CN101475584B - Preparation of methyltin stabiliser - Google Patents
Preparation of methyltin stabiliser Download PDFInfo
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- CN101475584B CN101475584B CN2009100255230A CN200910025523A CN101475584B CN 101475584 B CN101475584 B CN 101475584B CN 2009100255230 A CN2009100255230 A CN 2009100255230A CN 200910025523 A CN200910025523 A CN 200910025523A CN 101475584 B CN101475584 B CN 101475584B
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- Prior art keywords
- tin
- stabilizer
- methyl
- methyl tin
- dimercapto
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims description 14
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000003381 stabilizer Substances 0.000 title description 22
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution 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
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000032050 esterification Effects 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical compound OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 239000001384 succinic acid Substances 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005406 washing Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000010992 reflux Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 abstract 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229920000915 polyvinyl chloride Polymers 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- -1 tin octylate series Chemical class 0.000 description 10
- 239000000344 soap Substances 0.000 description 9
- GHKCSRZBNZQHKW-UHFFFAOYSA-N 1-sulfanylethanol Chemical class CC(O)S GHKCSRZBNZQHKW-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 description 5
- 229960001545 hydrotalcite Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- QNNVICQPXUUBSN-UHFFFAOYSA-N 2-sulfanylpropan-1-ol Chemical compound CC(S)CO QNNVICQPXUUBSN-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 230000000452 restraining effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- 241000521948 Acmella Species 0.000 description 1
- 235000016936 Dendrocalamus strictus Nutrition 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a methyl tin stabilizer and a method for preparing the same and relates to the technical field of organic chemistry. The method comprises: in the presence of a catalyst, mixing and refluxing an alkyl diacid, mercaptoethanol and a solvent; after the reaction finishes, washing the solution with water and obtaining a dimercaptoester; and adding the obtained dimercaptoester into an aqueous solution of methyltin trichloride or/and dimethyltin dichloride, adjusting the pH value of the system by using an alkaline solution, carrying out an pre-esterification reaction before heat preservation, heating for carrying out a post-esterification reaction, washing an organic phrase after the reaction finishes, separating the organic phrase from a water phrase, carrying out vacuum water removal and obtaining the methyl tin stabilizer. The methyl tin stabilizer has high transparency, weather resistance, compatibility, pressure analysis, non-toxicity, excellent high-temperature stability and low tin content. The low tin-content methyl tin has higher thermal stability than the prior methyl tin, so final PVC products can achieve the same stability with even smaller amount of added methyl tin stabilizer, the use of tin is reduced and the production costs of terminal clients are reduced at last.
Description
Technical field
The present invention relates to field of chemical technology, especially for the organo-tin het stabilizer technical field of preparation polyvinyl chloride.
Background technology
Polyvinyl chloride (PVC) has superior corrosion resistance, flame retardancy and strong mechanical performance, again because cheap, raw material sources are abundant, the manufacturing process maturation, therefore goods are widely used in industries such as light industry, machinery, electronics, building, weaving, aviation, medicine food packing, are the substitute products of a kind of ideal steel, timber.
Owing to contain two keys, branch point and initiator residue etc. in the polrvinyl chloride structure, be heated to 100 ℃ and promptly be accompanied by the dehydrochlorination reaction degraded, under processing temperature (170 ℃ or higher), DeR is accelerated, and macromolecules cross-linking takes place rapidly.To add polyvinyl chloride chemical property and physical property loss of energy in man-hour in order reducing to greatest extent, to need to add some chemical substances of the thermostability of improving polymkeric substance, these materials are called thermo-stabilizer.The thermo-stabilizer that is used for polyvinyl chloride (PVC) is intended to prevent in the high temperature process process, the degraded that takes place because of the existence of chlorallylene, and it is often relevant with the absorption of the stability of chlorallylene and hydrogenchloride.
Existing P VC thermo-stabilizer mainly contains following several big class:
One, metallic soap class and substitute thereof
The stablizer of this quasi-representative comprises cadmium soap, lead soap, basic metal and alkaling earth metal base and their substitute thereof, wherein cadmium soap, lead soap are no longer produced because of their toxicity, other barium soap, the less stable at calcium soap initial stage, zinc soap later stage less stable, metallic soap class more easily produce the spraying phenomenon, and in various stablizers pressure are analysed and have the greatest impact.The alternative kind that shiploads of merchandiseization has been arranged at present, Witco company mainly contains Mark6736,4716,6448,6747,4776,6729,4753,4782, it is solid calcium/zinc stabilizer that the kind of Baerocher company exploitation has MC-KA41, MC-KA60, can satisfy multiple demand, but in high transparent article of hard and medicine food wrapping material, this class stablizer can't satisfy the demands.
