DE1543413A1 - Process for the production of organotin compounds - Google Patents

Description

Dr, Walter Beil ^^ ^ & Alfred Hoeppener \ 1 VV. i - ^> - ** ^u '\ / ο / ι ο

Dr.fta Jccaiirn Wolff U ^^^ 1 5 4 3 A 1 3 Dr. Hans Chr. Beil

Lawyers Our No. 12 583

Frankfurt a. M. -Highly

Adeloustrajje 58 - Tel. 31 26 49

Chas. Pfizer & Go., Inc.
New York, USA

Process for the preparation of organotin compounds

The invention relates to a method for production of new polymerizable organotin compounds which are valuable as such or in polymerized form as antimicrobial ones Agents and stabilizers for vinyl synthetic resins can be used.

The compounds that can be prepared according to the invention have the general formula:

OO OR « ¹

H H H I

R _n Sn (OCR ¹ -0-0-RW-OCC = OH ₂ ) ₄ _ _n

in the η an integer from 1-3,

R is a hydrocarbon radical, namely an alkyl, alkenyl, Alkynyl, cycloalkyl, cycloalkenyl, a mono- or bicyclic aryl radical or an alkaryl radical with up to 18 carbon atoms,

R ^{A is} a divalent radical, namely an alkylene, an alkenylene, an alkynylene, a cycloalkylene, a cycloalkenylene, a mono- or bicyclic arylene radical or an alkarylene radical

009834/1466

R 4 3 A 1 3

with up to 18 carbon atoms,::. ..

R "is a divalent best, namely an alkyl en-, a - alkenylene · - ,, an alkynylene, a cycloalkylene, or a Zyklogii-ke-nylenrest with up to 18 carbon atoms and ^,. · - · .. · :.

R "'is hydrogen or an alkyl radical having 1-18 carbon atoms is.

Because of their double bonds, these new monomers can be homopolymerized as well as with ethylenically unsaturated monomers Monomers are copolymerized. Suitable ethylenically unsaturated monomers are polymerizable compounds with at least one terminal methylene group, i.e. CHp = CiC, such as vinyl chloride, vinyl acetate, styrene, methyl vinyl ketone, Methyl and ethyl acrylates, acrylonitrile, butadiene, isoprene and chloroprene. If the new monomers according to the Invention can be polymerized with other monomers, these other monomers can make up a greater or lesser proportion of the polymer. A representative polymer can be made from a larger amount of polyvinyl alcohol and a smaller amount of the organotin compound.

The above polymers contain at least one organotin unit in their polymeric structure, as follows is shown;

R "»

= O

C =

O
ι

R "

C = O

C = O

9 0 9 8 3 4/1466 BAD original

In this. Structural formula η, R, R ¹ , R "and R '" have the meanings given above. It is clear that in homopolymers the repeating unit is the same, ie the organotin unit, while in mixed polymers the polymeric chain has different units.

When a disubstituted organotin monomer is used ee forms a polymeric unit that can be represented as follows:

0 0 OR ¹ "

HN If I

R ₂ Sn / oC-R'-CO-RW-OCC-ChJ ₂

These bis compounds are useful as crosslinking agents.

The polymerization conditions used in the preparation of the synthetic resins containing the new monomers are usual.

The polymerization can either be in solution, or in emulsion, or as a bulk polymerization in the absence of a non-reactive Solvent or a dispersion medium are carried out. Suitable solvents are e.g. toluene, Tetrahydrofuran and water. Usually a polymerization initiator is used and heated during the reaction to cause the Accelerate polymerization. The technique commonly used in the polymerization of vinyl monomers is for Satisfactory polymerization of the monomers according to the invention. The polymerization temperatures used in the Manufacture of yinyl polymers applied complied .. As Polymerization initiators or catalysts are the so-called peroxy catalysts, such as benzoyl peroxide, lauroyl peroxide, tertiary alkyl peroxides, di- (tert. alkyl) peroxides, alkali metal persulfates, such as potassium persulfate and other polymerization

909834/1466

catalysts such as azo-bis- (isobutyronitrile) are used. Free Free radical forming catalysts can also be used. The amount of catalyst depends on the rate of polymerization desired and the polymerization temperature.

The new compounds according to the invention, which comprise the monomers, homopolymers and copolymers, can be due to Coatings and adhesives as well as synthetic resins are added to their antimicrobial properties. It also proved these compounds are used in pest control on plants, e.g. to fight various types of fire, and valuable as a stabilizer for synthetic resins against the adverse effects of heat and light.

The compounds which can be prepared according to the invention include tributyl compounds of the above formula in which η * 3, Rn-butyl, R ^{1 is} ethylene, R "is methylethylene and R" ^{1 is} hydrogen. These compounds are suitable for making rot-resistant paints for shipping, as antimicrobial coatings, as clear rot-resistant coatings for underwater instruments and as adhesive antimicrobial coatings, as well as for other types of applications where an antimicrobial effect is desired. The tributyltin compounds mentioned are easily obtained by reacting tributyltin oxide with a suitable acrylyl glycol ester according to the following scheme!

0 0 OR ¹¹¹

Il M Wl .

Cn-Bu ₅ Sn) ₂ O + 2H0-C-R'-C-0-R "-0-CC = CH ₂ i

OOOR ¹ "η 11 nt

2n-Bu ₅ Sn-O-C-R'-CO-RW-OCC ₂ g

where Λ represents the application of heat. It is clear to the person skilled in the art that there are a large number of chemically equivalent reactions for this reaction.

