CN107033183B - The preparation process and its product of Methyl stannum mercaptide, application - Google Patents

The preparation process and its product of Methyl stannum mercaptide, application Download PDF

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CN107033183B
CN107033183B CN201710318842.5A CN201710318842A CN107033183B CN 107033183 B CN107033183 B CN 107033183B CN 201710318842 A CN201710318842 A CN 201710318842A CN 107033183 B CN107033183 B CN 107033183B
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catalyst
aminoethyl
reaction
follows
weight ratio
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CN107033183A (en
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杨学强
俞永峰
张建根
张冲
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Qidong Qiangqiang Trade Co.,Ltd.
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NANTONG ADVANCE CHEMICALS CO Ltd
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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 Table
    • 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
    • C08K5/58—Organo-tin compounds containing sulfur

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of preparation method of organic tin substance more particularly to the preparation processes and its product of a kind of Methyl stannum mercaptide, application.The preparation process for specifically disclosing Methyl stannum mercaptide, at least includes the following steps: step 1: alkane halogenation；Step 2: displacement reaction；Step 3: esterification；Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；The metallic tin powder, monochloro methane, the molar ratio between isooctyl thioglycolate are as follows: 1:(1.2~1.5): 5.

Description

The preparation process and its product of Methyl stannum mercaptide, application
Technical field
The present invention relates to a kind of preparation method of organic tin substance more particularly to a kind of preparation processes of Methyl stannum mercaptide And its product, application.
Background technique
The method of production organotin mainly has Grignard, Wu Zifa, alkyl aluminum method and direct iodine method, grignard both at home and abroad at present Fado is used with American-European countries, and Wu Zifa has realized that industrialized production, alkyl aluminum method are also adopted in East Germany in the U.S. and East Germany With.Direct iodine method is widely applied in Japan.Grignard advantage is that product form can be controlled at any time, but step is more, and grignard Reaction is exothermic reaction, and solvent boiling point is very low, therefore necessary Cautious control temperature and reaction speed, to avoid explosion；Though iodine method Right step recycling few compared with grignard, but must being advised, two methods have in common that magnesium metal, iodine and raw metal tin Price is all more expensive, and wherein organic tin chloride toxicity is higher, therefore the method for not using iodide is sought in general industry production.
Methyl tin is since its carbochain is short, no tertiary carbon, quaternary carbon atom, is difficult to be alkylated reaction or item using the above method Part is extremely harsh, and not scale application in actual production.Current industrial method mainly uses chemical raw material 1 and metal Tin direct alkylation reaction under high temperature, high pressure, catalysts conditions generates methyl chloride tin.This method has process simple, straight The advantages of connecing, but there are reaction controlling difficulty is big, to the demanding disadvantage of reaction kettle.
In organic tin heat stabilizer, there are commonly tin octylate, butyl tin, ester group tin, methyl tin, although four kinds organic Tin has their own characteristics and advantage, but in contrast, and methyl tin has distinctive feature: when having inhibition PVC product outstanding processing Tinctorial property early period, brilliant UV resistant and long-time stability；With good mobility, color retentivity when processing It is good, product excellent transparency；Especially its photo and thermal stability is reached the international leading level, and can effectively realize that secondary operation recycles It uses；Since it does not have toxicity, dosage is few, and thermal stability is excellent, and compatibility is strong, and processing performance is good.In polyvinyl chloride resin only 1% or so amount is added, so that it may so that PVC product becomes colorless and transparent, sparkling and crystal-clear bright, therefore, make stabilizer using methyl tin PVC sheet be widely used in the packaging of food, drug and beverage.
Thiol methyl tin production technology is to add catalyst one-step synthesis production technology.Experimental studies have found that using S class chemical combination Object makees catalyst and has the following problems: the first, catalytic effect is not high, and a batch reaction more than hour will could be completed substantially at 8； The second, service life is too short, fails too fast, general with one month or so, catalyst failure, it is necessary to remove bottom material, cause tin A large amount of losses of material.Meanwhile methyl tin (SM501) mainly contains the 20% trisulfides second of monomethyl tin in the domestic market The different monooctyl ester of acid and 80% stannous methide curing 2-ethyl hexyl ethanoate, need to adjust tri-thiol 2-ethyl hexyl ethanoate according to different situations The content of methyl tin and dimercapto 2-ethyl hexyl ethanoate stannous methide.For above situation, it is necessary to the more applicable catalyst of selection, It could preferably solve the above problems.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides the preparation process of Methyl stannum mercaptide, until Less the following steps are included:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 150~180 DEG C, carry out 5~10h of alkane halogenation, obtain dimethyltin chloride；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220~230 DEG C, be forced into 0.5MPa carries out displacement reaction, obtains displacement reaction solution, then distills displacement reaction solution, obtains monomethyl tri-chlorination Tin and dimethyltin chloride aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 20~30 DEG C at be stirred to react 5~20min, so After add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica, be stirred to react 20 at 30~50 DEG C ~60min, and the pH value for adjusting reaction is 7, then at 40 DEG C, is stirred to react 4~5h, static, cooling, layering；It isolates Organic layer, and carry out washing 1~3 time；Second catalyst is tetrabutylammonium bromide, bi-tristearin, dimethyl Asia The mixture of sulfone；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, the molar ratio between isooctyl thioglycolate are as follows: 1:(1.2~1.5): 5.
As a preferred technical solution of the present invention, first catalyst is hexadecyltrimethylammonium chloride and shell The weight ratio of glycan compound, hexadecyltrimethylammonium chloride and chitosan is 10:1.
