CN106279249A - A kind of mixed anion methyl stannum and its preparation method and application - Google Patents
A kind of mixed anion methyl stannum and its preparation method and application Download PDFInfo
- Publication number
- CN106279249A CN106279249A CN201610576576.1A CN201610576576A CN106279249A CN 106279249 A CN106279249 A CN 106279249A CN 201610576576 A CN201610576576 A CN 201610576576A CN 106279249 A CN106279249 A CN 106279249A
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- methyl
- stannum
- compound
- mixed anion
- aqueous solution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention relates to a kind of mixed anion methyl stannum and preparation method and application, the structural formula of this methyl tin compound is: R is straight chain or the straight chained alkyl of C4 C14, methyl tin compound is prepared as follows and obtains: (1) is with dimethyltin chloride aqueous solution and mercaptan compound as raw material, with ammonia as catalyst, single thiol methyl tin is synthesized；(2) in the reaction system of step (1), add appropriate aliphatic carboxylic acid, with liquid caustic soda as catalyst, methyl tin compound is synthesized.The present invention obtains mixed anion its feature of methyl tin compound: this methyl stannum is with tin mercaptides and carboxylic acid stannum structure, tin mercaptides provides excellent long-time stability and antioxidation, carboxylic acid stannum then provides initial coloring and lubricity, therefore it can embody more preferable lubrication in the PVC course of processing, reduce in the course of processing due to PVC particle between, frictional heat between PVC and process equipment, delays PVC to degrade, the favourable heat stability improving PVC and lubricity.
Description
Technical field
The present invention relates to a kind of compound and preparation method thereof, more particularly to a kind of mixed anion methyl stannum and
Preparation method and application.
Background technology
Thiol methyl tin heat stabilizer is widely used in sheet material, plate with stability, the compatibility and the weatherability of its excellence
In material, tubing and the processing of hollow injection-molded item, heat stabilizer field has unshakable leading status.
As far back as the seventies, Morton chemical company of the U.S. develops stannous methide double (isooctyl thioglycolate), i.e. TM～
181FS, it is with methyl tin chloride and isooctyl thioglycolate as raw material midbody, uses grignard reagent method to prepare, tool
Body step is all discussed in detail in US3810868, US3887519, US351966.Domestic manufacturer's its life the most improved at present
Production. art, such as Chinese patent CN1117495A, CN1597764A, CN1137048A, CN1737003A, it is common that use raw material
Isooctyl thioglycolate, water, sodium bicarbonate, solvent are added in reactor, and the aqueous solution of dropping methyl tin chloride reacts,
Product is mainly dimethyl dimercapto 2-ethyl hexyl ethanoate, and this is current domestic and international the most widely used thiol methyl tin class heat
Stabilizer, such as product designation SS218, YT181, ZT181 etc..But the anionicsite of such stable stannum is TGA
Different monooctyl ester, and content is generally at 18-19%, in the PVC hard product processing that condition is harsh, its stability is with self lubricity still
Aobvious inadequate, in use must use with lubricant collocation.
Summary of the invention
An object of the present invention is to solve the deficiencies in the prior art, it is provided that a kind of mixed anion methyl stannum, this first
Base stannum stabilizer effect is notable, and preparation method is easily achieved, and prepared methyl stannum can be widely applied in PVC processing, tool
There are good heat stability and self lubricity.
The two of the purpose of the present invention are to provide the preparation method of a kind of mixed anion methyl stannum.
The three of the purpose of the present invention are to provide the application of a kind of mixed anion methyl stannum.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of mixed anion methyl stannum, the structural formula of this methyl tin compound is:
R is the straight or branched alkyl of C4-C14, and described methyl tin compound is pressed
Following method is prepared:
(1) with dimethyltin chloride aqueous solution and mercaptan compound as raw material, with ammonia as catalyst, list is synthesized
Thiol methyl tin,
(2) in the reaction system of step (1), add appropriate aliphatic carboxylic acid, with liquid caustic soda as catalyst, first is synthesized
Base tin compound,
Preferably, in step (1), the mass ratio of dimethyltin chloride aqueous solution, mercaptan compound and ammonia is 100:
(50～58): (7～20), wherein, in dimethyltin chloride aqueous solution, the mass fraction of chlorine is 17.2%, and the concentration of ammonia is
10-30wt%, mixes in proportion dimethyltin chloride aqueous solution and mercaptan compound, is heated to 45-55 DEG C, while stir
Mix limit dropping ammonia, drip complete follow-up continuous stirring reaction 50-70min.