BATH ORIGINAL SQ9834 / 1466

As will be set out below, the above implementation most expediently simply by heating a mixture of the corresponding acrylyl glycol ester and bis-tributylinoxide carried out until the implementation is complete. Then the product is cooled. It is particularly useful two moles of the ester with one mole of the tin compound in the presence of a small amount of a polymerization inhibitor

to be heated to 120 ° until all of the water of reaction has been removed. With acrylyl propylene glycol maleate and bis-tributyltin oxide a transparent, straw-colored liquid is obtained which, with benzoyl peroxide at 100 °, becomes a clear, viscous liquid Elastomers can be polymerized.

The scope of the invention also includes the butyl compounds of the formula given above, in which η = 2, R η-butyl, R ^{1 is} ethylene, R "is methylethylene and R ^{MI is} hydrogen. These compounds are used as such in the stabilization of synthetic resins, especially of halogenated synthetic resins and especially of polyvinyl chloride polymers and copolymers containing polymerized vinyl chloride, effective against darkening and the loss of physical properties that occur when they are exposed to heat and light. Particularly noteworthy is the ability of the new monomers that they can be copolymerized with halogenated hydrocarbon monomers, such as vinyl chloride, which contain stabilizers in a built-in, non-extractable form for such uses as packaging material for foodstuffs, bottles and the like. The dibutyltin-bis-acrylyl esters can be prepared by processes as they go through that the following scheme are explained

0 0 OR ¹ · ¹

If Il It I

H-Bu ₉ SnO + 2H0-CR ^f -C-0-R «-0-CC = CH _Q τ *

^d 0 0 OR ' ¹ ' ^d ^

H H H I

H-Bu ₂ Sn / OGR • -COR "-0-CC-CH ^ ₂ + HgO

BATH 909834 / U66

or by appropriate, chemically equivalent processes. In this process, dibutyltin oxide is conveniently used with 2 equivalents of acrylyl glycol dicarboxylate reacted until the reaction has ended and the water has been removed. That Product is obtained by cooling the reaction mixture and can be obtained in the presence of a catalytic amount of benzoyiperoxide are rapidly polymerized at 100 °, especially It is advantageous to heat the reactants to 120 ° until all of the water has been removed. If that Reaction mixture of dibutyltin oxide and acrylylpropylene glycol maleate Cooling to room temperature gives a slightly yellow, viscous liquid.

A compound of the formula given above in which η = 3, R is phenyl, also falls within the scope of the invention R 'ethylene, R "methylethylene and R" · hydrogen is. This connection can be made according to the following scheme

0 0 OR " ¹

• I It Il I

(C ₆ H ₅ ) ₃ SnOH + HO-C-R'-C-O-R "-0-CC = CH ₂

0 0 OR "«

HH Nt

(C ₆ H ₅ ) ₃ Sn-OC-R'-COR ^II -CC = CH ₂

or by a chemically equivalent process. It is particularly useful to use an acrylyl glycol ester with the same molar amount of triphenyltin hydroxide to mix and to 105 to heat. When the reaction is complete, this will The product of acrylylpropylene glycol aleate is cooled and a clear, extremely viscous material is obtained By adding a catalytic amount of benzoyl peroxide and heating to 105 °, an infusible resin is obtained,

BATH ORIGINAL 90983A / U66

This product is characterized by low phytotoxicity when used to combat potato fire, presumably due to its polymeric nature and its very limited solubility.

All compounds according to the invention can after a where the following reaction sequences are produced, depending on which value η have in the desired end product

0 0 OH " ¹

It If MI

RSnOOH + 3H0-CR ¹ -0-0-11 "-0-CC = CH ₉

0 0 OR " ¹

K Il St.

R ₀ SnO + 2H0-0-R'-COR "- 0-GC = CH ²

0 0 OH ¹ "

η η mi

O + 2H0-CR * -C-0-R "-0-CC = CH ₂ -HgO ^}

0 0 OR "«

Il H Il I

(D (2) (5) _; R _n Sn (0-CR ^f -COR "-OCC = CH ₂ ) ₄ _

where R, R ', R " ^{1 have} the meaning given above and the reaction sequences (1), (2) and (3) lead to compounds in which η is 1, 2 and 3.

The starting materials for these reaction sequences are readily available or can be easily prepared by processes known to those skilled in the art. Examples of commercially available tin-containing starting materials are bis-tributyltin oxide, dibutyltin oxide, butylstannic acid and triphenyl tin hydroxide. In general it is with the

BATH ORIGINAL 90983A / U66

Production of starting materials with different R groups advantageous, a modification of the classic Grignard To apply procedures, see H.V. Smith "Organotin Stabilizers", Tin Research Institute, Middlesex, England, page 5, (1959). Examples of preferred R groups according to the invention are the methyl, ethyl, n-propyl, η-butyl, n-octyl, phenyl, Benzyl, o-tolyl, cyclopentadienyl, n-octadecyl, 2-iithylhexyl, Ethynyl, cyclohexyl, cyclohexenyl group and the like.

