DE1520385C3 - Process for the preparation of organo-bismuth polymers - Google Patents

Description

3 4

nyl bismuth bis (10-hydroxystearate), 2-butenyl bismuth instead, where Ar, R ' _s, M and X have the above meaning

bis- (α-aminocaprylate); S-pentenyl bismuth-bis-flaktat), ^ and Z 'have a replaceable group, such as O, CO ^

Hexenyl bismuth bis (/ 8-hydroxyethyl-p-benzoate), or etc. is. From this it can be seen that when Z is bivalent

Öktenylwisrnut-bis- (4-hydroxybutyl-mercaptide). is, the organosmuth component has the formula Ar ₃ BiZj

R can also be a cycloalkyl radical _{and preferably 5, e.g. Ar 3 BiCO 3} :

a monocyclic cycloalkyl radical, e.g. B. Cyclohexyl; These representations of the invention to be

Be cycloheptyl, cyclooctyl or cyclopentyl. Preference is given to bismuth compounds

R is preferably cyclohexyl. R can also be an inert süb- wise in the presence of a liquid diluent

substituted cycloalkyl radical; such as chlorocyclohexyl, Me * means, e.g. B. toluene, ether, aliphatic carbon

be ethylcyclohexyl or ethoxycyclohexyl. io hydrogen, etc., can be carried out.

. Preferred organosismuth compounds h, where R Reaction temperatures might be more useful Cycloalkyl are: Dicyclohexyl bismuth-hydroxy-wise be approximately between 15 and 120 ° C j where acetate, di- (4-methylcyclohexyl) bismuth-2 "hydroxy- stirring is preferred.

ethyl mercaptide,. Di- ^ äthöxycyclohexyty-bismuth-rizi- The Orgänowisrhutverbihdung can by cooling

noleate, dicyclohexyl bismuth-e-aminocaproate, cyclization and filtering the reaction mixture

hexyl bismuth bis (p-aminobenzoate), 4-methylcyclo- stripping the liquid diluent, preferably

Hexyl bismuth bis (p-hydroxybenzoate) or ethoxy ^ can be isolated under vacuum, etc.

cyclohexylwisrnut-bis-ilO-hydroxystearate). The organo-science to be used according to the invention

R can also be a monocyclic alkyl radical confluence compounds are due to unexpectedly high bio ^

finally be inert substituted aryl radicals. R can be 20 logical activity, especially against bacteria;

for example phenyl, chlorophenyl, tolyl, bromine including highly resistant gram negative bacteria

phenyl- * XyIyI-, ethylphehyl or methoxyphenyl radical.

being. . . . Isocyanates that can be used are in particular 2,4-tolylene ¹

; Typical organowisfnut compounds, where R is a diisocyanate, nv phenylene diisocyanate, hexamethylene

Aryl radical are: diphenyl bismuth hydroxyacetate, di-isocyanate and pentamethyleh diisocyanate; furthermore also

p-tolyl bismuth-2'hydroxyäthylmercaptid, Di-chldfphe * Diphenylmethandiisocyanate, Dianisidindiisocyanatej

nylon bismuth ricin oleate, dixylyl bismuth e ^ aminocaproate; such as ^{3,3'-dimethoxy-4,4'-bis-L} phenylendiisocyänat, bi-

Di-bromophenyl bismuth-p-aminobenzoate, di-p-ethyltolylene diisocyahaV such as 3,3 '- <dimethyl-4; 4'-biphenylene-

phenyl bismuth p'hydroxybenzoate, phenyl bismuth bis * diisocyanate, diphenyl diisocyanates, such as 3,3'-diphenyl

(2-hydroxyethyl mercaptide); p-Tolyl bismuth-bis-hydr- 30 4,4'-biphenylenediisocyanate, 4,4 ', - biphenylenediisocy-

oxyacetate, chlorophenyl bismuth bis-ricinoleate, p-ethyl anate, dichlorxenylene diisocyanatej such as 3,3'-dichloro

phenyl bismuth bis (p-aminobenzoate), xylyl bismuth bis 4,4'-biphenylene diisocyanate and triisocyanates such as di-

(p-hydroxybenzoate) or phenyl bismuth bis-ClO-hydrphenyl ether-2,4,4'-triisocyanate.

oxystearate). The organosismuth compounds and the organic

The organowismutyl compound can be in the form of polyisocyanate in substantially equivalents

Ar ₃ BiX ₂ are present, where Ar is a monocyclic aryl amounts, ie in amounts that are sufficient to one

radical including inertly substituted aryl radical. Isocyanate group per hydroxyl or amino group for

For example, Ar_ can provide a Phehyl-j chlorophenyl ·, implemented.

