CN106117263A - A kind of Methyl stannum mercaptide stabilizer of environmental protection - Google Patents
A kind of Methyl stannum mercaptide stabilizer of environmental protection Download PDFInfo
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- CN106117263A CN106117263A CN201610468818.5A CN201610468818A CN106117263A CN 106117263 A CN106117263 A CN 106117263A CN 201610468818 A CN201610468818 A CN 201610468818A CN 106117263 A CN106117263 A CN 106117263A
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- methyl
- weight
- catalyst
- environmental protection
- tin
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- -1 Methyl stannum Chemical compound 0.000 title claims abstract description 36
- 239000003381 stabilizer Substances 0.000 title claims abstract description 25
- 230000007613 environmental effect Effects 0.000 title claims abstract description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 230000026030 halogenation Effects 0.000 claims abstract description 7
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 38
- 239000000654 additive Substances 0.000 claims description 34
- 230000000996 additive effect Effects 0.000 claims description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 235000014121 butter Nutrition 0.000 claims description 8
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 208000035126 Facies Diseases 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 5
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 5
- 239000011807 nanoball Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000012163 sequencing technique Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- IRDJCBNSDNPDSA-ZOKJKDLISA-H (Z)-but-2-enedioate methyltin(3+) Chemical compound C[Sn+3].C[Sn+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O IRDJCBNSDNPDSA-ZOKJKDLISA-H 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of organic tin material, particularly relate to the Methyl stannum mercaptide stabilizer of a kind of environmental protection.It is prepared from by following steps: (1) stannum: put in reactor by metallic tin and catalyst, then pass to chloromethanes at a temperature of 150 170 DEG C, heat mix homogeneously, after carrying out halogenation 0.2 0.4h, add reallocation agent and be warmed up to 235 245 DEG C, be forced into 0.5 0.8MPa and carry out stannum and react 12 hours；(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst, alkane diacid and regulator, stirring reaction 0.2 0.4 hours at temperature 5 15 DEG C, add the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 79, then heat to 60 70 DEG C, react 34 hours, static, lower the temperature, be layered；Regulator includes the first composite regulator 69 parts and the second composite regulator 7 11 parts by mass parts；(3) washing；(4) distillation.Product of the present invention has color inhibition and resistance to volatilization precipitation property, and Heat stability is good, low tin content.
Description
Technical field
The present invention relates to the preparation method of a kind of organic tin material, the Methyl stannum mercaptide particularly relating to a kind of environmental protection is stable
Agent.
Background technology
Organic tin compound is used in polyvinyl chloride resin and makees stabilizer oneself has many patents, as United States Patent (USP) 3222317,
3396185 etc., mainly butyl tin and tin octylate, because propyl group stannum scent of, and ethyl stannum is poisonous and is replaced.
The main kind of organotin has three series such as monoalkyltin, double tin alkyl and trialkyltin, wherein three alkane
Base stannum series toxicity is the strongest, it is impossible to use as stabilizer;Monoalkyltin has monomethyl stannum, Monobutyltin, single tin octylate etc.;Double
Tin alkyl has stannous methide, dibutyl tin, dioctyl tin etc..At present, the own PVC packed in medicine food through given application of European Union
Material prohibits the use of butyl tin and tin octylate series, and methyl stannum series is still widely used in due to its distinctive character
In various high-grade PVC product.
Methyl stannum (SM501) on market is mainly containing 20% tri-thiol 2-ethyl hexyl ethanoate methyl stannum and 80% 2 at home
Isooctyl thioglycolate stannous methide, its Theil indices is 19. 4, in the actual course of processing, this methyl stannum on market
Can move to surface from the inside of goods, finally separate out from product surface, form speckle flower, have impact on the quality of goods, here it is
So-called ooze out (or weighing up antiperspirant);It addition, in the course of processing, the easy roll banding of batch, release property, lubricity are poor, are unfavorable for
The Continuous maching of product produces.
