CA1238050A - Continuous process for the preparation of alkyltin thiocarboxylic acid esters - Google Patents
Continuous process for the preparation of alkyltin thiocarboxylic acid estersInfo
- Publication number
- CA1238050A CA1238050A CA000416898A CA416898A CA1238050A CA 1238050 A CA1238050 A CA 1238050A CA 000416898 A CA000416898 A CA 000416898A CA 416898 A CA416898 A CA 416898A CA 1238050 A CA1238050 A CA 1238050A
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- process according
- acid esters
- alkyltin
- reaction system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 thiocarboxylic acid esters Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000010924 continuous production Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000004820 halides Chemical class 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 10
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000011552 falling film Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 230000003019 stabilising effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000002585 base Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical class CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- KHUFWSCEDYFQCV-UHFFFAOYSA-N C(C)C(C[Sn](CCCCCCCC)CCCCCCCC)CCCC Chemical compound C(C)C(C[Sn](CCCCCCCC)CCCCCCCC)CCCC KHUFWSCEDYFQCV-UHFFFAOYSA-N 0.000 description 1
- 241000861718 Chloris <Aves> Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 101100490488 Mus musculus Add3 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000145178 Trichloris Species 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- ATADHKWKHYVBTJ-UHFFFAOYSA-N hydron;4-[1-hydroxy-2-(methylamino)ethyl]benzene-1,2-diol;chloride Chemical compound Cl.CNCC(O)C1=CC=C(O)C(O)=C1 ATADHKWKHYVBTJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical class CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- DHHKPEUQJIEKOA-UHFFFAOYSA-N tert-butyl 2-[6-(nitromethyl)-6-bicyclo[3.2.0]hept-3-enyl]acetate Chemical class C1C=CC2C(CC(=O)OC(C)(C)C)(C[N+]([O-])=O)CC21 DHHKPEUQJIEKOA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LXDHBOICPCPCKD-UHFFFAOYSA-N tetradecyl 2-sulfanylacetate Chemical compound CCCCCCCCCCCCCCOC(=O)CS LXDHBOICPCPCKD-UHFFFAOYSA-N 0.000 description 1
- 125000005300 thiocarboxy group Chemical group C(=S)(O)* 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- 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
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)
Abstract
Abstract Continuous process for the preparation of alkyltin thiocarboxylic acid esters A process for the production of alkyltin thiocarboxylic acid esters from alkyltin halides and thiocarboxylic acid esters in the presence of an acid acceptor, which process comprises carrying out the reaction continuously in a reaction system comprising 1 to 5 agitator vessels with an average dwell time of 1 to 60 minutes, at a constant pH value in the range from 3 to 8, and in a temperature range from 40° to 80°C and separating the product drawn off from the reaction system from the aqueous phase and subsequently drying it.
The alkyltin thiocarboxylic acid esters obtained by the process of the invention are used for stabilising homo- and copolymers of vinyl chloride.
The alkyltin thiocarboxylic acid esters obtained by the process of the invention are used for stabilising homo- and copolymers of vinyl chloride.
Description
~3~
Case 3-13693/CGM 264/1+2/=
. . _ Continuous process for the preparation of alkyltin thiocarboxylic acid esters Alkyltin thiocarboxylic acid esters are known stabilisers for homopolymers and numerous copolymers of vinyl chloride.
Their preparation is described e.g in Houben-Weyl, Methoden der Organischen Chemie , Vol. XIII/6 (1978), pp. 348-350. It is carried out by discontinuous reaction of alkyltin oxides or alkyltin halides, in particular alkyltin chlorides, with thiocarboxylicacid esters. The re~tion with alkyltin chloride is preferably carried out in the presence of a base as acld acceptor, under different temperature, time and pH conditions.
The preparation of alkyltin thiocarboxylic acid esters from the corresponding alkyltin halides is normally carried out in the presence of an organic solvent, as described e.g. in US patent 2 832 751. It is also known from the literature to carry out the reaction without a solvent (q.v. US patent 3 716 568).
In the batchwise process~ using an organic solvent, it is possible to carry out the reaction both at relatively low and at more elevated temperature. In this reaction, the aqueous phase is usually well and cleanly separated from ~he product p`hase.
The processes carried out without a solvent result in a ~ higher space/time yield~ Further, the step of ; regenerating the solvent is made redundant in these processes.
The essential drawbacks of the process~s carried out with an organic solvent are that the space/time yield is dras~icaliy reduced and the solvent employed has to be removed by distillation in the working up phase, resulting in energy consumption and in spent air and wastewater pollution. In addition, the flash point of the product falls sharply on account of solvent residues, so that greater safety measures are required in the plant.
