CN102079755A - Preparation method of methyl tin heat stabilizer - Google Patents
Preparation method of methyl tin heat stabilizer Download PDFInfo
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- CN102079755A CN102079755A CN201010563560XA CN201010563560A CN102079755A CN 102079755 A CN102079755 A CN 102079755A CN 201010563560X A CN201010563560X A CN 201010563560XA CN 201010563560 A CN201010563560 A CN 201010563560A CN 102079755 A CN102079755 A CN 102079755A
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Abstract
The invention belongs to the technical field of organic chemistry and relates to a preparation method of a methyl tin heat stabilizer. The method comprises the following two steps: a) preparation of a methyl tin chloride intermediate: using tin, chloromethane and stannic chloride to perform alkane halogenation reaction so as to obtain the methyl tin chloride intermediate, and adding water for absorption so as to obtain a methyl tin chloride aqueous solution; and b) esterification-condensation reaction: adding MEO, sodium sulfide and ammonia water in the aqueous solution of methyl tin chloride to perform esterification-condensation reaction, and dewatering after fully reacting to obtain a methyl tin heat stabilizer product. The whole process of the preparation method is easy to control, and the cost is low; the methyl tin heat stabilizer product obtained by the method provided by the invention has an excellent heat stabilizing effect and can completely displace lead salt and cadmium heat stabilizers; and the product has the advantages of linear dosage control performance, low dosage and obviously lowered formula cost, and can be widely used in the manufacturing and processing fields of the PVC (polyvinyl chloride) plastic products.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to a kind of preparation method of methyl tin heat stabilizer.
Background technology
The methyl tin heat stabilizer is the good merchantable brand in the plastics thermo-stabilizer, is used widely in processing in calendering, blowing, extrusion molding, the injection moulding of polyvinyl chloride (PVC).Compare with thermo-stabilizers such as plumbous, cadmium salt class and stearates, it has fabulous thermostability, the remarkable transparency, good consistency, nontoxic, advantages such as consumption is few, flowability and good weatherability.This product also is widely used in plastic door-window, water supply pipeline, the finishing material; And, be used for the PVC goods of food and medicine packing through Bundesgesundheitsamt (BGA) and U.S. food Surveillance Authority (FDA) approval.Application number provides a kind of PVC preparation method with thermo-stabilizer methyl tin isooctyl mercaptoacetate base tin for 200410060772.0 Chinese patent application, the product that this method obtains is widely used in fields such as the calendering, pellet of PVC goods processing, but because of methyl tin isooctyl mercaptoacetate base tin valuable product, cause production cost higher, should not be as in the actual processing of PVC building materials, section bar and tubing.At present, the manufacturing enterprise of hard PVC goods such as domestic PVC section bar, tubing generally uses the lead salts product to add as thermo-stabilizer.And the product of examples of such additives processing exists more serious heavy metal pollution problem such as to separate out in daily use, so can not be used for being added on the process for processing of upper hose and daily plastic product.
Summary of the invention
The heavy metal that the present invention is directed to existing hard PVC technical products is separated out, the technological deficiency of production cost height, dosage broad aspect provides a kind of preparation method of methyl tin heat stabilizer, the methyl tin heat stabilizer that this method makes is a kind of thermo-stabilizer of efficient, nontoxic, environment-friendly type, not leaded harmful heavy metal, the better heat stability of waiting.
Above-mentioned technical problem of the present invention is implemented by the following technical programs:
A kind of preparation method of methyl tin heat stabilizer, this method comprise following two-step reaction: a,
The preparation of methyl tin chloride intermediate:Obtain the methyl tin chloride intermediate by metallic tin, methyl chloride and tin tetrachloride through the alkane halogenating reaction, add and obtain the methyl tin chloride aqueous solution after water absorbs; B,
The esterification condensation reaction:Add MEO, sodium sulphite and ammoniacal liquor and carry out the esterification condensation reaction in the described methyl tin chloride aqueous solution, fully the dehydration of reaction back obtains methyl tin heat stabilizer product.Methyl tin heat stabilizer of the present invention, chemistry is by name: the two methyl tin of the two sulfurations of the contrary basic alcohol ester of sulfuration, the products molecule structural formula is: (CH3) xSn (SCH2COOC8H17) y, little have a peculiar smell, faint yellow transparent oily liquid is mainly used in the machine-shaping of the complicated expressing techniques of hard PVC goods high speed such as industrial plastic.Methyl tin heat stabilizer of the present invention is by formulation methyl tin chloride mixed aqueous solution (abbreviation intermediate), after by a certain percentage methyl tin chloride mixed aqueous solution and MEO, Na2S, ammoniacal liquor are carried out the esterification condensation reaction, after reaction finishes work in-process layering dehydration is the contrary based tin heat stabilizer of finished product.