These methods include the treatment of the appropriately substituted tin compound, which must be able to to form a carboxylate with the carboxylic acid derivatives prepared by the process described below will. If water is one of the reaction products, the reaction is completed by simply heating the reactants until the water is removed is. The reactants are expediently heated to a temperature above the boiling point of water; 120 ° has proven to be particularly effective for this. It is advantageous, but not essential, to carry out the reaction in the presence to carry out a polymerization inhibitor. If an inhibitor is used, it is preferable to put it in an amount from 0.05% to about 3 # based on the amount of the tin present. Any known inhibitor for vinyl polymerization can be used for this purpose. Examples are hydroquinone, t-butylcatechol, nitrobenzene and the same.

The acrylyl glycol ester starting materials can be prepared according to the following process

0 0 OR "'

it it tt ι

HO-C-R'-C-OH + H0-R "-0-CC = CH ₂ *

0 0 OR '"

Il (I Il I

HO-C-R'-C-O-R "-0-C-C = CH

8AD ORIGINAL 909834/1 466

They can also be produced by chemically equivalent processes, e.g. by reacting a dicarboxylic acid anhydride or a hexicyl chloride with a suitable acrylyl glycol. jeidpieit, for the group R 'are the ethylene, hexylene, uct ^ decyien, hexadecylethylene, ethylene, methylethylene, nth Ln ^ len, 2-utynylene, cyclohexylene, oyclohexenylene, r ^ e ^ len-, joiylen-, naphthylen- and similar groups.

^ ir.xiie of the acrylyl glycols, e.g. acrylyl propylene glycol available in d'-mdei. The others can easily be named after Processes can be obtained, e.g., by transesterification -.vuc.hen a glycol and an unsaturated acid ester uac: the following equation;

OR ¹ "0 R"'

H0-H-0H ₊ RO-CC = CH ₂ > H0-R «-0-CC = CH ₂ * ROH

woüei R, R "and R". ' have the meaning given above ". ever. this procedure is appropriately substituted Glycol in the presence of a transesterification catalyst with a Treated ester of an unsaturated acid. Examples of preferred groups R ″ obtained by this method are the ethylene, hexylene, uctadecylene, Methylethylene, 2-butynylene, cyclohexylene, cyclohexenylene group and similar groups. Examples of preferred groups R "'that can be introduced by this method are Hydrogen, ethyl, butyl, dodecyl, octadecyl, 2-ethylhexyl groups and similar.

Polymers from the new compounds can be obtained by treating the monomers in emulsion, solution, suspension or mass can be obtained with polymerization catalysts. Suitable catalysts are, for example, peroxy catalysts, persalts and Azo compounds. Benzoylperox ^ may be mentioned as an illustration

90983 (/ USl

Lauroyl peroxide, potassium persulfate, azo-bis-isobutyronitrile and similar.

The new compounds according to the invention, which are effective antimicrobial agents, are used in particular in paints and coatings that are susceptible to micro; ial attack, in particular by fungi. They are distinguished by the essential advantage that they offer good protection against undesired growth of Mi kr ο or gani and are significantly less toxic than the mercury compounds commonly used. Paints in which the antimicrobial agents according to the invention are contained can be produced by methods which are within the range of the craftsmanship of the person skilled in the art. The antimicrobial agents according to the invention can be added to the paints after or during their production. With regard to the coatings to be added to the amount and the desired effect of guaranteeing the antimicrobial agent was found that about 0.01 to 1.0 wt. I »enables effective control. Although the paints are effectively stabilized when used in an amount greater than 1.0% by weight, the improvement in stability does not appear to be too great with increasing amounts to justify the cost of the larger additive.

Others of the compounds according to the invention have calibration in the Stabilization of synthetic resins, especially polyvinyl chloride polymers and copolymers shown to be effective. Synthetic resins that contain about 25 - about 1,000 parts by weight of stabilizers contained per million parts of the synthetic resin are resistant to microbial attack. One of the advantages when using the compounds according to the invention, there is a relatively low toxicity in comparison to the extremely toxic known stabilizers, among which phenyl mercuric acetate should be mentioned.

909834/1466

BATH ORIGINAL

The synthetic resins stabilized using the products of the process can be produced by known processes. If, for example, a plasticized polyvinyl chloride resin is to be produced, the stabilizing agents according to the invention can be mixed well with the powdery resin, whereupon the entire mixture is homogenized and then cast into films. In particular, reference should be made to a copolymer of vinyl chloride which contains 3 parts by weight of a compound of the formula in which R is n-butyl _T R-ethylene, R "is methylethylene and R ^{HI is} hydrogen, each 100 parts of vinyl chloride in this way a material with a built-in, non-extractable stabilizer for packaging material for foodstuffs, bottles, and the like.

The following processes can be used to prepare the starting materials for the valuable new polymerizable compounds be applied according to the invention.

Procedure A Acrylyl propylene glycol

A solution containing 86 g (1.0 mol) of methyl acrylate, 76 g (1.0 mol) of propylene glycol and 0.5 g of b-toluenesulfonic acid in 500 ce of benzene is refluxed for 16 hours. The solvents are distilled at 4OC, and 20 mm. Ed. Removed. The distillation residue consists of acrylylpropylene glycol of suitable purity for conversion into the dicarboxylate according to method B.