CN102503972B (2015-6-17) discloses a kind of Methyltin maleate and preparation method thereof, but how
Prepare and still have much room for improvement on the Methyl stannum mercaptide stabilizer of the environmental protection that Theil indices reduces, thermal stability is good.
Summary of the invention
The Methyl stannum mercaptide that it is an object of the invention to provide the environmental protection that a kind of Theil indices reduces, thermal stability is good is stable
Agent.
The above-mentioned technical purpose of the present invention has the technical scheme that the methyl mercaptan of a kind of environmental protection
Stannum stabilizer, it is prepared from by following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes 150-170 DEG C of temperature
Heat mix homogeneously under degree, after carrying out halogenation 0.2-0.4h, add reallocation agent and be warmed up to 235-245 DEG C, pressurization
Carry out stannumization to 0.5-0.8MPa to react after 1-2 hour, distill and accept gas temperature at 150-230 DEG C of interior fraction, then
Methyl tin chloride aqueous solution is obtained by absorbing pure water；Described methyl alkene chloride includes dimethyltin chloride and monomethyl three
Stannic chloride；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, alkane
Diacid and regulator, stirring reaction 0.2-0.4 hour at temperature 5-15 DEG C, add the continuously stirred reaction of alkali liquor until reacting
System pH reaches 7-9, then heats to 60-70 DEG C, reacts 3-4 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, regulator, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-
0.5): (0.1-0.3): (3-4)；
Described regulator includes first composite regulator 6-9 part and second composite regulator 7-11 part by mass parts；
Described first composite regulator is by tricaprylmethyl ammonium bromide, glycerol and poly-four of the proportioning of 1:3-4:1-2 in mass ratio
Fluorothene forms；
Described second composite regulator is by the diphenylamines of the proportioning of 1:2-4:1-3 in mass ratio, 2,6-di-t-butyl and benzo three nitrogen
Azoles forms；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain methyl tin mixture after vacuum distillation drying.
The methyl tin mixture finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and
Wherein, m is 2 and above integer, and n is 3 and above integer, and g is 1 or 2；
Mixture, wherein the quality accounting of stannous methide is 40-60%.
The present invention uses specific stannum, synthesis technique, especially controls distillation and accepts gas temperature at 150-230 DEG C
In fraction, be more beneficial for the carrying out of follow-up synthetic reaction, make steady as stabilizer for plastics of finally prepd methyl stannum material
Determine effect more preferable.There is after regulator proportioning of the present invention dispersion and the stability of excellence；Described second composite regulator
There is after proportioning antioxidation and bright and clean corrosion-resistant function；Two kinds of composite regulators are combined and can be reached Synergistic and make
With；Make methyl stannum material more preferable as the stablizing effect of stabilizer for plastics, increase color inhibition effect.
Product of the present invention has high transparent, weatherability, the compatibility and resistance to volatilization precipitation property, and avirulence, high heat stability
Property is good, and low tin content, the thermostable effect of the methyl stannum of this low tin content is better than existing methyl stannum, for final PVC
Goods to reach same stablizing effect, and the addition of Methyltin stabiliser will be less, just can reduce stannum consumption further,
Reduce the production cost of client terminals eventually.
As preferably, described first catalyst is that quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide are according to molal weight
Mixture than 1:2-3 composition.
Entering of the employing present invention specific first catalyst beneficially halogenation, stannumization reaction and follow-up synthetic reaction
OK, make finally prepd methyl stannum material more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide compares 1:1-according to molal weight
The mixture of 4 compositions.
Use the carrying out of the present invention specific second catalyst beneficially synthetic reaction, make finally prepd methyl stannum material
Stablizing effect as stabilizer for plastics is more preferable.
As preferably, described quaternary ammonium salt phase catalyst is that tetrabutyl ammonium bromide, tetrabutyl chlorination are by, tetrabutyl hydrogen sulfate
Ammonium or tri-n-octyl methyl ammonium chloride.
As preferably, described reallocation agent is butter of tin.
As preferably, the weight of described first catalyst accounts for the 1-3% of metallic tin weight.