At home, national seven ministries and commissions have put into effect on February 28th, 2006 " electronics and IT products pollution control management way " for the WEEE and the ROHS instruction of reply European Union, and heavy metal products such as lead, cadmium have been made related setting.Spelling out nationwide use PVC-U water-supply pipe in the nation-building portion bulletins in 2004 must be non-lead salts thermo-stabilizer.The GB/T10002.1 new standard that on August 1st, 2006 came into effect indicates drinking water using pvc pipe material and is necessary for non-lead salts thermo-stabilizer.The not leaded harmful heavy metal that waits of methyl tin heat stabilizer of the present invention, the PVC goods that are processed into this stablizer in use also heavy metal free separate out phenomenon.Product trimethylammonium content is controlled at below 0.1%, by U.S. NSF and the authentication of PPI hygienic standard, meets the hygienic requirements of national upper hose product.The thermostable effect excellence of this methyl tin heat stabilizer product, can substitute lead salt, cadmium type thermal stabilizing agent fully, and have straight line and add consumption control usefulness, addition is little on year-on-year basis, obviously reduce formulation cost, can in PVC plastics process for processing field, be used widely.
As preferably, alkane halogenating reaction process is as follows among the described step a
:The reacting by heating still makes still temperature rise to 120～130 ℃, open vacuum system, make the still internal pressure reduce to-0.01 to-0.05MPa, after in reactor, dropping into metallic tin, tetramethyl ammonium chloride, feed methyl chloride, the control reacting kettle inner pressure stirs after being warming up to 180～190 ℃ then in the 0.3-0.5MPa scope, and the control stirring velocity is at 100-125rpm.The still internal pressure descends and represents the reaction beginning, after stop the heating, progressively add tin tetrachloride and methyl chloride, the speed and the add-on that add methyl chloride are standard with still internal pressure data presentation, and the still internal pressure is controlled at 1.1-1.5Mpa to sufficient reacting in the entire reaction course.
As preferably, add methyl chloride and tin tetrachloride by a small amount of mode repeatedly in the described reaction process.
As preferably, described step a also comprises following process: the still kettle temperature is preheated to 120 ℃, the material that reaction is good is depressed into still kettle from reactor, stir, keep vacuum tightness in the reaction system at-0.08-0.1Mpa, the distillation that heats up, control still temperature is at 120-180 ℃ in the still-process, water absorbs cut, obtains the methyl tin chloride aqueous solution.
As preferably, described alkane halogenating reaction adopts tetramethyl ammonium chloride as catalyzer.Further preferably, described catalyst consumption is 2～5% of a tin weight.Suitably the catalyzer of consumption adds the process that can effectively improve the alkane halogenating reaction, generates high boiling SnCL2 but tetramethyl ammonium chloride also can carry out the part association reaction with tin, and this thing can not utilize.So excessive use catalyzer also can cause the loss of tin.Catalyzer also can use alkyl dimethyl ammonium chloride, trimethyl ammonium chloride.
As preferably, described step b is specific as follows
:MEO is put into esterifying kettle, the still temperature that makes esterifying kettle is after 15～20 ℃ of scopes, ammoniacal liquor, methyl tin chloride intermediate, sodium sulphite are added dropwise in the esterifying kettle simultaneously, stir, the control agitator shaft speed is at 65～75rpm, keep about 50～60 ℃ of still temperature during esterification, the pH value is controlled between 5～8, and fully after the reaction, standing demix is more than 2 hours, take off the little yellow translucent liquid of layer, obtain product behind the distillation dehydration.
As preferably, the weight part proportioning of described tin, methyl chloride and tin tetrachloride is: 7～10 parts in tin, 7.5～10.5 parts of methyl chloride, 10～13 parts of tin tetrachloride.The necessary standard of the component of tin tetrachloride is directly connected to monomethyl, dimethyl, trimethylammonium methyl conversion proportion in this proportioning, and the monomethyl content span of control in this methyl tin product is at 75-95%; Trimethylammonium content＜0.1%.