On the other handJ the absence of a solvent in the 10 solvent-free processes is a disadvantage~ as usually a very poor separation o the organic product phase from the aqueous phase results. This means long standing times and also product loss through the ~ormation of an intermediate phase. In addL~on~ lengthy distill.ation times are requir~ed 15 for the residual water because of the difficulty of separating it from the organic phase, with the consequence that the product is subjected to prolonged exposure to heat.
Low temperatures are necessary for the batchwise reaction of alkyltin halides with thiocarboxylic acid este~.The 20 reaction is so strongly exothermic that the addition of base can only be made as quickly as the removal of heat through the reactor jacket permits, thus resulting in lengthy reaction times in large-scale production and, accordingly,in a lower space/time yield. Moreover, at the start of the 25 addition of base the pH of the reaction mixture is ln the strongly acid range (below pEI 1) and then gradually rises to the neutral range. During the reaction in the acid range, undesirable saponification reactions may occur7 e.g.
of the thiocarboxylates, which impair the quality of the product. In addition, previous experience has shown that 7 in batchwise operation, the final pH value must be adjusted exactly, so that uniform production is only ensured ~2 ~
by very careful monitoring. Exceeding the pH value results in diminished product quality and in product loss.
The reaction of alkyl tin oxides with e.g. thio~rboxylic acid esters necessitates the technically complicated intermediate isolation and drying of the alkyltin oxides. The process described in German Auslegeschrift 2 209 336 affords no advantages, as the thin-film process requires complicated reaction apparatus.
I~ is the object of the present invention to provide a 10 continuous process for the preparation of alkyltin thiocarboxylic acid esters, which process makes it possihle to react the reactanta in simple apparatus with short dwell times, at constant pH and and in a wide temperature range, iE
desired without coollng or removing the heat of reaction 15 and neu~ralisation, thereby eliminating the pre~iously descr~bed drawbacks of the known processes.
;
Accordingly, the present invention relates to a process for the preparation of alkyltin thiocarboxylic acid es-ters from alkyltin halides and thiocarboxy~c acid esters in the presence of 20 an acid acceptor~ which process comprises carrying out the reaction continuously in a system consisting of 1 to 5 agitator vessels with an average dwell time of 1 to 60 minutes~ at a constant pH value in the range from 3 to 8, ~ ; and in a temperature range from 40 to 80C.
: ~ :
Surprisingly, it has been found that only in a continuous operation~ as opposed to a discontinuous process, does no loss of qualiSy occur, as the product is exposed to high temperatures only for a short time and at a constant pH
value, preerabl~ in the neutral range. Accordingly~ it is possible to obtain products in a continuous process, e.g.
~ 5~
at 75 C and pH 6.5, without loss of quality and in substantially hi~her space/time yield. In addition, the desired pH range can be easily adjusted during the entire reactiOn. The process is carried ou~ in a continuously operating reaction system consisting of 1 to 5 reaction vessels, preferably of two reaction vessels.
If the reac~ion is carried out in a two-stage agitator - vessel cascade~ the dwell time in the first vessel will be from 1 to 60 minutes, preferably from 1 to 10 minutes, bu~
io most preferably from 1 to 5 minutes. The vessels of the two-stage cascade may be of the same or different size.
The dwell times in the individual reaction vessels will there~ore correspondingly dif~er. The reaction temperature is in the range from 40 to 80C, preferably Erom 50 to 15 60C. By appropriate choice of temperature when charging the reaction vessels with the starting materials~ it is also possible to carry oùt the reaction adiabatically This is done by adding the starting materials continuously at low temperature, preferably in the range from 20 to 30C.
20 The heat o reaction and neutralisation need not be removed, so that cooling energy can be saved.
In the continuous operation of this invention, the pH range is kept between 3 and 8, preferably at a constant value between 5 and 7, during the entire reaction. The pM can be 25 adjusted in simple manner, e.g. by a pH meter~ with a base.
Suitable bases are: alkali metal hydroxldes and alkaline earth metal hydroxides such as sodium~ potassium or calcium hydroxide; alkaline earth oxides such as calcium oxide; and also ammonia or alkali me~al carbonates such 30 as sodium carbonate or potassium carbonate. They are preferably used in the form of 10 to 50 % solutions.
Particularly advantageous is e.g. 18 to 20 % sodium ~ 3 hydroxide solution. However, tertiary amines such as triethylamine or pyridine may also be used, if desired, It i9 preferred to carry out the reaction of this invention without an organlc solvent However, the reaction may also be carried out in the presence of an inert organic solvent.
Examples of suitable solvents are aliphatic and aromatic hydrocarbons, ethers, esters and ketones, such as he~ane, petroleum ether, toluene, xyLenes, methyl isobutyl ketone or methyl acetate.
