Cyanoacetylureas for stabilizing halogenated polymers

Details Cyanoacetylureas for stabilizing halogenated polymers Cyanoacetylureas for stabilizing halogenated polymers

1999-06-02

2001-04-03

Michl, Paul R. (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

Reexamination Certificate

active

06211270

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Technical Field
The invention relates to the compositions consisting of chlorine-containing polymers and cyanoacetylureas which are of the formula I depicted below and are intended for stabilizing these polymers, especially PVC.
2. Prior Art
PVC can be stabilized by a range of additives. Compounds of lead, of barium and of cadmium are particularly suitable for this purpose but are nowadays controversial on ecological grounds or because of their heavy metal content (cf. “Kunststoffadditive”, R. Gächter/H. Müller, Carl Hanser Verlag, 3rd ed., 1989, pages 303-311, and “Kunststoff Handbuch PVC”, volume 2/1, W. Becker/D. Braun, Carl Hanser Verlag, 2nd ed., 1985, pages 531-538; and also Kirk-Othmer: “Encyclopedia of Chemical Technology”, 4
th
ed., 1994, Vol. 12, Heat Stabilizers, pp. 1071-1091). The search therefore continues for effective stabilizers and stabilizer combinations which are free from lead, barium and cadmium.
Some of the compounds of the formula I are novel substances while others are known. Representatives of the formula I have been described, for example, in U.S. Pat. No. 2,598,936 and J. Org. Chem. 16, 1879-1890 (1951) and can be prepared by known methods in one or more process steps. The initial ureas are obtainable commercially or can be prepared by known methods.
SUMMARY OF THE INVENTION
It has now been found that cyanoacetylureas of the general formula I
where
X is oxygen or sulfur, and
R is C
2
-C
22
-acyloxyalkyl or C
1
-C
12
-alkyl which may be interrupted by 1 to 3 oxygen atoms and/or substituted by 1 to 3 OH groups, or is C
3
-C
8
-alkenyl, C
7
-C
10
-phenylalkyl, C
5
-C
8
-cycloalkyl, C
7
-C
10
-alkylphenyl, phenyl or naphthyl, where the aromatic radical in each case may be substituted by —OH, C
1
-C
12
-alkyl and/or OC
1
-C
4
-alkyl, and
R
1
is hydrogen or is as defined for R, are particularly suitable for stabilizing chlorine-containing polymers such as PVC, for example.
For compounds of the formula I:
C
1
-C
4
-alkyl is, for example, methyl, ethyl, n-propyl, iso-propyl, n-, i-, sec- or t-butyl.
C
1
-C
12
-alkyl is, for example, the radicals just mentioned and also pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, i-octyl, decyl, nonyl, undecyl or dodecyl. Preference is given to C
1
-C
4
-alkyl, uninterrupted or interrupted by —CO
2
—.
C
5
-C
8
-Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cyclohexyl.
C
7
-C
10
-Alkylphenyl is, for example, tolyl, xylyl or mesityl, especially tolyl and xylyl.
C
7
-C
10
-Phenylalkyl is, for example, benzyl, 1- or 2-phenylethyl, 3-phenylpropyl, &agr;,&agr;-dimethylbenzyl or 2-phenylisopropyl, preferably benzyl and 2-phenethyl, especially benzyl.
If the aromatic radical is substituted then it is preferably substituted by three, two or, in particular, one substituent and the substituents are, in particular, hydroxyl, methyl, ethyl, methoxy or ethoxy.
C
3
-C
8
-Alkenyl is, for example, allyl, methallyl, 1-butenyl, 1-hexenyl, 1-octenyl or 2-octenyl, preferably allyl or methallyl.
Examples of C
2
-C
22
-acyloxyalkyl are branched or straight-chain radicals such as, for example, acetoxyethyl, propionyloxyethyl, acetoxypropyl, acetoxybutyl, propionyloxybutyl, benzoxyethyl, benzoxypropyl, benzoxybutyl, phenylpropionyloxyethyl, phenylpropionyloxypropyl, phenylpropionyloxybutyl, etc., where the phenyl radical may be substituted by 1 to 3 —OH and/or 1 to 3 C
1
-C
4
-alkyl radicals (branched and unbranched).
Preference is given, for example, to acetoxyethyl and benzoxyethyl.
Preference is given to compounds of the formula I in which X is oxygen, and to those in which the radicals R and R
1
are identical. Also judicious are compounds in which X is sulfur.
Preference is also given to compounds of the formula I in which R and R
1
are C
1
-C
8