As preferably, this technology by distillation plant with the methyl tin chloride behind high-temperature gasification, from reaction residues, separate, general serous coat absorption system goes into to absorb with configuration is water-soluble.Original process using vertical compression mode, the methyl tin chloride that reaction is good is purified without distillation and directly is pressed in the configuration water, has a large amount of impurity in the methyl tin chloride aqueous solution, and color and luster is darker, also directly influences the effect of esterification condensation reaction, reduces product yield.The distillation purifying technique has guaranteed the high purity of methyl tin chloride, and transparent color and luster, can improve product yield 2-2.5% behind esterification condensation.Configuration water effect therein is a carrier, and addition is 30 parts the 2.5-3 of tin weight (are doubly).The too much water yield can increase environmental protection treatment pressure.The water yield influences assimilation effect very little, causes part gaseous state methyl tin chloride to be taken away loss by vacuum system.
As preferably, the weight part proportioning of the methyl tin chloride aqueous solution, MEO, sodium sulphite and ammoniacal liquor is: 20～25 parts of the methyl tin chloride aqueous solution, 40～52 parts of MEO, 0.2～0.3 part in sodium sulphite, mass concentration are 1.5～2 parts of 20% ammoniacal liquor.Each raw-material weight is wanted accurately in this proportioning, and the amount of the methyl tin chloride aqueous solution and MEO is directly connected to the height and the production material cost of product tin content; The addition of sodium sulphite can be related to finished product sulphur content index; Ammoniacal liquor has been participated in the acid-base neutralisation reaction in the esterification condensation reaction, has played catalytic effect simultaneously, and the addition of ammoniacal liquor is directly connected to the span of control and the reaction effect of pH value in the reaction process, also can have influence on finished product acid number index.The acid-base neutralisation that a lot of producers use mineral alkalis such as NaOH, KOH, Ca (OH) 2 to participate in the esterification condensation reaction reacts, but is easy to generate a large amount of saponification side reaction materials, reduces product yield.This prescription adopts 20% the alternative above-mentioned mineral alkali of ammoniacal liquor, has solved saponified formation.
Method of the present invention, whole process are easy to control, environmental friendliness, and the methyl tin heat stabilizer that makes according to the inventive method has the following advantages:
Harmful heavy metals such as 1, methyl tin heat stabilizer product of the present invention is not leaded, trimethylammonium content＜0.1% by U.S. NSF and the authentication of PPI hygienic standard, meets the hygienic requirements of national upper hose product.The thermostable effect excellence of product, and have straight line and add consumption control usefulness, addition is little on year-on-year basis, has obviously reduced formulation cost.
2, can give thermostability good in the PVC course of processing, keep moulding good in the product processing and tinctorial property and excellent surface smoothness, give PVC product vivid color and luster, smooth in appearance such as fat.
3, use contrary ester tin heat stabilizer to have more outstanding plasticizing capacity and ease for operation in the PVC course of processing, cut down the consumption of energy, remedied some defective that the equipment soffening is poor, shearing force is low simultaneously.And can give outstanding low-temperature impact property of product and very high fillet weld strength.But cooperate material production diversification tubing, section bar products such as other lubrication prescription.
Description of drawings
Fig. 1 is a thermo-stabilizer of the present invention and with the rheology effect comparative graph of type thermal stabilizing agent T-178.
Embodiment
To content of the present invention and application, be elaborated by following most preferred embodiment, but the present invention is not limited to these embodiment.
Employed technology in following examples unless stated otherwise, is routine techniques known to those skilled in the art; Employed plant and instrument, reagent etc., only this specification sheets specifies, is that the research of this area and technician can be by public approach acquisition.