Tolyl-, Brdmphenyl-, Äthylphenyl- or Methoxy- In the production of the new organowismüthal-

be phenyl radical. 4 ° term, polymers according to the invention, can expediently

Typical organo-bismuth compounds of the formula moderately the organo-bismuth compound and the

Ar ₃ BiX ₂ are triphenyl bismuth bis-hydroxyacetate, tri-organic polyisocyanate, if appropriate together

Tolyl bismuth bis (2-hydroxyäthylmercaptid), tri- (me- can be mixed with a polyether or polyester.

thoxyphenyl) bismuth bis ricinoleate, tri- (chlorophenyl) - Inert solvents and other liquid thinners

bismuth-bis- (e-aminocaproate), tri- (ethylphenyl) -wis- 45 can be used, z. B. to the

mut-bis- (p-hydroxybenzoate), triphenyl bismuth-bis-Cp- improve heat transfer, but are such

aminobenzoate) or trixylyl bismuth-bis- (10-hydroxy solvent and diluent not absolute

stearate). necessary.

The preparation of the catalysts used according to the invention can be used or

Trivalent bismuth compounds can be followed by 50 heat to cause the polymerization if necessary

de equation are shown: start. In general, the polymerizations are exo ^

RaBiZ ₃ -O + (3 - ä) MX -> R ₀ BiX ₃ -O + (3 - a) MZ, therm and can essentially be shortened in one

where R, R ', α and X have the above meanings, time periods are ended; typically about

M is a hydrogen atom or a metal, preferably 60 minutes or less.

Alkali or ammonium is * and Z is a replaceable 55 The resulting polymers vary in their physical

Group such as OH, Cl, O etc. It is clear that when the properties vary depending on the used

replaceable group Z is divalent, e.g. B. O, the Or- organosmuth compound, the organic polyiso-

ganowismut component the form RBiZ, z. B. RBiO, cyanate and the corresponding polyether or poly-

owns. ester. In general they vary from soft;

Such organo-bismuth compounds can, however, harden up to 60 sticky or Käutschuk-like substances,

also according to the equation: infusible masses.

R ₃ Bi + (3 - a) HX - * »R ₀ BiX ₃ -O + (3 - a) RH Preferred polyurethane or polyurea poly-

mere with the above-mentioned organosismuth compounds

getting produced. ,, fertilizers can be foamed to cellular poly-

In the production of the urethanes or polyureas to be used according to the invention. These hay show-

turning five-valued organo-bismuth compounds material polymers can be produced »by marl

the reaction takes place _e i _{NEN χ} ε π _o of the entire polyester or poly-

Ar ₃ BiZ ₂ '+. 2 MX - ¥ ■ Ar ₃ BiX ₂ + 2 MZ 'ether components of a polyurethane * or polyharn-

5 6

Fabric foam formulation usable by the serving adhesives according to the invention, replaced in paper mills for organo-bismuth compound. Thus, the reac control of the sludge and in processes for contraction mixing for the production of foamed polytrolls of Staphylococcus aureaus in hospitals, urethane polymers at least one compound from You can also be useful and effective Komder group R _a BiX ₃ -a and Ar ₃ BiX ₂ , where 5 components in sanitary detergents and can have the above meaning for R, Ar, X and α , contain an organic polyisocyanate and water for these and other purposes in the form of aerosols. be turned.