10 Various alkyltin thiocarboxylic acid esters may be prepared by the process of this invention. Particularly interesting compounds are those of the formula Rxsn[s(cH2)ncooR ]4-x wherein x and n are l or 2, R is methyl, butyl, octyl~
15 Lauryl or the -CH~C~2C00-n-C4Hg group, and R' is a -cl6alkYl group R às butyl may be n-butyl, isobutyl or tert-butyL, with n-butyl being preferred. R as octyl may be n-octyl or
Case 3-13693/CGM 264/1+2/=
. . _ Continuous process for the preparation of alkyltin thiocarboxylic acid esters Alkyltin thiocarboxylic acid esters are known stabilisers for homopolymers and numerous copolymers of vinyl chloride.
Their preparation is described e.g in Houben-Weyl, Methoden der Organischen Chemie , Vol. XIII/6 (1978), pp. 348-350. It is carried out by discontinuous reaction of alkyltin oxides or alkyltin halides, in particular alkyltin chlorides, with thiocarboxylicacid esters. The re~tion with alkyltin chloride is preferably carried out in the presence of a base as acld acceptor, under different temperature, time and pH conditions.
The preparation of alkyltin thiocarboxylic acid esters from the corresponding alkyltin halides is normally carried out in the presence of an organic solvent, as described e.g. in US patent 2 832 751. It is also known from the literature to carry out the reaction without a solvent (q.v. US patent 3 716 568).
In the batchwise process~ using an organic solvent, it is possible to carry out the reaction both at relatively low and at more elevated temperature. In this reaction, the aqueous phase is usually well and cleanly separated from ~he product p`hase.
The processes carried out without a solvent result in a ~ higher space/time yield~ Further, the step of ; regenerating the solvent is made redundant in these processes.
The essential drawbacks of the process~s carried out with an organic solvent are that the space/time yield is dras~icaliy reduced and the solvent employed has to be removed by distillation in the working up phase, resulting in energy consumption and in spent air and wastewater pollution. In addition, the flash point of the product falls sharply on account of solvent residues, so that greater safety measures are required in the plant.
On the other handJ the absence of a solvent in the 10 solvent-free processes is a disadvantage~ as usually a very poor separation o the organic product phase from the aqueous phase results. This means long standing times and also product loss through the ~ormation of an intermediate phase. In addL~on~ lengthy distill.ation times are requir~ed 15 for the residual water because of the difficulty of separating it from the organic phase, with the consequence that the product is subjected to prolonged exposure to heat.
Low temperatures are necessary for the batchwise reaction of alkyltin halides with thiocarboxylic acid este~.The 20 reaction is so strongly exothermic that the addition of base can only be made as quickly as the removal of heat through the reactor jacket permits, thus resulting in lengthy reaction times in large-scale production and, accordingly,in a lower space/time yield. Moreover, at the start of the 25 addition of base the pH of the reaction mixture is ln the strongly acid range (below pEI 1) and then gradually rises to the neutral range. During the reaction in the acid range, undesirable saponification reactions may occur7 e.g.
of the thiocarboxylates, which impair the quality of the product. In addition, previous experience has shown that 7 in batchwise operation, the final pH value must be adjusted exactly, so that uniform production is only ensured ~2 ~
by very careful monitoring. Exceeding the pH value results in diminished product quality and in product loss.
The reaction of alkyl tin oxides with e.g. thio~rboxylic acid esters necessitates the technically complicated intermediate isolation and drying of the alkyltin oxides. The process described in German Auslegeschrift 2 209 336 affords no advantages, as the thin-film process requires complicated reaction apparatus.
I~ is the object of the present invention to provide a 10 continuous process for the preparation of alkyltin thiocarboxylic acid esters, which process makes it possihle to react the reactanta in simple apparatus with short dwell times, at constant pH and and in a wide temperature range, iE
desired without coollng or removing the heat of reaction 15 and neu~ralisation, thereby eliminating the pre~iously descr~bed drawbacks of the known processes.
;
Accordingly, the present invention relates to a process for the preparation of alkyltin thiocarboxylic acid es-ters from alkyltin halides and thiocarboxy~c acid esters in the presence of 20 an acid acceptor~ which process comprises carrying out the reaction continuously in a system consisting of 1 to 5 agitator vessels with an average dwell time of 1 to 60 minutes~ at a constant pH value in the range from 3 to 8, ~ ; and in a temperature range from 40 to 80C.
: ~ :
Surprisingly, it has been found that only in a continuous operation~ as opposed to a discontinuous process, does no loss of qualiSy occur, as the product is exposed to high temperatures only for a short time and at a constant pH
value, preerabl~ in the neutral range. Accordingly~ it is possible to obtain products in a continuous process, e.g.
