrogen Polysiloxane Fluid finished product that above-described embodiment 1～9 is obtained is added up, as shown in table 10:

Table 10

By the mean value of the Methyl Hydrogen Polysiloxane Fluid finished product parameter index of above-mentioned table 1 gained and patent documentation CN102516545B(documents 1), CN103554502A(documents 2), CN102030905B(documents 3), CN102643428A(documents 4), CN103788377A(documents 5) average index of containing hydrogen silicone oil finished product of gained compares, as shown in table 11:

Table 11

The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction, and any simple modification, equivalent variations that every foundation technical spirit of the present invention is done above embodiment, within all falling into protection scope of the present invention.

Claims (17)

1. the processing method of a solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid, it is characterized in that: this processing method is to take organosilane monomer to produce the preparation method that by product is produced Methyl Hydrogen Polysiloxane Fluid finished product as raw material, described organosilane monomer is produced by product and is comprised dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane, and the parameter index of described Methyl Hydrogen Polysiloxane Fluid finished product comprises:

Hydrogen content: 1.50～1.66%; Viscosity: 10～50(25 ℃, mm ²/ s);

Density: 0.950～1.015(25 ℃, g/cm ³); Fugitive constituent: < 3%(150 ℃, 3h);

Refractive index: 1.390～1.410(25 ℃); Acid number: 0.001～0.01(mgKOH/g).

2. the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid according to claim 1, is characterized in that: described processing method comprises the following steps:

(a) hydrolysis: by dimethyl dichlorosilane (DMCS) and tri-methyl-chlorosilane by weight (10～60): 1 ratio is added to and in mixing kettle, is mixed and made into monomer mixture, by this monomer mixture, water, low-boiling-point substance by weight 1:(1～5): the ratio of (0～0.5) continues to be added to the reaction in loop of being hydrolyzed in tubular reactor, obtain acidic hydrolysis material, temperature of reaction is 5～30 ℃, and the mean residence time in controlled hydrolysis loop is 30～90min;

(b) layering: hydrolysis loop acidic hydrolysis material is out sent into first layer device and carry out layering, obtain the thick silicone oil in upper strata and lower floor's hydrochloric acid, the acid content of described thick silicone oil is 1000～3000mg/L, and controlling the residence time of acidic hydrolysis material in quantizer is 40～90min;

(c) washing extraction: the thick silicone oil that step (b) is obtained is sent into extracting system, after washing extraction, layering, obtaining acid content is the silicone oil hydrolyzate of 150～500mg/L successively, the residence time is controlled at 50～100min;

(d) telomerize: the silicone oil hydrolyzate that step (c) is made send into dehydration tower dry after, the silicone oil that acquisition moisture content is 15～50mg/L, and send into and telomerizing of catalyzer adjust silicone oil molecular-weight average in device is housed to balance, the residence time is 30～120min;

(e) de-low: the silicone oil that above-mentioned steps (d) is obtained is sent in preheater and heated, temperature is heated to after 60～100 ℃, again silicone oil is sent in de-low device, under 120～180 ℃ of temperature, vacuum-60～-99.5Kpa, silicone oil is taken off to reduction process, de-low rear acquisition Methyl Hydrogen Polysiloxane Fluid finished product.

3. the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid according to claim 2, it is characterized in that: described processing method also comprises: the silicone oil that step (d) is obtained carries out acid number balance adjustment, described acid number balance adjustment comprises that employing balance reagent carries out acid base equilibrium adjusting to the silicone oil telomerizing after balance, the adjustment time is 30～120min, after the pH value of silicone oil is adjusted to 6.8～7.2, then send into the operation of completing steps in preheater (e).

4. the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid according to claim 3, is characterized in that: described balance reagent is that pH value is 7.5～8.5 weakly alkaline reagent.

5. the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid according to claim 4, is characterized in that: described weakly alkaline solution is calcium carbonate soln or sodium hydrogen carbonate solution.

6. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: in described tubular reactor, be loaded with concentration and be 10～30% hydrochloric acid soln, by weight, the ratio of described monomer mixture and hydrochloric acid soln is (1～5): 1.

7. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: in described step (a), temperature of reaction in hydrolysis loop is controlled by water cooler, and temperature of reaction span of control is 5～25 ℃.

8. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: in described step (b), the lower floor's hydrochloric acid obtaining after layering is admitted in hydrochloric acid tank standby, and the concentration of described hydrochloric acid is 10～30%.

9. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: described extracting system is mainly comprised of extraction stirring tank, water-and-oil separator, and described step (c) comprising:

(c.1) choose inorganic salt solution or water as extraction liquid, the thick silicone oil that step (b) is obtained is sent in extraction stirring tank and is washed extraction, and washing temperature is 25～60 ℃, obtains oil-water mixture;

(c.2) oil-water mixture is sent into water-and-oil separator, remove after the moisture in oil-water mixture, the silicone oil hydrolyzate that acquisition acid content is 150～500mg/L.

10. the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid according to claim 9, is characterized in that: described inorganic salt solution is neutrality or weakly alkaline inorganic salt solution.

The processing method of 11. a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluids according to claim 9, it is characterized in that: the concentration of described inorganic salt solution is 5～20%, comprise a kind of in sodium chloride aqueous solution, calcium chloride water or sodium bicarbonate aqueous solution.

The processing method of 12. a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluids according to claim 9, it is characterized in that: described water-and-oil separator comprises the second quantizer and the 3rd quantizer, in described step (c.2), oil-water mixture is admitted to successively the second quantizer and the 3rd quantizer carries out after oily water separation, obtain silicone oil hydrolyzate, the moisture that the second quantizer and the 3rd quantizer are separated out is all admitted to extraction liquid system, as the extraction liquid use in step (c.1) or the solvent of extraction liquid, uses.

13. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: described step (d) comprising:

(d.1) silicone oil hydrolyzate step (c) being made is sent in dehydration tower, at the temperature of 25～50 ℃, blasts dry gas and takes away the moisture in silicone oil hydrolyzate, and obtain the silicone oil that moisture content is 15～50mg/L;

(d.2) silicone oil above-mentioned steps being obtained is sent into interchanger and is heated to after 40～60 ℃, then sends into telomerize and in device, be adjusted to balance.

The processing method of 14. a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluids according to claim 13, is characterized in that: described dry gas is dry air or the drying nitrogen that provided by nitrogen system.

The processing method of 15. a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluids according to claim 13, is characterized in that: it is carclazyte or the diatomite of 5～20 mgKOH/g that described catalyzer is selected acidity value.

16. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: in described step (e), preheater and de-low device provide thermal source by heat-conducting oil system; The tail gas that silicone oil produces in preheater heating, the de-low step of de-low device is admitted in tail gas purification tower to be processed; Silicone oil reclaims by taking off the low molecule condensation after metering that low device removes, standby or send in step (a) as process byproducts, as low-boiling-point substance batching, reclaims and uses.

17. according to the processing method of a kind of solvent-free continuous production Methyl Hydrogen Polysiloxane Fluid described in claim 2 or 3 any one, it is characterized in that: in described step (e), described de-low device adopts thin-film evaporator, and it is controlled parameter and comprises: 125～160 ℃ of vacuum pressure-90～-99.5Kpa, de-low temperatures.