As a preferred technical solution of the present invention, the weight ratio of the metallic tin powder and the first catalyst are as follows: 100: (0.1~5).
As a preferred technical solution of the present invention, in second catalyst, tetrabutylammonium bromide, double stearic acid are sweet Grease, dimethyl sulfoxide mixture between weight ratio are as follows: 1:(1~5): (10~15).
As a preferred technical solution of the present invention, the isooctyl thioglycolate and N- (2- aminoethyl) -3- ammonia third Weight ratio between base trimethoxy silane improved silica is 100:(1~8).
As a preferred technical solution of the present invention, N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane changes Property silica in, weight ratio of the N- (2- aminoethyl) between -3- aminopropyl trimethoxysilane and silica be (1~ 10): 3.
As a preferred technical solution of the present invention, N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane changes Weight ratio between property silica and the second catalyst are as follows: 1:(0.1~1).
The second aspect of the invention provides Methyl stannum mercaptide, is obtained using above-mentioned preparation method.
The third aspect of the invention provides environment-friendly type PVC, and the environment-friendly type PVC includes at least in parts by weight,
100 parts of polyvinyl chloride resin；
0.1~0.5 part of Methyl stannum mercaptide；
0.1~0.5 part of auxiliary agent；
The fourth aspect of the invention provides application of the Methyl stannum mercaptide in rubber, plastics, catalyst field.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily to understand Open content.A large amount of terms can be referred in following description and claims, these terms are defined as following meanings.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device." optional " or " optionally " refer to and describe thereafter Item or event may or may not occur, and the description includes the situation and the situation that does not occur of event that event occurs.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1~2 ", " 1~2 and 4~ 5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end Value and all integers and score in the range.
In order to solve the above-mentioned technical problem, the first aspect of the invention provides the preparation process of Methyl stannum mercaptide, until Less the following steps are included:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 150~180 DEG C, carry out 5~10h of alkane halogenation, obtain dimethyltin chloride；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220~230 DEG C, be forced into 0.5MPa carries out displacement reaction, obtains displacement reaction solution, then distills displacement reaction solution, obtains monomethyl tri-chlorination Tin and dimethyltin chloride aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 20~30 DEG C at be stirred to react 5~20min, so After add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica, be stirred to react 20 at 30~50 DEG C ~60min, and the pH value for adjusting reaction is 7, then at 40 DEG C, is stirred to react 4~5h, static, cooling, layering；It isolates Organic layer, and carry out washing 1~3 time；Second catalyst is tetrabutylammonium bromide, bi-tristearin, dimethyl Asia The mixture of sulfone；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, the molar ratio between isooctyl thioglycolate are as follows: 1:(1.2~1.5): 5.
Step 1
Step 1 of the invention is to carry out alkane halogenation, detailed process are as follows:
Metallic tin powder, the first catalyst are added in reaction kettle, monochloro methane is then passed through into reaction kettle, is increased anti- It answers temperature to 150~180 DEG C, carries out 5~10h of alkane halogenation, obtain dimethyltin chloride；
In the application, the metallic tin powder can be different shape, can be tin flower, or glass putty；Preferably tin Powder.
In the application, first catalyst is hexadecyltrimethylammonium chloride and chitosan complexes；
Term " hexadecyltrimethylammonium chloride and chitosan complexes " refers to grafting cetyl front three on chitosan Ammonium chloride, obtained compound.
In a preferred embodiment, the preparation side of the hexadecyltrimethylammonium chloride and chitosan complexes Method the following steps are included:
100g water, 1g chitosan are added in a kettle and adds 10g cetyl front three at room temperature after mixing evenly Ammonium chloride, control reaction temperature be 20~45 DEG C, then add the sodium hydroxide of 0.1g, at 30~60 DEG C react 5~ After 12 hours, after being neutralized and wash repeatedly with ethyl alcohol with hydrobromic acid, suction filtration and dry hexadecyltrimethylammonium chloride and shell Glycan compound.
In first catalyst, the weight ratio of hexadecyltrimethylammonium chloride and chitosan is 10:1.
The chitosan refers to that deacetylation is 80% chitosan.
In a preferred embodiment, the weight ratio of the metallic tin powder and the first catalyst are as follows: 100:0.1.
The specific chemical reaction occurred in step 1 are as follows:
Inventors have found that the conversion ratio of metallic tin powder can be improved in the first catalyst of the application, to improve metallic tin powder Utilization rate, meanwhile, the present inventor is found surprisingly that, by adjusting the adjustable monomethyl trichlorine of usage amount of the first catalyst Change the weight ratio of tin and dimethyltin chloride, with the increase of the usage amount of the first catalyst, dimethyltin chloride contains Amount increases, and then can control the trisulfides 2-ethyl hexyl ethanoate of monomethyl tin and diformazan of product by the usage amount of the first catalyst Base tin curing 2-ethyl hexyl ethanoate ratio.Meanwhile side reaction can also be inhibited using the first catalyst: Sn+SnCl4→2SnCl2 Generation.
Step 2
Step 2 of the invention is to carry out displacement reaction, detailed process are as follows:
To tin tetrachloride is added in step 1, reaction temperature is increased to 220~230 DEG C, 0.5MPa is forced into, is replaced Reaction obtains displacement reaction solution, then distills displacement reaction solution, obtains monomethyl tin trichloride and dimethyl dichloride Tin aqueous solution；
The specific chemical reaction occurred in step 2 are as follows:
(CH3)2SnCl2+SnCl4→2CH3SnCl3。
In the step 2 of the application, side reaction will not substantially occur, Sn+SnCl will not especially occur4→2SnCl2, greatly The utilization rate of raw material is improved greatly.