-alkyl, C
3
-C
5
-alkenyl, benzyl or 2-phenethyl.
Particular preference is given to compounds of the formula I in which R and R
1
are C
1
-C
4
-alkyl, allyl or benzyl.
In order to achieve stabilization in the chlorine-containing polymer, the compounds of the formula I are to be used in a proportion of judiciously from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight and, in particular, from 0.1 to 3% by weight.
It is also possible to employ combinations of compounds of the general formula I with other customary additives and stabilizers, for example with polyols and disaccharide alcohols and/or perchlorate compounds and/or glycidyl compounds and/or zeolite compounds and/or layered lattice compounds (hydrotalcites) and also, for example, light stabilizers. Examples of such additional components are listed and elucidated below.
SUMMARY OF THE INVENTION
Polyols and Disaccharide Alcohols
Examples of suitable compounds of this type are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol (cyclitols), polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol (hexitols), maltitol, isomaltitol, cellobiitol, lactitol, lycasine, mannitol, lactose, leucrose, tris(hydroxyethyl) isocyanurate, tris(hydroxypropyl) isocyanurate, palatinitol, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, xylitol, arabinitol (pentitols), tetritols, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-O-&agr;-D-glycopyranosyl-D-mannitol dihydrate.
Of these, preference is given to the disaccharide alcohols.
It is also possible to use polyol syrups, such as sorbitol, mannitol and maltitol syrup.
The polyols can be employed in an amount of, for example, from 0.01 to 20, judiciously from 0.1 to 20 and, in particular, from 0.1 to 10 parts by weight per 100 parts by weight of PVC.
Perchlorate Compounds
Examples are those of the formula M(ClO
4
)
n
, in which M is Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La or Ce. Depending on the valency of M, the index n is 1, 2 or 3. The perchlorate salts can be present as solutions or can have been complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The ester alcohols also include the polyol partial esters. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers are also suitable, such as di-, tri-, tetra- and polyglycols and also di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization. Other suitable solvents are phosphate esters and also cyclic and acyclic carbonates.
In this context, the perchlorate salts can be employed in various common forms of presentation; for example, as a salt or solution in water or an organic solvent as such, or adsorbed on a support material such as PVC, Ca silicate, zeolites or hydrotalcites, or bound by chemical reaction into a hydrotalcite or into another layered lattice compound. As polyol partial ethers, preference is given to glycerol monoethers and glycerol monothioethers.
Further embodiments are described in EP 0 394 547, EP 0 457 471 and WO 94/24200.
The perchlorates can be employed in an amount of, for example, from 0.001 to 5, judiciously from 0.01 to 3, and, with particular preference, from 0.01 to 2 parts by weight per 100 parts by weight of PVC.
Glycidyl Compounds
These contain the glycidyl group
attached directly to carbon, oxygen, nitrogen or sulfur atoms, and in such compounds R
1
and R
3
are either both hydrogen and R
2
is hydrogen or methyl and n is 0 or R
1
and R
3
together are —CH
2
—CH
2
— or —CH
2
—CH
2
—CH
2
— and in that case R
2
is hydrogen and n is 0 or 1.
I) Glycidyl esters and &bgr;-methylglycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule with epichlorohydrin or glyceroldichlorohydrin or &bgr;-methylepichlorohydrin. The reaction takes place judiciously in the presence of bases.
As compounds having at least one carboxyl group in the molecule it is possible to use aliphatic carboxylic acids. Examples of these carboxylic acids are glutaric, adipic, pimelic, suberic, azelaic and sebacic acid or dimerized or trimerized linoleic acid, acrylic and methacrylic acid, caproic, caprylic, lauric, myristic, palm

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