CN107089678A - A kind of preparation method and applications of butter of tin - Google Patents
A kind of preparation method and applications of butter of tin Download PDFInfo
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- CN107089678A CN107089678A CN201710383524.7A CN201710383524A CN107089678A CN 107089678 A CN107089678 A CN 107089678A CN 201710383524 A CN201710383524 A CN 201710383524A CN 107089678 A CN107089678 A CN 107089678A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/04—Halides
- C01G19/08—Stannic chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
Body of the present invention provides a kind of preparation method of butter of tin, comprises the following steps：Tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then is passed through chlorine, and control temperature in the kettle, less than 100 DEG C, Stress control reacts 16h in 0.5MPa, chlorine flowrate control in 31m3/h；Obtain butter of tin；Wherein, the mesoporous silicon oxide is the mesoporous silicon oxides of SBA 15；The weight ratio of the tin and the butter of tin solution, the mesoporous silicon oxide is 1：(0.5‑1.5)：(0.2‑0.7).
Description
Technical field
The present invention relates to a kind of manufacture method of inorganic compound, in particular it relates to a kind of system of butter of tin
Preparation Method and its application.
Background technology
Butter of tin is the primary raw material of organo-tin compound, and organo-tin compound is used for PVC product and as thermally-stabilised
The international consumption consumption of agent increases year by year.Anhydrous stannic chloride can be used as the raw material and chlorinating agent of organotin synthesis, textile industry
In soft dose of coal, manufacture blueprint paper, sensitive paper, the additive of lubricating oil and the field such as tin plating.At present, most of butters of tin
Contract be with metallic tin grain or anhydrous stannous chloride and chlorine reaction intermittent operation.
Because tin, chlorine reaction are exothermic reactions, reaction temperature exceedes the melting temperature of tin quickly within a very short time
(231.5 DEG C), so usually because the fusing of tin causes chlorine channel blockage in course of reaction, thus cause to stop production.In addition,
In course of reaction, chlorine is small in tin surfaces contact area, and the residence time is short, causes chlorine utilization low, and influence butter of tin is received
Rate.Had greater environmental impacts simultaneously as chlorine content is too high in tail gas.
The present invention provides a kind of preparation method of butter of tin regarding to the issue above, using butter of tin as reaction medium, plus
Enter mesoporous silicon oxide, improve the contact area of tin and chlorine, improve reaction efficiency and yield；Also prepare a kind of SnCl in addition4/
Polymer composite, it has very strong catalytic activity, water-resistance and heat endurance high.
The content of the invention
In view of the above-mentioned problems, first aspect present invention provides a kind of preparation method of butter of tin, comprise the following steps：
Tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then is passed through chlorine, and control temperature in the kettle
Less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reacts 16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：(0.5-1.5)：(0.2-0.7).
In one embodiment, the weight ratio of the tin and the butter of tin solution, the mesoporous silicon oxide is
1：0.8：0.4.
Second aspect of the present invention provides a kind of SnCl4/ polymer composite, the SnCl4The preparation of/polymer composite
Raw material includes melamine, eight (oxosilanes of aminophenyl three), phenol, formaldehyde, stannic chloride pentahydrate；The melamine and institute
State phenol, the mol ratio of the formaldehyde is 1:(1-2)：(3-5)；The melamine and described eight (oxosilanes of aminophenyl three)
Mol ratio be 1：(0.01-0.1).
Third aspect present invention provides a kind of SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 50-60 DEG C, is added dropwise after formalin, completion of dropping,
80-90 DEG C is warming up to, insulation reaction 5-10h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2-3h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Alkane is dried under reduced pressure 20h under the conditions of washing filter cake, 80 DEG C, obtains SnCl4/ polymer composites.
In one embodiment, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：
4.2。
In one embodiment, the mol ratio of the melamine and described eight (oxosilanes of aminophenyl three) is 1：
0.07。
In one embodiment, melamine described in the step (1) and the mass fraction for 50% methanol/
Aqueous solution weight ratio is 1：6.
In one embodiment, benzoxazine monomer described in the step (2) and the methanol, the five water tetrachloro
The weight ratio for changing tin is 1：5：(0.2-0.5)；The weight ratio of the benzoxazine monomer and the methyl-silicone oil is 1：15.
In one embodiment, benzoxazine monomer described in the step (2) and the methanol, the five water tetrachloro
The weight ratio for changing tin is 1：5：0.36.