Step 3
Step 3 of the invention is to carry out esterification, detailed process are as follows:
Monomethyl tin trichloride obtained in step 2 and the addition of dimethyltin chloride aqueous solution are sequentially added second and urged Agent, isooctyl thioglycolate are stirred to react 5~20min at being 20~30 DEG C in reaction temperature, then add N- (2- ammonia Ethyl) -3- aminopropyl trimethoxysilane improved silica, 20~60min is stirred to react at 30~50 DEG C, and adjust anti- The pH value answered is 7, then at 40 DEG C, is stirred to react 4~5h, static, cooling, layering；Organic layer is isolated, and is washed 1~3 time；Second catalyst be tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture；
Term " N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica " refers to N- (2- aminoethyl) - 3- aminopropyl trimethoxysilane is to silica surface graft modification.In the application, N- (2- aminoethyl) -3- aminopropyl is added In the esterification reaction, first aspect can interact trimethoxy silane improved silica with the second catalyst, improve The service life of second catalyst increases the number that repetitive cycling uses, plays the role of co-catalysis；The second aspect can mention The catalytic efficiency of high second catalyst, improves the conversion ratio of monomethyl tin trichloride and dimethyltin chloride, while can inhale The hydrogen chloride generated in reaction system is received, reaction forward is promoted to carry out.
In a preferred embodiment, the modified dioxy of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane The preparation process of SiClx the following steps are included:
In the reactor, solvent 100ml toluene is added and then N- is added in 1g nano silica, ultrasonic disperse 10min (2- aminoethyl) -3- aminopropyl trimethoxysilane is added the triethylamine solution that volumetric concentration is 10%, flows back at 100 DEG C 2h is reacted, filtering ethanol washing 3 times, is dried to obtain the modified titanium dioxide of N- (2- aminoethyl) -3- aminopropyl trimethoxysilane Silicon.
In a preferred embodiment, the isooctyl thioglycolate and N- (2- aminoethyl) -3- aminopropyl front three Weight ratio between oxysilane improved silica is 100:(1~8).
In a preferred embodiment, the modified dioxy of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane In SiClx, the weight ratio between amino silicane coupling agent and silica is (1~10): 3.
In a preferred embodiment, in second catalyst, tetrabutylammonium bromide, bi-tristearin, Weight ratio between the mixture of dimethyl sulfoxide are as follows: 1:(1~5): (10~15)；Preferably, in second catalyst, four Butylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between weight ratio are as follows: 1:(2~4): (12~14)； Most preferably, in second catalyst, tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between Weight ratio are as follows: 1:3:13.
In a preferred embodiment, the modified dioxy of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane Weight ratio between SiClx and the second catalyst are as follows: 1:(0.1~1).
The specific chemical reaction occurred in step 3 are as follows:
(CH3)2SnCl2+2HSCH2COOC8H17→(CH3)2Sn(SCH2COOC8H17)2+2HCl；
2CH3SnCl3+3HSCH2COOC8H17→CH3Sn(SCH2COOC8H17)3+3HCl。
Finally Methyl stannum mercaptide is obtained through the distillation in step 4, drying process；
The metallic tin powder, monochloro methane, the molar ratio between isooctyl thioglycolate are as follows: 1:(1.2~1.5): 5.
The second aspect of the invention provides Methyl stannum mercaptide, is obtained using above-mentioned preparation method.
The third aspect of the invention provides environment-friendly type PVC, and the environment-friendly type PVC includes at least in parts by weight,
100 parts of polyvinyl chloride resin；
0.1~0.5 part of Methyl stannum mercaptide；
0.1~0.5 part of auxiliary agent；
In the application, what the Methyl stannum mercaptide was synthesized using above-mentioned preparation method.
In the application, what the auxiliary agent can be enumerated has: antioxidant, plasticizer, fire retardant, filler, ultraviolet radiation absorption Agent, pigment, enters delustering agent, weather resisting agent, antistatic agent, anti-coloring agent etc. at antibacterial agent.
What the antioxidant can be enumerated has: phenolic antioxidant, phosphite ester antioxidant, containing in sulphur ester antioxidant It is at least one.