Preferably, in step (2) dimethyltin chloride aqueous solution and aliphatic carboxylic acid mass ratio be 100:(21.5～
42.8), wherein, in dimethyltin chloride aqueous solution, the mass fraction of chlorine is 17.2%, and the concentration of liquid caustic soda is 5-12wt%, will
Mix homogeneously in the reaction system of aliphatic carboxylic acid addition step (1), dropping liquid caustic soda is to aqueous phase pH >=6.0 while stirring, dropping
After react 50-60min, then stand more than 1 hour, layering, take oil phase dehydration, filter.
A kind of preparation method of mixed anion methyl stannum, described method is carried out as follows:
(1) with dimethyltin chloride aqueous solution and mercaptan compound as raw material, with ammonia as catalyst, list is synthesized
Thiol methyl tin,
(2) in the reaction system of step (1), add appropriate aliphatic carboxylic acid, with liquid caustic soda as catalyst, first is synthesized
Base tin compound,
The application of a kind of mixed anion methyl stannum, as halo ethylene resin heat stabilizer.
Preferably, described halo ethylene resin is polrvinyl chloride, adds 0.8 part～1.0 in the polrvinyl chloride of every 100 mass parts
The mixed anion methyl tin compound of part.
The mixed anion methyl stannum of the present invention, outward appearance is light yellow clear liquid, and technical parameter is:
Density (20 DEG C, g/cm3): 1.16～1.68；Viscosity (25 DEG C, Pa.s): 0.020～0.080；Content: >=99%
The present invention utilizes specific catalyst, under certain condition by anti-to muriatic for a stannous methide chlorine root and mercaptan
Should, generate single thiol methyl tin intermediate, then with aliphatic carboxylic acid, another chlorine root is reacted, thus obtain mixed anion first
Base tin compound.Compared with traditional thiol methyl tin, its feature is: this methyl stannum with tin mercaptides and carboxylic acid stannum structure,
Tin mercaptides provides excellent long-time stability and antioxidation, and carboxylic acid stannum then provides initial coloring and lubricity, therefore it
Can embody more preferable lubrication in the PVC course of processing, reduce in the course of processing between due to PVC particle, PVC and adding
Frictional heat between construction equipment, delays PVC to degrade, the favourable heat stability improving PVC and lubricity.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail.
In embodiment, agents useful for same is all commercial conventional reagent, and in dimethyltin chloride aqueous solution, the mass fraction of chlorine is
17.2%.
Embodiment 1
By 100g dimethyl tin dichloride aqueous solution, 51g TGA in the there-necked flask equipped with thermometer and agitator
Isooctanol ester mixes, stirring, is heated to 50 DEG C, and slowly dropping 7.1g ammonia (30wt%), shuts separatory funnel after dropping,
React 50 minutes, add 35.7g isooctyl acid, slowly drip sodium hydroxide (12wt%) to aqueous phase pH >=6.5, react 60 points
Clock, stands 1 hour, layering, takes oil phase dehydration, filters, obtain mixed anion methyl stannum 1#, and through analyzing, Theil indices is
22.4%.
Embodiment 2
By 100g dimethyl tin dichloride aqueous solution in the there-necked flask equipped with thermometer and agitator, 58.2g sulfydryl second
Acid isodecyl alcohol ester mixing, stirring, it is heated to 50 DEG C, slowly dropping 14.4g ammonia (15wt%), after dropping, shuts separatory leakage
Bucket, react 60 minutes, adds 35.7g caprylic acid, slowly drips sodium hydroxide (10wt%) to aqueous phase PH >=6.5, reaction 50
Minute, stand 1 hour, layering, take oil phase dehydration, filter, obtain mixed anion methyl stannum 2#, through analyzing, Theil indices is
21.3%.
Embodiment 3
By 100g dimethyl tin dichloride aqueous solution, 51g TGA in the there-necked flask equipped with thermometer and agitator
N-octyl alcohol ester mixes, stirring, is heated to 50 DEG C, and slowly dropping 7g ammonia (30wt%), shuts separatory funnel, instead after dropping
Answer 60 minutes, add the acid of 42.8g isodecyl, slowly drip sodium hydroxide (6wt%) to aqueous phase PH >=6.3, react 55 minutes, quiet
Putting 1 hour, layering, take oil phase dehydration, filter, obtain mixed anion methyl stannum 4#, through analyzing, Theil indices is 21.5%.