Using the same procedure but using suitable, higher alkyl substituted acylates instead of methyl acrylate and using appropriately substituted glycols instead of Pre ^ ylene glycol, the following glycol acrylates obtain:

909834/1466 _ßA0

HO - R "- O -

R "

-CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CHgCH ₂ - - CH ₂ (CH ₂ J ₂ CH ₂ - -CH ₂ (CH ₂ ) ₁₆ CH ₂ .

-CH ₂ -CH ^- CH-CH ₂ - -C (CH ₃ ) -CH-CH ₂ - -CH ₂ -CeC-CH ₂ -CH ₂ -CeC-CH ₂ -CH ₂

CH - CH ₂

-CH CH-

CH ₂ - CHg CH - CH -CH .CH-

TJHo- CHo CHg R

CH ₃ -

CH3 (CHg) ₂ CH ₂ - -

CH ₃ (CHg) ₁₀ CHg-

CH ₃ (CHg) ₁₆ CH ₂ -

CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ -

HHHHHHHH CH ₃ -

909834/1466

Procedure B

Acrylylpropylene glycol maleEt

Acrylylpropylene glycol, prepared by method A. 130 g, 1 mole, and maleic anhydride, 98 g, 1.0 mole, are heated to 120 for two hours. Then leave to cool down. The product, acrylyl propylene glycol maleate, is used in the manufacture of the polymerizable organotin derivative According to the invention of more satisfactory Unity.

Another method is acrylyl propylene glycol, 130 g, 1 mole, maleic acid, 98 g, 1 mole, and 1.0 g of p-toluenesulfonic acid heated under reflux for 16 hours as a catalyst in 1,000 cm of benzene. After removing the water Acrylylpropylene glycol maleate is obtained as a residue by azeotropic distillation and the solvent in vacuo.

If, instead of maleic anhydride or the acid by the alternative process, stoichiometric equivalents Quantities of corresponding acids or their derivatives are used, the following connections are obtained:

BATH ORIGINAL

909834 / U6 6

HO -

R '

-CH-CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH-CH- -CH-CH- -CH = CH-

-R '-CO ₇ R "-0-C- C - CH ₂ R " R * ' -CH (CH ₃ ) CH ₂ - CH ₃ - -CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ ) 2CH ₂ - -CH (CH ₃ ) CH ₂ - CH ₃ (CHa) ₁₀ CH ₂ - -CH (CH ₃ ) CH ₂ - ' CH ₃ (CH ₂ ) 16CH ₂ - —CHo-CHp- CH ₃ -CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ ) 5CH (C ₂ H ₅ ) CH- -CH ₂ CHp- H -CH ₂ (CH ₂ J ₄ CH ₂ - H -CH ₂ (CH ₂ J ₁ OCH ₂ - H ₂ - H. -CH ₂ -CH = CH-CH ₂ - H -C (CH ₃ ) = CH-GH ₂ - H -CH ₂ -CsC-CH ₂ - H -CH ₂ -CC-CHg-CH ₂ - H 909834 / U66 SAD ORIGINAL.

1S

R *

-CH-CH-

R "

- CHg

J3H - CH

-CH-CH-

-CHgCHg-

-CHg (CHg) ₂ CHg-

-CHg (CHg) ₁ OCHg

-C «C-

-CH ₂ -CeC-CHg-, CH ₂ - CH ₂ - CH ₂

/ CH --CH

N-

CH-

^ S-

-CH (CHj) CHg- -CH (CHj) CHg- -CH (CHj) CHg-

-CH (CHj) CH ₂ - -CH (CHj) CH ₂ - -CH (CHj) CH ₂ - -CH (CHj) CH ₂ -

-CH (CHj) CH ₂ -

^ (DH- -CH (CHj) CH ₂ -

-CH (CHj) CH ₂ -

-CH (CHj) CH ₂ -

H H H H H H H

H H H H

S / ^ v-

-C (CHj) CH ₂ -

-CH ₂ -CH ₂ -

909834 / U66 BAD

The following examples explain the preparation of the compounds according to the invention.

Example I. Tributyltin acrylyl propylene glycol maleate

45.6 g (0.2 mol) of acrylylpropylene glycol maleate, prepared according to the method B, are added to 59.6 g (0.1 Mo]) of bis-tributyltin oxide which contains 50 mg of hydroquinone. The mixture is slowly heated to 120 ° with stirring to complete the reaction and drive off the water. Then au! ' 25 dry. A clear, straw-colored liquid is obtained which can be homopolymerized with benzoyl peroxide to form a clear, zuheii elastomer.

In an analogous manner, the monomeric reaction product is with Methyl methacrylate and styrene copolymerized in the following way: A mixture of 20 parts by weight of the monomer, 80 parts by weight of methyl methacrylate or styrene and 0.2 parts by weight Benzoyl peroxide, based on the total charge, is heated to 100 ° for about 4 to 6 hours. After cooling down the product is isolated in the form of a resin. Have both the monomeric and polymeric reaction products antimicrobial properties.

Example II Iripropyltin acrylylpropylene glycol maleate

This compound is prepared according to the method of Example 1, using bis-tripropyltin oxide obtained comparable results instead of bis-tributyltin oxide.

909334/1466

BATH ORIGINAL

The isolated monomeric reaction product is after For their des. Example 1 homopolymerized and with Iviethyl methacrylate or styrene copolymerized.