Methyl tin heat stabilizer of the present invention obtains through two step reaction, at first obtains the methyl tin chloride intermediate by tin, methyl chloride and tin tetrachloride through the alkane halogenating reaction, obtains the methyl tin chloride aqueous solution after being dissolved in water; Secondly, add MEO, sodium sulphite and ammoniacal liquor and carry out the esterification condensation reaction in the described methyl tin chloride aqueous solution, fully the dehydration of reaction back obtains methyl tin heat stabilizer product.Wherein the prescription of methyl tin chloride intermediate is: metallic tin (Sn) 7～10kg, methyl chloride (CH3Cl) 7.5～10.5 kg, water 30 kg, tetramethyl ammonium chloride ((CH3) 4NCl) 0.2～0.5 kg, tin tetrachloride (SnCl4) 10～13 kg.Each proportioning raw materials is in the esterification condensation reaction
:20～30 parts of methyl tin chloride ((CH3) xSnCly) aqueous solution, mass concentration are 5～6.5 parts of 20% ammoniacal liquor (NH3H2O), 2.5～3 parts in sodium sulphite (Na2S), MEO:40～52 part.
MEO, molecular structural formula are HSCH2CH2OCOC17H35.Long night chemical industry company limited provides by Sichuan, model: vegetable seed oleic acid goods.
Embodiment 1:The preparation of methyl tin chloride intermediate
Reaction formula:
3Sn + 6CH3Cl?=CH3SnCl3+（CH3）2SnCl2+（CH3）3SnCl
（CH3）3SnCl?+?SnCl4=?CH3SnCl3+（CH3）2SnCl2
Net reaction:
Catalyzer (CH3) 4NCl
Sn +?CH3Cl +?SnCl4 → （CH3）xSnCly
The equipment that present embodiment is used: reactor (joining stirring system), still kettle (joining stirring system), distillation absorption unit, test tank.
1, alkane halogenating reaction: check that reactor, transmission mechanism, instrument, pipeline, absorption unit make it be in standard state.The reacting by heating still makes still temperature rise to 120 ℃, opens vacuum system and makes place's micro-vacuum state in the still, closes dog-house after opening the charging opening of reactor and adding metallic tin, tetramethyl ammonium chloride, feeds methyl chloride, makes the still internal pressure in the 0.3-0.5MPa scope.Continue to improve about still temperature to 180 ℃, turn on agitator, the control stirring velocity is at 100-125rpm.Instrument shows that the still internal pressure descends, and material begins reaction in the expression still, can close down heating system.Reaction is the step-down temperature-rise period, and the whole process reaction time is 7 hours, adds methyl chloride and tin tetrachloride by a small amount of mode repeatedly in the reaction process.Temperature, pressure in the reactor no longer are changed to reaction end.
2, distillation absorbs: the still kettle temperature is preheated to 120 ℃, opens feed valve, the material that reaction is good is depressed into still kettle from reactor, opens the still kettle stirring system after finishing whole binder programs.300kg water input is absorbed in the container, open vacuum system and water absorption system, keep the system vacuum degree in-0.08-0.1Mpa, distillation heats up.Control the still temperature in the still-process at 120-130 ℃, 1 hour whole still-process time spent.Explanation distillation that temperature rises to about 180 ℃, water temperature begins to descend absorbs and finishes.
The add-on of each material of present embodiment is: metallic tin (Sn) 85kg, methyl chloride (CH3Cl) 102kg, tetramethyl ammonium chloride ((CH3) 4NCl) 2.5kg, tin tetrachloride (SnCl4) 125kg, water 300kg.The reaction time spent is 6.5 hours.Metering obtains the methyl tin chloride aqueous solution 574.2kg of mass concentration 47.75%, yield 97.2%.Aqueous solution color and luster water white transparency.
Embodiment 2:The preparation of methyl tin chloride intermediate
Concrete scheme is with embodiment 1, and difference is that the add-on of each material is: metallic tin (Sn) 80kg, methyl chloride (CH3Cl) 95 kg, tetramethyl ammonium chloride ((CH3) 4NCl) 3.2 kg, tin tetrachloride (SnCl4) 120 kg, water 300 kg.The reaction time spent is 7 hours.Control the still temperature in the still-process at 150-160 ℃, 1.5 hours whole still-process times spent.Metering obtains the intermediate water solution 558.8kg of mass concentration 46.31%, yield 96.62%.Aqueous solution color and luster water white transparency.
Embodiment 3:The preparation of methyl tin chloride intermediate
Concrete scheme is with embodiment 1, and difference is that the add-on of each material is: metallic tin (Sn) 95 kg, methyl chloride (CH3Cl) 102 kg, tetramethyl ammonium chloride ((CH3) 4NCl) 3.2 kg, tin tetrachloride (SnCl4) 128 kg.Water 300 kg.Control the still temperature in the still-process at 170-180 ℃, 1 hour whole still-process time spent.It is 49.54% intermediate water solution 594.5kg that metering obtains mass concentration, yield 97.0%, aqueous solution color and luster water white transparency.