Phenolic antioxidant can be enumerated: 1- hydroxy-3-methyl -4- cumene, 2,6- DI-tert-butylphenol compounds, 2,6-, bis- uncle Butyl -4- ethyl -phenol, 2,6-di-tert-butyl p-cresol, 2,6- di-t-butyl -4- normal-butyl phenol, 4- methylol -2,6- bis- Tert-butyl phenol, butylhydroxy anisole, 2- (1- methylcyclohexyl) -4,6- xylenol, the tertiary fourth of 2,4- dimethyl -6- Base phenol, 2- methyl -4,6- dinonyl phenol, 2,6- di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4,6- tri-butyl benzenes Phenol, 6- (4- hydroxyl -3,5- di-tert-butyl amido) bis- (octylsulfo) -1,3,5-triazines of -2,4-, 4,6- it is bis- (hydroxyl -3 4-, 5- di-t-butyl phenoxy group) -2- n-octylthio -1,3,5-triazines, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid first Ester, β-(4-hydroxyls-3,5-di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester, styrenated phenol, 4,4 '-dihydroxy connection Benzene, butylated octylated phenol, butylated stytrene cresols, 2,2 '-methylene bis (4- methyl-6-tert-butylphenol) or 2, 2 '-methylene bis (6- tert-butyl -4- cresols), 2,2 '-methylene bis (4- ethyl -6- tert-butyl phenol), 2,2 '-methylene bis (4- first Base -6- cyclohexylphenol), 4,4 '-methylene bis (2,6- DI-tert-butylphenol compounds), (6- α-methylbenzyl is to first for 2,2 '-methylene bis Phenol), 1,1- bis- (4- hydroxy benzenes) hexamethylenes, 2,2 '-methylene bis (4- methyl -6- (Alpha-Methyl cyclohexyl) phenol) or 2,2 '-two Hydroxyl -3,3 '-two (Alpha-Methyl cyclohexyl) -5,5 '-dimethyl diphenylmethanes, 1,3,5- trimethyls -2,4,6- tri- (3,5- bis- Tertiary butyl-4-hydroxy benzyl) benzene, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, four (3- (3 ' 5 '-two uncles Butyl -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, 4,4 '-thiobis (6- tert-butyl -3- methylphenol) or 4,4 '-is thio Bis- (6- tert-butyl-m-cresols), 4,4 '-thiobis (2- methyl-6-tert-butylphenol) or 4,4 '-thiobis (6- tert-butyl o first Phenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenol), bis- (β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid of hexylene glycol Ester), 2,2 '-thiobis (3 ,-(3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate), N, bis- (3,5- bis- uncles of N '-hexamethylene Butyl-4- hydroxyl hydrocinnamamide), 1,3,5- tri- (4- tert-butyl-3- hydroxyl-2,6- dimethyl benzyl) 1,3,5-triazines-2,4, 6- (1H, 3H, 5H)-triketone, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) guanamines, 4,6- (1H, 3H, 5H) three Ketone or isocyanuric acid three (3,5- di-tert-butyl-4-hydroxyl benzyl ester), [β-(3, the 5- di-t-butyl -4- hydroxy benzenes of isocyanuric acid three Base) propionyloxy ethyl ester], bis- [3,3- bis- (3 '--4 '-hydroxy phenyl of tert-butyl) butyric acid] glycol esters, 1,1 '-thiobis (2- Naphthols), bis- (3,5- di-tert-butyl-4-hydroxyl benzyl) thioethers, 2,5- di-tert-butyl hydroquinone, 2,5-, bis- tertiary pentyl is to benzene two Phenol, 3,5- di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate (18) ester, 3,5- di-tert-butyl-4-hydroxyl benzyl diethyl phosphate, three One of glycol double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester, hydroquinone dibenzyl ethers.
Phosphite ester antioxidant can be enumerated: triphenyl phosphite, phosphorous acid three (nonyl phenyl ester), phosphorous acid three are different pungent Ester, triisodecyl phosphite ester, phosphorous acid benzene diisodecyl ester, trilauryl trithiophosphite, trilauryl phosphite, phosphorous acid Three (octadecyl esters), diphosphorous acid pentaerythrite diisodecyl ester, diphosphorous acid pentaerythrite distearyl alcohol ester, 4,4 '-fourths fork are bis- (sub- Phosphoric acid (3- methyl-6-tert butyl phenyl) two (tridecyl) esters), isooctyl diphenyl phosphite, phosphorous acid benzene di-isooctyl, Asia Diphenyl octyl phosphate, diphenyl isophthalate, dioctyl phosphite, phosphorous acid dilauryl, dimethylphosphite, phosphorous acid Double 13 esters of two oleyl alcohol esters, didecyl phosphite, dibutyl phosphite, phosphorous acid, phosphorous acid double 14 esters, phosphorous triethylenetetraminehexaacetic acid Ester, tributyl phosphite, triisopropyl phosphite, three monooctyl ester of phosphorous acid or phosphorous acid three (2- ethylhexyl), phosphorous acid-benzene are double One of (nonyl benzene) ester, phosphorous acid hexichol nonyl phenyl ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
It can be enumerated containing sulphur ester antioxidant: dilauryl thiodipropionate, thio-2 acid 2 stearyl ester or thio Dipropionic acid two (octadecyl ester), β, thio two butyric acid two (18) ester of β '-, thio-2 acid laurel octadecyl ester, thio-2 acid two (13) ester, thio-2 acid two (14) ester are medium.
The plasticizer can be enumerated: dioctyl phthalate, diisooctyl phthalate, terephthalic acid (TPA) two are pungent One of ester, trioctyl trimellitate (TOTM) or dioctyl sebacate are a variety of.And then preferred cold resistant plasticizer DOS (decanedioic acid Dioctyl ester) or DOP (dioctyl phthalate) etc..
The fire retardant can be enumerated: brominated organic based flame retardant, phosphoric acid based flame retardant, antimony trioxide, magnesium hydroxide, red Phosphorus etc..
The filler can be enumerated: silica, aluminium oxide, kaolinite, wollastonite, mica, talcum, clay, sericite, Magnesium carbonate, magnesium sulfate, calcium oxide, silicon carbide, antimony trisulphide, artificial gold, copper sulfide, iron sulfide, bismuth sulfide, zinc sulphide, metal Powder, glass powder, glass flake, montmorillonite, glass microballoon etc..