Two, rare earth thermal stabilizer
Rare-earth mineral is the resource of China's uniqueness, account for 80% of world saving, therefore utilize rare earth resources overdevelopment stablizer richly endowed by nature, this stablizer has thermostability, promotion fusion preferably, good processability, good, the good transparency of coupling increase-volume, plasticising and increasing tougheness, weathering resistance and safety non-toxic are arranged, but rare-earth stabilizer is little to PVC fluidity of molten, plasticizing rate influence, has the effect of quickening gelation, in the time of large usage quantity, material undesirable from roller has to press and analyses tendency.
Three, hydrotalcite thermo-stabilizer
The hydrotalcite thermo-stabilizer is at the inorganic thermo-stabilizer newly developed eighties in 20th century by Japan, widely used anionic pillared material, what hydrotalcite thermo-stabilizer research at present was more is the Mg-Al hydrotalcite, main applied research concentrates on and other thermo-stabilizers, as thermo-stabilizer, further improve the PVC thermostability as organotin, lead or zinc salt etc.; Simultaneously can improve PVC light stability and weathering resistance with other auxiliary agent is shared; In addition, hydrotalcite-based compound is because its structure singularity, can also be as fire retardant, antifog anti-drip agent, lubricant etc., but this class stablizer can not play thermostable effect separately.
Four, organo-tin het stabilizer
Organo-tin het stabilizer is the best and the most promising thermo-stabilizer of present PVC, be applicable to high transparent article, the thermostability height, consistency is fabulous, bloom can not occur and phenomenon such as ooze out, nearly all organotin can not cause to press analyses, and toxicity is low, almost being accepted by market very soon appears in each product innovation, therefore develops very active.
U.S.'s organo-tin het stabilizer consumption accounts for 28% of the total consumption of thermo-stabilizer at present according to incompletely statistics, and Japan and West Europe also reach respectively about 25% and 18%, and China only accounts for about 5%.
The main kind of organotin has three series such as monoalkyltin, two tin alkyl and trialkyltin, and wherein trialkyltin series toxicity is very strong, can not use as stablizer; Monoalkyltin has monomethyl tin, Monobutyltin, single tin octylate etc.; Two tin alkyls have tin methide, dibutyl tin, dioctyl tin etc.At present, European Union given application bans use of butyl tin and tin octylate series in the PVC material of medicine food packing, and methyl tin series still is widely used in the various high-grade PVC goods owing to its distinctive character.
Methyl tin (SM501) on the market mainly is to contain 20% tri-thiol 2-ethyl hexyl ethanoate methyl tin and 80% dimercapto 2-ethyl hexyl ethanoate tin methide at home, its tin content is 19.4%, in the course of processing of reality, this methyl tin on the market can move to the surface from the inside of goods, separate out from product surface at last, formation spot flower has influenced the quality of goods, Here it is so-called oozing out (or weighing up sweat); In addition, in the course of processing, the easy roll banding of admixtion, release property, oilness are relatively poor, are unfavorable for the continuous processing of product; The cost of methyl tin mainly is the cost of tin than higher, how can reduce the content of tin in the product, the stabilising effect that strengthens methyl tin, the content of reduction methyl tin in the PVC goods, and this has just proposed a direction of scientific rersearch to us.
Summary of the invention
The object of the invention is to invent a kind of novel methyl tin stabilizer, is applicable to the high transparent PVC goods of hard, has high transparent, weathering resistance, consistency, plate-out.
Methyl tin stabilizer of the present invention has following molecular structural formula:
Wherein, m is 1 and above integer,
N is 1 and above integer,
G is 1 or 2.
Through test, product of the present invention has high transparent, weathering resistance, consistency and plate-out, and nontoxicity, high thermal stability is good, low tin content, and the thermostable effect of the methyl tin of this low tin content is better than existing methyl tin, for final PVC goods will reach same stabilising effect, the addition of methyl tin stabilizer will still less just can further reduce the tin consumption, has finally reduced the production cost of client terminals.