Embodiment 4:The preparation of methyl tin chloride intermediate
Concrete scheme is with embodiment 1, and difference is that the add-on of each material is: metallic tin (Sn) 70 kg, methyl chloride (CH3Cl) 75 kg, tetramethyl ammonium chloride ((CH3) 4NCl) 2 kg, tin tetrachloride (SnCl4) 100 kg.Water 300 kg.It is 42.54% intermediate water solution 522.1kg that metering obtains mass concentration, yield 96.8%.Aqueous solution color and luster water white transparency.
Embodiment 5:The esterification condensation reaction
Reaction formula:
(CH3)xSnCly+HSCH2CH2OCOC17H35+Na2S+NH3·H2O→(CH3)xSn(SCH2COOC8H17)y?+NaCl?+NH4Cl+H2O
The equipment that present embodiment is used: esterifying kettle, the distillation dehydration still drips jar (3), separator tank, vacuum apparatus, filter plant, device of condensation recovery.
1, esterification: the methyl tin chloride aqueous solution 200kg that previous step is obtained, and sodium sulphite 25kg, mass concentration are that 20% ammoniacal liquor 50kg injects the dropping jar that links to each other with esterifying kettle respectively, with in the 400kg MEO suction esterifying kettle, open and stir again, the control rotating speed is between 65-75rpm.The still temperature of regulating esterifying kettle makes the dropping jar be communicated with esterifying kettle and begins to drip after 15-20 ℃.Adjust the speed of dropping, ammoniacal liquor, methyl tin chloride intermediate, sodium sulphite are joined in the esterifying kettle synchronously.Keep about 50 ℃ of still temperature during esterification, the pH value is between 5-8.The whole esterification time spent was at 5 hours.Each raw material drips and finishes back stirring 1 hour.Shut down standing demix 2 hours.
2, layering
:Orlop is work in-process, is weighed as 496kg, is little yellow translucent liquid, and the middle layer is reacted accessory substances, and the superiors are waste water.
3, distillation dehydration
:In work in-process suction dehydration still, start stirring, air in the still is drained, progressively promote the still temperature to 100-150 ℃.Distilled whole process time 2.5 hours.Cool to below 50 ℃ after insulation finishes and filter, obtaining color is product faint yellow, that be the transparent liquid shape.Obtain product 480.5kg after the filtration, finished color is a light yellow transparent liquid.Product yield is 92.3%.
The add-on of each material of present embodiment is: the methyl tin chloride of mass concentration 47.75% ((CH3) xSnCly) aqueous solution 200kg, mass concentration is 20% ammoniacal liquor (NH3H2O) 50kg, sodium sulphite (Na2S) 25kg, MEO:400kg.
Technical target of the product and sample detection that present embodiment obtains the results are shown in Table 1.
Embodiment 6:The esterification condensation reaction
Concrete scheme is with embodiment 5, difference is that the add-on of each raw material is: methyl tin chloride ((CH3) xSnCly) aqueous solution 250 kg that get the mass concentration 46.31% that embodiment 2 makes, mass concentration is 20% ammoniacal liquor (NH3H2O) 53 kg, sodium sulphite (Na2S) 28 kg, MEO:400 kg.7 hours esterification times spent.
The work in-process stratification state is better, is weighed as 568kg, light yellow, and band is muddy slightly.To carry out distillation dehydration in the work in-process suction dehydration still.Distilled whole process time 3 hours.Obtain product 552.2kg after the filtration, finished color is a light yellow transparent liquid.Product yield is 93.0 %.
Technical target of the product and sample detection that present embodiment obtains the results are shown in Table 2.
Embodiment 7:The esterification condensation reaction
Concrete scheme is with embodiment 5, difference is that the add-on of each raw material is: methyl tin chloride ((CH3) xSnCly) aqueous solution 300 kg that get the mass concentration 49.54% that embodiment 3 makes, mass concentration is 20% ammoniacal liquor (NH3H2O) 60 kg, sodium sulphite (Na2S) 30 kg, MEO:400 kg.