Example 11 1 Tributyltinme thacry 1.yläthylonKl.y c olmaleate

This compound is made according to the procedure of Example 1 using i ^ ethacrylylethylene glycol maleate instead of Acrylylpropylen ^ lycolmaleait lait comparable successful established.

The isolated monomeric reaction product is horopolymerized and copolymerized with ethyl methacrylate or styrene. The procedure of Example 1 is used again.

Example IV
TriQctyltin methacrylylethylene ^ lycolmaleate

This compound is according to the procedure of Example 1 using methacrylylethylene glycol maleate and bis-trioctyltin oxide instead of acrylylpropylene glycol maleate and bis-tributyltin oxide produced with comparable success.

The isolated monomeric reaction product is in turn after the method of Example 1 homopolymerized and with Lethyl methacrylate or styrene mispolymerized.

Example V

Following the procedure of Example 1 were using the maleates according to method B instead of acrylylpropylene glycol maleate and correspondingly substituted tin oxides instead from bis-tributyltin oxide the following are trisubstituted obtained unsaturated tin compounds according to the invention.

909834 / U66 _{oirMM &} ,

BAD LOCATION ¹ NAL

■ V

15th

20th

25th

30th

R ₃ Sn - O

CH ₂

CH ₃ (CH ₂ ) ₂ CH ₂ -

CH

CHo (CH ₂ ) ₂ CHo—

CH ₃ (CH ₂ ) 2 ^CH 2-CH ₃ (CH ₂ ) 2 ^CH 2 "

CH,

CH,
CH

HL - Hü H! L

-CH = CH- -CH (CH ₃ ) CH ₂ - CH ₃ -

-CH = CH- -CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ J ₂ CH ₂ -

-CH = CH- -CH (CH ₃ JCH ₂ -

-CH = CH- -CH (CH ₃ JCH ₂ -

-CH = CH- -CH (CH ₃ JCH ₂ - CH ₃ (CH ₂ J ₃ CH (C ₂ H ₅ JCH ₂

-CH = CH- -CH (CH ₃ JCH _{2 -H}

-CH = CH- -CH (CH ₃ JCH ₂ - "H

-CH = CH- -CH (CH ₃ JCH ₂ - CHq-

-CH = CH- -CH (CH ₃ ) CH ₂ -

CH ₃ (CH ₂ J ₂ CH ₂ - -CH = CH- -CH (CH ₃ ) CH ₂ - H CHq (CH ₂ Jo nn— -CH = CH- -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ ) ₂ CH ₂ - -CH = CH- -CH (CH ₃ ) CH ₂ - Ή CH ₃ (CH ₂ ) ₂ CH ₂ - -CH = CH- -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ ) ₂ CH ₂ - -CH = CH- -CH (CH ₃ ) CH ₂ - H PH Γ> Ί1 ~.
/ OiI ₂ - CH ₂ , ^ CH-, (CH «UCH" - -CH = CH- -CH ^d CH- H

CHq \ CHp / pCHp

CH ₃ (CH ₂ ) ₂ CH ₂ CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ - CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CF ₂ - -CH = CH-

-CH

CH

CH-

-CH ₂ CH ₂ , - -CH (CH ₃ JCH ₂ - H

-CH ₂ (CH ₂ J ₂ CH ₂ - -CH (CH ₃ JCH ₂ - H -CH ₂ (CH ₂ J ₁ OCH ₂ - -CH (CH ₃ ) CH ₂ -. H

-Url / Urlip ^ OJIp ) η huflo / yllp-. —Oll \ * '"3' 2

-C (CH ₃ ) -CH- -CH (CH ₃ ) CH _{2 -H}

-CsC- -CH (CH ^) CH _{2 -H}

-CH ₂ -CeC-CH ₂ - -CH (CH ₃ ) CH _{2 -H}

BATH

• R "

• R

λττ Γ * ΧΧ

-CH CH- -CH (CH ₃ ) CH ₂ -

C. -CH

- CHr

H - CH,

- CHc

'CK- -CH (CH ₃ ) CH _{2 -H}

CH ₃ (CH ₂ ) ₂ CH ₂ -

-s7 V-

-CH (CH ₃ ) CH ₂ -H

octadecenyj.

-CH = CH-

-CH-

-CH ₂ CH ₂ -

CH ₃ (CH ₂ ) ₂ CH ₂ - -CH = CH- -CH (CH ₃ ) CH ₂ - H -CH = CH- CH ₃ -CH (CH ₃ ) CH ₂ - H -CH (CH ₃ ) CH ₂ - H

-CH ₂ -

-CH = CH-

-CH (CH ₃ ) CH ₂ -H

CHc

-CH = CH- - CHp
² ; ch-
- CH ₂ ^ -CH = CH- -CH (CH ₃ ) CH ₂ - H : - y ~ -CH = CH- • CH
N) H- -CH = CH-
909834/1466 -CH (ClH ₃ ) CH2- H GH ₃ (CH ₂ ) xgCrf2- -CH = CH-
CH ₃ (CH ₂ ) ₃ CH (C2H ₅ ) CH ₂ - -CH = CH-
HCaC- -CH = CH- -CH (CH ₃ ) CH2-
-CH (CH ₃ ) CH2-
-CH (CH ₃ ) CH2- H
H
H chX ' ² -CH (CH ₃ ) CH ₂ - H ^ CH
CHjf -CH (CH ₃ ) CH ₂ - H BATH ORIGINAL

These products that themselves have antimicrobial properties are suitable for the production of polymers and copolymers with antimicrobial properties.