~ 5~
at 75 C and pH 6.5, without loss of quality and in substantially hi~her space/time yield. In addition, the desired pH range can be easily adjusted during the entire reactiOn. The process is carried ou~ in a continuously operating reaction system consisting of 1 to 5 reaction vessels, preferably of two reaction vessels.
If the reac~ion is carried out in a two-stage agitator - vessel cascade~ the dwell time in the first vessel will be from 1 to 60 minutes, preferably from 1 to 10 minutes, bu~
io most preferably from 1 to 5 minutes. The vessels of the two-stage cascade may be of the same or different size.
The dwell times in the individual reaction vessels will there~ore correspondingly dif~er. The reaction temperature is in the range from 40 to 80C, preferably Erom 50 to 15 60C. By appropriate choice of temperature when charging the reaction vessels with the starting materials~ it is also possible to carry oùt the reaction adiabatically This is done by adding the starting materials continuously at low temperature, preferably in the range from 20 to 30C.
20 The heat o reaction and neutralisation need not be removed, so that cooling energy can be saved.
In the continuous operation of this invention, the pH range is kept between 3 and 8, preferably at a constant value between 5 and 7, during the entire reaction. The pM can be 25 adjusted in simple manner, e.g. by a pH meter~ with a base.
Suitable bases are: alkali metal hydroxldes and alkaline earth metal hydroxides such as sodium~ potassium or calcium hydroxide; alkaline earth oxides such as calcium oxide; and also ammonia or alkali me~al carbonates such 30 as sodium carbonate or potassium carbonate. They are preferably used in the form of 10 to 50 % solutions.
Particularly advantageous is e.g. 18 to 20 % sodium ~ 3 hydroxide solution. However, tertiary amines such as triethylamine or pyridine may also be used, if desired, It i9 preferred to carry out the reaction of this invention without an organlc solvent However, the reaction may also be carried out in the presence of an inert organic solvent.
Examples of suitable solvents are aliphatic and aromatic hydrocarbons, ethers, esters and ketones, such as he~ane, petroleum ether, toluene, xyLenes, methyl isobutyl ketone or methyl acetate.
10 Various alkyltin thiocarboxylic acid esters may be prepared by the process of this invention. Particularly interesting compounds are those of the formula Rxsn[s(cH2)ncooR ]4-x wherein x and n are l or 2, R is methyl, butyl, octyl~
15 Lauryl or the -CH~C~2C00-n-C4Hg group, and R' is a -cl6alkYl group R às butyl may be n-butyl, isobutyl or tert-butyL, with n-butyl being preferred. R as octyl may be n-octyl or
2-ethylhexyL, with n-octyl being preferred.
20 R' may be e.gO straight chain or branched octyl, decyl, ~` - dodecyl, tetradecyL and hexadecyL, as well as the commercially a~ailable mixtures of alcohols known as alfols, which contain substantially alkyl groups having the same number of carbon atoms and are mainly branched.
~;; 25 The alkyl groups are here known as "aLfyls"
The starting materials employed for ~he proces~ are alkyltin haLides and thiocarboxylic acid esters. The alkyltin haLides ~ 5 employed are chlorides, bromides or iodides, preferably alkyltin chlorides or bromides in an amount of 85 to 115 mole %, based on the thiocarboxylic acid esters. The thio-carboxylic acid esters are known compounds. Thioglycolic and thiopropionic acid esters are especial]y preferred.
The initiation of the continuous reaction is conveniently effec~ed batchwise, beginning first with the addition of the reagents, then adding the a~ueous solution of ~he base for adjusting the desired pH range, and finally adding 10 both reaction omponents and the solution of the base continuously.
The starting alkyltin halides and thiocarboxyLic acid esters may be added to the reactor at 20-30C either as a previously prepared mixture or added separately at different 15 temperatures The process of the invention may be carried out e.g. in the following system:
To initiate the reaction, the appropriate alkyltin chlori~e or chlorides and the corresponding thiocarboxylic acid ester 20 are pumped in the required molar ratio into the reactor until this latter is about half full, With stirring, an aqueous solution of the base is then added until the desired pH value is reached, after wh~l the continuous addition of the sodium hydroxide solutiona the alkyltin chloride(s) 25 and the thiocarboxylic ~d ester is commenced with. When the controlled volume has been reached, the reaction mixture is pumped into the second reactor such that the controlled volume in the second ag~ator vessel is maintained.
~: :
After an average dweLl time o~ 1 to 60 minutes, pre~erably 30 of 1 to 10 minutes and, most preferably, of 1 to 5 minutes, ~238C3 the reaction mixture is discharged con~inuously from ~he reactor in order to separate the organic phase from the aqueous phase, The separa~ion of the water from the reac~ion mixture drawn off from the reactor is preferably effected by a continuously operating liquid-liquid extractor or else also by suitable separating columns.