Another purpose of the present invention is to invent a kind of production method with methyl tin stabilizer of above feature:
Preparation method one of the present invention:
Under the condition that catalyzer exists, earlier alkane diacid, mercaptoalcohol and solvent are refluxed, after reaction finishes, wash with water, steam solvent after drying, get corresponding dimercapto; Under 0～40 ℃ envrionment temperature, the dimercapto of obtaining is added in the aqueous solution of monomethyl tin trichloride or dimethyltin chloride, transferring the pH value of system with alkaline solution is 7～9, esterification was 2～6 hours before insulation was carried out, and was warming up to 40～90 ℃ then and carried out the back esterification 2～6 hours, after reaction finishes, divide the phase of anhydrating, organic phase washes the back again with water and divides the phase of anhydrating, and removes moisture content with vacuum, promptly gets methyl tin stabilizer.
Product structure molecular formula or be
Or be
Wherein, m is 1 and above integer,
N is 1 and above integer.
The former has the characteristics of better stability in early stage, and the latter has the characteristics of later stage better stability.
Preparation method two of the present invention:
Under the condition that catalyzer exists, earlier alkane diacid, mercaptoalcohol and solvent are refluxed, after reaction finishes, wash with water, steam solvent after drying, get corresponding dimercapto; Under 0～40 ℃ envrionment temperature, the dimercapto of obtaining is added in the mixed aqueous solution of being made up of monomethyl tin trichloride and dimethyltin chloride, transferring the pH value of system with alkaline solution is 7～9, esterification was 2～6 hours before insulation was carried out, and was warming up to 40～90 ℃ then and carried out the back esterification 2～6 hours, after reaction finishes, divide the phase of anhydrating, organic phase washes the back again with water and divides the phase of anhydrating, and removes moisture content with vacuum, promptly gets methyl tin stabilizer.
The product that adopts method two to make has simultaneously
Wherein, m is 1 and above integer,
N is 1 and above integer.
Because the existence of two kinds of different molecular structures features makes product both have in earlier stage stability preferably, also has the later stage better stability, is best production decision.
In addition, the mol ratio of alkane diacid of the present invention and mercaptoalcohol is 1: 1.9～4, and alkane diacid and mercaptoalcohol cumulative volume are 1: 1～10 with solvent cumulative volume ratio.
In method one, the normal mol ratio of chlorine is 1: 1 in described dimercapto and monomethyl tin trichloride or the dimethyltin chloride aqueous solution.
In method two, the normal mol ratio of chlorine is 1: 1 in described dimercapto and monomethyl tin trichloride and the dimethyltin chloride mixed aqueous solution, and wherein, the mol ratio of monomethyl tin trichloride and dimethyltin chloride is 1: 2～6.
The above alkane diacid is propanedioic acid or Succinic Acid or pentanedioic acid or hexanodioic acid.
Described mercaptoalcohol is 2 mercapto ethanol or 3-mercaprol or 4-Mercaptobutanol.
Described catalyzer is p-methyl benzenesulfonic acid or Phenylsulfonic acid or methylsulphonic acid.
Described solvent is sherwood oil or normal hexane or hexanaphthene or chloroform or benzene or toluene.
In a word, technology of the present invention is reasonable, is easy to production control, and product stability is good.
Embodiment
Embodiment one
With 118 gram (1mol) Succinic Acid (or propanedioic acid, or pentanedioic acid) after (2.2mol) 2 mercapto ethanols mix with 172 grams, add 200 gram toluene, add 0.5 gram p-methyl benzenesulfonic acid again and reflux, after reaction finishes, with 200ml water washing three times, after the drying, steam solvent, high vacuum is extracted lower boiling solvent and water out, get 226 gram Succinic Acid dimercapto ethyl esters, yield 95%.
It is 1 mole 1: 4 monomethyl tin trichloride that 238 gram (1mol) Succinic Acid dimercapto ethyl esters are splashed into the chlorine equivalent: the mixed aqueous solution of dimethyltin chloride, temperature is 25～40 ℃, the pH value of adjusting system with ammonia soln (or aqueous sodium hydroxide solution or sodium bicarbonate aqueous solution) is 7～8, dropwise, the PH of system remains on 7～8, esterification was 2 hours before insulation was carried out, heat up then and carry out the back esterification, temperature is 40～60 ℃ of reactions 4 hours, after reaction finishes, divide the phase of anhydrating, organic phase with 300 gram water washings 3 times, is divided the phase of anhydrating again, remove moisture content with high vacuum, obtain 285 gram clarifying colourless thick liquids (being methyl tin stabilizer), yield 94%, tin content are 17.8%.