Example VI Dibutyltin.-bis-acryl.vlpr ο p.yler.glycol maleate

24.9 g (0.1 mol) of dibutyltin oxide, 45.6 g (0.2 mol) of acrylylgropylene glycol maleate and 50 mg of hydroquinone are slowly heated to 120 ° and kept at this temperature until the reaction has ended and the water has been removed. It is then cooled to room temperature, whereupon a clear, slightly yellow _Ί viscous liquid is obtained. It can be homopolymerized into a resinous product. This is achieved by heating to 100 with 0.5% by weight of benzoyl peroxide for 16 hours.

In an analogous manner, the monomeric reaction product can with Ethylnie acrylate and styrene copolymerized in the following way be: A mixture of 20 parts by weight of the monomer, 80 parts by weight of methyl methacrylate or styrene and, based on the total charge, 0.2 wt. # benzoyl peroxide is heated et./a 4 to 6 hours to 100 °. After cooling, the product becomes in the form of a resin isolated. The reaction product and the polymers made from it have similarly favorable properties as stabilizers for polyvinyl chloride such as dibutyltin bisisooctyl maleate.

Example VII Dioctyltin-bis-acrylylpropylene glycol maleate

This compound is obtained by following the procedure of Example 6 with comparable success if, instead of Dibutyltin oxide dioctyltin / viBrv / ends.

909834/1466 ORIGINAL BATHROOM

The isolated monomeric reaction product is again homopolymerized and with methyl methacrylate and styrene copolymerized using the procedure of Example 6.

Example VIII Dibutyltin-bis-methacrylylethylene-glycole maleate

This compound is prepared according to the method of the example, instead of acrylylpropylene glycol maleate Methacrylylethylene glycol maleate ends with the same success.

The isolated monomeric reaction product is after Method of Example 6 homopolymerized and copolymerized with vinyl methacrylate and btyrene.

Example IX Dioctyltin-bis-methacrylylethi ^ ylene ^ lycolmaleate

This compound is obtained with the same success by following the procedure of Example 6 if methacrylylethylene glycol maleate is used instead of acrylylpropylene glycol maleate.

The isolated monomeric reaction product is after Method of Example 6 homopolymerized and copolymerized with methyl methacrylate and styrene.

Example X

Following the procedure of Example 6 using suitable disubstituted tin oxides instead of dibutyltin oxide and the maleates according to method B are as follows Links:

909834 / U66 _BAD OBIG-NAL

R _o Sn (- O-O -R • -COR "-OCC-CH ₂ J ₂

CH3 (CH ₂ ) 2 ^ H ₂ ■ CH ₃ (CH ₂ ) ₂ CH ₂ -CH3 (CH ₂ ) ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ -CHo (CH ₂ J ₂ CHq-CH ₃ ( CH ₂ ) ₂ CH ₂ -CH ₃ (CH ₂ ) ₂ CH ₂ -CH ₃ (CHg) ₂ CH ₂ - CH ₃ (CH ₂ ) 2 ^CH 2 "CH ₃ (CHg) ₂ CH ₂ -CH ₃ (CH ₂ ) ₂ CH ₂ -CH ₃ (CH ₂ ) 2CH ₂ -CH ₃ (CH ₂ ) 2CH2-

-CH-CH-

-CH-CH-

-CH-CH-

-CH-CH-

-CH-CH-

-CH-CH-

CH-CH-

-CH-CH-

CH-CH-

CH-CH-

CH-CH-

CH-CH-

CH-CH- -CH (CH ₃ ) CH2- CH ₃ -

-CH (CH ₃ ) CH2- CH ₃ (CH ₂ ) 2 «

-CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ ) IOCH ₂ -

-CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ J ₁ OCH ₂ -

-CH (CH ₃₎ CH ₂ - CH ₃ (CH ₂₎ 3 CH (C ₂ H ₅₎ CH;

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH2-

H H H H H H H H

CH- (CH ₂ J ₂ CH ₂ - -CH-CH- -CH

CH 3 (CH _{2) 2} CH ₂ - -CH-CH- -OiT

CH - CK

^N CH-

CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ - CH ₃ (CH ₂ J ₂ CH ₂ - CH ₃ (CH ₂ J ₂ CH ₂ -CH ₃ (CH ₂ J ₂ CH ₂ -

CH ₃ (CH ₂ J ₂ CH ₂ - -CH CH ₂ - CH2

-CH ₂ CH ₂ - -CH (CH ₃ ) CH ₂ -
-CH ₂ (CH ₂ ) ₂ CH ₂ - -CH (CH ₃ ) CH ₂ - - -CH (CH ₃ ) CH ₂ -

H H H

-CH _i / ÜH ₂ (CH2) i4CH ₃ -7CH ₂ - -CH (CH ₃ ) CH ₂ - H

-C (CH ₃ J-CH- -CH (CH ₃ JCH ₂ -

-CeC- -CH (CH ₃ JCH ₂ -

-CH ₂ -C ^ C-CH ₂ - -CH (CH ₃ ) CH ₂ -

CH ₂ - CH _2>

CH ₂ - CH ₂ .