As preferably, the weight of described second catalyst accounts for the 6-9% of isooctyl thioglycolate weight.
As preferably, in described step (2), the mass fraction of alkali liquor is 10-20%.
As preferably, in synthesis step, in the addition continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then, during heating up, add first solid additive of the 1-3% accounting for isooctyl thioglycolate weight according to sequencing and account for
Second solid additive of the 3-6% of isooctyl thioglycolate weight.
As preferably, the particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for institute
State the 20-40% of the first solid additive gross weight；The granule of 1-2 micron accounts for the 10-30% of described first solid additive gross weight；Remaining
Amount is the granule of 3-5 micron；
Described first solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight divides
Cloth index is 3.1:
I
Described second solid additive be the molybdenum disulfide nano ball of particle diameter 10-20 nanometer with the regulation grain of particle diameter 6-9 micron by
Mixture according to mass ratio 1:2-5 composition.
In first solid additive, Mw is weight average molecular weight, and Mn is number-average molecular weight.
Different-grain diameter and the first solid additive of kind and the second solid additive are increasing methyl stannum stability, reduction
While Theil indices, moreover it is possible to give methyl stannum more preferable resistance to volatilization precipitation property.
As preferably, described alkane two tart flavour malonic acid or succinic acid or 1,3-propanedicarboxylic acid.
Detailed description of the invention
Embodiment one
The Methyl stannum mercaptide stabilizer of environmental protection, it is prepared from by following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 150 DEG C
Heating mix homogeneously, after carrying out halogenation 0.2h, adds reallocation agent butter of tin and is warmed up to 235 DEG C, is forced into
0.5MPa carries out stannumization and reacts 1 hour, then, distills and accepts gas temperature at 150 DEG C of interior fractions, then using absorbing pure water
Obtain methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst be tetrabutyl ammonium bromide and
The mixture that dimethyl sulfide forms than 1:2 according to molal weight；The weight of the first catalyst accounts for the 1% of metallic tin weight.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst,
Regulator and 1,3-propanedicarboxylic acid, at temperature 5 DEG C, stirring reaction 0.2 hour, adds the alkali liquor that mass fraction is 10% continuously stirred instead
60 DEG C should be then heated to until pH value of reaction system reaches 7, react 3 hours, static, lower the temperature, be layered；1,3-propanedicarboxylic acid weight accounts for
The 8% of isooctyl thioglycolate weight；
The mixture that second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:1 according to molal weight；Second
The weight of catalyst accounts for the 6% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, regulator, the mol ratio of isooctyl thioglycolate are 1:1.5:0.2:
0.1:4；
Regulator includes the first composite regulator 6 parts and the second composite regulator 11 parts by mass parts；
First composite regulator is by tricaprylmethyl ammonium bromide, glycerol and the politef group of the proportioning of 1:3:2 in mass ratio
Become；
Second composite regulator is made up of the diphenylamines of the proportioning of 1:2:3 in mass ratio, 2,6-di-t-butyl and BTA；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain methyl stannum after vacuum distillation drying.
The methyl tin mixture finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) andMixture, wherein stannous methide
Quality accounting is 40-60%.