The work in-process stratification state is better, is weighed as 545kg, light yellow, and band is muddy slightly.To carry out distillation dehydration in the work in-process suction dehydration still.Distilled whole process time 2.5 hours.Obtain product 528kg after the filtration, finished color is a light yellow transparent liquid.Product yield is 91.2 %.
Technical target of the product and sample detection that present embodiment obtains the results are shown in Table 3.
Embodiment 8:The esterification condensation reaction
Concrete scheme is with embodiment 5, difference is that the add-on of each raw material is: methyl tin chloride ((CH3) xSnCly) aqueous solution 300 kg that get the mass concentration 42.54% that embodiment 4 makes, mass concentration is 20% ammoniacal liquor (NH3H2O) 54 kg, sodium sulphite (Na2S) 26 kg, MEO:400 kg.
The work in-process stratification state is better, is weighed as 517kg, light yellow, and band is muddy slightly.To carry out distillation dehydration in the work in-process suction dehydration still.Distilled whole process time 2.5 hours.Obtain product 506kg after the filtration, finished color is a light yellow transparent liquid.Product yield is 91.4 %.
Technical target of the product and sample detection that present embodiment obtains the results are shown in Table 4.
Embodiment: product performance application testing contrast
Test purpose: compare by this rheology effect of inventing the same type thermal stabilizing agent T-178 of thermo-stabilizer (natural laws TT690) that described embodiment 5 makes and external certain manufacturer production.
Testing tool: XSSS-300 torque rheometer.
Instrument parameter is provided with: 1,2,3 interval temperature are 180 ℃; Rotating speed 65rpm; Load 5kg.Weight of material 65g.
Raw material ratio: PVC powder: 100 g, titanium dioxide: 1 g, PE wax: 1 g, calcium stearate: 0.8 g, lime carbonate: 5 g, thermo-stabilizer: 0.4 g.
The graphic representation of Fig. 1 is the flow curve of operation 0-210 between second.Block curve is embodiment 5 thermo-stabilizers (natural laws TT690) effect curves among Fig. 1, and dashed curve is for being used for the same type thermal stabilizing agent product T-178 of hard PVC processing in the market.
1. the reinforced peak of reinforced peak: embodiment 5 thermo-stabilizers moment of torsion is 73Nm, 34 seconds time; The reinforced peak of T-178 moment of torsion is 76Nm, 37 seconds time.Embodiment 5 thermo-stabilizer moments of torsion are compared the low 3Nm of T-178, time and are compared and reduce 3 seconds; The low moment of torsion of embodiment 5 thermo-stabilizers can reduce turns round damage stress to equipment.
2. moment of torsion Schwellenwert: the moment of torsion Schwellenwert is approaching, all about 23Nm, and 56 seconds time.
3. second peak torque of second peak value: embodiment, 5 thermo-stabilizers is 42.5Nm, 78 seconds time; Second peak torque of T-178 is 46Nm, 85 seconds time.Embodiment 5 thermo-stabilizer moments of torsion are compared the low 3.5Nm of T-178, and the time is compared T-178 and shortens 7 seconds.Draw embodiment 5 thermo-stabilizer plasticity-and be better than T-178.
From the flow curve of 85-200 second as can be seen embodiment 5 thermo-stabilizers later stage stability obviously steadily, stable.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (9)
1. the preparation method of a methyl tin heat stabilizer is characterized in that this method comprises following two-step reaction:
A,
The preparation of methyl tin chloride intermediate:Obtain the methyl tin chloride intermediate by metallic tin, methyl chloride and tin tetrachloride through the alkane halogenating reaction, add and obtain the methyl tin chloride aqueous solution after water absorbs;
B,
The esterification condensation reaction:Add MEO, sodium sulphite and ammoniacal liquor and carry out the esterification condensation reaction in the described methyl tin chloride aqueous solution, fully the dehydration of reaction back obtains methyl tin heat stabilizer product.
2. preparation method according to claim 1 is characterized in that alkane halogenating reaction process is as follows among the described step a
:The reacting by heating still makes still temperature rise to 120～130 ℃, open vacuum system, make the still internal pressure reduce to-0.01 to-0.05MPa, after in reactor, dropping into metallic tin, tetramethyl ammonium chloride, feed methyl chloride, the control reacting kettle inner pressure stirs after being warming up to 180～190 ℃ then in the 0.3-0.5MPa scope, and the control stirring velocity is at 100-125rpm.