Liquid-liquid extractors are conventional separators used in chemical engineering. Particulars on the individual extraction methods are to be found in Ullmann, 10 Enzyklop-adie der technischen Chemie, Vol. 2, 4th edition (1972)~ on page 553, and a description of ~he individual apparatus and extractors will be found on pp. 560-564. The continuously operating liquid-liquid centrifugal extractor is particularly advantageous for 15 separating water from the reackion mixture drawn of from the reactor 9 preferably at 4~-50C.
The so isolated product phase may conveniently also be dried continuously, e.g. by continuous spray drying or al50 with ~he aid of a thin-film or falling film 20 evaporator.
Spray drying, thin-film or falling film evaporators are also known drying or evaporating systems. Such equipment is described e.g in Ullmann, Enzyklopadie der technischen Chemie. Vol. 2, 4th Edition (197Z) on pp, 712-713 25 (spray driers) and on pp. 655-656 (thin-film and fal~ing film evaporators).
The following Examples describe the invention in more detail ~38 Example 1: 100 parts by weight of a mixture of 30 mole %
of mono-n-octyltin trichloride and 70 mole % of di-n-octy~in dichloride together with 104 parts by weight of 2-ethylhexyl thioglycolate are pumped continuously at a temperature of 60C into a reactor system comprising a cascade of two reactors each equippecl with stirrer, level meter,pH meter and thermome~er. With efficient stirring~
aqueous sodium hydroxide solution is simultaneously added to the reaction mass such that a pH of 6.5-7.0 is lQ maintained in the first reactor. The addition of sodium hydroxide is controlled by the pH meter in the first reactor. The reaction mixture is pumped into the second reactor, the volume being controlled by the level meter.
Feed and discharge of the reaction mixture are controlled 15 such that the dwell time of the reaction mass in the first reactor is 5 minutes. The heat of reaction liberated during the reaction is removed such that a constant temperature of 60C is kept in the fir~t and in the second reactor.
20 Aqueous sodium hydroxide(very little~ is also introduced into the second reactor in order to maintain a constant pH
of 6.9 (control of addition by pH meter). The reaction mass is then pumped from the second reactor into a liquid-liquid extractor, in which the salt-containing aqueous phase is 25 separated continuously from the product. The product is then spray dried and clarified by filtration, ~o give a viscous liquid consisting of a mixture of 30 mole % of 2-ethylhexyl mono-n-octyltin tristhioglycolate and 70 mole % oE 2-ethylhexyl di-n-octyltin bisthioglycolate.
30 The yield is 98 % of theory, based on the two starting mono and dioctyltin chlorides.
Analysis: Sn (theory) : 15.5 %; S: 9.0 %
Sn (found) : 15.2 %; S: 8.9 %.
~38~5 Example 2: 100 parts by weight of mono-n-butyltin trichlori.de and 307 parts by weight of tetradecyl thioglycolate are pumped continuously a.t a temperature of 30C into a reactor system comprising a cascade of two reactors each equipped with stirrer, l.evel meter~
pH meter and thermometer Aqueous sodium hydroxide is introduced in~o the first reactor (control of addition by pH meter) such that a p~ of about 5 is kept therein. The reaction mass is then pumped into the second reactor, the 10 volume being controlled by the level meter Feed and discharge are so controlled that the dwell time of ~he reaction mass in the first reactor is 2 minutes. The heat : of reaction is removed so that the temperature in the first and second reactor does not exceed 50 C.
15 Aqueous sodium hydroxide is also introduced into the second reactor in order to obtain a constant pH of 5 (control of addition by pH meter). The reaction mass is pumped from the second reactor into a continuously operating liquid-liquid extractor which separa~es the aqueous 20 phase from the product phase. The produc~ phase is then spray dried and clarified by filtration, affording a viscous liquid of the formula n-C4HgSn(SCH2COOC14H29)3.
The yield is 96 % of theory, based on the starting mono-n-butyltin tri~hloride.
25 Analysis: Sn (theory) : 11.4 %; S: 9 3 %
Sn (found) : 11.2 %; S: 901 %, E~ A previously prepared mixture of 100 parts by weight of di-n-octyltin dichloride and 98 parts by weight of 2-ethylhexyl thioglycolate is pumped con~inuously at room temperature into a reactor system comprising a cascade of two reactors each equipped with stirrer, level meter, pH meter and thermometer. Simultaneously, aqueous sodium hydroxide solution is added, with efficient stirring, to the reaction mass such that 2 pH of 6.5 to 7.0 is maintained in the first reactor. The addition of sodium hydroxide is 10 controlled by the pH meter in the first reactor. The heat of reaction liberated during the reaction is not removed.