909834/1466 HHH

"CH- -CH (CH ₃ JCH _{2 -H}

BATH ORIGINAL

• -23 -

R_L

CH - CH, - -Cff ^ ^X CH-

CH ₃ (CH ₂ ) ₂ CH ₂ -CH3 (CH ₂ I ₂ CH ₂ -CH3 (CH ₂ ) ₂ CH ₂ -

CH-

-CH-CH-

-CH-CH-

-CH-CH-

CH-

-CH-CH-

-CH (CH ₃ ) CH ₂ - -CH (CH3) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -

-CH (CH ₃ ) CH ₂ -H

-CH-CH- -CH-CH- -CH (CH ₃ ) CH ₂ - H ^ AL V ^ OMJH- . -CH-CH- -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ ) XoCH ₂ - CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ - -CH-CH- -CH-CH- -CH (CH ₃ ) CH ₂ - H HCeC 909834 / U66 -CH (CH3) CH ₂ - H 25 ^ CH ₂ - CH _2n
² NJH ₂ - CH ₂ ^ -CH (CH ₃ ) CH ₂ - H ^ CH - .H _n
CH ₂ CH- -CH (CH ₃ ) CH2- H BAD ORIGU

The products and the polymers made from them are suitable for stabilizing halogenated hydrocarbon resins against the harmful effects of heat and light.

Example XI Butyl tin tris-acrylyl propylene glycol maleate

20.9 g (0.1 mol) of butylstannic acid, 68.4 g (0.3 mol) of acrylylpropylene glycol raleate and 50 mg of hydroquinone are slowly heated to 120 ° and kept at this temperature until the reaction is complete and the water is removed. A viscous product is obtained on cooling to room temperature. The polymerization with enzoyl peroxide at 10O ⁰ C results in an infusible resin.

Example XII Triphenyltin acrylyl propylene glycol maleate

22.8 g (0.1 mole) acrylyl propylene glycol maleate added to 105 heated and within 1 hour 36.7 g (0.1 mol) of triphenyltin hydroxide are added in proportions. After cooling a clear, very viscous product is obtained. By heating 50 g of this product to 0.2 g for 16 hours Benzoyl peroxide at 105 ° results in an infusible polymer ··. Both the monomer and the polymer have antimicrobial properties. Since polymers iet especially valuable in combating potato brandy. ·

Example XIII

Following the procedure of Example 11 using suitable monosubstituted stanoic acids instead of Butylstanoic acid and suitable maleates instead of acrylyl propylene glycol maleate the following connections »

909834 / Uli BAD o _RIG , _NAt

R - Sn / ρ Ο
R.

CH ₃ (CHg) ₂ CH ₂ -

CH ₃ (CHg) ₂ CH ₂ CH ₃ (CHg) ₂ CH ₂ CH ₃ (CH ₂ ) ₂ CH ₂ CH ₃ (CH ₂ ) gCHg CH ₃ (CH ₂ J ₂ CH ₂ CH ₃ (CHg) ₂ CH ₂ CH ₃ (CH ₂ J ₂ CH ₂ CH ₃ (CH ₂ ) ₂ CH ₂

R · -FM

-CH-CH- -CH-CH- -CH = CH- -CH = CH-

- ο

CH ₂ 7 ₃

CH ₃ -

-CH (CH ₃ ) CH ₂ - -CH (CH ₃₎ CH ₂ - CH ₃ (CH _2); -CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ ) ₁₀ CH ₂ -

-CH (CH ₃ ) CH ₂ - CH ₃ (CH ₂ )! 6CH ₂ - -CH = CH- -CH (CH ₃ CH ₂ - CH ₃ (CHg) ₃ CH (C ₂ H ₅ ) CH ₂ - -CH = CH- -CH (CH ₃ ) CH ₂ -H

-CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ -

- -CH = CH- -CH (CH ₃ ) CH ₂ -

-CH-CH- -CH (CH ₃ ) CHg- '

H H H H H

-CH-CH- -CH (CH ₃ ) CH2-

CH ₃ (CHg)! 6CH ₂ - -CH = CH- -CH (CH ₃ ) CHg-CH ₃ (CHg) ₃ CH (CgH ₅ ) CHg- -CH-CH- -CH (CH ₃ ) CH ₂ HCaC- -CH-CH- -CH (CH ₃ ) CH ₂ -