In one embodiment, the SnCl4It is methyl lactate field that/polymer composite, which is applied to sucrose inversion,.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific
Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means by polymerizeing polymer prepared by least two different monomers.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (it is typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymer by polymerizeing more kinds of monomers and manufacturing.
" blend " means that two or more polymer passes through polymer formed by physics or chemistry the common mixing of method.
First aspect present invention provides a kind of preparation method of butter of tin, comprises the following steps：
Tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then is passed through chlorine, and control temperature in the kettle
Less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reacts 16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：(0.5-1.5)：(0.2-0.7).
In one embodiment, the weight ratio of the tin and the butter of tin solution, the mesoporous silicon oxide is
1：0.8：0.4.
In the present invention, Yin Xi is exothermic reaction with chlorine reaction and chlorine solubility in butter of tin is big, with four chlorinations
Tin is reaction medium, not only improves reaction efficiency, while the heat that also effectively cooling tin is produced with chlorine reaction for exothermic reaction；
SBA-15 mesoporous silicon oxides are added, special structure not only promotes scattered, the effective group for alleviating tin of chlorine gas flow being passed through
The reunion of the heat produced in poly- and course of reaction, and then effectively improve the yield of reaction and the quality of butter of tin.
Second aspect of the present invention provides a kind of SnCl4/ polymer composite, the SnCl4The preparation of/polymer composite
Raw material includes melamine, eight (oxosilanes of aminophenyl three), phenol, formaldehyde, stannic chloride pentahydrate；The melamine and institute
State phenol, the mol ratio of the formaldehyde is 1:(1-2)：(3-5)；The melamine and described eight (oxosilanes of aminophenyl three)
Mol ratio be 1：(0.01-0.1).
Third aspect present invention provides a kind of SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 50-60 DEG C, is added dropwise after formalin, completion of dropping,
80-90 DEG C is warming up to, insulation reaction 5-10h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2-3h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Alkane is dried under reduced pressure 20h under the conditions of washing filter cake, 80 DEG C, obtains SnCl4/ polymer composite.
Carbohydrate comes from the most abundant and renewable green resource of biomass, it is converted into by chemical method high attached
Value added chemicals, significant for human kind sustainable development, catalyst plays the work of key in this conversion process
With.Lewis acid and the sour composite catalysts of Bronst for lactic acid derivative have higher efficiency to saccharide converted.
Using butter of tin and benzoxazine as raw material in the present invention, synthesized by anti-phase suspension solidification method simple and easy to apply
Sn (IV) in metal organic frame Lewis acid and the sour compounding solid catalysts of Bronst, catalyst, which has, promotes sugar in first
The phenolic hydroxyl group in the effect of methyl lactate, benzoxazine is dissolved and be converted into alcohol has weak Bronst acid, improves sugar
Transformation efficiency.
In addition with melamine, eight (oxosilanes of aminophenyl three), phenol synthesis benzoxazine, obtained benzene in the present invention
Phenolic hydroxyl group in Bing oxazines has weak Bronst acid, improve the transformation efficiency of sugar, and eight (oxosilanes of aminophenyl three) draw
Enter, also improve the water resistance and heat endurance of catalyst, eight (oxosilanes of aminophenyl three) further improve SnCl in addition4/ high
The pore size of molecular complex, it is to avoid the impurity of the carbonization of sucrose be covered in the surface of catalyst not easy cleaning and cause to lose
It is living.
In one embodiment, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：
4.2。
In one embodiment, the mol ratio of the melamine and described eight (oxosilanes of aminophenyl three) is 1：
0.07。
In one embodiment, melamine described in the step (1) and the mass fraction for 50% methanol/
Aqueous solution weight ratio is 1：6.
In one embodiment, benzoxazine monomer described in the step (2) and the methanol, the five water tetrachloro
The weight ratio for changing tin is 1：5：(0.2-0.5)；The weight ratio of the benzoxazine monomer and the methyl-silicone oil is 1：15.
In one embodiment, benzoxazine monomer described in the step (2) and the methanol, the five water tetrachloro
The weight ratio for changing tin is 1：5：0.36.
In one embodiment, the SnCl4It is methyl lactate field that/polymer composite, which is applied to sucrose inversion,.