Other components of the reaction mixture, the foamed polyurethanes and polyureas

are used, where appropriate, catalysts can be particularly useful in their highly efficient

ren, such as N-ethylmorpholine, tin octoate, triethylene- io desired and permanent bacteriostatic properties

diamine, etc., cell modifiers such as silicones. Foam articles, e.g. B. mattresses, pillows

Polyether and polyester etc. etc., from the new organo-bismuth foam polymers

The new organo-bismuth polymers are permanently resistant to growth

high degree of effectiveness against microorganisms - composed of microorganisms including bacteria

men, especially bacteria, including grief.

positive and gram-negative bacteria, marked in the explanatory examples, all parts are marked, parts unless otherwise stated.

These new polymers can thus advantageously be used in areas where the wax example 1
such organisms are undesirable. Organo- 20

bismuth polymers, especially those that are relatively high in phenyl bismuth bis (2-hydroxyethyl mercaptide), the

Contain quantities of organobismuth compounds from triphenyl bismuth (22 parts) with 2-mercaptoethanol

can be used per se to protect material (7.8 parts) in 90 parts of toluene by refluxing

will. When used per se, they are often made in for 2 hours and not dated

the material is separated during the production and processing 25 toluene is ^{cooled to 30 0} C, and

incorporated. . 8.7 parts of tolylene diisocyanate were added. An un-

But they can also be used as adhesives. An indirect exothermic reaction is observed. Has

If, for surface coating by dipping, the exothermic reaction subsided, the

Padding, etc., masses in which the polymer refluxes the mixture for 1 hour, then

active component can be cooled and filtered for such applications. The polyurethane is in a

fertilizing can be used. Lot of 22 parts received. The polyurethane structure

Liquid masses can be used, in door is confirmed by infrared analysis. The PoIy

where the organobismuth polymer dissolved and / or in merisate has a softening point of about

is suspended in a solvent. Fixed preparation 120 ⁰ C. ·.

can be applied, whereby the organo 35 Beist> iel2
bismuth polymers with a carrier, e.g. B. a

diluent, is mixed. The carrier can be inert with phenyl bismuth-bis-hydroxyacetate (13 parts)

such as lime, clay, diatomaceous earth, Mehrl, etc. or tolylene diisocyanate (5.3 parts) by refluxing

have an activity such as that of quaternary am- the two reactants 2 hours in 45 parts

monium compounds is shown. The liquid addition 40 toluene reacted. A polyurethane polymer is used in

Emulsion-type preparations often contain a 14-part dispersion in the form of a highly viscous one

persisting agents, such as anionic, cationic or non-polymer solution,

ionic surfactants. For fungicidal or bak-. ■ \%

tericidal agents with an extremely broad activity - Example 3

The organic suppression polymers with other 45 100 parts polyethers with hydroxyl end groups,

be mixed with active substances, such as tri-organo- 1 part tin octoate, 1 part phenyl bismuth-bis- (2-hydroxy-

tin, pentachlorophenol, copper-4-, quinolinolate, bis-ethyl mercaptide) and 9.1 parts of tolylene diisocyanate are

phenols, o-phenylphenol, polybrominated salicylanides mixed together at room temperature. the

liden and metal (e.g. zinc) - dialkyldithiocarbama - exothermic polymerisation yields a solid polyurethane

ten. Plastics, textiles, paper products and paints 50 with a softening point of about 260 ^° C.
are examples of substances that are resistant to attack

can be made resistant by microorganisms Example 4

NEN, if by applying these polymers to, 100 parts of polyether with terminal hydroxy I-

the surface and / or treated by incorporation groups, 1 part dimethylpolysiloxane, 0.3 part N-

have been. 55 ethyl morpholine, 0.3 part tin octiate, 0.1 part tri

Protective plastics in solid and fiber form ethylenediamine, 0.5 parts phenyl bismuth-bis- (2-hydroxysind Polyurethanes, vinyl polymers, acrylic polymers, ethyl mercaptide), 2.9 parts of water and 38.6 parts Polyesters, polyamides, polyolefins and natural syn-tolylene diisocyanate become unthetic at room temperature Rubbers. set. The foaming and the polymerization are reduced. Protectable natural fiber products are paper products, 60 run en exothermic and provide a resilient polyhemp and felt. urethane foam.