3. still internal pressure decline expression reaction beginning, after stop the heating, progressively add tin tetrachloride and methyl chloride, the speed and the add-on that add methyl chloride are standard with still internal pressure data presentation, and the still internal pressure is controlled at 1.1-1.5Mpa to sufficient reacting in the entire reaction course.
4. preparation method according to claim 1 is characterized in that: add methyl chloride and tin tetrachloride by a small amount of mode repeatedly in the described reaction process.
5. preparation method according to claim 2, it is characterized in that described step a also comprises following process: the still kettle temperature is preheated to 120 ℃, the material that reaction is good is depressed into still kettle from reactor, stir, keep vacuum tightness in the reaction system at-0.08-0.1Mpa, the distillation that heats up, control still temperature is at 120-180 ℃ in the still-process, water absorbs cut, obtains the methyl tin chloride aqueous solution.
6. methyl tin heat stabilizer according to claim 1 and 2 is characterized in that: described alkane halogenating reaction adopts tetramethyl ammonium chloride as catalyzer, and consumption is 2～5% of a tin weight.
7. according to claim 1 or 2 or 3 described methyl tin heat stabilizers, it is characterized in that: the weight part proportioning of described tin, methyl chloride and tin tetrachloride is: 7～10 parts in tin, 7.5～10.5 parts of methyl chloride, 10～13 parts of tin tetrachloride.
8. preparation method according to claim 1 is characterized in that described step b is specific as follows
:MEO is put into esterifying kettle, the still temperature that makes esterifying kettle is after 15～20 ℃ of scopes, ammoniacal liquor, methyl tin chloride intermediate, sodium sulphite are added dropwise in the esterifying kettle simultaneously, stir, the control agitator shaft speed is at 65～75rpm, keep about 50～60 ℃ of still temperature during esterification, the pH value is controlled between 5～8, and fully after the reaction, standing demix is more than 2 hours, take off the little yellow translucent liquid of layer, obtain product behind the distillation dehydration.
9. according to claim 1 or 7 described preparation methods, it is characterized in that: the weight part proportioning of the methyl tin chloride aqueous solution, MEO, sodium sulphite and ammoniacal liquor is: 20～25 parts of the methyl tin chloride aqueous solution, MEO40～52 part, 0.2～0.3 part in sodium sulphite, mass concentration are 1.5～2 parts of 20% ammoniacal liquor.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516290A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Method for preparing mixture of methyl tin chloride |
| CN102516289A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
| CN102863467A (en) * | 2012-08-30 | 2013-01-09 | 云南锡业股份有限公司 | Method for preparing high-tin high-sulfur methyl tin mercaptide product |
| CN106280076A (en) * | 2016-08-05 | 2017-01-04 | 衢州建华东旭助剂有限公司 | Itaconic acid methyl stannum stabilizer for plastics and production method |
| CN113717216A (en) * | 2021-10-15 | 2021-11-30 | 上海沃凯生物技术有限公司 | Preparation method of trimethyltin chloride |
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| CN1253965A (en) * | 1998-10-13 | 2000-05-24 | 莫顿国际股份有限公司 | Aromatic method for stabilizing halopolymer |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516290A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Method for preparing mixture of methyl tin chloride |
| CN102516289A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
| CN102516290B (en) * | 2011-11-22 | 2015-04-08 | 湖北南星化工总厂 | Method for preparing mixture of methyl tin chloride |
| CN102516289B (en) * | 2011-11-22 | 2015-07-15 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
| CN102863467A (en) * | 2012-08-30 | 2013-01-09 | 云南锡业股份有限公司 | Method for preparing high-tin high-sulfur methyl tin mercaptide product |
| CN102863467B (en) * | 2012-08-30 | 2016-02-17 | 云南锡业股份有限公司 | A kind of preparation method of high tin high-sulfur thiol methyl tin product |
| CN106280076A (en) * | 2016-08-05 | 2017-01-04 | 衢州建华东旭助剂有限公司 | Itaconic acid methyl stannum stabilizer for plastics and production method |
| CN113717216A (en) * | 2021-10-15 | 2021-11-30 | 上海沃凯生物技术有限公司 | Preparation method of trimethyltin chloride |
| CN113717216B (en) * | 2021-10-15 | 2024-05-10 | 上海沃凯生物技术有限公司 | Preparation method of trimethyltin chloride |
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