Synthesis of organotin oxides

Details Synthesis of organotin oxides Synthesis of organotin oxides

2001-02-20

2002-04-23

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

Reexamination Certificate

active

06376693

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the synthesis of organotin oxides which are useful as intermediates in the preparation of organotin stabilizers and additives for paints and coatings.
BACKGROUND OF THE INVENTION
Organometallics, compounds containing carbon-metal bonds, tend to be compatible with polar polymers such as PVC. Most organometallics have disadvantages: toxicity (alkyl lead, zinc and mercury compounds), violent reactivity to air or water (organo-aluminum and titanium compounds), or high reactivity towards polar substrates (silanes). An exception is the case of mono- and dialkyltin derivatives. In a typical stabilizer, tin, in the (IV) oxidation state, is covalently bound to either one or two alkyl groups, and, correspondingly, either two or three reactive ligands. The latter are capable both of displacing labile chlorine and scavenging HCl. The resultant mono- and diorganotin compounds form a group of valuable stabilizers, principally for rigid PVC, but with some flexible PVC use. The generalized stabilizer formula is R
2
SnX
2
or R
2
SnX
3
.
In the first generation of tin stabilizers to appear in the late 1930's in the United States, the R-group used in the above general formula was n-butyl, because of the availability and relative low cost of n-butyl chloride, and its suitability in the Grignard reaction with magnesium, as follows:
R—Cl+Mg→R—Mg—Cl  (1)
The resultant Grignard reagent reacts rapidly with tin halides, replacing chloride with the R-group. In practice, tin tetrachloride was converted to tetrabutyltin, originally with butylmagnesium chloride, more recently with the corresponding aluminum trialkyl.
SnCl
4
+4R—MgCl→R
4
Sn+4MgCl
2
  (2)
3SnCl
4
+AIR
3
→3R
4
Sn+4AlCl
3
  (3)
The resultant tetraalkyltin is then reacted further with tin tetrachloride, causing disproportionation into a range of alkyltin chlorides, which are separated by fractional distillation.
R
4
Sn+SnCl
4
→RSnCl
3
+R
2
SnCl
2
, etc.  (4)
The disproportionation process and fractionation can be controlled to yield mixtures of almost entirely mono and diorganotin chlorides, ranging from an equilibrium 65/35 di/mono ratio to pure mono- or di-, depending on reaction conditions. These intermediates are then reacted with carboxylic acids or with ligands containing mercaptan groups to yield actual stabilizers.
Dimethyltin dichloride intermediate is now produced directly from tin and methyl chloride.
Sn+2CH
3
Cl→(CH
3
)SnCl
3
  (5)
Similarly, monomethyltin trichloride is synthesized from stannous chloride:
SnCl
2
+CH
3
Cl→CH
3
SnCl
3
  (6)
These methods are cost effective and, in addition, directly yield intermediates without the need for fractional distillation of a mixture. However, these alkyltin chloride intermediates are corrosive, require glass lined reactors, and have undesirably toxic properties.
It would be very advantageous to eliminate the need to produce alkyltin chloride intermediates in making organotin stabilizers. New methods are also desired for producing organotin compounds to overcome the disadvantages of known methods.
SUMMARY OF THE INVENTION
This invention is directed to a method of making organotin oxides. These organotin oxides have many uses including their use as intermediates in the preparation of tin stabilizers for polymer compositions, especially vinyl halide polymers.
The method involves preparation of monoalkyltin, dialkyltin and trialkyltin oxides directly from tin powder and alcohols. Powdered tin metal is reacted with an alcohol at an elevated temperature, on the order of about 200 -400° C. in the presence of an acidic catalyst to produce the desired alkyltin oxide. Monomethyltin oxide, monobutyltin oxide, dimethyltin oxide, dibutyltin oxide, trimethyltin oxide and tributyltin oxide have been produced employing the method of this invention.
The objectives and advantages of this invention will be understood with reference to the following detailed description and operating examples.
PREFERRED MODE AND DETAILED DESCRIPTION
The method of this invention is practiced by reacting powdered tin metal with a primary alcohol in the presence of an acidic catalyst at an elevated temperature. The powdered tin metal has a particle size range on the order of about 200 mesh or finer, preferably from about 300 to about 400 mesh. A number of primary alcohols may be used in the invention including methanol, butanol, and octanol. A Lewis acid catalyst is preferred in order to obtain quantitative yields in a shorter reaction period. The yields with primary alcohols go down as the molecular weight increases. A number of different acidic catalysts may be employed including anhydrous stannous chloride, anhydrous aluminum Chloride or Boron trifluoride. The temperatures of the reaction will vary depending upon the reactants; however, usually temperatures on the order of about 200 to about 400° C. are employed. The alkyltin oxide is collected upon cooling at temperatures below 0° C., preferably −20° C. to −60° C., and under vacuum.
The following examples illustrate the practice of the invention, but are not considered to be limiting the broader aspects of the inventive method.


REFERENCES:
patent: 3376329 (1968-04-01), Kobetz et al.
patent: 3390159 (1968-06-01), Katsumura et al.
patent: 3448130 (1969-06-01), Oakes et al.
patent: 3466311 (1969-09-01), Mizuno et al.
patent: 3493592 (1970-02-01), Shapiro et al.
patent: 3711524 (1973-01-01), Leebrick et al.
patent: 3813424 (1974-05-01), Hayashi et al.
patent: 4968823 (1990-11-01), Kiyama et al.

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