Embodiment two
The Methyl stannum mercaptide stabilizer of environmental protection, it is prepared from by following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 170 DEG C
Heating mix homogeneously, after carrying out halogenation 0.4h, adds reallocation agent butter of tin and is warmed up to 235-245 DEG C, pressurization
Carry out stannumization to 0.5-0.8MPa to react 2 hours, then, distill and accept gas temperature at 230 DEG C of interior fractions, then with pure
Water absorbs and obtains methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst be tetrabutylammonium chloride and
The mixture that dimethyl sulfide forms than 1:3 according to molal weight；The weight of the first catalyst accounts for the 3% of metallic tin weight.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst,
Regulator and malonic acid, at temperature 5-15 DEG C, stirring reaction 0.4 hour, adds the alkali liquor that mass fraction is 20% and persistently stirs
Mix reaction until pH value of reaction system reaches 7-9, then heat to 70 DEG C, react 4 hours, static, lower the temperature, be layered；Malonic acid
Weight accounts for the 8% of isooctyl thioglycolate weight；
The mixture that second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:1-4 according to molal weight；The
The weight of two catalyst accounts for the 6-9% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, regulator, the mol ratio of isooctyl thioglycolate are 1:2:0.5:
0.2:3；
Regulator includes the first composite regulator 9 parts and the second composite regulator 7 parts by mass parts；
First composite regulator is by tricaprylmethyl ammonium bromide, glycerol and the politef of the proportioning of 1:4:1 in mass ratio
Composition；
Second composite regulator is made up of the diphenylamines of the proportioning of 1:4:1 in mass ratio, 2,6-di-t-butyl and BTA；
(3) washing: separate organic facies and wash 2 times；
(4) distillation: obtain methyl stannum after vacuum distillation drying.
The methyl tin mixture finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) andMixture, wherein stannous methide
Quality accounting is 60%.
Embodiment three
The Methyl stannum mercaptide stabilizer of environmental protection, it is prepared from by following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 160 DEG C
Heating mix homogeneously, after carrying out halogenation 0.3h, adds reallocation agent butter of tin and is warmed up to 240 DEG C, is forced into
0.6MPa carries out stannumization and reacts 1.5 hours, then, distills and accepts gas temperature at 200 DEG C of interior fractions, then inhaling with pure water
Gather in the crops to obtain methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is tricaprylmethyl chlorination
The mixture that ammonium and dimethyl sulfide form than 1:2.5 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
2%。
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst,
Regulator and succinic acid, at temperature 10 DEG C, stirring reaction 0.3 hour, adds the alkali liquor that mass fraction is 15% continuously stirred
Reaction, until pH value of reaction system reaches 8, then heats to 65 DEG C, reacts 3.5 hours, static, lower the temperature, be layered；Succinic acid weight
Amount accounts for the 6% of isooctyl thioglycolate weight；
The mixture that second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:3 according to molal weight；Second
The weight of catalyst accounts for the 8% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, regulator, the mol ratio of isooctyl thioglycolate are 1:1.8:0.3:
0.3: 3.5；
Regulator includes the first composite regulator 8 parts and the second composite regulator 9 parts by mass parts；
First composite regulator is by tricaprylmethyl ammonium bromide, glycerol and the polytetrafluoroethyl-ne of the proportioning of 1:3.5:1.5 in mass ratio
Alkene forms；
Second composite regulator is made up of the diphenylamines of the proportioning of 1:3:2 in mass ratio, 2,6-di-t-butyl and BTA；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain methyl stannum after vacuum distillation drying.
The methyl tin mixture finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) andMixture, the wherein matter of stannous methide
Amount accounting is 50%.
Embodiment four
With embodiment one, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 7, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 1% the first solid additive and
Account for isooctyl thioglycolate weight 6% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 20% of agent gross weight；The granule of 1-2 micron accounts for the 30% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:2 composition.
Embodiment five
With embodiment two, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 9, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 3% the first solid additive and
Account for isooctyl thioglycolate weight 3% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 40% of agent gross weight；The granule of 1-2 micron accounts for the 10% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:5 composition.
Embodiment six
With embodiment three, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 8, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 2% the first solid additive and
Account for isooctyl thioglycolate weight 5% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 30% of agent gross weight；The granule of 1-2 micron accounts for the 20% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:3 composition.
Comparative example one
With embodiment one, except for the difference that stannum step distilled and accept gas temperature at 140 DEG C of interior fractions, in synthesis step
Gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, stir at temperature 25 DEG C
React 0.8 hour, add the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 10, then heat to 60 DEG C, react 1
Hour.