What the ultraviolet absorbing agent can be enumerated has: 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2- (2- hydroxyl- 5- butyl phenyl) benzotriazole, 2- (2- hydroxyl -5- octyl phenyl) benzotriazole, 2- (3- tert-butyl -2- hydroxy-5-methyl base benzene Base) the enumerate BTA systems ultraviolet absorbing agent such as -5- chlorobenzotriazole, 2- (3,5- bis- tertiary pentyl -2- hydroxy phenyl) benzotriazole； The benzophenone series ultraviolet absorbing agents such as ESCALOL 567,2- hydroxyl -4- n-octyl oxygroup benzophenone； 2- [4,6- bis- (2,4- 3,5-dimethylphenyl) -1,3,5-triazines -2- bases] -5- (octyl oxygroup) phenol, 2- (4,6- diphenyl -1, 3,5- triazine -2- bases) the triazines system ultraviolet absorbing agent such as -5- (hexyl oxygroup) phenol；P-t-butylphenyl salicylate, salicylic acid The salicylates such as phenyl ester system ultraviolet absorbing agent etc..
What the antibacterial agent can be enumerated has: silver ion class antibacterial agent, zinc oxide, copper oxide, ammonium dihydrogen phosphate, carbonic acid Lithium, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols formic acid, sorbic acid, has anilid class Machine iodine, nitrile, sulphur cyanogen, copper agent, three halogenation allyl compounds, organic nitrogen sulfur compound, chitin, mustard, castor oil, horseradish Deng.
In a preferred embodiment, the preparation method of the environment-friendly type PVC, comprising the following steps:
By the polyvinyl chloride resin, Methyl stannum mercaptide, auxiliary agent of corresponding parts by weight, in 140~190 DEG C of progress melting mixings, through screw rod Extruder extrusion molding.
In the application, Methyl stannum mercaptide thermostabilization principle is divided into lower two steps, and first step reaction: the tin of organic tin stabilizer is former With polyvinyl chloride molecule unstable chlorine atom ligand complex, while the sulphur atom in organotin and carbon corresponding in PVC occur for son Atom complexing；Second step reaction: the sulphur atom of organotin is replaced with unstable chlorine atom in ligand, when there is HC1 to deposit When, coordinate bond divides, and sulfydryl is securely joined with carbon atom in PVC molecule, thus inhibit further take off HCl formed The reaction of double bond.
The fourth aspect of the invention provides application of the Methyl stannum mercaptide in rubber, plastics, catalyst field.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available,
Embodiment 1:
The present embodiment 1 provides a kind of Methyl stannum mercaptide, the preparation process of the Methyl stannum mercaptide, comprising the following steps:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 150 DEG C, carry out alkane halogenation 8h, obtain dimethyltin chloride；Described first urges Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220 DEG C, be forced into 0.5MPa after carrying out displacement reaction 3 hours, obtains displacement reaction solution, then distills displacement reaction solution, obtain monomethyl Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 30 DEG C at be stirred to react 5min, then add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica is stirred to react 20min at 30 DEG C, and adjusts anti- The pH value answered is 7, then at 40 DEG C, is stirred to react 1h, static, cooling, layering；Organic layer is isolated, and carries out washing 3 It is secondary；
Second catalyst is the mixture of chitosan, bi-tristearin, dimethyl sulfoxide；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, tin tetrachloride, the molar ratio between isooctyl thioglycolate are as follows: 1:1.2:2: 5。
The weight ratio of the metallic tin powder and the first catalyst are as follows: 100:0.1；
The preparation process of first catalyst is as follows:
100g water, 1g chitosan are added in a kettle and adds 10g cetyl front three at room temperature after mixing evenly Ammonium chloride, control reaction temperature are 45 DEG C, then add the sodium hydroxide of 0.1g, after reacting 5 hours at 30 DEG C, use hydrogen After bromic acid neutralizes and uses ethanol washing 3 times, filter and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between Weight ratio are as follows: 1:1:10.
Second catalyst the preparation method is as follows: at 50 DEG C, tetrabutylammonium bromide is dissolved in dimethyl sulfoxide, After mixing evenly, bi-tristearin is added in dimethyl sulfoxide, is uniformly mixing to obtain the second catalyst.
The preparation process of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica is as follows: being added Then 1g N- aminoethyl -3- aminopropyltriethoxy is added in solvent 100ml toluene and 3g nano silica, ultrasonic disperse 10min 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second is added in dimethoxysilane Alcohol washs 3 times, is dried to obtain N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica.The silica It is purchased from extra large moral foundation (Beijing) Biotechnology Co., Ltd；
In N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica, N- (2- aminoethyl) -3- ammonia Weight ratio between propyl trimethoxy silicane and silica is 1:3.
Weight of the N- (2- aminoethyl) between -3- aminopropyl trimethoxysilane improved silica and the second catalyst Measure ratio are as follows: 1:0.1.
Between the isooctyl thioglycolate and N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica Weight ratio be 100:1.
Embodiment 2:
The present embodiment 2 provides a kind of Methyl stannum mercaptide, the preparation process of the Methyl stannum mercaptide, comprising the following steps:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 150 DEG C, carry out alkane halogenation 8h, obtain dimethyltin chloride；Described first urges Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220 DEG C, be forced into 0.5MPa after carrying out displacement reaction 3 hours, obtains displacement reaction solution, then distills displacement reaction solution, obtain monomethyl Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 30 DEG C at be stirred to react 5min, then add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica is stirred to react 20min at 30 DEG C, and adjusts anti- The pH value answered is 7, then at 40 DEG C, is stirred to react 1h, static, cooling, layering；Organic layer is isolated, and carries out washing 3 It is secondary；
Second catalyst is the mixture of chitosan, bi-tristearin, dimethyl sulfoxide；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, tin tetrachloride, the molar ratio between isooctyl thioglycolate are as follows: 1:1.2:2: 5。
The weight ratio of the metallic tin powder and the first catalyst are as follows: 100:0.3；
The preparation process of first catalyst is as follows:
100g water, 1g chitosan are added in a kettle and adds 10g cetyl front three at room temperature after mixing evenly Ammonium chloride, control reaction temperature are 45 DEG C, then add the sodium hydroxide of 0.1g, after reacting 5 hours at 30 DEG C, use hydrogen After bromic acid neutralizes and uses ethanol washing 3 times, filter and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between Weight ratio are as follows: 1:1:10.