Make the molecular structural formula of methyl tin stabilizer:
Embodiment two
146 gram (1mol) hexanodioic acids and 148 restrain (1.9mol) 2 mercapto ethanols (or 3-mercaprol, 2-methyl-2 mercapto ethanol or 4-Mercaptobutanol) mix after, add 200 gram toluene (or sherwood oil or normal hexane or hexanaphthene or chloroform or benzene), add 2 gram Phenylsulfonic acid or methylsulphonic acids again) reflux, after reaction finishes, with 200ml water washing three times, after the drying, steam solvent, high vacuum is extracted lower boiling solvent and water out, the 250 diacid dimercapto ethyl esters of restraining oneself, yield 94%.
It is 1 mole 1: 6 monomethyl tin trichloride that 266 gram (1mol) hexanodioic acid dimercapto ethyl esters are splashed into the chlorine equivalent: the mixed aqueous solution of dimethyltin chloride, temperature is 0～30 ℃, the pH value of adjusting system with ammonia soln (or aqueous sodium hydroxide solution or sodium bicarbonate aqueous solution) is 7～8, dropwise, the PH of system remains on 7～8, esterification was 2 hours before insulation was carried out, heat up then and carry out the back esterification, temperature is 60～90 ℃ of reactions 6 hours, after reaction finishes, divide the phase of anhydrating, organic phase with 300 gram water washings 3 times, is divided the phase of anhydrating again, remove moisture content with high vacuum, obtain 316.7 gram clarifying colourless thick liquids (being methyl tin stabilizer), yield 95%, tin content are 16.6%.
Make the molecular structural formula of methyl tin stabilizer:
Embodiment three
146 gram (1mol) hexanodioic acids and 312 restrain (4mol) 2 mercapto ethanols (or 2-methyl-2 mercapto ethanol or 4-Mercaptobutanol) mix after, add 400 gram normal hexane or hexanaphthene or chloroform or benzene), add 5 gram Phenylsulfonic acid or methylsulphonic acids again) reflux, after reaction finishes, with 200ml water washing three times, after the drying, steam solvent, high vacuum is extracted lower boiling solvent and water out, the 250 diacid dimercapto ethyl esters of restraining oneself, yield 94%.
It is 1 mole 1: 2 monomethyl tin trichloride that 266 gram (1mol) hexanodioic acid dimercapto ethyl esters are splashed into the chlorine equivalent: the mixed aqueous solution of dimethyltin chloride, temperature is 0～30 ℃, the pH value of adjusting system with ammonia soln (or aqueous sodium hydroxide solution or sodium bicarbonate aqueous solution) is 7～8, dropwise, the PH of system remains on 7～8, esterification was 2 hours before insulation was carried out, heat up then and carry out the back esterification, temperature is 60～90 ℃ of reactions 6 hours, after reaction finishes, divide the phase of anhydrating, organic phase with 300 gram water washings 3 times, is divided the phase of anhydrating again, remove moisture content with high vacuum, obtain 313.5 gram clarifying colourless thick liquids (being methyl tin stabilizer), yield 96%, tin content are 15.6%.
The molecular structural formula of the product that forms is:
Embodiment four
146 gram (1mol) hexanodioic acids and 148 restrain (1.9mol) 2 mercapto ethanols (or 3-mercaprol, 2-methyl-2 mercapto ethanol or 4-Mercaptobutanol) mix after, add 300 gram toluene (or sherwood oil or normal hexane or hexanaphthene or chloroform or benzene), add 2 gram Phenylsulfonic acid or methylsulphonic acids again) reflux, after reaction finishes, with 200ml water washing three times, after the drying, steam solvent, high vacuum is extracted lower boiling solvent and water out, the 250 diacid dimercapto ethyl esters of restraining oneself, yield 94%.