In one embodiment, the SnCl4/ polymer composite catalysing sucrose prepares the preparation method of methyl lactate
It is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.07；Melamine described in the step (1) and the matter
It is 1 to measure the methanol/water solution weight ratio that fraction is 50%：6；Benzoxazine monomer described in the step (2) and the first
Alcohol, the weight ratio of the stannic chloride pentahydrate are 1：5：0.36；The weight ratio of the benzoxazine monomer and the methyl-silicone oil
For 1：15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Embodiment 2
The preparation method of the butter of tin, tin, butter of tin solution, nano silicon are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the nano silicon is purchased from Hangzhou Wanjing New Material Co., Ltd.；The tin and the butter of tin
Solution, the weight ratio of the nano silicon are 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.07；Melamine described in the step (1) and the matter
It is 1 to measure the methanol/water solution weight ratio that fraction is 50%：6；Benzoxazine monomer described in the step (2) and the first
Alcohol, the weight ratio of the stannic chloride pentahydrate are 1：5：0.36；The weight ratio of the benzoxazine monomer and the methyl-silicone oil
For 1：15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Embodiment 3
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is MCM-41；The tin and the butter of tin solution, the meso-porous titanium dioxide
The weight ratio of silicon is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.07；Melamine described in the step (1) and the matter
It is 1 to measure the methanol/water solution weight ratio that fraction is 50%：6；Benzoxazine monomer described in the step (2) and the first
Alcohol, the weight ratio of the stannic chloride pentahydrate are 1：5：0.36；The weight ratio of the benzoxazine monomer and the methyl-silicone oil
For 1：15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Embodiment 4
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.01；Melamine described in the step (1) and the matter
It is 1 to measure the methanol/water solution weight ratio that fraction is 50%：6；Benzoxazine monomer described in the step (2) and the first
Alcohol, the weight ratio of the stannic chloride pentahydrate are 1：5：0.36；The weight ratio of the benzoxazine monomer and the methyl-silicone oil
For 1：15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Embodiment 5
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.1；Melamine described in the step (1) and the quality
The methanol/water solution weight ratio that fraction is 50% is 1：6；Benzoxazine monomer described in the step (2) and the methanol,
The weight ratio of the stannic chloride pentahydrate is 1：5：0.36；The weight ratio of the benzoxazine monomer and the methyl-silicone oil is 1：
15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Embodiment 6
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.07；Melamine described in the step (1) and the matter
It is 1 to measure the methanol/water solution weight ratio that fraction is 50%：6；Benzoxazine monomer described in the step (2) and the first
Alcohol, the weight ratio of the stannic chloride pentahydrate are 1：5：0.2；The weight ratio of the benzoxazine monomer and the methyl-silicone oil is
1：15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Embodiment 7
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction
It is added in reactor, stirs for 50% methanol/water solution, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, rises
Temperature is to 85 DEG C, and insulation reaction 7h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The melamine
Mol ratio with described eight (oxosilanes of aminophenyl three) is 1：0.07；Melamine described in the step (1) and the matter
It is 1 to measure the methanol/water solution weight ratio that fraction is 50%：6；Benzoxazine monomer described in the step (2) and the first
Alcohol, the weight ratio of the stannic chloride pentahydrate are 1：5：0.5；The weight ratio of the benzoxazine monomer and the methyl-silicone oil is
1：15；
The SnCl4The preparation method that/polymer composite catalysing sucrose prepares methyl lactate is as follows：
SnCl is added into reactor4/ polymer composite, sucrose, methanol, are warming up to 160 DEG C, react 20h, react it
Afterwards, add NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L)
To in above-mentioned solution so that sodium lactate is converted into lactic acid, then using the above-mentioned solution of efficient liquid phase chromatographic analysis with obtain lactic acid and
The percent of total content of methyl lactate；The SnCl4/ polymer composite compares 1 with the sucrose, the weight of the methanol：3：
20；The sucrose and the NaOH solution, the HCl weight ratio are 1：5：5.
Comparative example 1
The preparation method of the butter of tin, is comprised the following steps that：
Tin, butter of tin solution are added into reactor, then is passed through chlorine, and control temperature in the kettle is less than 100 DEG C,
Stress control reacts 16h in 0.5MPa, chlorine flowrate control in 31m3/h；Obtain butter of tin；
The SnCl4The preparation method of/polymer composite, the SnCl4/ polymer composite catalysing sucrose prepares breast
The preparation method be the same as Example 1 of sour methyl esters, difference is no added mesoporous silicon oxide in the preparation method of the butter of tin.