Embodiment 4
By 100g dimethyl tin dichloride aqueous solution in the there-necked flask equipped with thermometer and agitator, 50.4g sulfydryl second
Acid isooctanol ester mixing, stirring, it is heated to 50 DEG C, slowly dropping 20g ammonia (10wt%), after dropping, shuts separatory leakage
Bucket, reacts 60 minutes, adds 21.5 butanoic acid, slowly drips sodium hydroxide (8wt%) to aqueous phase PH >=6, reacts 60 minutes, quiet
Putting 1 hour, layering, take oil phase dehydration, filter, obtain mixed anion methyl stannum 5#, through analyzing, Theil indices is 25.4%.
Embodiment 5
By 100g dimethyl tin dichloride aqueous solution in the there-necked flask equipped with thermometer and agitator, 57.4g sulfydryl second
Acid isodecyl alcohol ester mixing, stirring, it is heated to 50 DEG C, slowly dropping 15g ammonia (15wt%), after dropping, shuts separatory leakage
Bucket, reacts 60 minutes, adds 21.5 butanoic acid, slowly drips sodium hydroxide (5wt%) to aqueous phase PH >=6, reacts 60 minutes, quiet
Putting 1 hour, layering, take oil phase dehydration, filter, obtain mixed anion methyl stannum 5#, through analyzing, Theil indices is 24.9%.
Thermal stability contrast experiment
Formula (PHR): PVC (SG～7) (Qilu Co., Ltd., China Petrochemical Corp): 100g, first prepared by embodiment 1-5
Based tin heat stabilizer: (Zhejiang Hai Pudun new material share has for 1.0g, DOP (Qilu Co., Ltd., China Petrochemical Corp): 2g, G16
Limit company): 0.8g, G70S (Zhejiang Province Haipoton Chemical Technology Co., Ltd): 0.4g, MBS (Japan Zhong Yuan company): 5g, ACR～
401 (Shandong Ruifeng Polymer Material Co., Ltd.): 1g.
The mixed anion methyl tin heat stabilizer that Example 1-5 prepares, makes PVC sample according to above-mentioned formula, and
Take commercially available Methyltin composite heat stabilizer: TM～181FS (U.S.'s ROHM AND HAAS) and 181 (east, the Zhejiang rising sun), according to joining equally
Side is respectively prepared PVC transparent goods, as comparison.
Test the thermal stability of PVC sample the most by the following method, static heat stability:
According to PVC formula, accurately weigh each component, with experiment mixer by material mix homogeneously, in open refining
Molding machine (Shanghai Hongyang Machinery Co., Ltd.) is upper mixing, and temperature is 190 ± 2 DEG C, and mixing time is about 5min, makes thickness about
For the coupons of 1mm, and prepared PVC coupons is cut into the sheet specimens of 1cm × 3cm, put into ageing oven (401A,
Shanghai silk screen instrument and meter company limited) in, drying sheet temperature is 190 DEG C ± 2, takes sheet every 10min, observes its color record
Yellow colour index.
Table 1: static heat stability energy
From experimental data it can be seen that the mixed anion methyl tin heat stabilizer for preparing of the present invention and commercial like product
Comparing, the static heat stability at initial stage can be the most excellent.
2. dynamic thermal stability:
According to PVC formula precise PVC compound, join torque rheometer (Brabender company of Germany) and carry out
Rheological behaviour is tested, and records rheological data.Experiment condition: milling device temperature is 185 DEG C, spinner velocity is 30r/min.Dynamic Thermal
Stabilization time: PVC is from plastifying to the time decomposed.
Table 2: dynamic thermal stability energy
From experimental data it can be seen that the mixed anion methyl tin heat stabilizer for preparing of the present invention and commercial like product
Comparing, processing moment of torsion substantially reduces, and Dynamic Thermal stabilization time extends, illustrate this stabilizer have more preferable dynamic thermal stability and
Lubricity.
Embodiment described above is the one preferably scheme of the present invention, not makees the present invention any pro forma
Limit, on the premise of without departing from the technical scheme described in claim, also have other variant and remodeling.