The reaction temperature is 65C. (The temperature is determined by the adiabatic mode of operation and is dependent on the temperature of the starting mixture of 15 dioctyltin dichloride and 2-ethylhexyl thioglycolate).
The reaction mass is then pumped into the second reactor (volume control by the level meter), Feed and discharge of the reaction mixture are so controlled that the dwell time of the reaction mass in the first reactor is 5 20 minutes.
Aqueous sodium hydroxide solution (very little) is also introduced into the second reactor in order to maintain a constant pH of 6.9 (control of addition by pH meter). The reaction mass is then pumped from the second reactor into a 25 liquid-liquid extractor, in which the salt containing aqueous phase is separated continuously from ~he product.
The product is subsequen~ly spray dried and clarified by filtration, affording a v~cous liquid consisting of 2-ethylhexyl di-n-octyltin bi~oglycolate The yield is 30 97 % of theory~ based on the starting di-n~octyltin dichloride.
Analysis : Sn (theory) : 15,8 %; S: 8.5 %
Sn (found) : 15~7 %; S: 8.3 %.
20 R' may be e.gO straight chain or branched octyl, decyl, ~` - dodecyl, tetradecyL and hexadecyL, as well as the commercially a~ailable mixtures of alcohols known as alfols, which contain substantially alkyl groups having the same number of carbon atoms and are mainly branched.
~;; 25 The alkyl groups are here known as "aLfyls"
The starting materials employed for ~he proces~ are alkyltin haLides and thiocarboxylic acid esters. The alkyltin haLides ~ 5 employed are chlorides, bromides or iodides, preferably alkyltin chlorides or bromides in an amount of 85 to 115 mole %, based on the thiocarboxylic acid esters. The thio-carboxylic acid esters are known compounds. Thioglycolic and thiopropionic acid esters are especial]y preferred.
The initiation of the continuous reaction is conveniently effec~ed batchwise, beginning first with the addition of the reagents, then adding the a~ueous solution of ~he base for adjusting the desired pH range, and finally adding 10 both reaction omponents and the solution of the base continuously.
The starting alkyltin halides and thiocarboxyLic acid esters may be added to the reactor at 20-30C either as a previously prepared mixture or added separately at different 15 temperatures The process of the invention may be carried out e.g. in the following system:
To initiate the reaction, the appropriate alkyltin chlori~e or chlorides and the corresponding thiocarboxylic acid ester 20 are pumped in the required molar ratio into the reactor until this latter is about half full, With stirring, an aqueous solution of the base is then added until the desired pH value is reached, after wh~l the continuous addition of the sodium hydroxide solutiona the alkyltin chloride(s) 25 and the thiocarboxylic ~d ester is commenced with. When the controlled volume has been reached, the reaction mixture is pumped into the second reactor such that the controlled volume in the second ag~ator vessel is maintained.
~: :
After an average dweLl time o~ 1 to 60 minutes, pre~erably 30 of 1 to 10 minutes and, most preferably, of 1 to 5 minutes, ~238C3 the reaction mixture is discharged con~inuously from ~he reactor in order to separate the organic phase from the aqueous phase, The separa~ion of the water from the reac~ion mixture drawn off from the reactor is preferably effected by a continuously operating liquid-liquid extractor or else also by suitable separating columns.
Liquid-liquid extractors are conventional separators used in chemical engineering. Particulars on the individual extraction methods are to be found in Ullmann, 10 Enzyklop-adie der technischen Chemie, Vol. 2, 4th edition (1972)~ on page 553, and a description of ~he individual apparatus and extractors will be found on pp. 560-564. The continuously operating liquid-liquid centrifugal extractor is particularly advantageous for 15 separating water from the reackion mixture drawn of from the reactor 9 preferably at 4~-50C.
The so isolated product phase may conveniently also be dried continuously, e.g. by continuous spray drying or al50 with ~he aid of a thin-film or falling film 20 evaporator.
Spray drying, thin-film or falling film evaporators are also known drying or evaporating systems. Such equipment is described e.g in Ullmann, Enzyklopadie der technischen Chemie. Vol. 2, 4th Edition (197Z) on pp, 712-713 25 (spray driers) and on pp. 655-656 (thin-film and fal~ing film evaporators).