Second catalyst the preparation method is as follows: at 50 DEG C, tetrabutylammonium bromide is dissolved in dimethyl sulfoxide, After mixing evenly, bi-tristearin is added in dimethyl sulfoxide, is uniformly mixing to obtain the second catalyst.
The preparation process of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica is as follows: being added Then 1g N- aminoethyl -3- aminopropyltriethoxy is added in solvent 100ml toluene and 3g nano silica, ultrasonic disperse 10min 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second is added in dimethoxysilane Alcohol washs 3 times, is dried to obtain N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica.The silica It is purchased from extra large moral foundation (Beijing) Biotechnology Co., Ltd；
In N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica, N- (2- aminoethyl) -3- ammonia Weight ratio between propyl trimethoxy silicane and silica is 1:3.
Weight of the N- (2- aminoethyl) between -3- aminopropyl trimethoxysilane improved silica and the second catalyst Measure ratio are as follows: 1:0.1.
Between the isooctyl thioglycolate and N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica Weight ratio be 100:1.
Embodiment 3:
The present embodiment 3 provides a kind of Methyl stannum mercaptide, the preparation process of the Methyl stannum mercaptide, comprising the following steps:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 180 DEG C, carry out alkane halogenation 6h, obtain dimethyltin chloride；Described first urges Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220 DEG C, be forced into 0.5MPa after carrying out displacement reaction 3 hours, obtains displacement reaction solution, then distills displacement reaction solution, obtain monomethyl Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 30 DEG C at be stirred to react 5min, then add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica is stirred to react 20min at 30 DEG C, and adjusts anti- The pH value answered is 7, then at 40 DEG C, is stirred to react 1h, static, cooling, layering；Organic layer is isolated, and carries out washing 3 It is secondary；
Second catalyst is the mixture of chitosan, bi-tristearin, dimethyl sulfoxide；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, tin tetrachloride, the molar ratio between isooctyl thioglycolate are as follows: 1:1.2:2: 5。
The weight ratio of the metallic tin powder and the first catalyst are as follows: 100:0.5；
The preparation process of first catalyst is as follows:
100g water, 1g chitosan are added in a kettle and adds 10g cetyl front three at room temperature after mixing evenly Ammonium chloride, control reaction temperature are 45 DEG C, then add the sodium hydroxide of 0.1g, after reacting 5 hours at 30 DEG C, use hydrogen After bromic acid neutralizes and uses ethanol washing 3 times, filter and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between Weight ratio are as follows: 1:1:10.
Second catalyst the preparation method is as follows: at 50 DEG C, tetrabutylammonium bromide is dissolved in dimethyl sulfoxide, After mixing evenly, bi-tristearin is added in dimethyl sulfoxide, is uniformly mixing to obtain the second catalyst.
The preparation process of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica is as follows: being added Then 1g N- aminoethyl -3- aminopropyltriethoxy is added in solvent 100ml toluene and 3g nano silica, ultrasonic disperse 10min 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second is added in dimethoxysilane Alcohol washs 3 times, is dried to obtain N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica.The silica It is purchased from extra large moral foundation (Beijing) Biotechnology Co., Ltd；
In N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica, N- (2- aminoethyl) -3- ammonia Weight ratio between propyl trimethoxy silicane and silica is 1:3.
Weight of the N- (2- aminoethyl) between -3- aminopropyl trimethoxysilane improved silica and the second catalyst Measure ratio are as follows: 1:0.1.
Between the isooctyl thioglycolate and N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica Weight ratio be 100:1.
Embodiment 4:
The present embodiment 4 provides a kind of Methyl stannum mercaptide, the preparation process of the Methyl stannum mercaptide, comprising the following steps:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 180 DEG C, carry out alkane halogenation 6h, obtain dimethyltin chloride；Described first urges Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220 DEG C, be forced into 0.5MPa after carrying out displacement reaction 3 hours, obtains displacement reaction solution, then distills displacement reaction solution, obtain monomethyl Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 30 DEG C at be stirred to react 5min, then add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica is stirred to react 20min at 30 DEG C, and adjusts anti- The pH value answered is 7, then at 40 DEG C, is stirred to react 1h, static, cooling, layering；Organic layer is isolated, and carries out washing 3 It is secondary；
Second catalyst is the mixture of chitosan, bi-tristearin, dimethyl sulfoxide；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, tin tetrachloride, the molar ratio between isooctyl thioglycolate are as follows: 1:1.2:2: 5。
The weight ratio of the metallic tin powder and the first catalyst are as follows: 100:0.7；
The preparation process of first catalyst is as follows:
100g water, 1g chitosan are added in a kettle and adds 10g cetyl front three at room temperature after mixing evenly Ammonium chloride, control reaction temperature are 45 DEG C, then add the sodium hydroxide of 0.1g, after reacting 5 hours at 30 DEG C, use hydrogen After bromic acid neutralizes and uses ethanol washing 3 times, filter and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between Weight ratio are as follows: 1:1:10.