Comparative example 2
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The SnCl4The preparation method of/polymer composite, comprises the following steps：
(1) benzoxazine monomers：In molar ratio by melamine, phenol, the methanol/water solution that mass fraction is 50%
It is added in reactor, stirs, be warming up to 55 DEG C, be added dropwise after formalin, completion of dropping, is warming up to 85 DEG C, insulation reaction 7h,
First alcohol and water is removed under reduced pressure, benzoxazine monomer is obtained；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzo is slowly added dropwise
Oxazine monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2h under the conditions of 200 DEG C, are cooled to room temperature, filter, hexamethylene
Filter cake is washed, 20h is dried under reduced pressure under the conditions of 80 DEG C, obtains SnCl4/ polymer composite；
Wherein, the mol ratio of the melamine and the phenol, the formaldehyde is 1:1.45：4.2；The step (1)
Described in melamine and the mass fraction be 50% methanol/water solution weight ratio be 1：6；Described in the step (2)
The weight ratio of benzoxazine monomer and the methanol, the stannic chloride pentahydrate is 1：5：0.36；The benzoxazine monomer with
The weight ratio of the methyl-silicone oil is 1：15；
The SnCl4/ polymer composite catalysing sucrose prepares the preparation method be the same as Example 1 of methyl lactate, and difference exists
Without eight (oxosilanes of aminophenyl three) when benzoxazine monomer is synthesized.
Comparative example 3
The preparation method of the butter of tin, tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then
Chlorine is passed through, and control temperature in the kettle, less than 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reaction
16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, institute
The weight ratio for stating mesoporous silicon oxide is 1：0.8：0.4；
The preparation method that the stannic chloride pentahydrate catalysing sucrose prepares methyl lactate is as follows：
Stannic chloride pentahydrate, sucrose, methanol are added into reactor, 160 DEG C are warming up to, 20h is reacted, after reaction, plus
Enter NaOH solution (0.5mol/L) to carry out 5h hydrolysis at 60 DEG C to obtain solution, add HCl (0.5mol/L) supreme
State so that sodium lactate is converted into lactic acid in solution, then using the above-mentioned solution of efficient liquid phase chromatographic analysis to obtain lactic acid and lactic acid
The percent of total content of methyl esters；The stannic chloride pentahydrate compares 1 with the sucrose, the weight of the methanol：3：20；The sucrose
Weight ratio with the NaOH solution, the HCl is 1：5：5.
Performance test：
1st, the yield of butter of tin and the utilization rate of chlorine are calculated；
2、SnCl4/ polymer composite applies mechanically number of times：Catalyst is more than or equal to 20% using standard-catalytic efficiency；
After catalyst use, 2h is stirred at room temperature with the acetone of 6 times of volumes, filters, 60 DEG C are dried under reduced pressure recycling after 10h；
3rd, the yield of methyl lactate.
The performance test results of table 1
As can be seen that a kind of preparation method for butter of tin that the present invention is provided, can efficiently be improved from above-mentioned data
Reaction efficiency, yield and chlorine utilization；A kind of SnCl prepared4/ polymer composite, with very strong catalytic activity, height
Imitate utilization rate and water-resistance and heat endurance is good.
Foregoing example is merely illustrative, some features for explaining the method for the invention.Appended right will
The scope as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is implemented according to all possible
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this hair
The selectional restriction of the example of bright feature.Some number ranges used also include sub- model within the claims
Enclose, the change in these scopes should be also construed to by appended claim covering in the conceived case.
Claims (10)
1. a kind of preparation method of butter of tin, it is characterised in that comprise the following steps：
Tin, butter of tin solution, mesoporous silicon oxide are added into reactor, then is passed through chlorine, and control temperature in the kettle is low
In 100 DEG C, Stress control is controlled in 31m in 0.5MPa, chlorine flowrate3/ h, reacts 16h；Obtain butter of tin；
Wherein, the mesoporous silicon oxide is SBA-15 mesoporous silicon oxides；The tin and the butter of tin solution, given an account of
The weight ratio of hole silica is 1：(0.5-1.5)：(0.2-0.7).
2. the preparation method of butter of tin according to claim 1, it is characterised in that the tin and the butter of tin are molten
Liquid, the weight ratio of the mesoporous silicon oxide are 1：0.8：0.4.