The following Examples describe the invention in more detail ~38 Example 1: 100 parts by weight of a mixture of 30 mole %
of mono-n-octyltin trichloride and 70 mole % of di-n-octy~in dichloride together with 104 parts by weight of 2-ethylhexyl thioglycolate are pumped continuously at a temperature of 60C into a reactor system comprising a cascade of two reactors each equippecl with stirrer, level meter,pH meter and thermome~er. With efficient stirring~
aqueous sodium hydroxide solution is simultaneously added to the reaction mass such that a pH of 6.5-7.0 is lQ maintained in the first reactor. The addition of sodium hydroxide is controlled by the pH meter in the first reactor. The reaction mixture is pumped into the second reactor, the volume being controlled by the level meter.
Feed and discharge of the reaction mixture are controlled 15 such that the dwell time of the reaction mass in the first reactor is 5 minutes. The heat of reaction liberated during the reaction is removed such that a constant temperature of 60C is kept in the fir~t and in the second reactor.
20 Aqueous sodium hydroxide(very little~ is also introduced into the second reactor in order to maintain a constant pH
of 6.9 (control of addition by pH meter). The reaction mass is then pumped from the second reactor into a liquid-liquid extractor, in which the salt-containing aqueous phase is 25 separated continuously from the product. The product is then spray dried and clarified by filtration, ~o give a viscous liquid consisting of a mixture of 30 mole % of 2-ethylhexyl mono-n-octyltin tristhioglycolate and 70 mole % oE 2-ethylhexyl di-n-octyltin bisthioglycolate.
30 The yield is 98 % of theory, based on the two starting mono and dioctyltin chlorides.
Analysis: Sn (theory) : 15.5 %; S: 9.0 %
Sn (found) : 15.2 %; S: 8.9 %.
~38~5 Example 2: 100 parts by weight of mono-n-butyltin trichlori.de and 307 parts by weight of tetradecyl thioglycolate are pumped continuously a.t a temperature of 30C into a reactor system comprising a cascade of two reactors each equipped with stirrer, l.evel meter~
pH meter and thermometer Aqueous sodium hydroxide is introduced in~o the first reactor (control of addition by pH meter) such that a p~ of about 5 is kept therein. The reaction mass is then pumped into the second reactor, the 10 volume being controlled by the level meter Feed and discharge are so controlled that the dwell time of ~he reaction mass in the first reactor is 2 minutes. The heat : of reaction is removed so that the temperature in the first and second reactor does not exceed 50 C.
15 Aqueous sodium hydroxide is also introduced into the second reactor in order to obtain a constant pH of 5 (control of addition by pH meter). The reaction mass is pumped from the second reactor into a continuously operating liquid-liquid extractor which separa~es the aqueous 20 phase from the product phase. The produc~ phase is then spray dried and clarified by filtration, affording a viscous liquid of the formula n-C4HgSn(SCH2COOC14H29)3.
The yield is 96 % of theory, based on the starting mono-n-butyltin tri~hloride.
25 Analysis: Sn (theory) : 11.4 %; S: 9 3 %
Sn (found) : 11.2 %; S: 901 %, E~ A previously prepared mixture of 100 parts by weight of di-n-octyltin dichloride and 98 parts by weight of 2-ethylhexyl thioglycolate is pumped con~inuously at room temperature into a reactor system comprising a cascade of two reactors each equipped with stirrer, level meter, pH meter and thermometer. Simultaneously, aqueous sodium hydroxide solution is added, with efficient stirring, to the reaction mass such that 2 pH of 6.5 to 7.0 is maintained in the first reactor. The addition of sodium hydroxide is 10 controlled by the pH meter in the first reactor. The heat of reaction liberated during the reaction is not removed.
The reaction temperature is 65C. (The temperature is determined by the adiabatic mode of operation and is dependent on the temperature of the starting mixture of 15 dioctyltin dichloride and 2-ethylhexyl thioglycolate).
The reaction mass is then pumped into the second reactor (volume control by the level meter), Feed and discharge of the reaction mixture are so controlled that the dwell time of the reaction mass in the first reactor is 5 20 minutes.
Aqueous sodium hydroxide solution (very little) is also introduced into the second reactor in order to maintain a constant pH of 6.9 (control of addition by pH meter). The reaction mass is then pumped from the second reactor into a 25 liquid-liquid extractor, in which the salt containing aqueous phase is separated continuously from ~he product.
The product is subsequen~ly spray dried and clarified by filtration, affording a v~cous liquid consisting of 2-ethylhexyl di-n-octyltin bi~oglycolate The yield is 30 97 % of theory~ based on the starting di-n~octyltin dichloride.
Analysis : Sn (theory) : 15,8 %; S: 8.5 %
Sn (found) : 15~7 %; S: 8.3 %.
Claims (14)
1. A process for the production of alkyltin thiocarboxylic acid esters from alkyltin halides and thiocarboxylic acid esters in the presence of an acid acceptor, which process comprises carrying out the reaction continuously in a reaction system comprising 1 to 5 agitator vessels with an average dwell time of 1 to 60 minutes, at a constant pH value in the range from 3 to 8, and in a temperature range from 40° to 80°C.