It is in 1 mole of monomethyl tin trichloride aqueous solution that 266 gram (1mol) hexanodioic acid dimercapto ethyl esters are splashed into the chlorine equivalent, temperature is 25～30 ℃, the pH value of adjusting system with ammonia soln (or aqueous sodium hydroxide solution or sodium bicarbonate aqueous solution) is 7～8, dropwise, the PH of system remains on 7～8, esterification was 2 hours before insulation was carried out, and heated up then and carried out the back esterification, and temperature is 60～90 ℃ of reactions 6 hours, after reaction finishes, divide the phase of anhydrating, organic phase with 300 gram water washings 3 times, is divided the phase of anhydrating again, remove moisture content with high vacuum, obtain 297.2 gram clarifying colourless thick liquids (being methyl tin stabilizer), yield 96%, tin content are 16.3%.
Make the molecular structural formula of methyl tin stabilizer:
Embodiment five
146 gram (1mol) hexanodioic acids and 148 restrain (1.9mol) 2 mercapto ethanols (or 3-mercaprol, 2-methyl-2 mercapto ethanol or 4-Mercaptobutanol) mix after, add 300 gram toluene (or sherwood oil or normal hexane or hexanaphthene or chloroform or benzene), adding 2 gram Phenylsulfonic acids or methylsulphonic acid again refluxes, after reaction finishes, with 200ml water washing three times, after the drying, steam solvent, high vacuum is extracted lower boiling solvent and water out, the 250 diacid dimercapto ethyl esters of restraining oneself, yield 94%.
It is in 1 mole of dimethyltin chloride aqueous solution that 266 gram (1mol) hexanodioic acid dimercapto ethyl esters are splashed into the chlorine equivalent, temperature is 25～30 ℃, the pH value of adjusting system with ammonia soln (or aqueous sodium hydroxide solution or sodium bicarbonate aqueous solution) is 7～8, dropwise, the PH of system remains on 7～8, esterification was 2 hours before insulation was carried out, and heated up then and carried out the back esterification, and temperature is 60～90 ℃ of reactions 6 hours, after reaction finishes, divide the phase of anhydrating, organic phase with 300 gram water washings 3 times, is divided the phase of anhydrating again, remove moisture content with high vacuum, obtain 325.8 gram clarifying colourless thick liquids (being methyl tin stabilizer), yield 96%, tin content are 17.5%.
Make the molecular structural formula of methyl tin stabilizer:
Application test
With SM501 respectively with embodiment one and embodiment two in methyl tin stabilizer be applied in and carry out static-aging test on the PVC sheet material, the amount of adding thermo-stabilizer is 0.9%, the PVC sheet material of making is 180 ℃ of insulations, kept sample standby every ten minutes, up to all flavescence of all sheet materials, altogether 110 minutes times spent, all samples of sheets are made form, obtain aging control experiment data so very intuitively, its result is as follows:
Table one: the static-aging test of methyl tin heat stabilizer on the PVC sheet material
| ? | SM501 | Embodiment one | Embodiment two |
| Stablizer addition % | 0.9 | 0.9 | 0.9 |
| Stablizer tin content % | 19.2 | 17.8 | 16.3 |
| Stablizer tin addition % | 0.173 | 0.160 | 0.147 |
| Sheet material begins xanthochromia time min | 40 | 60 | 70 |
| Min of complete xanthochromia time of sheet material | 60 | 100 | 110 |
From table one as can be seen: the novel methyl tin of the present invention development has and good thermostable effect, under equal consumption condition, than the best thermo-stabilizer xanthochromia time lengthening of now selling more than half times, and the tin content in the novel thermo-stabilizer has descended about 1.4%.If reach the equal effect of SM501, the addition of new stabilizer can still less can reduce the production cost of PVC producer so significantly, reaches cheap purpose.
Claims (9)
1. the preparation method of a methyl tin stabilizer, described methyl tin stabilizer has following molecular structural formula:
Wherein, m is 1 and above integer, and n is 1 and above integer, and g is 1 or 2;
Under the condition that catalyzer exists, earlier alkane diacid, mercaptoalcohol and solvent are refluxed, after reaction finishes, wash with water, steam solvent after drying, get corresponding dimercapto; It is characterized in that: under 0～40 ℃ envrionment temperature, the dimercapto of obtaining is added in the aqueous solution of monomethyl tin trichloride or dimethyltin chloride, transferring the pH value of system with alkaline solution is 7～9, esterification was 2～6 hours before insulation was carried out, and was warming up to 40～90 ℃ then and carried out the back esterification 2～6 hours, after reaction finishes, divide the phase of anhydrating, organic phase washes the back again with water and divides the phase of anhydrating, and removes moisture content with vacuum, promptly gets methyl tin stabilizer.