Colors can be protected "in the jug" Example5. '. ■. "■

and also after application. Typical colors that P

can be protected are indoor and outdoor The procedure of Example 4 is repeated

Vinyl latias and alkyd paints, the older, non-synthetic 65 but instead of phenyl bismuth-bis- (2-hydroxy-

tables, natural matt paints, paints on acrylic ethyl mercaptide) the equivalent amount of phenyl

base, ship floor paints, etc. bismuth bis (p-aminobenzoate) are used and a poly-

- The organo-bismuth polymers are also manufactured as conurethane with polyuret bonds.

Example 6

Phenyl bismuth bis (p-hydroxybenzoate) (16.2 parts) is mixed with tolylene diisocyanate (5.2 parts) in 90 parts Toluene reacted by refluxing for 2 hours. The reaction mixture is cooled, filtered and 18.5 parts of a white, infusible polymer are obtained. Infratroanalysis confirms the structure of the polyurethane.

All the polymers tested have a high level of biological activity, especially against Bacteria. The product of Example 1 was tested, for example, according to the known agar diffusion test and gives very satisfactory inhibitions against Staphylococcus aureaus (Gram-positive bacteria), Aerobacter aerogenes (Gram-negative bacterium), Pseudomonas aeruginosa (Gram-negative Bacterium), Candida albicans (yeast) and Aspergillus flavus (fungus). The foamed polyurethanes and polyureas from the organo-bismuth compounds used according to the invention completely inhibit this Growth of organisms on it.

309 532/509

Claims (4)