2. A process according to claim 1, wherein the reaction system consists of two reaction vessels.
3. A process according to claim 1, wherein the reaction system consists of one reaction vessel.
4. A process according to claim 1, wherein the reaction is carried out in the reaction system with a dwell time of 1 to 10 minutes.
5. A process according to claim 1, wherein the reaction is carried out in the reaction system at a pH from 5 to 7.
6. A process according to claim 1, wherein the reaction is carried out in the reaction system in the temperature range from 50° to 60°C.
7. A process accoding to claim 13 wherein the starting materials are fed into the reaction system at a temperature of 20° to 30°C and the reaction itself is carried out adiabatically.
8. A process according to claim 1, wherein the reaction is carried out in the absence of an organic solvent.
9. A process according to claim 1, wherein the product drawn off from the reaction system is separated from the aqueous phase and subsequently dried.
10. A process according to claim 9, wherein the product phase drawn off from the reaction system is separated from the aqueous phase by a continuously operating liquid-liquid extractor or a separating column.
11. A process according to claim 9, wherein the product phase drawn off from the reaction system is separated from the aqueous phase by a continuously operating liquid-liquid centrifugal extractor.
12. A process according to claim 9, wherein the product phase is dried by continuous spray drying or with the aid of a thin-film or falling film evaporator.
13 A process according to claim 1, wherein alkyltin thiocarboxylic acid esters of the formula RxSn[S(CH2)nCOOR,]4-x wherein x and n are 1 or 2, R is methyl, butyl, octyl, lauryl or the -CH2CH2COO-n-C4H9 group, and R' is a C8-C16alkyl group, are prepared from the corresponding alkyltin halides and the corresponding thiocarboxylic acid esters, the term halide denoting chloride, bromide or iodide.
14. A process according to claim 1, wherein alkyltin thiocarboxylic acid esters of the formula RxSn[S(CH2)nCOOR']4-x wherein x and n are 1 or 2, R is methyl, butyl, octyl or the -CH2CH2COO-n-C4H9 group, and R' is a C8-C16 alkyl group, are pre-pared from the corresponding alkyltin halides and the corresponding thiocarboxylic acid esters, the term halide denoting chloride, bro-mide or iodide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH777281 | 1981-12-04 | ||
| CH7772/81-1 | 1981-12-04 | ||
| CH468/82-3 | 1982-01-26 | ||
| CH46882 | 1982-01-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1238050A true CA1238050A (en) | 1988-06-14 |
Family
ID=25684667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416898A Expired CA1238050A (en) | 1981-12-04 | 1982-12-02 | Continuous process for the preparation of alkyltin thiocarboxylic acid esters |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0081458B1 (en) |
| CA (1) | CA1238050A (en) |
| DE (1) | DE3271056D1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2139625B (en) * | 1983-05-03 | 1987-05-13 | Ciba Geigy Ag | Novel organo-tin pvc stabilisers |
| EP0433473A1 (en) * | 1989-12-18 | 1991-06-26 | Chemische Werke München Otto Bärlocher GmbH | Method for the direct synthesis of organotin compounds and their use |
| US5470995A (en) * | 1993-06-29 | 1995-11-28 | Morton International, Inc. | Continuous process for making a dialkyltin thiocarboxylic acid ester |
| CA2123359C (en) * | 1993-06-29 | 1997-01-28 | Kevin S. Kolin | Continuous process for making a dialkyltin thiocarboxylic acid ester |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3716568A (en) * | 1970-09-01 | 1973-02-13 | Argus Chem | Reaction products of dioctyltin oxide and dioctyltin monohydric aliphatic saturated alcohol thioglycolate esters and process |
| US3660442A (en) * | 1970-09-11 | 1972-05-02 | Synthetic Products Co | Organotin mercaptoacid esters and their method of preparation |
| DE3063632D1 (en) * | 1979-12-07 | 1983-07-07 | Ciba Geigy Ag | Mixture of n-octyl tin compounds, process of their preparation and their use as stabilizers for halogen containing thermoplastics |
-
1982
- 1982-11-29 EP EP82810510A patent/EP0081458B1/en not_active Expired
- 1982-11-29 DE DE8282810510T patent/DE3271056D1/en not_active Expired
- 1982-12-02 CA CA000416898A patent/CA1238050A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0081458B1 (en) | 1986-05-07 |
| EP0081458A3 (en) | 1984-04-25 |
| EP0081458A2 (en) | 1983-06-15 |
| DE3271056D1 (en) | 1986-06-12 |
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