CHp - CHg

"NJH- -CH-CH-

- GH,

- CH _n

CH- -CH-CH- -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ -

H H H

H H

BATH ORIGINAL

5 CH ₃ (CH ₂ ) ₂ CH ₂ - CH3 -CH = CH- -CH (CH ₃ ) CH2- io7CH ₂ - -CH (CH ₃ ) CH ₂ H CH ₃ (CH ₂ ^ CH ₂ * -CH = CH- -CH (CH ₃ JCH ₂ - -CH (CH ₃ ) CH ₂ - H CH ₃ (CHg) ₂ CH ₂ - -CH-CH- CH ₂ - CHp
-CH 'nCH-
Cn ₂ - υη ₂ -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ ) ₂ CH ₂ - -CH = CH- ^ CH - CH
-CH ^X CH -CH (CH ₃ ) CH ₂ - H 10 CH ₃ (CH ₂ ) ₂ CH ₂ - -CH ₂ CH ₂ - -CH (CH3) CH ₂ - ^{? S} CH- -CH (CH ₃ JCH ₂ - H CH ₃ (CH ₂ J ₂ CH ₂ - -CH ₂ (CH ₂ J ₂ CH ₂ - -CH (CH ₃ JCH ₂ - JH- -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ J ₂ CH ₂ - -CH ₂ (CH ₂ ) 16CH ₂ - -CH (CH ₃ ) CH ₂ - -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ J ₂ CH ₂ - - CHZCH ₂ (CH ₂ ) XiICI H CH ₃ (CH ₂ J ₂ CH ₂ - -C (CH ₃ ) = CH- -CH (CH ₃ ) CH ₂ - H 15th CH ₃ (CH ₂ J ₂ CH ₂ - -CaC- -CH (CH ₃ ) CH ₂ - H OH ₃ (CH ₂ J ₂ CH ₂ - -CH ₂ CsC-CH ₂ - H 20th CH ₃ (CH ₂ J ₂ CH ₂ - .CH ₂ - CH,
-CH -CH (CH ₃ ) CH ₂ - H CH ₃ (CH ₂ J ₂ CH ₂ - ^ CH --CH
-CH, C
Vj-ITT nil ^
On ₂ "- On ₂ H CHo (CH ₂ ) ₂ CH ₂ - H CH ₃ 25th CH ₃ (CH ₂ J ₂ CH ₂ - H CD
O
CO CH ₃ (CH ₂ J ₂ CH ₂ - H CQ
CO • <> __ * -CH-CH- H 00

. -CH (CH ₃ ) CH ₂ - H BAD ORIGIN _AL

Claims (10)

Claims 1. Process for the preparation of an organotin compound of general formula. 0 0 OR "» Il Il Il t R _n Sn (OCR ^f -COR ^ -OCC-CH ₂ ) ₄ _ _n in the η an integer from 1-3, R is a hydrocarbon substituent, namely an alkyl, Alkenyl, alkynyl, cycloalkyl, cycloalkenyl, a mono- or bicyelic aryl or an alkaryl radical rait up to 10 carbon atoms, R ^{1 is} a divalent radical, namely an alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, a mono- or bicyelic aryl, or an alkarylene radical with up to 18 carbon atoms, R "is a divalent radical, namely an alkylene, alkenylene, alkynylene, cycloalkylene or cycloalkenylene radical with up to to 18 carbon atoms and R "'is hydrogen or an alkyl radical with 1-10 carbon atoms is, characterized in that an organotin compound is reacted with an acrylyl glycol ester and optionallyB the product obtained is homo- or copolymerized. 2. The method according to claim 1, characterized in that the reaction is carried out according to the following scheme 0 0 OE * ' HH Nt RSnOOH + 3HO-C-R'-COR »-OCC-CH ₂ 0 0 OR ¹ · ¹ Il H Nt R ₂ SnO + 2H0-C-R'-C-0-R "-0-CC * CH ₂ 0 0 OH" ¹ it M Nt. (R, Sn) ₂ 0 + 2H0-CR ¹ -COR "-0-CC-CH ₂ 0 0 CR " ¹ HN Nt (D (2) (3) t RnSn (0-0-1 • -COE "-OCC» CH ,, L " 80983 4 / UIt in which R, R ¹ and R ″ have the meaning given above and the reaction sequences (1), (2) and (3) lead to compounds in which η is 1, 2 and 3, respectively. 3. The method according to claim 1 or 2 for the preparation of an organotin compound of the formula given above, in which η = 3, R is the η-butyl or propyl radical, R ^{1 is} the ethylene radical, R "is the Methyläthylenreet and R" ^{1 is} hydrogen. 4. The method according to claim 1 or 2 for the preparation of an organotin compound of the formula given above, in which η = 2, R is the n-butyl radical, R ^{1 is} the Äthylenylenreat, R "is the methylethylene ^{radical and R 1} " is hydrogen. ■ 5. Process according to Claim 1 or 2 for the preparation of an organotin compound of the formula given above, in which η = 3, R is the phenyl or n-octyl radical, R 'is the ethylene radical, R "is the methylethylene radical and R" ^{1 is} hydrogen. 6. The method according to claim 1 or 2 for the preparation of an organotin compound of the formula given above, in which η = 3, R the η-butyl or n-octyl radical, R ¹ the ethylene radical, R "the ethylene radical and R"'the Is methyl radical. 7. The method according to claim 1 or 2 for the preparation of an organotin compound of the formula given above, in which η = 2, R is the η-butyl or n-octyl radical, R ^{1 is} the ethylene radical, R "is the ethylene radical and R" ^{1 is} the Is methyl radical. 8. A method for producing a polymer according to claim 1, characterized in that in the polymeric structure at least one organotin unit of the following general Formula included is: ORIGINAL 90983A / U66 RlIt I I ^^ C = O 0 R " C = O R ¹ ι C = O 0-Sn-R ₅ in which R, R ', R "and R" ^{1 have} the meaning given above. 9. A method for producing a polymer according to claim 8, characterized in that the mixed polymer is the organotin unit in lesser and methyl methacrylate or Contains styrene in large quantities. 10. A method for producing a polymer according to any one of the preceding claims, characterized in that it contains in its polymeric structure at least one organotin unit of the following general formula 0 OR »· Il Il N I R ₂ Sn ^ OCR · -C-0-R "-0-CC-CHg2 in which R, R ', R" and R "' have the meaning given above. Pure Chas. Pfizer * Co., Ine 909834/1466