Claims (6)
1. a mixed anion methyl stannum, it is characterised in that: the structural formula of this methyl tin compound is:
R is the straight or branched alkyl of C4-C14, and described methyl tin compound is by as follows
Method is prepared:
(1) with dimethyltin chloride aqueous solution and mercaptan compound as raw material, with ammonia as catalyst, single mercaptan is synthesized
Methyl stannum,
(2) in the reaction system of step (1), add appropriate aliphatic carboxylic acid, with liquid caustic soda as catalyst, methyl stannum is synthesized
Compound,
Mixed anion methyl stannum the most according to claim 1, it is characterised in that: dimethyltin chloride in step (1)
The mass ratio of aqueous solution, mercaptan compound and ammonia is 100:(50～58): (7～20), wherein, dimethyltin chloride is water-soluble
In liquid, the mass fraction of chlorine is 17.2%, and the concentration of ammonia is 10-30wt%, by dimethyltin chloride aqueous solution and Thiolation
Compound mixes in proportion, and is heated to 45-55 DEG C, drips ammonia while stirring, drips complete follow-up continuous stirring reaction 50-
70min。
Mixed anion methyl stannum the most according to claim 1, it is characterised in that: dimethyltin chloride in step (2)
Aqueous solution and aliphatic carboxylic acid mass ratio are 100:(21.5～42.8), wherein, the matter of chlorine in dimethyltin chloride aqueous solution
Amount mark is 17.2%, and the concentration of liquid caustic soda is 5-12wt%, aliphatic carboxylic acid adds mixing in the reaction system of step (1) equal
Even, dropping liquid caustic soda is to aqueous phase pH >=6.0 while stirring, reacts 50-60min, then stand more than 1 hour after dropping, point
Layer, takes oil phase dehydration, filters.
4. the preparation method of the mixed anion methyl stannum described in a claim 1-3 any one, it is characterised in that: described
Method is carried out as follows:
(1) with dimethyltin chloride aqueous solution and mercaptan compound as raw material, with ammonia as catalyst, single mercaptan is synthesized
Methyl stannum,
(2) in the reaction system of step (1), add appropriate aliphatic carboxylic acid, with liquid caustic soda as catalyst, methyl stannum is synthesized
Compound,
5. the application of the mixed anion methyl stannum described in a claim 1-3 any one, it is characterised in that: as halogen second
Olefine resin heat stabilizer.
The application of mixed anion methyl stannum the most according to claim 5, it is characterised in that: described halo ethylene resin is poly-
Vinyl chloride, adds the mixed anion methyl tin compound of 0.8 part～1.0 parts in the polrvinyl chloride of every 100 mass parts.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034477A (en) * | 2018-01-04 | 2018-05-15 | 杭州聚星新材料科技有限公司 | A kind of bio-based, without sulphur, without phosphorus lubrication oil antiwear agent and combinations thereof and application |
| CN117645630A (en) * | 2024-01-26 | 2024-03-05 | 山东和隆新材料科技有限公司 | Compound with ultraviolet light absorption and PVC thermal stability and stabilizer for PVC |
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| CN102796282A (en) * | 2012-08-21 | 2012-11-28 | 衢州建华东旭助剂有限公司 | Aliphatic acid mercaptoethanol ester methyl tin heat stabilizer and preparation method thereof |
| CN104804034A (en) * | 2015-02-01 | 2015-07-29 | 云南锡业锡化学品有限公司 | Preparation method of butyltin tris(2-ethylhexanoate) catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1905898A1 (en) * | 1969-02-06 | 1970-08-20 | Baerlocher Chem | Organotin compounds, stabilizers of halo- - gelated polymers against heat and light effects |
| US3962296A (en) * | 1973-10-11 | 1976-06-08 | Sankyo Organic Chemicals Co., Ltd. | Process for the preparation of stabilizers for synthetic resins |
| JPS5120250A (en) * | 1974-08-12 | 1976-02-18 | Cincinnati Milacron Chem | JUKISUZUGAN JUANTEIZAI |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034477A (en) * | 2018-01-04 | 2018-05-15 | 杭州聚星新材料科技有限公司 | A kind of bio-based, without sulphur, without phosphorus lubrication oil antiwear agent and combinations thereof and application |
| CN108034477B (en) * | 2018-01-04 | 2020-12-22 | 杭州聚星新材料科技有限公司 | Bio-based sulfur-free and phosphorus-free lubricating oil antiwear agent, composition and application thereof |
| CN117645630A (en) * | 2024-01-26 | 2024-03-05 | 山东和隆新材料科技有限公司 | Compound with ultraviolet light absorption and PVC thermal stability and stabilizer for PVC |
| CN117645630B (en) * | 2024-01-26 | 2024-04-16 | 山东和隆新材料科技有限公司 | Compound with ultraviolet light absorption and PVC thermal stability and stabilizer for PVC |
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Application publication date: 20170104 |