Application test contrasts:
Product comparative example one prepared is enterprising in PVC sheet with the products application in embodiment one to embodiment six respectively
Row static burn in is tested, and the amount adding heat stabilizer is 0.8%, and the PVC sheet made, 180 DEG C of insulations, was stayed every ten minutes
Sample is standby, until all of sheet material all turns yellow, and used time 110 minutes altogether, all samples of sheets are made form, the most directly perceived
Obtain aging control experiment data, its result is as follows:
As can be seen from Table I: the product of developing of the present invention has more excellent thermostable effect, under the conditions of equal consumption,
Than the product xanthochromia time lengthening more than half times of comparative example one, and Theil indices have dropped about 4%.Can significantly drop
The production cost of low PVC producer, reaches cheap purpose.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
The present embodiment can be made after reading this specification by member as required does not has the amendment of creative contribution, but as long as at this
All protected by Patent Law in the right of invention.
Claims (10)
1. the Methyl stannum mercaptide stabilizer of an environmental protection, it is characterised in that it is prepared from by following steps:
(1) stannum: metallic tin and catalyst are put in reactor, then passes to chloromethanes and heat at a temperature of 150-170 DEG C
Mix homogeneously, after carrying out halogenation 0.2-0.4h, adds reallocation agent and is warmed up to 235-245 DEG C, is forced into 0.5-
0.8MPa carries out stannumization and reacts after 1-2 hour, distills and accepts gas temperature at 150-230 DEG C of interior fraction, then using pure water
Absorb and obtain methyl tin chloride aqueous solution；Described methyl alkene chloride includes dimethyltin chloride and monomethyl tri-chlorination
Stannum；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, alkane
Diacid and regulator, stirring reaction 0.2-0.4 hour at temperature 5-15 DEG C, add the continuously stirred reaction of alkali liquor until reacting
System pH reaches 7-9, then heats to 60-70 DEG C, reacts 3-4 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, regulator, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-
0.5): (0.1-0.3): (3-4)；
Described regulator includes first composite regulator 6-9 part and second composite regulator 7-11 part by mass parts；
Described first composite regulator is by tricaprylmethyl ammonium bromide, glycerol and poly-four of the proportioning of 1:3-4:1-2 in mass ratio
Fluorothene forms；
Described second composite regulator is by the diphenylamines of the proportioning of 1:2-4:1-3 in mass ratio, 2,6-di-t-butyl and benzo three nitrogen
Azoles forms；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain methyl tin mixture after vacuum distillation drying.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 1, it is characterised in that: synthesis step heats up
During, add according to sequencing account for first solid additive of 1-3% of isooctyl thioglycolate weight and account for TGA different
Second solid additive of the 3-6% of monooctyl ester weight；
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for described first solid and adds
Add the 20-40% of agent gross weight；The granule of 1-2 micron accounts for the 10-30% of described first solid additive gross weight；Surplus is 3-5 micron
Granule；
Described first solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight divides
Cloth index is 3.1:
I
Described second solid additive be the molybdenum disulfide nano ball of particle diameter 10-20 nanometer with the regulation grain of particle diameter 6-9 micron by
Mixture according to mass ratio 1:2-5 composition.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 2, it is characterised in that: described first catalyst
The mixture formed than 1:2-3 according to molal weight for quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 3, it is characterised in that: described second catalyst
The mixture formed than 1:1-4 according to molal weight for phthalic acid dibutyl ester and dimethyl sulfoxide.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 3, it is characterised in that: described quaternary ammonium salt phase
Catalyst is tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tri-n-octyl methyl ammonium chloride.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 5, it is characterised in that: described reallocation agent is
Butter of tin.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 3, it is characterised in that: described first catalyst
Weight account for the 1-3% of metallic tin weight.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 4, it is characterised in that: described second catalyst
Weight account for the 6-9% of isooctyl thioglycolate weight.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 6, it is characterised in that: in described step (2)
The mass fraction of alkali liquor is 10-20%.
The Methyl stannum mercaptide stabilizer of a kind of environmental protection the most according to claim 6, it is characterised in that: described alkane diacid
For malonic acid or succinic acid or 1,3-propanedicarboxylic acid, its weight accounts for the 5-8% of isooctyl thioglycolate weight.
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