3. a kind of SnCl4/ polymer composite, it is characterised in that the SnCl4The preparing raw material of/polymer composite includes three
Poly cyanamid, eight (oxosilanes of aminophenyl three), phenol, formaldehyde, stannic chloride pentahydrate；The melamine and the phenol, institute
The mol ratio for stating formaldehyde is 1:(1-2)：(3-5)；The mol ratio of the melamine and described eight (oxosilanes of aminophenyl three)
For 1：(0.01-0.1).
4. SnCl according to claim 34The preparation method of/polymer composite, it is characterised in that comprise the following steps：
(1) benzoxazine monomers：It is by melamine, eight (oxosilanes of aminophenyl three), phenol, mass fraction in molar ratio
50% methanol/water solution is added in reactor, stirring, is warming up to 50-60 DEG C, is added dropwise after formalin, completion of dropping, is risen
Temperature is to 80-90 DEG C, and insulation reaction 5-10h is removed under reduced pressure first alcohol and water, obtains benzoxazine monomer；
(2)SnCl4/ polymer composite：Methyl-silicone oil is added into reactor, 200 DEG C is warming up to, benzoxazine is slowly added dropwise
Monomer, methanol, stannic chloride pentahydrate mixture, insulation reaction 2-3h under the conditions of 200 DEG C, are cooled to room temperature, filter, and hexamethylene is washed
Wash and be dried under reduced pressure 20h under the conditions of filter cake, 80 DEG C, obtain SnCl4/ polymer composite.
5. SnCl according to claim 34/ polymer composite, it is characterised in that the melamine and the phenol, institute
The mol ratio for stating formaldehyde is 1:1.45：4.2.
6. SnCl according to claim 34/ polymer composite, it is characterised in that the melamine and the eight (amino
The oxosilane of phenyl three) mol ratio be 1：0.07.
7. SnCl according to claim 44The preparation method of/polymer composite, it is characterised in that institute in the step (1)
It is 1 to state the methanol/water solution weight ratio that melamine is 50% with the mass fraction：6.
8. SnCl according to claim 44The preparation method of/polymer composite, it is characterised in that institute in the step (2)
The weight ratio for stating benzoxazine monomer and the methanol, the stannic chloride pentahydrate is 1：5：(0.2-0.5)；The benzoxazine
The weight ratio of monomer and the methyl-silicone oil is 1：15.
9. SnCl according to claim 84The preparation method of/polymer composite, it is characterised in that institute in the step (2)
The weight ratio for stating benzoxazine monomer and the methanol, the stannic chloride pentahydrate is 1：5：0.36.
10. SnCl according to claim 34/ polymer composite, it is characterised in that the SnCl4/ polymer composite should
It is methyl lactate field for sucrose inversion.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538063A (en) * | 2009-04-30 | 2009-09-23 | 北京工业大学 | Method for synthesising mesoporous tin oxide by three-dimensional mesoporous silicon dioxide hard template |
| CN102180514A (en) * | 2011-03-05 | 2011-09-14 | 招远市松鹤化工有限公司 | Production process of tin tetrachloride |
| CN104724752A (en) * | 2015-02-27 | 2015-06-24 | 海门市金麒麟红木投资发展有限公司 | Normal-temperature synthesis method of tin tetrachloride |
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| US20140024853A1 (en) * | 2010-11-10 | 2014-01-23 | Microvast, Inc. | Synthesis of Lactic Acid and Alkyl Lactate from Carbohydrate-Containing Materials |
| CN102516288B (en) * | 2011-11-22 | 2015-09-02 | 南通艾德旺化工有限公司 | The synthesis technique of dimethyltin chloride |
| CN103506140B (en) * | 2012-06-18 | 2016-02-03 | 微宏动力系统（湖州）有限公司 | Lactic acid catalyst for synthesizing and synthetic method |
| CN103626650A (en) * | 2012-08-27 | 2014-03-12 | 微宏动力系统（湖州）有限公司 | Preparation method of lactic acid and derivative thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538063A (en) * | 2009-04-30 | 2009-09-23 | 北京工业大学 | Method for synthesising mesoporous tin oxide by three-dimensional mesoporous silicon dioxide hard template |
| CN102180514A (en) * | 2011-03-05 | 2011-09-14 | 招远市松鹤化工有限公司 | Production process of tin tetrachloride |
| CN104724752A (en) * | 2015-02-27 | 2015-06-24 | 海门市金麒麟红木投资发展有限公司 | Normal-temperature synthesis method of tin tetrachloride |
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| 余家会: "《纳米生物医药》", 31 December 2011 * |
| 蒋晨: "《纳米药物》", 31 August 2015 * |
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