2. the preparation method of a methyl tin stabilizer, described methyl tin stabilizer has following molecular structural formula:
Wherein, m is 1 and above integer, and n is 1 and above integer, and g is 1 or 2;
Under the condition that catalyzer exists, earlier alkane diacid, mercaptoalcohol and solvent are refluxed, after reaction finishes, wash with water, steam solvent after drying, get corresponding dimercapto; It is characterized in that: under 0～40 ℃ envrionment temperature, the dimercapto of obtaining is added in the mixed aqueous solution of being made up of monomethyl tin trichloride and dimethyltin chloride, transferring the pH value of system with alkaline solution is 7～9, esterification was 2～6 hours before insulation was carried out, and was warming up to 40～90 ℃ then and carried out the back esterification 2～6 hours, after reaction finishes, divide the phase of anhydrating, organic phase washes the back again with water and divides the phase of anhydrating, and removes moisture content with vacuum, promptly gets methyl tin stabilizer.
3. according to claim 1 or 2 described preparation methods, the mol ratio that it is characterized in that described alkane diacid and mercaptoalcohol is 1: 1.9～4, and alkane diacid and mercaptoalcohol cumulative volume are 1: 1～10 with solvent cumulative volume ratio.
4. according to the described preparation method of claim 1, it is characterized in that the normal mol ratio of chlorine is 1: 1 in described dimercapto and monomethyl tin trichloride or the dimethyltin chloride aqueous solution.
5. according to the described preparation method of claim 2, it is characterized in that the normal mol ratio of chlorine is 1: 1 in described dimercapto and monomethyl tin trichloride and the dimethyltin chloride mixed aqueous solution, wherein, the mol ratio of monomethyl tin trichloride and dimethyltin chloride is 1: 2～6.
6. according to claim 1 or 2 described preparation methods, it is characterized in that described alkane diacid is propanedioic acid or Succinic Acid or pentanedioic acid or hexanodioic acid.
7. according to claim 1 or 2 described preparation methods, it is characterized in that described mercaptoalcohol is 2 mercapto ethanol or 3-mercaprol or 4-Mercaptobutanol.
8. according to claim 1 or 2 described preparation methods, it is characterized in that described catalyzer is p-methyl benzenesulfonic acid or Phenylsulfonic acid or methylsulphonic acid.
9. according to claim 1 or 2 described preparation methods, it is characterized in that described solvent is sherwood oil or normal hexane or hexanaphthene or chloroform or benzene or toluene.
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| CN102061010A (en) * | 2010-11-29 | 2011-05-18 | 杭州天道实业有限公司 | Tin methyl heat stabilizer |
| CN102558608A (en) * | 2010-12-27 | 2012-07-11 | 泰安市蓝天助剂有限公司 | Sebacic acid mercapto ethyl ester dimethyl tin heat stabilizing agent and preparation method thereof |
| CN102796282B (en) * | 2012-08-21 | 2014-06-04 | 衢州建华东旭助剂有限公司 | Aliphatic acid mercaptoethanol ester methyl tin heat stabilizer and preparation method thereof |
| CN104710334B (en) * | 2013-12-13 | 2017-01-25 | 湖北南星化工总厂 | Metal thiolate compound for PVC stabilization and preparation method thereof |
| CN106117262A (en) * | 2016-06-25 | 2016-11-16 | 安徽升华新奥特化工有限公司 | A kind of production technology of the methyl stannum of environmental protection |
| CN106117263A (en) * | 2016-06-25 | 2016-11-16 | 安徽升华新奥特化工有限公司 | A kind of Methyl stannum mercaptide stabilizer of environmental protection |
| CN106045084A (en) * | 2016-06-25 | 2016-10-26 | 安徽升华新奥特化工有限公司 | Environment-friendly methyltin wastewater treatment process |
| US20200071269A1 (en) | 2018-08-28 | 2020-03-05 | Pmc Organometallix, Inc. | Low free 2-mercaptoethanol ester and uses thereof |
| CN110551323A (en) * | 2019-09-04 | 2019-12-10 | 云南锡业锡化工材料有限责任公司 | High-tin-content lauric acid reverse ester methyl tin mercaptan heat stabilizer and preparation method thereof |
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