Second catalyst the preparation method is as follows: at 50 DEG C, tetrabutylammonium bromide is dissolved in dimethyl sulfoxide, After mixing evenly, bi-tristearin is added in dimethyl sulfoxide, is uniformly mixing to obtain the second catalyst.
The preparation process of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica is as follows: being added Then 1g N- aminoethyl -3- aminopropyltriethoxy is added in solvent 100ml toluene and 3g nano silica, ultrasonic disperse 10min 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second is added in dimethoxysilane Alcohol washs 3 times, is dried to obtain N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica.The silica It is purchased from extra large moral foundation (Beijing) Biotechnology Co., Ltd；
In N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica, N- (2- aminoethyl) -3- ammonia Weight ratio between propyl trimethoxy silicane and silica is 1:3.
Weight of the N- (2- aminoethyl) between -3- aminopropyl trimethoxysilane improved silica and the second catalyst Measure ratio are as follows: 1:0.1.
Between the isooctyl thioglycolate and N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica Weight ratio be 100:1.
Embodiment 5:
The present embodiment 5 provides a kind of Methyl stannum mercaptide, the preparation process of the Methyl stannum mercaptide, comprising the following steps:
Step 1: alkane halogenation: metallic tin powder, the first catalyst are added in reaction kettle, are then led into reaction kettle Enter monochloro methane, increases reaction temperature to 180 DEG C, carry out alkane halogenation 6h, obtain dimethyltin chloride；Described first urges Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220 DEG C, be forced into 0.5MPa after carrying out displacement reaction 3 hours, obtains displacement reaction solution, then distills displacement reaction solution, obtain monomethyl Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3: esterification: monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution being added Enter to sequentially add the second catalyst, isooctyl thioglycolate, reaction temperature be 30 DEG C at be stirred to react 5min, then add N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica is stirred to react 20min at 30 DEG C, and adjusts anti- The pH value answered is 7, then at 40 DEG C, is stirred to react 1h, static, cooling, layering；Organic layer is isolated, and carries out washing 3 It is secondary；
Second catalyst is the mixture of chitosan, bi-tristearin, dimethyl sulfoxide；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, tin tetrachloride, the molar ratio between isooctyl thioglycolate are as follows: 1:1.2:2: 5。
The weight ratio of the metallic tin powder and the first catalyst are as follows: 100:1；
The preparation process of first catalyst is as follows:
100g water, 1g chitosan are added in a kettle and adds 10g cetyl front three at room temperature after mixing evenly Ammonium chloride, control reaction temperature are 45 DEG C, then add the sodium hydroxide of 0.1g, after reacting 5 hours at 30 DEG C, use hydrogen After bromic acid neutralizes and uses ethanol washing 3 times, filter and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide mixture between Weight ratio are as follows: 1:1:10.
Second catalyst the preparation method is as follows: at 50 DEG C, tetrabutylammonium bromide is dissolved in dimethyl sulfoxide, After mixing evenly, bi-tristearin is added in dimethyl sulfoxide, is uniformly mixing to obtain the second catalyst.
The preparation process of N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica is as follows: being added Then 1g N- aminoethyl -3- aminopropyltriethoxy is added in solvent 100ml toluene and 3g nano silica, ultrasonic disperse 10min 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second is added in dimethoxysilane Alcohol washs 3 times, is dried to obtain N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica.The silica It is purchased from extra large moral foundation (Beijing) Biotechnology Co., Ltd；
In N- (2- the aminoethyl) -3- aminopropyl trimethoxysilane improved silica, N- (2- aminoethyl) -3- ammonia Weight ratio between propyl trimethoxy silicane and silica is 1:3.
Weight of the N- (2- aminoethyl) between -3- aminopropyl trimethoxysilane improved silica and the second catalyst Measure ratio are as follows: 1:0.1.
Between the isooctyl thioglycolate and N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica Weight ratio be 100:1.
Comparative example 1:
1 detailed process of comparative example is with embodiment 5, the difference lies in that not including the first catalyst in step 1, other portions Divide with embodiment 5.
Comparative example 2:
2 detailed process of comparative example is with embodiment 5, the difference lies in that the first catalyst in step 1 is changed to cetyl Trimethyl ammonium chloride, other parts are the same as embodiment 5.
Comparative example 3:
3 detailed process of comparative example is with embodiment 5, the difference lies in that the first catalyst in step 1 is changed to chitosan, Other parts are the same as embodiment 5.
Comparative example 4:
4 detailed process of comparative example is with embodiment 5, the difference lies in that the first catalyst in step 1 is changed to dimethyl disulfide Ether, other parts are the same as embodiment 5.
Comparative example 5:
5 detailed process of comparative example is with embodiment 5, the difference lies in that will not include the second catalyst, other portions in step 2 Divide with embodiment 5.
Comparative example 6:
6 detailed process of comparative example is with embodiment 5, the difference lies in that will not include N- (2- aminoethyl) -3- ammonia in step 2 Propyl trimethoxy silicane improved silica, other parts are the same as embodiment 5.
Comparative example 7:
7 detailed process of comparative example with embodiment 5, the difference lies in that by step 2 by N- (2- aminoethyl) -3- aminopropyl Trimethoxy silane improved silica is changed to N- (2- aminoethyl) -3- aminopropyl trimethoxysilane, and other parts are the same as real Apply example 5.
Comparative example 8:
8 detailed process of comparative example is with embodiment 5, the difference lies in that will not include N- (2- aminoethyl) -3- ammonia in step 2 Propyl trimethoxy silicane improved silica is changed to silane coupling agent kh560 improved silica, and other parts are the same as implementation Example 5.
