Stabiliser combinations for chlorine-containing polymers

Details Stabiliser combinations for chlorine-containing polymers Stabiliser combinations for chlorine-containing polymers

1998-06-30

2001-02-27

Sanders, Kriellion (Department: 1714)

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

Synthetic resins

Processes of preparing a desired or intentional composition...

C524S399000, C252S402000

Reexamination Certificate

active

06194494

ABSTRACT:

The invention relates to stabiliser combinations consisting of a compound of formula I shown below and at least one further substance from the following groups: the perchlorate compounds, glycidyl compounds, beta-diketones, beta-keto esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali aluminosilicates, hydrotalcites and alkali aluminocarbonates (dawsonites), alkali-(or alkaline earth-) carboxylates,-(bi)carbonates oder -hydroxides, antioxidants, lubricants or organotin compounds which are suitable for stabilising chlorine-containing polymers, especially PVC. PVC can be stabilised by a number of additives. Compounds of lead, barium and cadmium are especially suitable for the purpose but are controversial today for ecological reasons or owing to their heavy metal content (cf. “Kunstoffadditive” (Plastics additives), R. Gächter/-H. Müller, Carl Hanser Verlag, 3
rd
Edition, 1989, pages 303-311, and “Kunststoff Handbuch PVC” (Plastics Handbook PVC), Volume 2/1, W. Becker/D. Braun, Carl Hanser Verlag, 2
nd
Edition, 1985, pages 531-538; and Kirk-Othmer: “Encyclopedia of Chemical Technology”, 4
th
Ed., 1994, Vol 12, Heat Stabilizers p. 1071-1091). Other effective stabilisers and stabiliser combinations that are free of lead, barium and cadmium are therefore sought. Compounds of formula I have already been described in DE-PS 1 694 873, EP 65 934 and EP 41 479 and can be prepared in one or several process step(s) by known methods. It has now been found that A) compounds of formula I
wherein R*
1
and R*
2
are each independently of the other C
1
-C
12
alkyl, C
3
-C
6
alkenyl, C
5
-C
8
cycloalkyl that is unsubstituted or substituted by from 1 to 3 C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
5
-C
8
cycloalkyl or hydroxy groups or chlorine atoms, or C
7
-C
9
phenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3 C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
5
-C
8
cycloalkyl or hydroxy groups or chlorine atoms,
and R*
1
and R*
2
may additionally be hydrogen and C
1
-C
12
alkyl, and
Y is S or O,
can be combined with B) at least one compound from the following group:
perchlorate compounds and/or
glycidyl compounds and/or
beta-diketones, beta-keto esters and/or
dihydropyridines, polydihydropyridines and/or
polyols, disaccharide alcohols and/or
sterically hindered amines (tetraalkylpiperidine compounds) and/or
alkali aluminosilicates (zeolites) and/or
hydrotalcites and/or
alkali aluminocarbonates (dawsonites) and/or,
alkali- (or alkaline earth-) carboxylates, -(bi)carbonates oder -hydroxides,
and/or antioxidants and lubricants and/or
organotin compounds
for the purpose of stabilising chlorine-containing polymers, especially PVC.
For compounds of formula I:
C
1
-C
4
Alkyl is, for example: methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert-butyl.
C
1
-C
12
Alkyl is, for example, in addition to the radicals just mentioned, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, nonyl, undecyl or dodecyl.
C
1
-C
4
Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.
C
5
-C
8
Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
C
7
-C
9
Phenylalkyl is, for example, benzyl, 1- or 2-phenylethyl, 3-phenylpropyl, &agr;,&agr;-dimethylbenzyl or 2-phenylisopropyl, preferably benzyl.
When the cycloalkyl groups or the phenyl group of the phenylalkyl radicals are substituted, then they are substituted preferably by two or one substituent and, of the substituents, especially by Cl, hydroxy, methyl or methoxy.
C
3
-C
6
Alkenyl is, for example, vinyl, allyl, methallyl, 1-butenyl or 1-hexenyl, preferably allyl.
Preference is given to compounds of formula I wherein
R*
1
and R*
2
are each independently of the other C
1
-C
4
alkyl and hydrogen. Especially preferably, either R*
1
and R*
2
are identical and are methyl, ethyl, propyl, butyl or allyl, or they are different and are ethyl and allyl.
To achieve stabilisation in a chlorine-containing polymer, the compounds of component A) are to be used in an amount of advantageously from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, and especially from 0.1 to 3% by weight.
The compounds of the groups mentioned under B) are illustrated as follows:
Perchlorate Compounds
Examples are those of formula M(ClO
4
)
n
, wherein M is Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce. According to the value of M, the index n is 1, 2 or 3. The perchlorate salts may be complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The ester alcohols include also the polyol partial esters. Also suitable in the case of polyhydric alcohols or polyols are their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and poly-glycols, and di-, tri- and tetra-pentaerythritol or polyvinyl alcohol in various degrees of polymerisation. The perchlorate salts can be introduced in various known forms, for example in the form of a salt or an aqueous solution applied to a substrate, such as PVC, calcium silicate, zeolites or hydrotalcites, or bound in a hydrotalcite by chemical reaction. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers. Other forms are described in EP 394 547, EP 457 471 and WO 94/24 200.
The perchlorates can be used in an amount of, for example, from 0.001 to 5, advantageously from 0.01 to 3, especially from 0.01 to 2, parts by weight, based on 100 parts by weight PVC.
Glycidyl Compounds
These contain the glycidyl group
which is bonded directly to carbon, oxygen, nitrogen or sulfur atoms and wherein either R
1
and R
3
are both hydrogen, R
2
is hydrogen or methyl and n=0, or R
1
and R
3
together are —CH
2
—CH
2
— or —CH
2
—CH
2
—CH
2
—, in which case R
2
is hydrogen and n=0 or 1.
I) Glycidyl and b-methylglycidyl esters obtainable by reacting a compound having at least one carboxy group in the molecule with epichlorohydrin or glycerol dichlorohydrin or b-methyl-epichlorohydrin. The reaction is advantageously carried out in the presence of bases.
Aliphatic carboxylic acids may be used as compounds having at least one carboxy group in the molecule. Examples of those carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, acrylic acid and methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and pelargonic acid, and the acids mentioned in connection with the organic zinc compounds.
It is, however, also possible to use cycloaliphatic carboxylic acids, such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
It is also possible to use aromatic carboxylic acids, such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.
Carboxy-terminated adducts, for example of trimellitic acid and polyols, such as glycerol or 2,2-bis(4-hydroxycyclohexyl)propane can also be used.
Other epoxide compounds that can be used within the scope of this invention are to be found in EP 0 506 617.
II) Glycidyl or (b-methylglycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxy group and/or phenolic hydroxy group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acid catalyst with subsequent treatment with an alkali.
Ethers of that type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentanol, and from monofunctional alcohols, such as isooctanol, 2-ethylhexanol, isodecanol and C
7
-C
9
alkanol and C
9
-C
11

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