1 2 or a phenyl, aralkyl or alkaryl group; where, claims: when a = 2, R 'is substituted by at least two hydroxyl or amino groups). 1. Process for the preparation of substituents which are inert towards the inert are substituents which are not attack by bacteria-resistant organo-bismuth-5 with the organo-bismuth compound itself or the polymer by reaction of polyisocyanates. Substances from which it is made react with at least two active hydrogen atoms. Typical inert substituents are organic compounds which point to hydrocarbons, thus substance, halogen, ether, etc. substituents.
characterized in that one can carry more than one hydroxyl or amine containing two active hydrogen atoms as at least R 'connecting substituents. It is clear that where R 'is alkenyl, fertilizers of the formulas RaBiX ₃ -O or Ar ₃ BiX ₂ do not use the amine or hydroxyl group directly on one (α = 1 or 2; R = alkyl or alkenyl of the carbon atoms of the double bonds linked group with less than 20 carbon atoms or can be. Cycloalkyl or monocyclic aryl group; Typical inert substituents are halogen or Ar = monocyclic aryl group; X = through Hy- 15 alkyl groups. ■ Hydroxy- or amino-substituted radical in the formula R ₀ BiX ₃ - _o , R can be selected from the group Formula - OOCR 'or by hydroxy groups of the alkyl radicals with less than 20 carbon atoms, substituted radical of the formula —SR '; R '= alkyl-alkenyl radicals with less than 20 carbon atoms, or alkenyl group with less than 20 carbon cycloalkyl radicals and monocyclic aryl radicals atoms or a phenyl, aralkyl or alkaryl be selected. R can be an alkyl radical with less than group; where, when a - 2 , R 'be at least 20 carbon atoms, such as methyl, ethyl, n- substituted by two hydroxy or amino groups - propyl, isopropyl, η-butyl, tert-butyl, amyl, hexyl, is tuated). Octyl, decyl, dodecyl, hexadecyl or octadecyl. 2. The method according to claim 1, characterized in that R preferably contains 1 to 8 carbon atoms, draws that one is an organo-bismuth compound 35 when it is an alkyl radical. used, in which R is phenyl. . Typical inert substituents are halogen, alkyl, 3. The method according to claim 1 or 2, characterized. Aryl, ether, etc. Typical inert substituted R radicals characterized in that one organosmuth ver-. 4-chlorobutyl, 2-ethylhexyl, w-phenylpropyl, 2-bond are used, in which a = 1. Ethoxyethyl etc. 4. The method according to any one of claims 1 to 3, 30 preferably used organobismuth compounds, characterized in that the reaction where R is alkyl are: di-n-butyl-bismuth hydroxyin Presence of water or inert propellant acetate, di-n-propyl bismuth-2-hydroxyethyl mercaptide, means. Di-n-octyl bismuth ricinoleate, diamyl bismuth-e-amino- caproate, -diisopropyl bismuth-ö-aminovalerate, disec- . 35 butyl bismuth-y-hydroxybutyrate, di-n-butyl bismuth-p- aminobenzoate, di-n-propyl bismuth p-hydroxybenzoate, Di-n-octoyl bismuth 10-hydroxystearate, diisobutyl bis- From the German Auslegeschrift 1 145 799 are mut-a-aminocyprylat, di-sec-butyl bismuth lactate, di-polymers known, the aromatically unsaturated cores isopropyl bismuth-yj-hydroxyathyl-p-benzoate, n-butyls as well as Elements of Group V of the Periodic Table 40 contain bismuth-bis- (4-hydroxybutyl-mercaptide), n-propylwis. As an element of the V group, in particular, bis-bis (ricinoleate), n-octoyl bismuth-bis (e-aminocasondere Called phosphorus. It is reported that the proat), amyl bismuth-bis - ((5-aminovalerate), isopropyl mentioned Polymers for a wide variety of purposes, bismuth-bis- (γ-hydroxybutyrate), sec-butyl bismuth-biswie z. B. protective coatings can be used. (p-aminobenzoate) ", n-butyl bismuth-bis- (p-hydroxyben-Daß the compounds especially resistant to bacteria 45 zoat), n-propyl bismuth bis (10-hydroxystearate), n-ok is not mentioned: tyl bismuth-bis- (a-aminocaprylate), isobutyl bismuth-bis- Also from British patent specification 939 191 are lactate, isobutyl bismuth-bis-lactate, sec-butyl bismuth-bis- - Bismuth-containing organic polymers are known. However (ß-hydroxyethyl-p-benzoate), isopropyl bismuth-bis - (/? - In this patent, too, nothing is said about a bak- hydroxyethyl-p-benzoate) or isopropyl bismuth-bis- teritive activity of the compounds mentioned. 50 (hydroxy acetate). It is the aim of this invention, new biologically active R can be an alkenyl radical with less than 20 carbon To produce organo-bismuth polymers. Substance atoms such as vinyl, allyl, 1-propenyl, 2-butenyl; The invention thus relates to a process for Her- 1-butenyl, 3-pentenyl, hexenyl, octenyl, decenyl, position of dodecenyl, hexadecenyl or octadecenyl against attack by bacteria, stable organo-bismuth polymers by reaction 55 Preferred alkenyl radicals are those with less than Use of polyisocyanates with at least two active 8 carbon atoms. Organic compound containing hydrogen atoms, R can also be an alkenyl radical with an inert sub- applications, and the novelty of the invention is that substituents, z. B. with. a halogen, alkyl, aryl, be considered to be at least two active hydrogen atoms on ether, etc. substituents. Typically inert substi- pointing compounds those of the formulas R _o BiX ₃ - _a 60 tuierte alkenyl radicals are chlorobuteny], isopropenyl, or Ar ₃ BiX _{2 is} used (a = I or 2; R = alkyl-2-ethylhexenyl, w-phenylhexenyl or ethoxybutenyl. or alkenyl group of less than 20 carbon-. Preferred organo-bismuth compounds, where R atoms or cycloalkyl or monocyclic aryl is an alkenyl radical are: diallyl bismuth hydroxyacetate, group; Ar = monocyclic aryl group; X = by divinyl bismuth-2-hydroxyethyl mercaptide, di-2-bute- Hydroxy or amino groups substituted radical of the 63 nyl bismuth rinoleate, di-3-pentanyl bismuth-s-aminoca- Formula —OOCR 'or by hydroxy groups sub- proate, dioktenyl bismuth <5-aminovalerate, dihexenyl- substituted radical of the formula —SR '; R '= alkyl or bismuth-y-hydroxybutyrate, di-1-butenyl bismuth-p-ami- Alkenyl group with less than 20 carbon atoms nobenzoate, allyl bismuth bis (p-hydroxybenzoate), Vi-