Test method:
1, using obtaining monomethyl tin trichloride and dimethyltin chloride aqueous solution in liquid chromatography for measuring step 2 In, the content of monomethyl tin trichloride and dimethyltin chloride, wherein the condition of liquid chromatogram are as follows: chromatographic column: C18, flowing It is mutually methanol, flow velocity 1mL/min, 35 DEG C of column temperature, wavelength 300nm, sampling volume is 10 microlitres；The model of liquid chromatogram Agilent 1100；
The standard sample for preparing monomethyl tin trichloride and dimethyltin chloride respectively, makes standard curve, measures guarantor Staying the time is 2.689min and 3.581min；
The product that 1~embodiment of embodiment 5 and 1~comparative example of comparative example 8 obtain is measured into monomethyl tri-chlorination respectively The content of tin and dimethyltin chloride.
2, according to the presence of the detection stannous chloride of analysis method specified in HG/T 2526-93.
3, the second catalyst repetitive cycling service life number is tested, when the conversion ratio of reactant is lower than 80%, catalysis Agent end of life records the access times of the second catalyst.
1 characterization test of table
From table 1 it follows that from embodiment 1 into embodiment 5, with the increase of the first catalyst usage amount, step 2 In obtain the weight percent of dimethyltin chloride and increase, can basis when it is added in PVC plastic as heat stabilizer Actual conditions adjust the content of different component in Methyl stannum mercaptide.In addition, it has also been found that, N- (2- ammonia second is added by experiment Base) -3- aminopropyl trimethoxysilane improved silica can greatly improve the service life of the second catalyst.
Embodiment 6
Embodiments herein 6 provides a kind of environment-friendly type PVC resin, the environment-friendly type PVC, in parts by weight, at least Including,
100 parts of polyvinyl chloride resin；
0.1 part of Methyl stannum mercaptide described in embodiment 5；
2,6- 0.5 part of DI-tert-butylphenol compounds.
The environment-friendly type PVC resin the preparation method comprises the following steps: by polyvinyl chloride resin, Methyl stannum mercaptide, 2, the 6- bis- under molten condition Tert-butyl phenol is added in screw extruder, extrusion molding.
After polyvinyl chloride resin is placed in outdoor application 1 year, observation appearance does not occur by the transformation of white to yellow, brown, And hydrogen chloride is not detected.Illustrate that the present invention has good thermostable effect.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment Combined selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention Feature exemplary selectional restriction.And the progress in science and technology will be formed language express it is inaccurate due to and not The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended Claim covering.

Claims (6)

1. a kind of preparation process of Methyl stannum mercaptide, which is characterized in that at least include the following steps:
Step 1: alkane halogenation: metallic tin powder, the first catalyst being added in reaction kettle, one is then passed through into reaction kettle Chloromethanes increases reaction temperature to 150~180 DEG C, carries out 5~10h of alkane halogenation, obtain dimethyltin chloride；
Step 2: displacement reaction: to tin tetrachloride is added in step 1, increasing reaction temperature to 220~230 DEG C, be forced into 0.5MPa carries out displacement reaction, obtains displacement reaction solution, then distills displacement reaction solution, obtains monomethyl tri-chlorination Tin and dimethyltin chloride aqueous solution；
Step 3: esterification: successively into monomethyl tin trichloride obtained in step 2 and dimethyltin chloride aqueous solution Be added the second catalyst, isooctyl thioglycolate, reaction temperature be 20~30 DEG C at be stirred to react 5~20min, then again plus Enter N- (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica, it is stirred to react 20 at 30~50 DEG C~ 60min, and the pH value for adjusting reaction is 7, then at 40 DEG C, is stirred to react 4~5h, static, cooling, layering；It has isolated Machine layer, and carry out washing 1~3 time；Second catalyst is tetrabutylammonium bromide, bi-tristearin, dimethyl sulfoxide Mixture；
Step 4: distillation: obtaining Methyl stannum mercaptide by vacuum distillation drying；
The metallic tin powder, monochloro methane, the molar ratio between isooctyl thioglycolate are as follows: 1:(1.2~1.5): 5；
First catalyst be hexadecyltrimethylammonium chloride and chitosan complexes, hexadecyltrimethylammonium chloride with The weight ratio of chitosan is 10:1.
2. the preparation process of Methyl stannum mercaptide as described in claim 1, which is characterized in that the metallic tin powder and the first catalysis The weight ratio of agent are as follows: 100:(0.1~5).
3. the preparation process of Methyl stannum mercaptide as described in claim 1, which is characterized in that in second catalyst, four fourths Base ammonium bromide, bi-tristearin, the weight ratio between dimethyl sulfoxide are as follows: 1:(1~5): (10~15).
4. the preparation process of Methyl stannum mercaptide as described in claim 1, which is characterized in that the isooctyl thioglycolate and N- Weight ratio between (2- aminoethyl) -3- aminopropyl trimethoxysilane improved silica is 100:(1~8).
5. the preparation process of Methyl stannum mercaptide as described in claim 1, which is characterized in that N- (2- the aminoethyl) -3- ammonia In propyl trimethoxy silicane improved silica, N- (2- aminoethyl) -3- aminopropyl trimethoxysilane and silica it Between weight ratio be (1~10): 3.
6. the preparation process of Methyl stannum mercaptide as described in claim 1, which is characterized in that N- (2- the aminoethyl) -3- ammonia Weight ratio between propyl trimethoxy silicane improved silica and the second catalyst are as follows: 1:(0.1~1).
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